Polymer Degradation and Stability 97 (2012) 2262e2272

Contents lists available at SciVerse ScienceDirect

Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

The effect of extensive mechanical recycling on the properties of low density

polyethylene
Huiying Jin, Joamin Gonzalez-Gutierrez, Pavel Oblak, Barbara Zupan

ci

c*, Igor Emri
Centre for Experimental Mechanics, Faculty of Mechanical Engineering, University of Ljubljana and Institute for Sustainable Innovative Technology, Pot za Brdom 104,
1125 Ljubljana, Slovenia

a r t i c l e i n f o a b s t r a c t

Article history: Low density polyethylene (LDPE) was exposed to one hundred (100) consecutive extensive extrusion
Received 25 May 2012 cycles to simulate mechanical recycling. Collected samples were characterized by means of small
Received in revised form amplitude oscillatory measurements to investigate rheological properties, by gel permeation chroma-
12 July 2012
tography (GPC) to measure molecular weight, and with differential scanning calorimetry (DSC) to study
Accepted 26 July 2012
Available online 14 August 2012
thermal properties. Finally, solid time-dependent mechanical properties were characterized by
measuring creep compliance. The results show that simulated recycling did not significantly change the
melting and crystallization temperatures of LDPE. However, results from rheological measurement,
Keywords:
Low density polyethylene
crystallinity, creep measurements and GPC suggest that thermal degradation and gelation of LDPE occur
Mechanical recycling after extensive extrusion which leads to simultaneous chain scission and crosslinking of the polymer
Extrusion chains. It can be concluded that processability, measured by rheological parameters at high frequency
Differential scanning calorimetry and durability of LDPE measured by creep compliance, are only affected after the 40th extrusion cycle.
Rheology These observations correspond to the molecular changes of LDPE measured through GPC, MFI and
Gel permeation chromatography crystallinity calculations obtained from DSC measurements.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction which is also called chemical recycling consists of turning polymer

Plastics are ubiquitous in our everyday life; they are used in an
enormous and expanding range of products as diverse as household
appliances, packaging, construction, medicine, electronics, auto-
motive and aerospace components. They have already displaced
many traditional materials, such as wood, stone, leather, paper,
metal, glass, and ceramic, in many applications.
In 2010, total plastic production in Europe was 57 million tons,
and post-consumer waste was 24.7 million tons of which
10.4 million tons (42%) were disposed of in landfills [1]. To reduce
this large amount of plastic waste going into landfills, as well as, to
conserve non-renewable fossil fuels used in plastic production,
a strategy for sustainable development should include plastic
recovery.
There are mainly three options for plastics recovery: mechanical
recycling, feedstock recycling and energy recovery [2]. Mechanical
recycling is also known as physical recycling because plastics are
ground down and then reprocessed into re-usable material through
a physical rather than a chemical process. Feedstock recycling
* Corresponding author. Tel.: þ386 1 6207 103; fax: þ386 1 6207 110.
E-mail address: barbara.zupancic@fs.uni-lj.si (B. Zupan

ci

c).
chain into shorter hydrocarbon components that can be used as
source for rebuilding new polymers. Energy recovery refers to
incineration of waste materials to recover inherent energy.
Mechanical recycling is the most widely practiced of these methods
as it is relatively easy and economic. However, properties of
mechanically recycled polymers do not remain the same because of
degradation from heat, mechanical stress, oxidation and ultraviolet
radiation during reprocessing and lifetime [3].
The nature of polymer and processing conditions determine the
degree and type of polymer degradation, but all changes to which
chemical structure was subjected are followed by the changes in
the properties of the material. Polymers with moderate molecular
weight under fairly mild processing conditions go through gener-
ally modest degradation. However, when applying more severe
processing conditions, or using polymers with high molecular
weight, and repeated processing operations can lead to a significant
decrease in polymer characteristics [3].
Degradation of polyolefins during processing has been studied
by several authors. In the literature, it is illustrated that during
processing, polymeric materials are exposed to thermo-mechanical
and thermo-oxidative degradation which are responsible for chain
scission, branching and crosslinking reactions. The commonly
accepted degradation mechanism of low density polyethylene

0141-3910/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymdegradstab.2012.07.039
 H. Jin et al. / Polymer Degradation and Stability 97 (2012) 2262e2272
(LDPE) is the simultaneous occurrence of both chain scission and
molecular enlargement, although it shows a higher tendency to
crosslink or chain branching whereas chain scission is overall
dominating for more linear polymers such as linear low density
polyethylene (LLDPE), high density polyethylene (HDPE) and
polypropylene (PP) [4e16].
Kabdi et al. [9] found that mechanically recycled LDPE samples
presented lower values of melt flow index (MFI) in comparison
with virgin LDPE and they explained that this behaviour is because
LDPE scraps were subjected to thermo- and photo-oxidative
degradation during the processing or use, which leads to some
crosslinking. Holmström et al. [11] stated that both chain scission
and molecular enlargement occur simultaneously during thermal
degradation of LDPE in nitrogen atmosphere having less than 1.16%
oxygen. These two degradation mechanisms have opposite effects
on the molecular weight and molecular weight distribution (MWD)
of the polymer. The molecular weight decreases with increasing
chain scission reaction whereas the molecular enlargement reac-
tion accounts for shifting the MWD towards the high molecular
weight end. La Mantia [3] reported, however, that in most pro-
cessing operations, the variations of molecular weight caused by
thermo-mechanical stress are very small, that is why only the
Newtonian viscosity or the viscosity at low shear rates is strongly
influenced by processing conditions.
Several research groups have investigated the effects of
mechanical recycling of a variety of polyolefins [7e19], but the
effect of extensive mechanical recycling has not been reported. The
current study investigates the effects of extensive mechanical
recycling on several physical properties of low density polyethylene
(LDPE). The obtained results can be used for defining or optimizing
LDPE processing conditions for different product applications, as
well as for predicting long-term (time-dependent) behaviour of
material.
2. Materials and methods
2.1. Materials
Low density polyethylene (LDPE) OKITENÒ 245S produced by
DIOKI (Croatia) with a density of 0.924 g/cm3 and melting point of
114  C was used for the purposes of this investigation. Suggested
uses of OKITENÒ 245S include manufacturing of thin slippery films,
films and containers for food packing and co-extrusion with other
Fig. 1. Arrangements of the co-rotating screws.
2263
polyolefins. The manufacturer indicated the presence of a slip agent
and a thermal stabilizer in the material, but no antiblocking agent.
However, no further details were provided.
2.2. Repeated extrusion process and sample preparation
Mechanical recycling was simulated by means of repeated
extrusion. A Haake Polylab PTW 16/40 OS twin screw extruder
produced by Thermo Scientific (Germany) was used to perform one
hundred extrusion cycles. Fig. 1 shows the arrangement of the co-
rotating extrusion screws used for the process of simulated recy-
cling. Detailed explanation of the configuration can be found
in [20].
LDPE was extruded at screw rotation of 150 min 1, a processing
temperature of 240  C and with a throughput between 1200 and
1300 g/h. For the first ten extrusions 45 cylindrical samples (with
diameter d ¼ 6 mm, and length l ¼ 200 mm) were collected from
each cycle and thereafter the same amount of samples from every
next tenth extrusion cycle. The remaining extruded material was
cooled in a water tank and then pelletized using a Thermo Haake
pelletizer (type 557-2685) before being submitted to a new
extrusion cycle (Fig. 2).
2.3. Sample characterization
2.3.1. Viscosity measurements
Rheological properties of each sample were measured in Haake
MARS (Modular Advanced Rheometer System), Thermo Scientific
(Germany). All frequency sweep tests were performed at 240  C,
using plateeplate geometry (D ¼ 20 mm, gap ¼ 0.5 mm), at
frequency increasing from 0.1 Hz (0.628 rad/s) to 100 Hz
(628.32 rad/s). All measurements were performed applying a shear
stress of 300 Pa, previously determined to be within the linear
viscoelastic domain of the material. For each recycled material ten
repetitions were performed. In this study, viscosity results are
presented as the magnitude of the complex viscosity (jh*j), which is
calculated as shown in equation (1),
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 0 2  00 2
G G
jh*j ¼ þ (1)
u u
where G0 is the shear storage modulus, G00 is the shear loss modulus
and u is the angular frequency.
2264 H. Jin et al. / Polymer Degradation and Stability 97 (2012) 2262e2272

Fig. 2. Simulated mechanical recycling method.

2.3.2. Melt flow index (MFI) measurements

Melt flow index (MFI) measurements were performed according
to standards ASTM D1238 and ISO 1133. For this purpose, an
Extrusion Plastometer of the Italian producer ATS Faar S.p.a., was
used. The melt flow properties were measured at the temperature
of 190  C by applying pressure via prescribed gravimetric weight of
2.16 kg. MFI measurements were performed for the virgin LDPE and
recycled materials from selected consecutive extrusions (1st, 10th,
40th, 60th and 100th) with two repetitions.

2.3.3. Differential scanning calorimetry Fig. 3. Scheme of shear creep torsiometer.

Differential scanning calorimetry (DSC) analysis was carried out
according to ISO 11357. All the measurements were performed on
DSC7 instrument, Perkin Elmer, USA, in a nitrogen atmosphere. proper gripping in the torsiometer. In the first phase of shear creep
Mass of used specimens was 5.5  0.1 mg. Heating and cooling rate measurements each LDPE sample was heated up from room
was 20  C/min. Average values of six replicates have been used. temperature to 90  C over a period of 3 h, kept at this temperature
Melting temperature Tm and crystallization temperature Tc as well for 4 h, and then gradually cooled to 30  C over a period of 8 h. After
as heat of fusion Hf were evaluated from a second heating run. The this phase, the measurement was continued with loading,
degree of crystallinity (Xcr) was estimated using equation (2), unloading and conditioning of the sample at various temperatures
DH100% crystalline ¼ 293 J/g [18], (30, 50, 60, 70 and 80  C). Loading phase lasted 3 h at a constant
temperature, then the loading torque was removed and the
DHf temperature was increased to the next measuring temperature. The
Xcr ¼ (2) process of heating, and then maintaining the specimen at this
DH100%
elevated temperature took about 3 h. The specimen was again
torque-loaded, and the procedure of exchanging the phases of
2.3.4. Creep measurements loading, unloading and conditioning was repeated over the selected
Creep measurements were performed in the Shear Creep Tor-
siometer which has been developed in the Centre for Experimental
Mechanics of the Faculty of Mechanical Engineering, University of
Ljubljana, and is presented in detail elsewhere [21e23]. Fig. 3
schematically presents this measuring system consisting of three
parts: (i) mechanical device enabling torsional loading of a test
specimen in solid state, (ii) heating chamber, and (iii) measure-
ments and regulation setup including a computer and software,
used for data acquiring and analysis. All moving parts have been
equipped with aerostatic bearings to minimize friction in the
measuring device. The smallest torque loading is 1  10 5 Nm, and
the smallest measurable twist is 1.0  10 4 rad, the twist measuring
range is from 0 to 2.8 or 0.05 rad. The test specimen is placed in the
heating chamber built for temperatures from room temperature to
160  C, which can maintain the temperature at 0.5  C during the
time interval of 104 s.
For the purpose of shear creep measurements LDPE cylindrical
sample of 5.70  0.05 mm in diameter and 40.0  1.0 mm in length, Fig. 4. Schematic representation of the temperature-loading profile of the shear creep
was fixed by an adhesive to metal holders, specifically adapted for measurements.
 H. Jin et al. / Polymer Degradation and Stability 97 (2012) 2262e2272 2265

measuring temperature range. Fig. 4 schematically presents the
temperature-loading profile of the performed creep experiments.
Time needed for each measurement was around 42 h. For each
recycled material creep measurements were performed on three
different specimens (i.e. three independent repetitions) according
to the temperature profile of one measuring cycle shown in Fig. 4.
The stresses applied to each specimen were selected as to
remain in the linear viscoelastic region for all materials and ranged
from s0 ¼ 6.7  104 Pa at 30  C to 2.7  104 at 80  C. Preliminary
measurements made it evident that the loadings selected do not
affect the linearity of the LDPE viscoelastic behaviour. The response
of the material was measured in terms of rotational angle of the
specimen, 4(t) as a function of time and then recalculated to the
material shear creep compliance:
r,4ðtÞ gðtÞ
JðtÞ ¼ ¼ (3)
l,s0 s0
where s0 is the applied stress, r denotes radius of the circular cross
section of the sample, l length of the sample, and g(t) time-
dependent shear strain response. Applied torsional load resulted
in shear strain not exceeding 0.04%, regarding each measured
segment of deformational response at different temperatures
following the profile displayed in Fig. 4.
2.3.5. Gel permeation chromatography
The molecular weight analysis of the samples was carried out by
high temperature gel permeation chromatography (HT GPC) at
Polymer Standards Service GmbH (PSS, Mainz, Germany). The
columns used were PSS Polefin columns, with a column length of
300 mm and a particle size of 10 microns and with solvent 1,2,4-
trichlorobenzen. The injection system used was PolymerChar
GPC-IR with injection volume of 200 ml, using a flow rate of 1.0 ml/
min, and the temperature was set at 150  C. The results are pre-
sented here as the number-average molecular weight, Mn, weight-
average molecular weight, Mw, and as polydispersity index (PDI).
recycling on the viscosity of LDPE at 240  C is shown in the flow
curves shown in Figs. 5 and 6. In Fig. 5, it can be clearly seen that the
complex viscosity (equation (2)) at low frequencies (jh*j at 0.628 rad/
s) drastically increases (approximately ten times) with extrusion
cycles. The complex viscosity (equation (2)) at high frequencies (jh*j
at 291.6 rad/s) is, on the contrary, less affected by the processing. This
is in agreement with information provided by La Mantia [3]. The
typical shear rates used in industrial processing operations is
between 100 and 1000 s 1, which through the CoxeMerz rule [24]
corresponds to 100e1000 rad/s. Within the high frequency range
a change by a factor of about 1.5 in the viscosity was observed as
a result of 100 extrusions. On the other hand, the complex viscosity
at low frequencies was found to differ by about one decade (Fig. 5).
This means, that during usual processing operations, mechanical
recycling would cause negligible variations of the viscosity and of
the extrusion pressure or torque at the selected processing
temperature (240  C).
At high frequency complex viscosity slightly decreases after first
extrusion then gradually increases from second extrusion until the
100th extrusion (Fig. 6). Due to the inherent characteristics of
polymeric materials, particularly polyethylene, they are unfavour-
ably affected by processing parameters such as temperature, shear
and the presence of oxygen. These three factors can lead to thermo-
mechanical and thermo-oxidative degradation as discussed in the
Introduction. Thermal degradation of polymers mainly results in
chain scission and/or crosslinking reactions competitively and
simultaneously. In the case of LDPE, both chain scission and
crosslinking reactions can occur during the simulated recycling
process. However, as shown in the literature LDPE has a higher
tendency to crosslink [4e16], and therefore the increase of viscosity
a
16000
-> min
T = 240 °C
Complex Viscosity (Pa.s)

12000
3. Results and discussion

3.1. Rheological and MFI measurements 8000

Simulated recycling of LDPE was carried out through melt

extrusion at high temperature (240  C) and at high extrusion speed 4000
(150 min 1) under atmospheric condition. All materials tested show
a decreasing value of viscosity as angular frequency increases (i.e.
shear thinning) in the frequency range studied (0.628e261.6 rad/s) 0
0 1 2 5 10 20 30 40 50 60 70 80 90 100
and selected temperature of 240  C (Fig. 5). The effect of simulated
Number of Extrusion Cycles
b
100000 200
T = 240 °C max-> max
T = 240 °C
Complex Viscosity (Pa.s)
Complex Viscosity (Pa.s)

10000 150

1000 100

100 50
Virgin LDPE
Extrusion 30
Extrusion 60
Extrusion 100
0
10
0 1 2 5 10 20 30 40 50 60 70 80 90 100
0.1 1 10 100 1000
Angular Frequency (rad/s) Number of Extrusion Cycles

Fig. 5. Complex viscosity as function of angular frequency for LDPE of different Fig. 6. Variation of complex viscosity in dependence of the number of extrusion cycles
extrusion cycles. at: (a) minimum (0.628 rad/s), and (b) maximum (291.6 rad/s) frequency.
2266 H. Jin et al. / Polymer Degradation and Stability 97 (2012) 2262e2272

a 10000
-> min
T = 240 °C
8000

6000
G' (Pa)

4000

2000

0
0 1 2 5 10 20 30 40 50 60 70 80 90 100
Number of Extrusion Cycles

b 40000
->
max max

T = 240 °C
32000

24000
G' (Pa)

16000

8000

0
0 1 2 5 10 20 30 40 50 60 70 80 90 100
Number of Extrusion Cycles

Fig. 7. Variation of storage modulus G0 in dependence of the number of extrusion

Fig. 8. Variation of loss modulus G00 in dependence of the number of extrusion cycles
cycles at: (a) minimum (0.628 rad/s), and (b) maximum (291.6 rad/s) frequency.
at: (a) minimum (0.628 rad/s), and (b) maximum (291.6 rad/s) frequency.

with extrusion cycles (Fig. 6) can be related to a reduction in
polymeric chain mobility due to crosslinking.
Storage modulus, G0 , and loss modulus, G00 , displayed in Figs. 7
and 8, follow a very similar trend as shown by the complex
viscosity. Viscoelastic moduli increase with the number of extru-
sion cycles, which is indicative of a compact and entangled
microstructural network [25].
The overall trend for the measured rheological moduli (G0 and
G00 ) as a function of extrusion cycles might be explained as follows:
due to mechanical and thermal degradation, chain scission and
crosslinking happens simultaneously, however, during the first
extrusion chain scission is slightly more dominant than cross-
linking, while from the second extrusion crosslinking prevails over
chain scission. The smaller polymeric chains produced after chain
scission, have more mobility under shear flow, while crosslinked
chains have reduced mobility under the same conditions. These
results are in accordance with the results presented by other
authors [8,9,13,14,17,18].
Fig. 9 shows storage modulus and loss modulus for extrusion
cycles 0, 40, and 100 as function of angular frequency at 240  C.
Virgin LDPE (Fig. 9a) showed a predominantly viscous response
(G00 > G0 ) at up to a frequency of 64 rad/s when both viscoelastic
moduli have the same value (G00 ¼ G0 ); as the frequency increased
beyond 64 rad/s virgin LDPE behaved more elastic than viscous
(G00 < G0 ). It was observed that after 30 extrusion cycles,
a predominant elastic behaviour (G00 < G0 ) is shown in the entire
frequency interval tested and there was no crossover point
between the two viscoelastic moduli (Fig. 9b), being almost parallel
to each other in the whole measurement range; this is a typical
behaviour of a gel structure [26]. As the number of extrusions
continued up to 100, the distance between values of G00 and G0
steadily increased (Fig. 9c) indicating a stronger solid-like behav-
iour for the extensively extruded LDPE at all the studied
frequencies.
The point when the storage modulus is equal to the loss
modulus can be considered a good estimate of the gel point [32]. At
the gel point polymers start to behave like a network with
restricted polymer chain mobility thus preventing easy flow. Fig. 10
displays the evolution of the crossing point between G0 and G00 as
function of angular frequency. The decrease of the angular
frequency at which G0 and G00 intersects indicates that the relaxa-
tion time of polymeric chains is increasing with extrusion cycles,
which additionally supports the idea that crosslinking has occurred
during the extrusion process. It is important to point out that
starting at the 30th extrusion cycle viscoelastic moduli were not
intercepting within the measuring window; this is the reason for
presenting interception angular frequency only up to the 20th
extrusion cycle (Fig. 10).
Fig. 11 presents the results of the melt flow index (MFI)
measurements. It is evident that the MFI decreases with extrusion
cycles, and there is practically no throughput when it comes to the
MFI of 100-times extruded material. Decrease in MFI with
consecutive extrusions indicates a decrease in the ability of molten
LDPE to flow under pressure. This suggests reduction in the
mobility of polymeric chains, which can be attributed to cross-
linking or molecular enlargement, since both mechanisms decrease
chain mobility. However, results presented below indicate that
crosslinking is probably a dominating mechanism. MFI measure-
ments are in agreement with the rheological data presented
previously.
 H. Jin et al. / Polymer Degradation and Stability 97 (2012) 2262e2272 2267

a 100000
T = 240 °C

10000
G' & G'' (Pa.s)

1000

Virgin LDPE

G'
G''
100
0.1 1 10 100 1000
Angular Frequency (rad/s)
Fig. 10. Variation of angular frequency at which G0 and G00 intersect as function of the
b 100000
number of extrusion cycles.
T = 240 °C

aliphatic vinyl); or as a result of increasing crosslinking which can

10000 reduce the close packing ability of the polymer chains, and hence
G' & G'' (Pa.s)

decrease the polymer crystallinity [5,10]. Therefore, a decrease in

crystallinity with increasing number of extrusion cycles is another
result that supports the hypothesis that crosslinking prevails over
1000 chain scission during mechanical recycling.

Extrusion 40
3.3. Effect of recycling on time-dependent properties
G'
G''
100 3.3.1. Shear creep compliance and temperature dependence
0.1 1 10 100 1000 Determining retained properties and durability is among the
Angular Frequency (rad/s)
most important tasks when evaluating the possibility of mechan-
c ical recycling of plastic waste. As previously described in the
100000
T = 240 °C research methodology, creep measurements were performed at
five different temperatures: 30, 50, 60, 70, and 80  C, approximately
3 h (slightly longer than 104 s) for each of them. The data obtained
10000 for virgin LDPE, LDPE exposed to 40 and 100 extrusion cycles is
G' & G'' (Pa.s)

given as an example to illustrate how the creep data is processed

in order to familiarize the reader with this kind of analysis
(Fig. 14aec). To study the effect of mechanical recycling on
1000 temperature stability of polymeric products, we generated
Extrusion 100
isochrones of the creep compliance in dependence of the temper-
G'
atures within the measuring temperature range (30e80  C) at the
G'' reference time of 1000 and 10,000 s (approximately 15 min and 3 h,
100 respectively). As an example, temperature-dependent values of the
0.1 1 10 100 1000
Angular Frequency (rad/s)
creep compliance for virgin LDPE at the two selected reference
times are indicated with the dots and arrows in Fig. 14a, and are
Fig. 9. G0 and G00 of LDPE after (a) 0, (b) 40, and (c) 100 Extrusion cycles. analysed in continuation.

3.2. Differential scanning calorimetry

Melting temperature and crystallization temperature of all

samples before and after recycling were measured. As can be seen
in Fig. 12, there is no significant difference in values measured
between virgin LDPE and recycled ones. The maximum differences
in melting temperature and crystallization temperature between
recycled and virgin LDPE are 2.93% and 1.17% respectively, which
are within experimental error.
The percentage of crystallinity (Xcr) of recycled LDPE is found to
be more or less constant up to the 40th extrusion cycle, and then
starts to decrease somewhere between the 40th and 50th extru-
sions as presented in Fig. 13. According to the literature, the
decrease in crystallinity could be attributed to the creation of
structural irregularity by formation of short branches in the back- Fig. 11. Melt flow index (MFI) in g/10 min for virgin LDPE, LDPE exposed to 1, 10, 40, 60
bone chain and groups (e.g. hydroxide, hydroperoxide, carbonyl, and 100 extrusions.
2268 H. Jin et al. / Polymer Degradation and Stability 97 (2012) 2262e2272

construct the creep compliance master curves of virgin LDPE

Fig. 12. Melting temperature and crystallization temperature in dependence of the
number of extrusion cycles.
(Fig. 17). Timeetemperature shifting of the response function
segments was performed by using the closed form shifting (CFS)
methodology [27]. Since no measurements were performed exactly
at 40  C, the shift factors for creating the master curve were
modelled by using Arrhenius equation to generate the master curve
at the reference temperature of 40  C. Several authors [28e30]
reported that far from the glass transition temperature (more
than 100  C above Tg) which is the case of investigated poly-
ethylene, the temperature shift factors follow an Arrhenius rela-
tionship. From Arrhenius-type modelling of the temperature shift
factors one can determine parameter H, i.e. the activation energy
for material flow regarding the investigated temperature range.
Fig. 16 shows the diagram of calculated activation energies in
dependence of the number of extrusion cycles by applying Arrhe-
nius model to obtained temperature shift factors.

As indicated in Fig. 14a we extracted values of creep compliance

from the segments, measured at different temperatures, and ana-
lysed temperature dependence via generated isochrones within
measuring temperature range. Since experimental window of each
measured segment is limited, the reference time can be selected
only up to 10,000 s. Isochrones of the creep compliance are pre-
sented in Fig. 15a and b at the reference times of 1000 and 10,000 s
for the case of virgin LDPE, and LDPE exposed to 10, 40, 60, and 100
extrusions. From Fig. 15a and b it can be seen that for the investi-
gated materials as the temperature increases there is also an
increase in the creep compliance at any of the selected times, which
is the expected behaviour for thermoplastic polymers.
Complete analysis of the temperature dependence including all
investigated materials exposed to different number of extrusions
has shown that the temperature stability worsens after the 60th
extrusion cycle up to approximately 25%, this can be seen in Fig. 15a
and b in which the creep compliances of the material extruded 60
times shows the highest increase in shear creep compliance as
a function of temperature. However as extrusion cycles increase
there is an improvement in the temperature stability; as observed
in Fig. 15a and b the curve for the material extruded 100 times
shows smaller values of shear creep compliances than material
extruded 60 times and the values even come close to the values of
virgin LDPE.

3.3.2. Shear creep compliance and time dependence

For the purpose of the time-dependent creep properties
a reference temperature of 40  C was selected and the timee
temperature superposition principle was applied, in order to

Fig. 14. Creep compliance as a function of time for (a) virgin LDPE, (b) LDPE exposed to
40 extrusions, and (c) LDPE exposed to 100 extrusions measured at T ¼ 30, 50, 60, 70,
Fig. 13. Variation of crystallinity in dependence of the number of extrusion cycles. and 80  C.
 H. Jin et al. / Polymer Degradation and Stability 97 (2012) 2262e2272
b
Fig. 15. Creep compliance as a function of temperature for virgin LDPE, and LDPE
exposed to 10, 40, 60, and 100 extrusions at the reference times (a) tref ¼ 1000 s, and
(b) tref ¼ 10,000 s.
Differences in obtained activation energies relatively to ob-
tained activation energy for the virgin LDPE are only up to 11.5%.
Nevertheless, decrease of activation energy that can be observed up
to the 5th extrusion cycle in respect to the virgin LDPE, may indi-
cate presence of chain scission process and higher mobility of
polymeric chains, while increase of activation energy in the 80the
100th back to the level of activation energy for the virgin LDPE
might be related to the crosslinking process, and decreased ability
for re-arrangement of the molecules.
Fig. 16. Activation energy in temperature range 30e80  C as function of the number of
extrusion cycles.
2269
Fig. 17. Creep compliance master curve as a function of time for virgin LDPE, LDPE
exposed to 40 and 100 extrusions at the reference temperature, Tref ¼ 40  C.
To study the effect of mechanical recycling on long-time
stability of polymeric products, the isochronal values of the creep
compliance after 3 years (t z 107.98 s) and 10 years (t z 108.50 s)
were chosen from master curves of recycled materials, shifted
according to Arrhenius equation to the reference temperature of
40  C. The two isochronal values of the creep compliance are
indicated in Fig. 17, which shows time-dependent shear creep
compliance of virgin and recycled materials at reference tempera-
ture of 40  C.
Comparison of creep compliance values after 3 and 10 year are
presented in Fig. 18 for virgin and recycled materials at reference
temperature of 40  C.
From Fig. 18, it can be seen that the maximum differences in
creep compliance between virgin LDPE and recycled ones is less
than 10% until the 40th extrusion cycle after 3, as well as after 10
years. However, after 40th extrusion cycle, there was a higher
increase of creep compliance which gave maximum differences of
approximately up to 25% and 26% after 3 years and 10 years,
respectively. These results are in accordance with the observed
change of crystallinity in DSC measurements (Fig. 13). At the
molecular level, crystalline regions provide resistance for polymer
chains rearrangement [31], therefore it is reasonable to expect that
magnitude of creep would be inversely proportional to the degree
of crystallinity.
In addition, the increase/decrease of creep compliance in
comparison to the creep compliance of virgin LDPE reflects the
changes in mobility of molecular chains. In this respect it relatively
well corresponds to the indicated decrease/increase in activation
energy (Fig. 16).
Fig. 18. Creep compliance as function of the number of extrusion cycles after 3 and 10
years.
2270 H. Jin et al. / Polymer Degradation and Stability 97 (2012) 2262e2272

Fig. 19. Proportions of the insoluble part of the material for virgin and extruded LDPE
in 1,2,4-trichlorobenzen solution.
b
3.4. Gel permeation chromatography

Gel permeation chromatography was performed on virgin and

extruded LDPE. Prepared solutions of extruded materials in
1,2,4-trichlorobenzen for GPC measurements revealed very
different proportions of insoluble parts of the material depending
on the number of recycling (extrusions) (Fig. 19). Solubility results
show that proportion of insoluble fraction of the material increases
significantly after five extrusions, and reaches a maximum of 37%
after 100 extrusions. Increase of the insoluble part is additional
proof of the occurrence of crosslinking during the extensive
extrusion of LDPE.
In continuation, three normalized molecular weight distribution
curves are shown in Fig. 20 as an example of GPC results. It can be
Fig. 21. (a) Mn, and (b) Mw as function of number of extrusion cycles.
seen that as the number of extrusions cycles increase there is a shift
in the peak of the molecular distribution to smaller values. The
shape of the distribution curve also changes as number of extru- (PDI) (Mw/Mn) was calculated from above two values and its
sions progress, for example after 40 extrusions the curve widens evolution with extrusion cycles is shown in Fig. 22.
and a tail at high molecular weight is visible, but after 100 extru- Results on molecular weight distribution (MWD) obtained from
sions the curve becomes narrower and tails disappears. These GPC can be used to investigate degradation of polymers. If chain
changes in the molecular weight distribution suggest that there are scission occurs, the molecular weight distribution drifts toward
processes that reduce the molecular weight such as chain scission; smaller values and the progressive changes in molecular weight
however at the same time there are processes of molecular distribution can be modelled if it can be assumed that scission
enlargement and crosslinking. A better way to summarize GPC occurs randomly. If crosslinking occurs, the molecular weight
results is to look at the average molecular number (Mn), average distribution drifts in the opposite direction. If both scission and
molecular weight (Mw) and the polydispersity index (PDI). crosslinking occur, then the shape of the molecular weight distri-
The number-average molecular weight, Mn and the weight- bution changes considerably [31] as shown in Fig. 20.
average molecular weight, Mw of all samples before and after GPC results indicate that thermal-mechanical and oxidative
recycling are shown in Fig. 21. In addition, polydispersity index degradation during mechanical recycling results in a general shift
of the molecular weight distribution (MWD) toward lower

Fig. 20. Normalized molecular weight distribution for virgin LDPE, extruded 40 and
100 times. Fig. 22. PDI as function of number of extrusion cycles.
 H. Jin et al. / Polymer Degradation and Stability 97 (2012) 2262e2272
molecular weights. As is shown in Fig. 21a, Mn decreases with
increasing extrusion cycles which suggests an increase in the
amount of low molecular weight material. This is an indication of
chain scission happening during extensive extrusion cycles.
However, molecular enlargement can also occur. This is evidenced
by an intermediate increase of Mw (Fig. 21b) between the 2nd and
10th, and 20th and 40th recycling cycle and similarly for PDI
between the 20th and 40th recycling cycle (Fig. 22), which indicates
the development of high molecular weight tail of the MWD. After
the 50th extrusion cycle all the MWD parameters decay, such
changes in MWD may be linked to a more extensive degradation
that also manifested as a decrease in crystallinity and an increase in
creep compliance after the 50th extrusion cycle. Therefore, these
results are additional evidence that chain scission and crosslinking
happened simultaneously during mechanical recycling.
4. Conclusions
In the present work, the effect of extensive simulated mechan-
ical recycling of LDPE by means of melt extrusion up to one hundred
(100) cycles on rheological, thermal and time-dependent
mechanical properties as well as molecular weight distribution
were evaluated. It is necessary to emphasize that conclusions based
on the obtained results are strictly valid for the temperature
conditions used in the experiments, and should be used with care
for describing behaviour of recycled materials in other conditions.
It was observed that rheological functions (G0 , G00 and jh*j)
change after each extrusion cycle. After one extrusion cycle rheo-
logical values dropped, but in the subsequent extrusion cycles there
was an increasing general trend. These changes indicate that
mechanical recycling leads to molecular rearrangements caused by
thermo-mechanical and thermo-oxidative degradation. Rheolog-
ical measurements indicate that chain scission and crosslinking are
happening simultaneously in LDPE. However, it seems that at
a particular extrusion one mechanism dominates over the other;
for example during the first extrusion chain scission is slightly more
dominant than crosslinking, whereas at higher number of extru-
sions the crosslinking prevails. MFI results are in agreement with
rheological results, and show that melt flow index decreases with
the number of extrusion cycles.
DSC measurement showed that there is no significant difference
in melting temperature and crystallization temperature measured
between virgin LDPE and recycled ones. However, a decrease in
crystallinity starting at the 50th extrusion was observed which can
be attributed to the creation of structural irregularities as a result of
increasing crosslinking which can reduce the close packing ability
of the polymer chains, and hence, decreases the polymer crystal-
linity. Therefore, decrease in crystallinity is another result that
supports the prevalence of crosslinking over chain scission during
extensive mechanical recycling.
From creep measurements, it can be seen that mechanical
recycling does not affect time-dependent mechanical properties
until the 40th extrusion cycle, since no significant change was
observed in the creep compliance at 3 and 10 years. However, after
the 50th extrusion cycle, there was a more pronounced increase of
creep compliance when analysing time as well as temperature
stability. This result is in accordance with the change of crystallinity
measured by DSC. Since, at the molecular level, crystalline regions
provide the stiff resistance for polymer chains to creep, therefore it
is reasonable to believe that the lower the crystallinity, the more
a solid polymer can creep.
GPC results show that Mn decreases with increasing extrusion
cycles which is an indication of chain scission happening during
repeated extrusion cycles. However, GPC measurements also indi-
cate that molecular enlargement may have occurred. This is
2271
evidenced by an increase of Mw and PDI which indicates the
development of a high molecular weight tail of the MWD. There-
fore, these results are additional evidence that chain scission,
molecular enlargement and crosslinking happened simultaneously
during mechanical recycling. Finally, solubility result of extruded
LDPE in 1,2,4-trichlorobenzen shows that extensive extrusion
increases the amount of insoluble part of the material, which brings
additional support to the reasoning that crosslinking occurs during
the repeated extrusions and is more dominant than the chain
scission as the number of extrusions increases.
With these results on hand, it could be concluded that LDPE
could be extruded for up to 40 times without significantly changing
its processability and long-time mechanical properties. This could
be attributed to the two competing structural rearrangement
mechanisms that simultaneously occur: chain scission and
crosslinking.
Acknowledgements
This work was conducted with the financial support by the
European Commission through the Erasmus Mundus Executive
Agency and the Slovenian Research Agency e ARRS.
We would like to acknowledge the ISOKON d.o.o. (Slovenia) for
performing melt flow index measurements.
Grateful acknowledgement goes also to Samo Kozoderc and
Matej Gabr
s
cek for their help in performing creep and DSC
measurements.
References
[1] Plastics-the facts 2011. An analysis of European plastics production, demand
and recovery for 2010. Plastics Europe 2011. p. 9.
[2] Goodship V. Introduction to plastics recycling. 2nd ed. UK: Smithers-Rapra
Technology Limited; 2007.
[3] La Mantia FP. Basic concepts on the recycling of homogeneous and hetero-
geneous plastics. In: La Mantia FP, editor. Recycling of PVC and mixed plastic
waste. Chem Tec Publishing; 1996. p. 63e76.
[4] Chanda M, Roy SK. Plastics technology handbook. 4th ed. Clemson: CRC Press;
2006.
[5] Choudhury A, Mukherjee M, Adhikari B. Thermal stability and degradation of
the post-use reclaim milk pouches during multiple extrusion cycles. Ther-
mochim Acta 2005;430:87e94.
[6] Vilaplana F, Karlsson S. Quality concepts for the improved use of
recycled polymeric materials: a review. Macromol Mater Eng 2008;293:
274e97.
[7] Luzuriaga S, Ková
rová J, Fortelný I. Degradation of pre-aged polymers exposed
to simulated recycling: properties and thermal stability. Polym Degrad Stab
2006;91:1226e32.
[8] Andersson T, Stålbom B, Wesselén B. Degradation of low-density poly-
ethylene, linear low-density polyethylene, and high-density polyethylene in
film extrusion. J Appl Polym Sci 2004;91:1525e37.
[9] Kabdi SA, Belhaneche-Bensemra N. Compatibilization of regenerated low
density polyethylene/poly(vinyl chloride) blends. J Appl Polym Sci 2008;110:
1750e5.
[10] Teteris G. Degradation of polyolefines during various recovery processes.
Macromol Symp 1999;144:471e9.
[11] Holmström A, Sörvik E. Thermal degradation of polyethylene in a nitrogen
atmosphere of low oxygen content. III. Structural changes occurring in low-
density polyethylene at oxygen contents below 1.2%. J Appl Polym Sci 1974;
18:3153e78.
[12] Waldman WR, De Paoli MA. Thermo-mechanical degradation of poly-
propylene, low-density polyethylene and their 1:1 blend. Polym Degrad Stab
1998;60:301e8.
[13] Mariani P, Carianni G, Menconi F, LaMantia FP. Correlation between proc-
essability and properties of a high density polyethylene by a rheological
approach. Macromol Chem Phys 2002;203:1602e5.
[14] Pospí
sil J, Horák Z, Kruli
s Z, Ne
sp
urek S, Kuroda S. Degradation and aging of
polymer blends I. Thermomechanical and thermal degradation. Polym Degrad
Stab 1999;65:405e14.
[15] Martins MH, De Paoli M. Polypropylene compounding with post-consumer
material: II. Reprocessing. Polym Degrad Stab 2002;78:491e5.
[16] Santos ASF, Agnelli JAM, Trevisan DW, Manrich S. Degradation and stabili-
zation of polyolefins from municipal plastic waste during multiple extrusions
under different reprocessing conditions. Polym Degrad Stab 2002;77(3):
441e7.
2272 H. Jin et al. / Polymer Degradation and Stability 97 (2012) 2262e2272
[17] Cheng SZD. Handbook of thermal analysis and calorimetry, volume 3-appli-
cations to polymers and plastics. Elsevier; 2002.
[18] Dostál J, Ka
spárková V, Zatloukal M, Lubomír Simek
JM. Influence of the
repeated extrusion on the degradation of polyethylene. Structural changes in
low density polyethylene. Eur Polym J 2008;44:2652e8.
[19] Dintcheva NT, La Mantia FP, Trotta F, Luda FP, Camino G, Paci M, et al. Effects
of filler type and processing apparatus on the properties of the recycled ‘light
fraction’ from municipal post-consumer plastics. Polym Adv Technol 2001;12:
552e60.
[20] Frender A, Jährling M. Laboratory-mixers & extruders for nanocomposite
application. http://www.mcik.com/data/database/D0024/1271993808071.
pdf, Thermo Fisher SCIENTIFIC. [last accessed 05.07.2012].
[21] Metlikovi
c P, Emri I. Naprava za merjenje lezenja torzijsko obremenjenih poli-
mernih preizku
sancev I. Strojni
ski vestnik e J Mech Eng 1989;35(4e6):56e8.
[22] Metlikovi
c P, Emri I. Naprava za merjenje lezenja torzijsko obremenjenih
polimernih preizku
sancev II. Strojni
ski vestnik e J Mech Eng 1989;35(7e9):
102e8.
[23] Metlikovi
c P, Emri I. An apparatus for measuring the torsional creep
compliance function. Strojni
ski vestnik e J Mech Eng 1990;36(7e9):E9e13.
[24] Cox WP, Merz EH. Correlation of dynamic and steady flow viscosities. J Polym
Sci 1958;28:619e22.
[25] Martin-Alfonso JE, Valencia C, Sánchez MC, Franco JM, Gallegos C. Develop-
ment of new lubricating grease formulations using recycled LDPE as rheology
modifier additive. Eur Polym J 2007;43:139e49.
[26] Wrolstad RE, Decker EA, Schwartz SJ, Sporns P. Measurement of gel rheology:
dynamics tests, in handbook of food analytical chemistry. Wiley; 2005.
[27] Gergesova M, Zupan
ci

c B, Saprunov I, Emri I. The closed form t-T-P shifting
(CFS) algorithm. J Rheol 2011;55:1e16.
[28] Mours M, Winter HH. Viscoelasticity of polymers during heating/cooling
sweeps. Ind Eng Chem Res 1995;34:3217e22.
[29] Park HE, Dealy J, Munstedt H. Influence of long-branching on time-pressure
and time-temperature shift factors for polystyrene and polyethylene. Rheol
Acta 2006;46:153e9.
[30] Ruymbeke E van, Stéphenne V, Daoust D, Godard P, Keunings R, Bailly C.
A sensitive method to detect very low levels of long chain branching from the
molar mass distribution and linear viscoelastic response. J Rheol 2005;49(6):
1503e20.
[31] Shyichuk AV, White JR. Analysis of chain-scission and crosslinking rates in the
photo-oxidation of polystyrene. J Appl Polym Sci 2000;77:3015e23.
[32] Kim SY, Choi DG, Yang SM. Rheological analysis of the gelation behaviour of
tetraethylorthosilane/vinyltriethoxysilane hybrid solutions. Korean J Chem
Eng 2002;19:190e6.