Polymer Degradation and Stability 111 (2015) 46e54

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Polymer Degradation and Stability

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

Size exclusion chromatography of photo-oxidated LDPE by triple

detection and its relation to rheological behavior

n-Garrido*, Matthias Kruse, Manfred H. Wagner
Víctor H. Rolo
Chair of Polymer Engineering/Polymer Physics, Berlin Institute of Technology (TU Berlin), Fasanenstrasse 90, D-10623 Berlin, Germany

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

Article history: Sheets of low-density polyethylene (LDPE) were subjected to photo-oxidation in the presence of air using
Received 17 September 2014 a xenon lamp to irradiate the samples for times between 1 day and 6 weeks. The formation of long-chain
Received in revised form branching (LCB) up to one week of degradation and the competition between chain scission and
20 October 2014
crosslinking at longer periods of radiation were investigated by rheological characterization, Fourier
Accepted 27 October 2014
transform infrared spectroscopy, and the solvent extraction method (Rolo
n-Garrido and Wagner. Polym
Available online 1 November 2014
Degrad Stabil 2014, 99:136, Rolo
n-Garrido and Wagner. J Rheol 2014, 58:199). In the present contribution
the same samples are studied by size exclusion chromatographic characterization using triple detection
Keywords:
Contraction factor
(concentration, light scattering and viscosity). The gel content is determined by filtration followed by the
Triple detection analysis of the soluble polymer fraction. The influence of photo-oxidation time on the molecular weight
Chromatography distribution (molar masses and polydispersity), the mean square radius of gyration and the intrinsic
Rheology viscosity contraction factors is discussed. The results are correlated with the model parameters (b and
MSF model 2 ) of the molecular stress function (MSF) theory, used to describe quantitatively the rheological data in
fmax
Photo-oxidative degradation uniaxial elongation. It is verified that LCB occurs as an aside process, which up to one week of degra-
dation dominates over chain scission, before gelation plays a critical role. It is confirmed that the model
parameter b correlates with the gel content, which reflects the competition between chain scission and
2
crosslinking, while fmax is found to correlate with the experimentally determined contraction factors. By
comparing the data of this study with those obtained earlier for polystyrene comb melts with well
defined structure, the influence of the branching frequency (i.e. the number of branch points per 1000
2
carbon atoms) on fmax becomes evident.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction response of the samples, measured in small amplitude oscillatory

The photo-oxidation of polymers is relevant not only from the
scientific [1,2], but also from the industrial point of view. The
induced structural modifications through irradiation have been
shown to be advantageous for exploring the application of recycled
materials [3], and for increasing the performance of polymer ma-
terials prior [4] or during processing like in thermoforming [5] or
film blowing [6].
The influence of photo-oxidation on low density polyethylene
(LDPE) has been studied recently at irradiation times varying from
one day, up to six weeks [7,8]. The experimental techniques applied
were the solvent extraction method, rheology and Fourier trans-
form infrared (FTIR) spectroscopy. In contrast to thermo- [9] and
thermo-oxidative degradation [9,10], the linear viscoelastic
* Corresponding author.

n-Garrido).
E-mail address: victor.h.rolongarrido@tu-berlin.de (V.H. Rolo
shear flow, was found to be strongly affected by the photo-
oxidative degradation [7]. The rheological data obtained in the
nonlinear regime, i.e. measured in uniaxial deformation, were
described quantitatively by the molecular stress function (MSF)
model for polydisperse randomly branched samples [11,12].
Photo-oxidative degradation causes chain scission and cross-
linking, although secondary reactions like chain branching can also
occur as a consequence of the free radical polymerization, similar to
thermal oxidation [1]. It is known that chain scission and recom-
bination compete and one of them predominates, characterizing
the overall behavior under weathering [13]. Since crosslinking and
chain scission take place at the same time [14,15], this competition
influences the gel content of the samples [16].
The rheological characterization allowed understanding that for
samples degraded for up to one week, i.e. when the gel content was
low, the induced increase in strain hardening was mainly due to the
formation of long-chain branching (LCB), overcoming possible
chain scission, as indicated by the non-linear parameters of the MSF

http://dx.doi.org/10.1016/j.polymdegradstab.2014.10.022
0141-3910/© 2014 Elsevier Ltd. All rights reserved.

n-Garrido et al. / Polymer Degradation and Stability 111 (2015) 46e54
V.H. Rolo
model [7]. The MSF model applied to quantify the data contains
only two parameters for uniaxial deformation, b and fmax 2 . b is
directly related to the molecular structure of the polymer and can
be predicted if the structure of the polymer is known [17e19],
otherwise it is determined from the slope of the elongational vis-
cosity after inception of strain-hardening [17] (Fig. 1). fmax2 is
determined by fitting to the suprema of the elongational viscosities
achieved experimentally (Fig. 1). For more details about the MSF
model and its applications, see Rolo
n-Garrido [20].
The gel content increased drastically between one and two
weeks of degradation, although it decreased at the third week. The
changes observed in the linear viscoelastic properties of the sam-
ples irradiated for three and five weeks were found to be a
consequence of the competition between the chain scission and
crosslinking. This was corroborated through the carbonyl index and
concentration of acid and aldehyde groups measured by the FTIR
technique [8], as well as the uniaxial elongational measurements by
the experimentally determined strain hardening index and the
non-linear parameters of the MSF model, where fmax 2 increases up
to infinity for the samples containing mainly a gel structure, and b
correlates with the gel content measured by the solvent extraction
method [7].
Size exclusion chromatography (SEC), also known in the litera-
ture as gel permeation chromatography (GPC), has been applied to
study photo-oxidative degradation of different types of poly-
ethylene [21e23], which also leads to an oscillating gel content
with increasing degradation time [24]. It should be noted that the
mass average molecular weights reported by SEC solely correspond
Fig. 1. Examples of uniaxial experiments (symbols) on photo-oxidative degraded LDPE
after a) one day and b) three weeks of treatment, compared to the predictions (lines) of
the MSF model obtained through the parameters b (determined by the slope at the
beginning of the strain hardening) and fmax 2 (determined by the suprema of the
elongational viscosities achieved experimentally). Reprinted from Rolo
n-Garrido and
Wagner. Polym. Degrad. Stabil. 99: 136e145. Copyright © 2014, with the kind
permission from Elsevier.
47
to the soluble fraction of the samples [13]. This technique has been
combined with rheology to study the molecular weight changes
during photo-oxidation of polyethylene nanocomposites [25] or the
influence of morphology on photo-degradation of LDPE films [26].
Although it was concluded that the SEC data strongly support the
results obtained from rheological measurements [26], both studies
were limited to characterization in the linear viscoelastic regime.
Studies applying SEC coupled with a multi-angle light scattering
(MALS) detector and the non-linear rheology of irradiated samples
have scarcely been performed, with the exception of polypropylene
treated through electron beam and gama-irradiation [4,27e30].
Coupling a SEC device to a viscosity and a MALS detector permits
to deepen the analysis of the LCB architecture of the samples
through the contraction factors [31,32]
〈R2g 〉br
g≡ (1)
〈R2g 〉l
½hbr
g
≡ (2)
½hl
where 〈R2g 〉 and [h] represent the mean square radius of gyration
and the intrinsic viscosity, respectively, of branched (br) and linear
(l) chains having the same molar mass.
It is the objective of this contribution to analyze the photo-
oxidatively degraded LDPE studied before [7,8], using triple-
detector SEC characterization, and to correlate the additional in-
formation obtained with the non-linear parameters of the MSF
model.
2. Experimental data
2.1. Materials
The characterized samples were taken from the same sheets
studied before [7,8]. For completeness, only a short description of
the degradation process is given. The reference sample was low-
density polyethylene (LDPE) 3020D produced by BASF. The sup-
plied granules were extruded and pressed to produce plates
denoted as reference sample LDPE T0. The photo-oxidized samples
were produced using previously prepared LDPE T0 plates. They
were radiated using a xenon lamp for times between 1, 3 and 5
days, and 1e6 weeks. The notation of the samples is based on the
treatment time, stating “D” for day, and “W” for week. Thus, LDPE
3D and LDPE 4 W mean that the samples were photo-oxidatively
treated three days and four weeks, respectively. The conditions
used to avoid thermo-mechanical degradation during the prepa-
ration of the LDPE T0 plates and further details about the photo
degradation process are given elsewhere [7].
2.2. Size exclusion chromatographic characterization
Size exclusion chromatographic (SEC) measurements were car-
ried out by use of a high temperature device (GPC-PL 220, Agilent)
with a refractive index (RI) and a viscosity (PL-BV 400HT) detector.
Three PLgel Mixed-B columns with a particle size of 10 mm were
used. The SEC is coupled with a multi-angle light scattering (MALS)
detector (DAWN HELEOS 8þ, Wyatt Technology Corporation). The
temperature of the measurements was 140  C, using 1,2,4-tri-
chlorobenzene (TCB) as solvent. The samples were prepared with a
concentration of 2 mg/mL, and dissolved in TCB at 160  C for 3 h
prior to the experiment [33]. At least four experiments were per-
formed for the reference sample and for each photo-oxidized
sample.
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n-Garrido et al. / Polymer Degradation and Stability 111 (2015) 46e54
V.H. Rolo

The samples were not filtered prior to their injection in the SEC
device. Therefore, crosslinked particles remained on the integrated
filter with a pore size of 2 mm located in front of the columns.
Consequently, the chromatograms measured correspond to the
soluble part of the samples. The area Adeg under the concentration
signal curve is therefore proportional to the total mass of the sol-
uble fraction of the degraded sample, while for the reference
sample, Aref represents the entire mass of the dissolved specimen.
Hence the gel fraction can be calculated as.
! been able to diffuse out during the dissolution time of the solvent

 Aref  Adeg
Gel wt:% ¼  100:
Aref
Comparing the magnitude of the gel content measured by SEC
and by the solvent extraction method [7], it is noticed that the
values obtained by SEC are lower than those measured by the
solvent extraction method. This may be a consequence of weak gel
particles being susceptible to shear degradation at the integrated
filter. It may also be that the gel particles on the filter are flushed by
the pressure driven solvent stream, thereby releasing branched
molecules located in the matrix of the network, but which are not
chemically bonded to the matrix. These molecules would have not
extraction method due to their entanglements with the polymer
(3)
matrix.

Eq. (3) can be also applied if the samples would be filtered prior 3.2. Molecular weight distribution
to their injection in the SEC device. The additional filtration espe-
cially at high temperatures can result in a loss of material, leading to The following results are discussed considering that the data
incorrect conclusion of the concentration. presented correspond to the soluble part of the samples, which
originate either from samples with low (Fig. 3a) or high (Fig. 3b) gel
3. Results and discussion content. In other words, the SEC technique is taken as a tool to
separate the gel content from the entanglement structure, and
3.1. Gel content hence this method allows obtaining a direct and specific insight
into the effect of the degradation time on the LCB content of the
The gel content was determined by SEC from Eq. (3) since the soluble fraction.
samples were not filtered previously to the injection in the device It can be observed that up to one week of degradation (Fig. 3a),
(Fig. 2). The amount of insoluble material remains low up to the the general molecular weight distribution (MWD) curve is shifted
first week of degradation. The gel content increases drastically from
the first to the second week, but is lower after the third week than
expected by comparison to the higher value obtained for LDPE 4W.
A similar reduction, although not as dramatic as for LDPE 3W, was
also observed for LDPE 5W, before the gel content increases again
for LDPE 6W.
This cyclic behavior, attributed to the competition between
chain scission and crosslinking [7], agrees with previous observa-
tions of the carbonyl index and the concentration of acid and
aldehyde groups measured by the FTIR technique [8], or with re-
sults of rheological experiments in the linear as well as in the non-
linear viscoelastic regime [7].
The unexpected decrease in physical properties of an irradiated
sample has also been observed in gel content and tensile strength
of ethylene-octene copolymers [16], in carbonyl index and shearing
modulus of an LLDPE/LDPE film [14], the yield stress, stress at break
and strain at break of linear low density polyethylene [34], density
in LDPE films [26], and the degree of crystallinity on LDPE films
[35].

Fig. 2. Gel content determined by SEC according to Eq. (3) (squares with error bars),
and the nonlinear parameter b of the MSF model (circles) as function of degradation Fig. 3. Change in MWD of photo-oxidatively degraded samples with a) low gel content
time. and b) high gel content.

n-Garrido et al. / Polymer Degradation and Stability 111 (2015) 46e54
V.H. Rolo
to lower molecular weights for every sample compared to the
reference. The high molecular weight tail tends to increase appar-
ently only for LDPE 5D and LDPE 1W, in comparison to LDPE T0. In
the case of samples degraded between two and six weeks (Fig. 3b),
LDPE 2W, LDPE 3W and LDPE 5W present a similar tendency as
observed in Fig. 3a. On the other hand, the MWD of LDPE 4W and
LDPE 6W is shifted to lower values of molecular weight compared
to LDPE T0 in the whole experimental window. For a detailed
analysis, the number average molecular weight, Mn, the poly-
dispersity (Mw/Mn) and the z-average molecular weight Mz, will be
used as a measure of the induced changes due to the photo-
oxidation in the low molecular weight tail, the broadness of the
MWD and the high molecular weight tail, respectively.
The number average molecular weight decreases continuously
from the reference sample up to LDPE 1W (Fig. 4a). This can be
Fig. 4. Changes in a) the number average molecular weight Mn, b) the polydispersity
(Mw/Mn), and c) the average molecular weight Mz (squares) and gel content (circles) of
photo-oxidatively degraded samples.
49
interpreted as the result of chain scission of the molecules. The
same trend has been reported for photo-oxidative degradation of
high density polyethylene (HDPE) [36]. The Mn value seems to
oscillate between LDPE 1W and LDPE 3W, before a drastic decrease
occurs from LDPE 3W to LDPE 4W, remaining at a similar low value
up to LDPE 6W. Fig. 4a shows the effect of degradation time on
chain scission, and the drastic reduction of Mn is related to the
observation that the samples LDPE 4W, LDPE 5W and LDPE 6W
became increasingly brittle at room temperature [8]. This is in
accordance with mechanical tests, which demonstrated that sig-
nificant brittle behavior seems to occur after 20 days of irradiation
[35].
An increase in the polydispersity as a function of the degrada-
tion time has been observed in thermo-oxidative degradation of
HDPE, based on MWD curves obtained from rheology measure-
ments [37]. This was interpreted as an indication that some
crosslinking occurs at the same time as chain scission. In the pre-
sent contribution, considering that the gel content is low up to
LDPE 1W, and that the soluble fraction contains only entangled and
not crosslinked molecules, the increase measured in Mz is rather a
consequence of an increase in LCB content (Fig. 4c) that occurs at
the same time as chain scission (Fig. 4a) and gel formation (Fig. 2),
as also identified through non-linear rheological measurements in
uniaxial deformation [7]. The change in polydispersity with
increasing degradation time due to the both countering reactions,
i.e. chain scission and LCB formation, is shown in Fig. 4b. Addi-
tionally, the oscillating character can be noticed starting from the
second week. The cyclic competition between chain scission and
crosslinking has been found to be responsible for the different
inherent structure of the gel content in LDPE 3W and LDPE 5W as
supported by different techniques [7,8] and also shown in Fig. 2.
The present analysis reveals that also in the soluble part of the
sample, more molecules with higher LCB content are present in
LDPE 5W and in LDPE 3W (Fig. 4c). This is not observed in LDPE 4W
and LDPE 6W where a higher amount of chain scission can be
inferred from the Mn and the Mz values.
The amount of LCB in the molecule influences the possible gel
formation in the case of further degradation [38]. If the LCB content
is low, further degradation would lead to a stiffer gel than if mol-
ecules with a high quantity of LCB are crosslinked. This would
explain why the gel stiffness of LDPE 6W was found to be lower
than of LDPE 5W, as determined by linear-viscoelastic character-
ization [7].
In the case of the high molecular weight tail (Fig. 4c), a
continuous increase up to LDPE 3W is detectable. This tendency and
the increase of LCB content explain the increase of strain hardening
in the uniaxial measurements [7], since it has been reported [39,40]
that high molar mass components determined by SEC can influence
the elongational viscosity even stronger than polydispersity [41].
The low values for LDPE 4W and LDPE 6W is the result of the
shifting of MWD towards lower molecular weights due to the
predominant crosslinking process in these samples. It is also
noticed that the higher LCB content produced in LDPE 5W
congruently reflects a high molecular weight tail in its MWD, which
does not necessarily mean a higher Mn.
3.3. Contraction factors
To obtain the contraction factors (Eq. (1) and Eq. (2)) based on
the experimentally determined radius of gyration and intrinsic
viscosity of the branched samples as obtained by the MALS and
viscosity detectors, respectively, it is necessary to have also the
respective values for the linear counterparts. The mean square
radius of gyration is related with the molar mass for linear poly-
ethylene by Ref. [42]
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n-Garrido et al. / Polymer Degradation and Stability 111 (2015) 46e54
V.H. Rolo
〈R2g;z 〉l ¼ 0:028Mz0:568 : (4)
The Mark-Houwink equation (also known as Mark-Houwink-
Kuhn or Mark-Houwink-Kuhn-Sakurada) relates the intrinsic vis-
cosity and molar mass as [31]
½hl ¼ KMa (5)
where the constants K and a depend on the polymer, solvent and
temperature. K ¼ 4.82  104(dL/g) and a ¼ 0.707 have been re-
ported for linear polyethylene in TCB at 140  C [43]. For a poly-
disperse sample, the intrinsic viscosity is related to the weight-
average molar mass [31], and therefore M in Eq. (5) is taken as
Mw. The mean square radius of gyration contraction factor g is
presented as function of the degradation time in Fig. 5a. Its value
decreases continuously up to LDPE 2W, corresponding to an in-
crease in the degree of branching [31]. At degradation times longer
than two weeks, it seems that a constant value is achieved,
although still a slight oscillation in the mean value of g is observed,
with slightly higher values for LDPE 4W and LDPE 6W. A clear
tendency is noticed in the increment of the error bars from the
third up to the sixth week of treatment. Considering that g reflects
predominantly the high molecular tail of the MWD, i.e. the most
branched fraction [42], this would mean a higher amount of mol-
ecules with a wider variety in their LCB content with increasing
degradation time.
Fig. 5. a) Mean square radius of gyration and b) intrinsic viscosity contraction factors
as function of the degradation time.
The intrinsic viscosity contraction factor g' is given as function of
the degradation time in Fig. 5b. Its value decreases continuously up
to LDPE 3W, before a clear oscillation in the mean value of g' is
observed, with clearly higher values for LDPE 4W and LDPE 6W. The
great advantage of the intrinsic viscosity is its high sensitivity to
relatively small branched molecules [31]. This explains the different
tendency observed in comparison to Fig. 5a. The values LDPE 4W
and LDPE 6W are an effect of the competition between chain
scission, crosslinking, and as stressed in this contribution, the for-
mation of LCB. Due to their low amount of LCB content (Fig. 4c),
they present a high value of g'. Both contraction factors are related
by.
g
¼ g 3 ; (6)
where 3 is a parameter related to drainability of a polymer chain,
which value is assumed to vary from 0.5 to 1.5, and depends on
solvent, molar mass, temperature and branching [31]. Taking the
parameter 3 as indication of the type of structure remaining in the
soluble part of the irradiated samples, it can be compared directly
with the respective gel content (Fig. 6a). The reference sample is
produced by a tubular reactor [10], from which it has been reported
that 3 takes values between 0.9 and 1, in agreement with Fig. 6a
[44], although higher values have been also reported [45,46]. In
terms of the type of structure, 3 has been reported close to 1 for
polymer combs [47,48] and 0.6 for a star structure [47]. An analysis
Fig. 6. a) Relation between the gel content and draining factor and b) close-up in the
region of samples with predominantly comb structure.

n-Garrido et al. / Polymer Degradation and Stability 111 (2015) 46e54
V.H. Rolo
of the transition between both types of structure has been also
presented [49]. Note that in Fig. 6a, and in Fig. 6b (a close-up for the
sake of clarity), samples with low gel content (up to 5 wt.%) contain
soluble counterparts with an 3 higher than 0.85, meaning that they
could have a predominantly comb structure. This means that when
LCB formation dominates chain scission, the type of structure
formed remains the same. On the other hand, samples with high gel
content (higher than 10 wt.%) have soluble counterparts with low 3,
meaning that they could have predominantly a star or globular
structure. In other words, a transition in the global branched
structure of the soluble molecules has occurred as the degradation
time increases, with the exception of LDPE 3W, where chain scis-
sion dominates over gel formation and again a predominant comb
structure is expected, in contrast to LDPE 5W, where rather a more
globular one is anticipated. This allows understanding that not only
gel structure of LDPE 3W and 5W is different [7], but also their
soluble parts. This concurrent alternating character of both soluble
and gel fraction and their dependence is also noticed in Fig. 4c. The
increase in high molecular tail and in LCB molecules occurs already
during the first week, where no gel is detectable. At 2 weeks even
higher molecules weights were formed and the formation of a
network started, since longer chains are more probable to get
incorporated into the network [38]. The following scission process
decreases the gel content and thus former gel molecules exist again
as LCB (LDPE 3W). Hence the oscillation demonstrates that at least a
part of the high molar mass specimens used to be a part of the gel
and a certain amount of LCB initiates the reformation of the gel.
Additionally an intermediate character at 5 weeks is demonstrated
and correlates with the data in Fig. 6. Therefore the formation of a
globular structure indicates the transition to a gel network.
3.4. Relation with results of the rheological characterization
Samples irradiated up to one week have predominantly entan-
gled structure, as proved with linear and non-linear viscoelastic
experiments [7], where LCB dominates over chain scission and
samples have a low gel content. In those samples, where the
rupture in uniaxial elongation is mainly ductile [8], it is possible to
obtain the zero shear viscosity h0. The combination of the SEC-
MALS and rheology techniques allows representing the results in
a h0Mw diagram, which has been used to characterize the type of
branching [50], considering that h0 is a very sensitive quantity for
probing the presence of small amounts of LCB in polyethylenes [51].
The h0Mw representation has been used not only for polyolefins
[53], but also for irradiated polypropylene [28,30]. In the present
study (Fig. 7), the zero shear-viscosity data have been shifted to
190  C according to previously measured shift factors [9] and the
reference line corresponding to linear polyethylene is taken to be
h0 ¼ 5:8  1014 Mw 3:41 at 190  C [52]. It is noticed that the reference
sample is located above the reference line for linear polyethylene,
in agreement with a previous result [53]. The longer the degrada-
tion time, the stronger the deviation from the reference line is,
reflecting the increase in LCB content, in agreement with the
reduction of the coil contraction factors (Fig. 5).
The constitutive modeling of the data presented here has been
published before [7]. From the present analysis, it can be seen from
Fig. 2 that the parameter b correlates with the gel content deter-
mined by SEC, as already noticed in the case of the gel content
obtained through the solvent extraction method [7]. Recalling that
the parameter b signifies the ratio of the number of all entangled
chain segments to the number of chain segments stretched [17], the
observation that the parameter b remains constant and equal to 2.0
for LDPE T0, LDPE 1D, LDPE 3D, can be interpreted as an indication
of the unchanged type of the random branched structure [12], i.e.
independently of the LCB formation due to the photo-oxidative
51
Fig. 7. Logelog plot of molar mass dependence of the zero shear-rate viscosity of
reference and degraded LDPE samples with mainly entangled structure. Continuous
line represents linear polyethylene, according to Janzen and Colby.[52].
treatment, the mass of the entangled branches remains on
average equal to the mass of the effective backbone. This is in
agreement with previous results analyzing the thermal [9] and
thermo-oxidative degradation of LDPE [9,10]. Taking the value of b
as an average quantity to describe the entangled or stretchable
structure, the fact that both LDPE 5D and LDPE 1W are described by
values of b being 2.2, or by a value of 3.0 in the case of LDPE 4W and
LDPE 6W, reflects that their structure is similar as proved through
the SEC-MALS characterization in this contribution, or previous
criteria like their strain hardening index [7] or rupture behavior [8] .
In the case of the parameter fmax2 , it has been obtained experi-
mentally as the ratio of the steady-state compliance of the poly-
disperse to the monodisperse components [40], although its
connection with the molecular structure has been less studied. First
observations based on polystyrene (PS) melts, having different well
defined comb structures, pointed toward the relevance of the
number and length of the sidechains [17]. Since large values of fmax2
indicates a large strain hardening effect [54] and respectively a
higher LCB content [55,9], fmax 2 was shown to be related to the
experimentally determined contraction factor based on the
intrinsic viscosity and a theoretically determined contraction factor
related to the mean square radius of gyration [18]. In contrast to this
work, based on nearly monodisperse samples, the present study is
based on a polymer containing polydisperse randomly branched
structure. Furthermore, both contraction factors have been exper-
imentally determined.
Up to LDPE 1W, the gel content is low (Fig. 2) and therefore, the
2
correlation of fmax with both contraction factors can be established
due to their predominantly entangled structure in the whole
sample (Fig. 8), leading to.
2
fmax ¼ 1:22  101 g8:04 (7)
and
2
fmax ¼ 1:22  102 g011:63 : (8)
Samples treated from two to six weeks cannot be considered in
Eqs. (7) and (8) because their rheological response is dominated not
by the soluble branched molecules, but by the gel structure [7,8],
reflected in the quantification of the uniaxial experiments with
2
infinite values of fmax [7].
It can be observed that with the experimentally determined
contraction factors decreasing, fmax 2 is increasing strongly,
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V.H. Rolo
Fig. 8. Correlation between the model parameter fmax 2 and the a) mean square radius
of gyration, g, and b) intrinsic viscosity, g
, contraction ratios.
supporting the fact that the strain hardening is growing with the
increasing LCB content the samples. Eqs. (7) and (8) have the same
functionality as in the case of PS combs [18], although the exponent
is higher in the present case, as a result of the randomly branched
structure generated by the irradiation.
The contraction factor g can be used further to characterize the
branching degree through the number of branch units per molecule
m [56]
 0:5
m0:5 4m
g¼ 1þ þ ;
7 9p
where it is assumed that the functionality of the branch unit is
three. This assumption is valid in branched polymers formed by
radiation, since formation of branch points with higher function-
ality is statistically improbable [27,28,31]. The branching frequency
l, i.e. the number of long-chain branches per 1000 monomer units
is given by Ref. [30]
m
l ¼ 1000 Mm ;
M
where Mm is the molar mass of the monomer unit and M is the
2
molar mass of the branched polymer. We compare relation of fmax
and branching frequency of oxidated LDPE samples to model PS
comb polymer melts [18]. The nomenclature PS-x-mG-y indicates
that x is the number average molar mass of the polydisperse
backbone, m the average number of grafted side chains per mole-
cule, which are randomly attached to the backbone, and y the
number average molar mass of the nearly monodisperse side
chains (in kg/mol). The sample PS-r-95 is the linear reference
sample with molar mass of 157 kg/mol. Since the structure of the
combs is well defined, Eq. (10) can be applied directly.
The results are presented in Fig. 9 for the photo-oxidatively
degraded LDPE with predominantly entangled structure, and the
PS combs, and can be described by.
2
fmax;LDPE ¼ 2:75l4:16 (11)
and
2 0:67
fmax;PS combs ¼ 38:15l : (12)
2
Thus it is demonstrated for the first time that fmax is extremely
influenced by the branching frequency not only in model systems,
but also in an industrially relevant polymer such as LDPE with
different degree of LCB induced by photo-oxidative degradation.
There is a critical difference to be stressed. The exponent of the
power law dependency of fmax 2 is less than one for PS combs, while
for LDPE based samples it is larger than one. This could be due to
the type of branching. While the side branches of the PS combs are
linear and nearly monodisperse, the photo-degraded LDPE samples
are rather randomly branched and polydisperse. Another reason for
the drastic difference could be the type of monomer. To achieve a
definite conclusion, more research is needed.
4. Conclusions
Previously characterized photo-oxidative degraded LDPE [7,8]
has been analyzed in this study by size exclusion chromato-
graphic (SEC) using triple detection. The technique used allowed
separating the gel content from the soluble fraction. Therefore the
gel content was determined quantitatively, and the respective
soluble fraction, i.e. the entangled and long-chain branched frac-
tion, can be studied in detail. The effect of photo-oxidation was
observed by the change of the molecular weight distribution,
including the low and high molecular weight components, by the
change of Mn and Mz, respectively, and by the change of poly-
dispersity. The contractions factors based on the mean square
radius of gyration and the intrinsic viscosity were also taken into
account. Up to one week of radiation, long chain branching (LCB)
dominates over crosslinking, in agreement with previous
(9)
(10)
Fig. 9. Correlation between the model parameter fmax2 and the branching frequency l
for photo-oxidative degraded LDPE (solid symbols) and PS melt combs (empty sym-
bols). The continuous line represents Eq. (11) and the discontinuous one Eq. (12).

n-Garrido et al. / Polymer Degradation and Stability 111 (2015) 46e54
V.H. Rolo
rheological characterization. The present analysis allows corrobo-
rating that in the case of two weeks of degradation and longer,
where the gel content starts to be significant in the bulk sample,
LCB formation still plays a role, together with the chain scission and
gel formation. Furthermore, the type of branching structure in the
soluble part changes as well.
In connection with the previous rheological characterization
and the respective quantitative description of the uniaxial viscosity
data by use of the molecular stress function (MSF) model, it was
confirmed that the parameter b correlates with the gel content,
which reflects the competition between chain scission and cross-
2 , which quantifies the
linking. The exponential dependency of fmax
degree of strain hardening in elongational flow, on the experi-
mentally measured contraction factors reveals that the smaller the
2 .
contraction factor, i.e. the higher the LCB content, the higher isfmax
2
fmax was also found to be exponentially dependent on the
branching frequency not only in the case of the photo-oxidatively
degraded LDPE considered here, but also in previously reported
model PS comb polymers with well defined structures. The type of
branching seems to have a strong influence on the fmax 2 - branching
frequency relation. More research is needed towards the promising
goal of relating the non-linear rheological macroscopic response to
the molecular characteristics of polymers.
Acknowledgments
Financial support by the German Science Foundation (DFG) is
gratefully acknowledged.
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