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DOI 10.1007/s00397-014-0822-y
ORIGINAL CONTRIBUTION
Received: 2 June 2014 / Revised: 26 October 2014 / Accepted: 10 November 2014 / Published online: 26 November 2014
# Springer-Verlag Berlin Heidelberg 2014
Abstract Molecular characterization of low-density polyethylene has long been faced with many challenges. Due to the
lack of control over the radical polymerization under very
high pressures, the low-density polyethylene (LDPE) molecular structure is very complex. This paper uses the attenuated
total reflectance (ATR)Fourier transform infrared characterization method to introduce a measuring tool to calculate the
average number of branches in LDPE molecular chain.
Among 28 gel permeation chromatography (GPC)-analyzed
LDPEs, two GPC-identical tubular LDPE were chosen. The
branching structures of the LDPEs are investigated by the vanGurp Palmen plot. To clarify the difference between rheological behavior of LDPEs, GPC, temperature rising elution
fractionation, ATR, dynamic oscillatory shear, and
elongational stress growth coefficient tests were performed.
It was found that high molecular weight portion of LDPE 2
has higher number of branches than LDPE 1, which is responsible for the different rheological behavior.
Keywords Rheology . Polyethylene . FTIR . Structure .
Gel permeation chromatography
Introduction
Nowadays, many polymerization methods are employed to
produce different kinds of polymers or even the same polymer
M. Khabazian Esfahani : N. G. Ebrahimi (*) : E. Khoshbakhti
Polymer Engineering Department, Chemical Engineering Faculty,
Tarbiat Modares University, P.O. Box 14115-114, Tehran, Iran
e-mail: ebrahimn@modares.ac.ir
M. Khabazian Esfahani
e-mail: Masood.khabazian@modares.ac.ir
E. Khoshbakhti
e-mail: Ehsan.khoshbakhti@modares.ac.ir
160
Material
ATR peak
intensities
Mixing
rule
HDPE
HD/LD (75/25)
HD/LD (50/50)
HD/LD (25/75)
LDPE 1
0.32
0.46
0.61
0.80
1
0.49
0.66
0.83
161
Fraction temperatures
Fraction
Fr-1
Fr-2
Fr-3
Fr-4
Fr-5
Fr-6
Fr-7
Temperature (C)
40
50
60
70
80
90
100
PI1378
LDPEM n
162
Table 3
Material
Mn
Mw
PDI
LDPE 1
LDPE 2
13,921
14,162
123,517
128,962
8.87248
9.10562
a0
at; t 0
2 r!
f 1
f 2
1
S 11 S 22
S S
1 11 22 f 2max 1
2
1
4
f
4
2
Experimental
Zt
t
0 0
0 0
m tt f 2 t; t S IA
DE t; t dt
163
LDPE 1
LDPE 2
130 C
Gi
160 C
i
5.74E+01
9.70E+01
3.79E+02
2.64E+01
1.36E+03
7.19E+00
3.37E+03
1.96E+00
7.14E+03
5.32E01
1.29E+04
1.45E01
2.16E+04
3.94E02
3.44E+04
1.07E02
4.70E+04
2.92E03
1.34E+05
7.95E04
0 =39,100 (Pa s)
Gi
7.08E02
2.54E+02
8.61E+00
5.53E+01
3.35E+02
1.20E+01
1.30E+03
2.62E+00
4.55E+03
5.70E01
1.04E+04
1.24E01
1.98E+04
2.70E02
4.04E+04
5.87E03
4.98E+04
1.28E03
1.54E+05
2.78E04
0 =12,700 (Pa s)
130 C
Gi
160 C
i
7.94E+02
5.21E+01
4.41E+03
6.09E+00
1.40E+04
7.12E01
3.29E+04
8.33E02
6.69E+04
9.74E03
6.61E+04
1.14E03
2.73E+05
1.33E04
7.22E+05
1.56E05
2.70E+07
1.82E-06
2.36E+05
2.13E07
0 =81,800 (Pa s)
Gi
7.12E01
2.76E+02
4.83E+01
6.22E+01
7.12E+02
1.40E+01
2.09E+03
3.16E+00
5.97E+03
7.11E01
1.20E+04
1.60E01
2.19E+04
3.61E02
3.84E+04
8.13E03
5.72E+04
1.83E03
1.35E+05
4.13E04
0 =27,200 (Pa s)
164
165
166
167
Mn
(kg/mol)
Average number
of branches per
molecule
LDPE 1
LDPE 2
0.020371
0.024926
13,921
14,162
10
12
Conclusions
Although both LDPEs have almost the same GPC plots, their
rheological behavior differs considerably in Newtonian and
non-Newtonian regions. It is concluded that the branching
structure of polymer is responsible for the different rheological behaviors. However, van-Gurp Palmen shows that the
topology of branches is the same for both LDPEs. It has been
seen that the predictions of MSF model over-predict the
168
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