International Journal of Materials Science and Applications

2014; 3(5): 168-176

Published online September 20, 2014 (http://www.sciencepublishinggroup.com/j/ijmsa)
doi: 10.11648/j.ijmsa.20140305.17
ISSN: 2327-2635 (Print); ISSN: 2327-2643 (Online)

Thermo-mechanical chain branching of commercial high

density polyethylene during extrusion
Yadollah Teymouri1, Saeed Houshmandmoayed2, Mohammad Adibfar2, Reza Rashedi2
1
Polymer Faculty, Amir Kabir University of Technology, Hafez Ave, Tehran, Iran
2
Research and Development Center, Jam Petrochemical Company, South pars Special Economic Zone (Asalouyeh) Iran

Email address:
yadi_1626@yahoo.com (Y. Teymouri)

To cite this article:

Yadollah Teymouri, Saeed Houshmandmoayed, Mohammad Adibfar, Reza Rashedi. Thermo-Mechanical Chain Branching of Commercial
High Density Polyethylene during Extrusion. International Journal of Materials Science and Applications.
Vol. 3, No. 5, 2014, pp. 168-176. doi: 10.11648/j.ijmsa.20140305.17

Abstract: Two different phenomena may affect average molecular weight (Mw) of molten polyethylene during extrusion
process. The first is crosslinking, which can be divided to two categories of chain branching and network formation, leading
to an increase in Mw. The second is chain scission which leads to a decrease in the average Mw. In this work, chain branching
of molten stabilized pipe grade high density polyethylene (HDPE) and unstabilized one, extruded in industrial twin screw
extruder, has been studied. Therefore a series of analytical techniques including melt flow rate (MFR), capillary rheometer,
differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and Fourier transform infrared spectroscopy
(FTIR) were employed. The unstabilized samples' MFR were lower than stabilized ones' which showed a higher melt
viscosity of unstabilized samples due to their higher Mw. By applying rheometry test in different modes, the unstabilized PE
samples showed a higher shear viscosity in comparison with stabilized ones agreeing with MFR results. DSC results showed
a difference in degree of crystallinity between samples. This difference was verified by DMA result of solid state which
showed a higher shear storage modulus for stabilized samples. Also, DMA results confirmed the obtained results from
rheometry test in melt state. Additionally, FTIR results of stabilized and unstabilized samples demonstrated the difference
between their chemical structures. Although it seems that the level of chain branching in this grade of HDPE is low howover,
all techniques' results are in a good agreement which makes the provided results and data reliable. Moreover, a combination
of the applied methods in this work can be helpful to determine the validity and efficiency of antioxidants.
Keywords: Thermo-Mechanical Chain Branching, High Density Polyethylene, Extrusion, Antioxidant

Even a small extent of reaction can have an enormous effect

1. Introduction on the physical properties of the polymer [5]. It is known
Although Polyethylene (PE) is one of the fastest growing that thermal degradation occurs by a radical mechanism, and
commercial thermoplastic polyolefin materials due to its low it offers many oligomers by hydrogen transfer from the
cost and desirable properties such as high strength, good tertiary carbon atom along the polymer chain to the radical
barrier properties, light weight, water resistance and higher site [6, 7].
stability [1], its weakness is tendency toward degradation Although chain scission and crosslinking occur
which may occur as an undesirable phenomenon at any stage, simultaneously, one may predominate, depending on such
from manufacture to end use. However, for most factors as molar mass, shape of molar-mass distribution,
applications, the melt-processing stage is characterized by chain branching level, oxygen concentration,
the most rapid degradation. Mechanical shear and polymerization catalyst system (and associated residues) [3,
temperatures between 180 oC and 280 oC are experienced 4, 8]. For example, it has been confirmed that the
during melt processing [2-4]. polyethylene with lower molecular weight (Mw) shows low
The conditions for melt processing of polymers, namely sensitivity to degradation during reprocessing [9]. Shorter
high temperature, the presence of oxygen, and substantial chains are more mobile, not suffering scission but instead
mechanical stresses, can cause chemical reactions to occur. are used for grafting the macroradicals, increasing the Mw.
Increase in the oxygen concentration, temperature, and vinyl
 International Journal of Materials Science and Applications 2014; 3(5): 168-176 169

end groups’ content facilitates the thermo-mechanical FTIR-spectroscopy in order to quantify vinyl,
degradation reducing the amount of both, longer chains via trans-vinylene, and vinylidene functionalities. Existence of
chain scission and shorter chains via chain branching, leads each functional group can help one to guess the mechanism
to narrowing the polydispersity [2]. of crosslinking including network formation and chain
The degradation of high-density polyethylene (HDPE) branching [1, 12, 19-29].
during processing is a subject of great interest not only for its This work is conducted to study chain branching
scientific importance but also for industrial reasons. The occurring during HDPE powder processing in an industrial
methods of HDPE polymerization give rise to differences in twin-screw extruder. Hence, for investigation of chain
the structure of polymer chains, like differences in branching occurrence, a series of techniques consists of
concentration and type of unsaturations, mainly vinyl, MFR, capillary rheometry, DSC, dynamic mechanical
transvinylene, and vinylidene groups. This is an important analysis (DMA) and FTIR were employed. For the first time
aspect to be considered since the thermo-mechanical in the case of HDPE grades, DMA technique was applied to
degradation mechanisms are affected by these unsaturations investigate the chain branching effect on the HDPE's storage
[2]. Depending on Polymerization catalyst system (ZN or modulus (G'). Moreover, by using the capillary rheometer,
Phillips), HDPE may undergo many radical reactions; chain thermal stability and activation energy of samples were
scission and chain branching leading to crosslinking are determined and investigated. Considering the obtained
generally favored [5, 10]. results in this work, for other research centers depending on
Different evidences have been obtained based on the their facilities and instruments, this study can be regarded as
applied catalyst system. S. V. Canevarolo et al. reported that an instruction to determine applied antioxidants efficiency
phillips HDPE produces a higher level of chain branching and validity.
than the Zieglere Natta’s type at the same processing
condition [2]. A study of reprocessing via multiple 2. Experimental
extrusions indicated that the main cause of properties loss in
unstabilized Phillips HDPE (Cr-catalysts) was crosslinking, 2.1. Material
whereas that of unstabilized Ziegler HDPE (Ti-catalysts)
was chain scission [9]. I. A. Hussein et al. reported that the Polyethylene granules used in this study were pipe grade
HDPE produced by Phillips process, which uses a Cr-based HDPE (HM 5010 T2N, EX3) supplied by Jam
catalyst, undergoes chain scission while that made by Petrochemical Company (JPC). This grade is designated
Ziegler-Natta catalyst goes through crosslinking [11]. with sample code of "EX3'' and produced by using
The effect of chain branching on the property of Ziegler-Natta catalyst and 1-Butene as comonomer. Samples
polyethylene has been studied. The chain branching leads to of "AOEX3" contained antioxidant (AO) and "NEX3" were
a change in polymer melt viscosity which can be observed in neat HDPE. The mixture of antioxidants used in this study
variation of melt flow rate (MFR) as a simple method and was a 50/100 blend of the primary AO, Irganox 1010
data from cone and plate rheometry. Using these methods, an {Phenol B, tetrakis[methylene 3-(30,50-di-t-butylphenol)
increase in molecular weight for reprocessed non-stabilized propionate]methane, Mw=1178 gr/mol}, and a secondary
HDPE has been reported [9, 12 -17]. AO, Irgafos 168 {P-1, tris[2,4-di-t-butylphenol] phosphite,
Using rheometry as a technique to investigate the effect of Mw= 646 gr/mol}. The primary and secondary antioxidants
any change in the chemical structure of polymer chains, i.e. are made by Song won of Korea and GCH of China,
chain branching, has been reported by researches [5, 11 and respectively. Normally, 0.1% (1000 ppm) of primary and
16]. Chain branching leads to a change in Mw and 0.2% (2000 ppm) of secondary antioxidants are used for
consequently has an effect on polymer rheology. Any polyethylene pipe grade.
change in Mw can be detected by comparison of samples' 2.2. Methods
viscosity vs. shear rate curves. Jiři Dostal et al. employed
capillary rheometry to study the influence of the repeated 2.2.1. Preparation of Granules
extrusion on the degradation of polyethylene [10]. The processing and granulating of polyethylene melt in
The changes in the material structure and properties were HDPE plant was carried out in a commercial
analyzed using DSC of which, based on research results counter-rotating, non-intermeshing twin-screw extruder
reported in the literature, chain scission or crosslinking are (model JSW, Japan Steel Work, Ltd.). Screw rotation speed
the causes. In the case of Ziegler-Natta HDPEs crosslinking and its L/D were 360 rpm and 11, respectively.
prevails. The effect of crosslinking, i.e. chain branching, is a
decrease in crystallinity [5, 9, 12, 17-25]. 2.2.2. Melt Flow Rate (MFR)
Although many researchers have reported that FTIR MFR technique was performed, according to ASTM
method is ineffective at detecting small structural changes, D1238, as the first and simplest method to investigate the
some employed FTIR as a reliable technique to detect any effect of AO absence and consequently degradation
changes in the structure and generated functionalities on the occurrence, either chain branching or chain scission. In this
polyethylene chain after degradation process. Degradation work, MI4 melt flow indexer from GÖTTFERT Co. in two
of polyethylene usually has been investigated by different loads of 5 and 21.6 Kg was employed.
170 Yadollah Teymouri et al.: Thermo-Mechanical Chain Branching of Commercial High Density Polyethylene during Extrusion

2.2.3. Rheometery Tests scans. The major picks were considered as an indication of
The steady state capillary flow properties were measured change in samples structures.
using a GÖTTFERT capillary rheometer, Rheograph 25.
Two dies with diameters, D, of 1 mm and lengths of 20 mm 3. Results and Discussion
and 0 mm were used. The Bagley and the standard
Rabinowitsch corrections were implied to calculate real data 3.1. Practical Evidences in an Industrial Extruder
of shear stress (τ), shear viscosity (η) and shear rate (γ˙).
In order to study the effect of chain branching An industrial twin screw extruder in HDPE plant of JPC
phenomenon on rheological properties of EX3 samples, the was employed to granulate polyethylene powder. Regarding
capillary rheometer was employed in different modes to the high molecular weight of polyethylene chains in the
including apparent viscosity (ηap) vs. apparent shear rate pipe grade, it is very critical to have a continuous infusion
(γ˙ap), thermal stability test and temperature shift test. EX3 and an effective mixing of additives in the polymer powder
granules were preheated and melted for 6 min in the barrel at in the mixer.
190 °C. Afterward, ηap vs. γ˙ap graphs ware plotted for 10
different shear rate points. In thermal stability test firstly,
EX3 samples ware preheated at 190 °C for 6 min and then, a
constant shear rate of 112.9 s-1 and the temperature of 190 °C
were applied to measure pressure variation during 45 min.
Similar to the first modes procedure were done at the
temperature of 180 °C and 200 °C to obtain temperature
shift factors and activation energy by WLF and Arrhenius
equations, respectively.
2.2.4. Differential Scanning Calorimetry (DSC)
Samples of 5-10 mg were sliced from the granules and
then were placed into aluminum sample pans for testing in a
TA Instruments DSC-823 from Mettler-Toledo Co. equipped
with a nitrogen gas flow established from a nitrogen cylinder;
this further protected the samples from oxidation. A scan Fig. 1. Discharge pressure of gear pump vs. time in the commercial twin
rate of 5 °C/min was applied to heat up the samples from screw extruder in HDPE plant.
25 °C to 200 °C in nonhermetic pans.
If additives infusion does not take place appropriately
2.2.5. Dynamic Mechanical Analysis (DMA) Test during the processing, pressure of polyethylene melt will be
In order to investigate samples storage modulus (G') as a increased, leading to an enhancement in discharge pressure
function of temperature, shear mode of dynamic mechanical of gear pump of extruder, and power consumption of mixer.
analysis (DMA) was performed. The samples were Regarding to Fig. 1, discharge pressure increased from,
hot-pressed at 200 °C during 60 seconds by using spacers in normal pressure of 208 bars, to 218 bars in absence of
order to produce films with a fixed thickness of 400 µm. The additives and again descended to a plateau at 208 bars after
prepared films were split up into smaller pieces with areas of injecting the additives.
4×5 mm2 to satisfy the dimensional requirements of the Considering mentioned problem, motivated us to
shear clamp test fixture. After mounting a prepared investigate the reason of this problem by using analytical
rectangular sample in the DMA shear clamp, the furnace was techniques which has been mentioned before in section 2.2.
sealed. Subsequently, using a flow of liquid nitrogen the The results of these techniques and related discussion have
rectangular sample was cooled down to 0 °C. Afterward, it been followed in the next sections.
was heated with the ramp of 5 °C/min from 0 °C to 200 °C.
Using a dynamic force with a frequency oscillation of 1 and 3.2. Melt Flow Rate (MFR)
amplitude of 0.7 µm, DMA test was down on the sample.
The storage modulus for each run was calculated as a MFR is a simple technical quantity determined by a
function of temperature. Finally, G' vs. temperature curves standard method. It is extensively used for the
were plotted for single frequency oscillation. characterization of various polymers, but it can be used
excellently for the monitoring of the melt stability of
2.2.6. FTIR Test polyolefins [13].
The characterization of the EX3 granules was conducted
Table 1. Results of MFR tests for NEX3 and AOEX3 samples.
by infrared spectroscopy; using IR-Tensor 27 from Bruker
Co. In order to produce films with a fixed thickness of 200 Sample Polymer MFR 190/5 (gr/10 MFR 190/21.6
µm, the samples were hot-pressed at 200 °C during 60 Name Grade min) (gr/10 min)
seconds using spacers. All spectra were measured in the AOEX3 HDPE 0.43 10.31
NEX3 HDPE 0.32 9.53
range of 4000-400 cm-1 at a resolution of 2 cm-1 after 32
 International Journal of Materials Science and Applications 2014; 3(5): 168-176 171

Based on the Table 1, NEX3 showed a lower MFR in 3.3. Rheometery Tests
comparison with AOEX3 which means that NEX3 samples
had higher viscosities and Mws, comparatively. Since the 3.3.1. Melt Viscosity Behavior
temperature was set on 190 oC and loads of 5 Kg and 21.6 Kg Rheometry diagrams, i.e. ηap vs. γ˙ap diagrams, can be used
were applied, the obtained difference shows to compare samples molecular microstructures. A sample
thermo-mechanical degradation with crosslinking with a higher viscosity has a higher Mw. Moreover, the slope
mechanism predominance in the case of NEX3 samples of the curve at the melt's non-Newtonian rheological behavior
which were vulnerable in such a condition [9]. region is a reliable criterion to compare samples molecular
What has been observed in NEX3 MFR results can be a weight distribution (MWD). The steeper curve is the broader
consequence of continuously decrease of number of vinyl MWD and/or more chain branching is [5, 16].
groups that has a relation with polymer's Mw and MFR. At low shear rates, the Newtonian viscosity simply
Addition of alkyl radicals to the vinyl group results in a represents the resistance to the shear flow due to coil
decrease of this functionality and in the decrease of MFR. volume (which is lower for branched polymers in contrary
Moreover, according to the hypothesis chain branches form to linear polymers) and number of active entanglements
during processing decreases MFR [12, 13]. Analysis of the between polymer chains (which is higher for branched
data indicates that a few chain branches form during polymers in contrary to linear polymers). Therefore it could
processing. A clear proof for the modification in the happen that branched polymers, here NEX3, may have
structure of the polymer chains, i.e. chain branching, has higher Newtonian viscosity at low deformation rates than
been supplied by the FTIR measurements which have been more linear polymers, here AOEX3, due to higher number
expressed in section 3.6. of active entanglements; whereas, at high shear rates, the
number of active entanglements is significantly reduced.

Fig. 2. Viscosity (η) vs. shear rate (γ˙) diagrams for NEX3 and AOEX3 samples at 190 ºC.

Fig. 2 depicts ηap vs. γ˙ap diagram of which was performed shear rate and 1-n, n is the power law index, respectively.
at 190 ºC and γ˙ap of 1-104 s-1. Regarding to this figure, at These data are reported in Table 2.
γ˙ap > 1000 s-1, NEX3 and AOEX3 samples ηaps are equal
which can be caused by higher mechanical stress, which Table 2. Rheological parameters for NEX3 and AOEX3 samples calculated
by capillary rheometer.
orientates the polymer chains in the same direction. In this
range of shear rate, generated chain branching during the Parameter AOEX3 NEX3
process does not have any significant effect on the viscosity η0 (Pa.s) 1.62×104 1.71×104
λ(s) 1.64×10-1 1.22×10-1
since the number of active entanglements reduces due to
mc 8.53×10-1 8.93×10-1
higher shear forces. On the other hand, at γ˙ap = 200 s-1, N 0.147 0.107
absence of AO leads to a significant increase of ηap which is r2 0.999 0.999
considered as a function of samples Mw and chain
branching [5, 10, 16]. Therefore, for more detailed Considering Table 2, ηo rose from 1.62×104 Pa.s (for
assessment, Carreau-Winter equation, Eq. 1, which was AOEX3) to 1.71×104 Pa.s (for NEX3) which was attributed to
defined by the instrument's software, was fitted on the possible differences in susceptibility toward chain branching
experimental data to calculate the equation's coefficients: due to absence of AO in NEX3. Higher number of active
entanglements of molten NEX3 samples, caused by higher
η= ηo/ (1+λ× γ˙)mc (1) content of chain branching, lead to higher ηo at lower shear
rate. On the other hand, power law index decreased from
which ηo, λ, γ˙ and mc are zero viscosity, relaxation time,
172 Yadollah Teymouri et al.: Thermo-Mechanical Chain Branching of Commercial High Density Polyethylene during Extrusion

0.147 to 0.107 in the absence of AO. This observation shows parameter associated with long-term stabilities of polymers.
a higher shear thinning due to NEX3samples more chain In order to ensure that HDPE samples will exhibit
branching during the process and less coil volume [9, 10]. acceptable long term stability, simple test by capillary
According to above, chain scission mechanism cannot be Rheometry needs to be preformed which will provide a
the predominant mechanism of our samples degradation. reliable indication of the stability of polyethylene. The
Hence, chain branching which leads to an increase in technique measures the pressure difference of the molten
molecular weight and finally enhancement in viscosity, is sample during 45min while temperature and shear rate have
assumed to be the main mechanism of degradation. Higher been remain constant. As a result, depends on the slope of
ηo of NEX3 and lower power law index support this claim. pressure against time (p-t) curve, three various observations
To probe our claim more deeply, thermal stability test was might be feasible: 1) pressure may increase which means the
applied on NEX3 and AOEX3. Acquired result has been chain branching on polymer chains has occurred, 2) pressure
discussed in the next section. can drop rooting from chain scission of polymer and 3)
pressure may stay unchanged, revealing no degradation has
3.3.2. Thermal Stability Test happened and polymer is stable.
Thermal stability test provides a valuable characterization

Fig. 3. Changes in melt pressure for NEX3 and AOEX3 samples at 190 ºC and constant shear rate.

EX3 samples were conditioned at 190oC and constant activation energy Ea were determined for both EX3 samples
shear rate of 100 s-1, for 45 minutes to measure pressure (Table 3)
changes, Fig. 3. NEX3 sample, reached a maximum melt
pressure of 200 bar in the end of test while AOEX3 melt Table 3. Results of temperature shift test for NEX3 and AOEX3 samples.
pressure remained unchanged at about 160 bar. This Parameter AOEX3 NEX3
difference shows that in the case of NEX3, due to the T0 (°C) 180 180
composed macro radicals and propagated active radicals, Ea(KJ/mol) 20.7 50.9
1=α180 1=α180
crosslinking or chain branching has occurred.
αT 0.92=α190 0.81=α190
0.79=α200 0.56=α200
3.3.3. Temperature Shift Test
r2 0.984 0.986
Samples were preheated in the barrels at 190 oC for 6
minutes. Then, the molten samples underwent 10 different When test temperature increases, shifting factor (αT)
ascending shear rates to calculate the related rheological decreases; indicating that the viscosity of samples in all
parameters. Similar procedures were carried out at 180 oC regions of shear rates will decrease by increasing the
and 200 oC. Using Arrhenius (Eq. 2) and WLF (Eq. 3) temperature. AOEX3 sample showed a decreased αT from
equations, related shifting factors and master curves were 1at 180 oC to around 0.79 at 200 oC. In contrast, NEX3
obtained. samples showed a significant drop from 1 at the reference
temperature to about 0.56 at 200 oC. These results reveal the
K=A×exp(-∆Ea/RT) (2)
instability of NEX3 samples in comparison with AOEX3
Log (ηT/ηTg)= -((1.744(T-Tg)/(51.6+(T-Tg))) (3) samples. According to Fig. 4, η-γ˙ master curve of NEX3
jumps obviously to a higher value in low shear rates in
Fig. 4 shows master curve of EX3 samples. Temperature comparison with AOEX3 samples. This observation can be
of 180 oC has been selected as reference temperature to regarded as an indication of chain branching between
obtain parameters and diagrams. Shifting factor (αT) and polymer chains in absence of AO. In addition of shifting
 International Journal of Materials Science and Applications 2014; 3(5): 168-176 173

factor, activation energy (Ea) as a measure of sensitivity of 51 KJ/mol for NEX3. This difference shows comparatively
viscosity to temperature was determined by harder movement of NEX3 chains attributed to increase in
Temperature-Shift test in capillary Rheometer [30]. their Mw caused by chain branching.
AOEX3's Ea was about 21 KJ/mol while it went up to about

Fig. 4. Viscosity (η) vs. shear rate (γ˙) master curves of NEX3 and AOEX3 samples.

3.4. Differential Scanning Calorimetry (DSC)

Fig. 5. DSC diagram of NEX3 and AOEX3 samples.

The DSC analysis was carried out after conditioning the rose to 132 oC for AOEX3. Similar trend was observed in Xc.
samples. All Samples were heated in the DSC under These differences, clearly suggest that structural changes
Nitrogen (N2) from 25 oC to 200 oC at a scan rate of 5 oC/min have taken place in the case of NEX3 sample caused by
DSC data were analyzed to probe any differences in the chain branching and Mw enhancement.
samples melting peak (Tm) and degree of crystallinity (Xc).
Xc was determined from Xc= ∆Hm/∆Hm100, where ∆Hm and Table 4. DSC results for NEX3 and AOEX3 samples.
∆Hm100 represent the melting enthalpy of the polymers Sample Tm Xc (%)
tested and that of a 100% crystalline polyethylene, AOEX3 132 60
respectively [9]. In current work, the latter value was taken NEX3 129 57.8
as 293.6 J/gr.
Chain branching and enhancement of Mw lead to a
A comparison between DSC diagrams of NEX3 and
decrease of the macromolecules mobility and thus induce a
AOEX3 is illustrated in Fig. 5. The results of Tm and Xc for
reduction in the possibility of the material to organize itself
both samples is given in Table 4.
in large crystalline domains. Therefore, crystallinity and Tm
The melting peak of NEX3 sample was 129 oC while it
turns lower due to difficulty of movement for chains to
174 Yadollah Teymouri et al.: Thermo-Mechanical Chain Branching of Commercial High Density Polyethylene during Extrusion

contribute in crystalline formation [5, 9]. These observations Shear mode of DMA test with the condition of single
support the rheology test results and suggest that chain frequency of 1 Hz and amplitude of 0.7 mm was performed
branching has occurred in NEX3 sample. on EX3 samples to determine storage modulus (G') changes
as a function of temperature.
3.5. Dynamic Mechanical Analysis (DMA) Test

Fig. 6. Storage shear modulus (G') vs. temperature for NEX3 and AOEX3 samples in single frequency of 1 Hz.

Fig. 6 shows DMA graphs of G' vs. temperature for the

different tested EX3 samples. 3.6. FTIR Test
The sudden drop in the storage modulus toward the When polyethylene is exposed to high temperatures, alkyl
middle of the test for both samples was due to the onset of macroradicals are formed. The alkyl radicals' abstract
the melting point around 117 oC. hydrogen from the backbone of the polymer, and alkyl
Below the melting temperature there was no significant macroradicals are formed [25]. The degree of
difference between the G' of NEX3 and AOEX3 samples functionalization or chain branching degree can be
except some small differences in their G' of room determined by FTIR [12, 19].
temperature (G' of AOEX3 is slightly higher). This Fig. 7 illustrates FTIR spectra of NEX3 and AOEX3
observation is due to higher crystallinity of AOEX3 sample samples. All samples display IR characteristic peaks at 720,
in comparison with NEX3 sample. In contrast, above the 1377 and 1465 cm-1 which assign to the CH2 rocking and
melting point, G' of NEX3 is higher than AOEX3 that means CH bending vibrations of methyl and methylene groups,
in the absence of AO, some parts of macroradicals, which respectively [22, 31].
has been generated under the heat and shear stress, Monosubstituted double bonds, vinyl, give rise to two
propagated and formed chain branching, leading to increase strong bands, one near 990 cm-1 and the other near 910 cm-1
the G' from 70.2 KPa in AOEX3 sample to 88.5 KPa in for alkyl-substituted alkenes. An overtone of the 910 cm-1
NEX3 sample at about185 oC. This observation confirms the band usually appears at 1820 cm-1 and helps confirm the
results which have been discussed in the previous sections. presence of vinyl group. Trans double bond absorbs near 970
cm-1.

Fig. 7. FTIR spectra of NEX3 and AOEX3 samples.

 International Journal of Materials Science and Applications 2014; 3(5): 168-176 175

Fig. 8. Intensity of vinyl group peaks for NEX3 and AOEX3 samples.

In AOEX3 sample, peaks of 910 cm-1, 970 cm-1,

comparatively small, and 1820 cm-1 were distinguished [12,
19 and 31]. These peaks have disappeared for NEX3 as is References
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