Materials Letters 257 (2019) 126689

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

High density polyethylene film toughened with polypropylene and

linear low density polyethylene
Wei-Li Wu ⇑, Yi-Wen Wang
College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006, China

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

Article history: High density polyethylene (HDPE) was toughened by linear low density polyethylene (LLDPE) and
Received 30 June 2019 polypropylene (PP) to prepare HDPE film, and the melt index, haze, mechanical properties and morphol-
Received in revised form 1 September 2019 ogy structure of the modified HDPE film were studied. The results showed that the toughening effect of
Accepted 15 September 2019
the 10%PP/30%LLDPE/60%HDPE composition was the best; the haze was reduced 6%, dart impact strength
Available online 16 September 2019
and elongation at break were increased 27.3% and 47%, respectively. The blend of 10%PP/30%LLDPE/60%
HDPE had good compatibility, and the toughness of modified HDPE film was improved.
Keywords:
Ó 2019 Elsevier B.V. All rights reserved.
Polymers
Thin films
High density polyethylene
Mechanical properties
Haze

1. Introduction
In recent years, the polyvinyl chloride (PVC) products have been
restricted in the food packaging film and medical devices due to its
toxicity, of which the heated PVC could produce hydrogen chloride
[1], with the decrease of the PVC film production, the demand for
linear low-density polyethylene (LLDPE) film is gradually increas-
ing [2]. However, as the price of LLDPE is dear [3], the researchers
attention has been attracted to the use of high-density polyethy-
lene (HDPE) [4] due to its outstanding mechanical properties,
abundant raw materials and low cost. Compared with the low den-
sity polyethylene (LDPE) [5], LLDPE and many other polymer mate-
rials [6], the HDPE has higher tensile strength, temperature
resistant performance [7] and the production capacity [8], but its
toughness is worse than those of PVC and LLDPE. In this work,
the toughness of HDPE film was improved by adding LLDPE and
PP as the toughening agents, and the melt index, mechanical prop-
erties and haze of the modified HDPE film were also improved.
2. Materials and methods
All materials were purchased from the National Petroleum Corp
(China). The HDPE (5000S, pellets with a density of 0.963 g/cm3,
average pellet sizes of 3 mm, melt flow index of 0.96 g/10 min)
was mixed with PP (T30S, average pellet sizes of 3 mm, pellets with
a Vicat softening point of 153 °C, melt flow index of 3.1 g/10 min)
and LLDPE (HPR18H10AX pellets with a density of 0.933 g/cm3,
average pellet sizes of 2 mm, melt flow index of 4.0 g/10 min) in
a mixing machine with the mixing ratio at variety components
PP/LLDPE/HDPE, and then extruded using a twin-screw extruder.
The temperatures of the twin-screw extruder were set to 172 °C,
182 °C, 183 °C, 183 °C and 178 °C (die). It was extruded into a gran-
ulator for the granulation. At last, the HDPE mixture was blown
using a film blowing machine as shown in Fig. 1, the temperature
of the film extruder die was set to 220 °C, the screw diameter was
20 mm, the drawing speed was 23 rpm, and the blow up ratio was
3.5, and the made-film thickness was 0.1 mm. The elongation at
break of the samples (50  10  0.1 mm) was determined by a
CSS-2200 universal testing instrument according to the ISO37
method. Dart impact tests were carried out by using an JBS-300B
impact testing machine according to ASTMD1709-03 on
30 mm  30 mm film. Haze were tested by WGT-S light transmit-
tance/haze meter. The melt flow index (g) of the samples was
tested by SRZ-400E melt flow rate meter at 230 °C under 2160g
load. The film samples were fractured in liquid nitrogen, and the
fracture surfaces of the specimens were examined by S-4300 scan-
ning electron microscopy. The film samples (5  5  0.1 mm3) for
IR analysis were dried, then the infrared spectra and infrared image
were recorded by using a Spectrum One Fourier transform infrared
spectrometer.

⇑ Corresponding author.
E-mail address: wuweili2001@163.com (W.-L. Wu).

https://doi.org/10.1016/j.matlet.2019.126689
0167-577X/Ó 2019 Elsevier B.V. All rights reserved.
2 W.-L. Wu, Y.-W. Wang / Materials Letters 257 (2019) 126689

strengths of LLDPE modified HDPE were far better than that of

Fig. 1. Process of HDPE film toughened with PP and LLDPE.
3. Results and discussion
HDPE, PP and LLDPE are non-polar crystalline polymers, so they
have good compatibility after blending. For a given chemical struc-
ture of a resin, the lower the melt index (MI) is, the greater the vis-
cosity, the more difficult to process. The MI of HDPE is higher, so it
is too difficult to prepare film. In addition, the haze is also an
important index, the higher haze would limit the application of
HDPE films. The MI and haze of modified HDPE films were shown
in Table 1. The MI of HDPE modified with PP and LLDPE was
increased due to the higher MI of the PP and LLDPE used, so the
MI of the modified HDPEs were much higher than that of HDPE.
The MI of the 10%PP/30%LLDPE/60%HDPE was the highest
(2.6 g
10 min 1) among all samples results.
It can be also seen that the haze of HDPE was 30.1%, and that of
LLDPE and PP was 24.6% and 25.1%, respectively; the haze of the
modified HDPE film decreased with adding LLDPE and PP with
the hazes (24%-25.5%) of all samples being similar to that of PP
and LLDPE except 20%LLDPE/80%HDPE (haze of 26.7%), the haze
of 10%PP/30%LLDPE/60%HDPE was the best of all sample; the rea-
son may be that the haze of LLDPE and PP was lesser than that of
HDPE, so both could reduce the haze.
Since the melt index and haze chances do not show whether PP
and LLDPE toughened the HDPE, the effects of PP and LLDPE on the
mechanical properties of HDPE were examined. It was anticipated
that the toughness would increase if the elongation at break and
dart impact strength increased. The elongation at break of the PP
and LLDPE modified HDPE films were much higher than that of
HDPE, and the dart impact strengths were also higher than that
of HDPE. In addition, the elongation at break and dart impact
PP, and PP/LLDPE modified HDPE was the best.
It could be considered that the PP melting temperature was too
high to mix fully with the other ingredients. For the LLDPE/HDPE
film, the elongation at break increased significantly with the addi-
tion of LLDPE; when the mass fraction of LLDPE components
exceeded 30%, the elongation at break showed a trend of slow
growth from 30%LLDPE/70%HDPE to 40%LLDPE/60%HDPE. It could
be explained by the toughening mechanism of thermoplastic mate-
rials [9]. When the interface strength between LLDPE and HDPE
was moderate and the stress was weak, a good bond between
LLDPE and HDPE was conducive to stress transfer. Under the action
of greater stress, the polymer chain segment on the interface
would debond or slide, and produce greater strain to resist the
stress and finally yield, which was a viscous drag effect and played
a role in the toughening. Similarly, for PP, the PP dispersed in HDPE
became a stress concentration under the action of force, when PP
and HDPE bond strength was large enough, the internal holes in
PP could cause silver grain or shear band to external force, so that
a lot of energy was consumed, the toughness of the material can be
improved. In addition, the PP could also control and stop the devel-
opment of silver grain, ending develop into crack. In brief, the PP
could induce the production of silver grain or shear action, ending
the deterioration of silver grain, on the other hand, the LLDPE could
significantly improve the toughness of materials due to its drag
effect. This could also be demonstrated by an infrared phase dia-
gram. As can be seen from Fig. 2, the LLDPE and PP were island
structures evenly dispersed in HDPE, the LLDPE was in a strip
shape due to the drag effect with HDPE, while the PP was in a
round shape due to the silver grain effect.
The dart impact strength can best reflect the toughness of the
films. In actual commercial production, the PE films are evaluated
according to this data. The dart impact strength of pure HDPE film
was 55 g, pure LLDPE film could reach 120 g, and the PP film was
60 g. Comparing the dart impact strength of several toughened
HDPE films, only the toughness of 10%PP/30%LLDPE/60%HDPE film
was higher than that of HDPE, the various LLDPE/HDPE and the other
PP/LLDPE/HDPE film, reaching a maximum of 70 g. So the dart
impact strength of modified HDPE film was increased by 27.3%.
In order to study the physical structure and morphology of the
toughened HDPE films, the samples were analyzed by SEM as
shown in Fig. 3, the cryo-fracture surface of the HDPE film did
not fluctuate much in Fig. 3(a), but there were many corrugations
on the sample surface. As shown in Fig. 3(b) the failure surface of
the 30%LLDPE/70%HDPE underwent crazing presented on the
surface. The fracture surface of the 10%PP/30% LLDPE/60%HDPE

Table 1
Elongations at break, dart impact strength and MI and haze of the toughened HDPE films.

Components Elongation at break Dart impact strength Melt index Haze

(%) (%) (g) (g
10 min 1) (%)
100HDPE 454 55 0.9 30.1
100LLDPE 606 120 3.3 24.6
100PP 202 60 3.0 25.1
5LLDPE/95HDPE 461 60 1.0 25.5
10LLDPE/90HDPE 505 65 1.6 25.4
20LLDPE/80HDPE 555 65 2.0 26.7
30LLDPE/70HDPE 570 70 2.4 25.4
40LLDPE/60HDPE 578 70 2.5 24.8
5PP/95HDPE 459 55 1.0 25.5
10PP/90HDPE 460 60 1.5 25.4
20PP/80HDPE 458 60 1.8 25.3
30PP/70HDPE 457 60 1.9 25.5
5PP/20LLDPE/75HDPE 560 65 1.9 25.2
10PP/10LLDPE/80HDPE 554 65 1.8 25.2
10PP/20LLDPE/70HDPE 557 65 2.1 25.0
10PP/30LLDPE/60HDPE 596 70 2.6 24.1
 W.-L. Wu, Y.-W. Wang / Materials Letters 257 (2019) 126689 3

Fig. 2. Infrared thermal phase of 10% PP/30% LLDPE/60% HDPE films.

10%PP/30%LLDPE/60%HDPE

C=O

100%HDPE

CH3
30%LLDPE/
70%HDPE
CH

CH2 CH2

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )

Fig. 3. IR curves and SEM of (a) 100%HDPE, (b) 30%LLDPE/70%0HDPE and (c) 10%PP/ 30%LLDPE/60%HDPE films.

film Fig. 3(c) was rough with poor regularity, and had silver grain
present, the reason could be explained by the previous toughening
mechanism.
In order to understand the crosslinking structure between
HDPE, PP and LLDPE, the IR test results of the modified HDPE were
analyzed. There was the methylene absorption peak –CH2- at
2850–2900 cm 1 and 1463 cm 1, –CH- at 730 cm 1 and methyl
characteristic peak at 1368 cm 1 in the three curves in Fig. 3; there
was a carbonyl (C = O) vibration peak near 1744 cm 1 in the HDPE
curve, but the C = O peak disappeared after adding PP and LLDPE, it
illustrated that a occur the cross-linking reaction between the PP,
LLDPE and HDPE, and further demonstrated the results obtained
in the mechanical properties testing.
4. Conclusions
The HDPE was toughened by LLDPE and PP, when the mass ratio
was 10%PP/30%LLDPE/60% HDPE, the toughening effect was the
best, the dart impact strength and elongation at break were
increased by 27.3% and 47%, respectively, and the haze was
reduced 6% and higher MI. The blend of 10%PP/30%LLDPE/60%HDPE
had good compatibility. The C=O peak of toughened HDPE film
4 W.-L. Wu, Y.-W. Wang / Materials Letters 257 (2019) 126689
disappeared, occurred the cross-linking reaction between the PP,
LLDPE and HDPE.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This work was financially supported by Fundamental Research
Funds in the Heilongjiang Provincial Universities of China (No:
YSTSXK201864).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.matlet.2019.126689.
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