Thermo- and Photo- Degradation of LDPE and PP Films Using Metal
Oxides as Catalysts
Sarinya Shawaphun1,a, Thara Manangan1,b and Sirirat Wacharawichanant2,c
1
Department of Industrial Chemistry, Faculty of Applied Science, King Mongkut's University of
Technology North Bangkok, Bangkok, 10800 Thailand
2
Department of Chemical Engineering, Faculty of Engineering and
Industrial Technology, Silpakorn University, Nakhon Pathom, 73000 Thailand
a
[email protected],
[email protected],
[email protected]Keywords: pro-oxidants, catalysts, photo-degradation, polyethylene, polypropylene
Abstract. In a study of photo-degradation of LDPE and PP films using the photo sensitive metal
oxides or pro-oxidants (e.g. Fe2O3, CuxO, ZnO, and TiO2 at various particle sizes) as the catalysts in
both thermo- and photo-oxidation of plastic films with oxygen followed by photolytic process to
give free radicals, our preliminary study in hexane solution found that the carbonyl index (CI)
increased under the shortwave ultraviolet (254nm) significantly greater than under the longer wave
(366nm) due to its greater energy and highly absorbed by the pro-oxidants generating more free
radical concentration which could then be photolysed into carbonyl compounds. The pro-oxidant
blended PE and PP films under ultraviolet (254nm) irradiation showed the carbonyl index elevation
at the beginning and then reducing to a constant level similarly in most cases. This probably
indicated that the carbonyl primarily formed and degraded into other free radicals. Moreover, the
LDPE film containing TiO2-200nm (1%w/w) was able to reduce the film tensile strength by 32%
within 72 hours with rutile TiO2 and by 55% with anatase TiO2 while the PE film containing
commercial TiO2 both with and without size sieving at 63µm lowering their tensile strength only by
7-10%. However, in PP film, the tensile strength tends to increase possibly due to cross linkage.
Introduction
Not only global warming has recently become major environmental problems worldwide, but
also the conventional fuel based plastic wastes have become worldwide major public concerns.
Polyethylene and polypropylene are the most popular plastics in packaging industries that caused
the gigantic amount of waste every year due to their useful mechnical properties and physical
properties for foods and household products packaging. However, it takes upto 450 years to
decompose a plastic bag, so many countries applied varous regulations, policies and managements
to overcome these problems e.g. recycle reuse and reduce protocol, yet it is far from success.
Biodegradable plastics such as modified starches, polylactic acids, polyhydroxyalkanoates and such
were brought up to research attentions in the last 45 years. However, their production costs and
limited applications have always been considerated.
In a natural pathway of auto-oxidative degradation of polyethylene and polypropylene which
were normally initiated by light or heat (so called photo-oxidative degradation or thermo-oxidative
degradation). This step usually is the slow process and becomes the rate determining step because
plastics have to combine with oxygen in the air and react to give the unstable peroxy compounds
which can then decompose to carbonyl and free radical intermediates e.g. alkyl radicals or hydroxyl
radicals.[1] Moreover, the carbonyl compounds can be photolysed to more free radicals. [2] The
radicals then undergo propagation step in the degradation chain reaction of polyethylene and
polypropylene and give more and more of oxygenated carbon skelatons in the plastics in form of
hydroxyls, aldehydes, ketones and carboxylic acids [3] which then can be further biodegraded at
low molecular weight finally resulting carbondioxide and water. [4] The objective of this research
is to accelerate the rate determining step by using pro-oxidants or pro-degradants which generate
carbonyl compounds during the processing step and induce degradaion of plastics under solar light
exposure after used and casted away. Typical pro-oxidants are metal oxides or metal salts such as
Mn2+/Mn3+, Fe3+, Zn2+, Zr2+, Ce2+ and Ti4+ have been used as photocatalysts. [5-9] Due to its supurb
charactoristics such as inexpensiveness, non-toxicity, stability and highly photoactiveness, TiO2
has become the excellent choice for photocatalyst.[10-11] To compare activity of TiO2 with other
metal oxides, the preliminary study was done in hexane solution. Furthermore, its photolytic
reactivity with carbonyl compounds was also investigated. Effects of particle size and surface area
were then also briefly looked at. Finally, TiO2 with various particle sizes were blended into LDPE
and PP, casted into a thin film, irradiated under ultraviolet light at 254nm and 366 nm to understand
their catalytic degradation pathways.
Experimental
Materials
Virgin grade LDPE (IRPC) and PP (IRPC) were used for the preparation of films. Ferric oxide
(Fe2O3, analytical grade), zinc oxide (ZnO, analytical grade), cupric oxide (CuO, analytical grade),
TiO2 (analytical grade), TiO2 (rutile, 200nm) and hexane (HPLC grade) were purchased from
Sigma Aldrich. TiO2 (63µm) was prepared by particle size sieving and oven dry for 24 hours.
Photo-degradation of hexane
The powders of Fe2O3, ZnO, CuO, TiO2 (63µm), TiO2 (anatase, 200nm) and TiO2 (rutile,
200nm) were separately mixed with hexane at 1, 2, 3, and 5% w/v in 10-ml Pyrex sealed tubes.
After vigorously shaken, the obtained suspensions then were exposed under a 20-watt shortwave
ultraviolet lamp (254nm) and a 20-watt long wave ultraviolet lamp (366nm) at 30 cm in distance.
Then they were taken out daily to determine the rate of oxygenation and/or degradation via
carbonyl index using a Perkin Elmer spectrum 2000 FTIR spectrometer. [12]
Thermo- and photo-degradation of PP and PP films
The powders of TiO2 (63µm), TiO2 (commercial), TiO2 (anatase, 200nm) and TiO2 (rutile,
200nm) were blended into both LDPE and PP at 1, 2, 3, and 5% w/w concentrations using a Twin-
Screw Extruder (TSE 16 TC; Intro enterprise Co., Ltd), and then casted to 10-micron thick films
using a Chill Roll Cast Film (LE 25-30/C; Labtec Engineering Co., Ltd). The plastic films then
were cut to 10x10 cm size and exposed under a 20-watt shortwave UV lamp (254nm) and a 20-watt
longwave UV lamp (366nm) at 30 cm in distance. The plastic films then were taken out daily to
determine carbonyl index using a Perkin Elmer spectrum 2000 FTIR spectrometer, tensile strength
using a Universal testing machine (Tensile H5K-T; Calserve Thailand), and % weight loss using
a Sartorius BP 2105 Electric balance.
Results and Discussion
Catalysed photo-degradation of hexane:
After irradiation of the hexane suspensions containing Fe2O3, ZnO, CuO, TiO2 (63µm), TiO2
(rutile, 200nm) and TiO2 (anatase, 200nm), the carbonyl index then was determined. Most catalytic
oxygenation under UV 254nm showed higher reactivity than under UV366nm. Moreover, only ZnO
and TiO2 showed good catalytic reactivity, especially both nanocrystalline TiO2. Furthermore, the
higher concentration of commercial ZnO and TiO2 did not show higher photolytic reactivity
possibly due to their low mobility in hexane.
In PE and PP films:
During the processing period, TiO2 with various particle sizes and concentrations showed
significant increasing of carbonyl index in both LDPE and PP films as shown in Fig. 1a and 1b.
However, the carbonyl formation in PP films did not increase linearly according to additives
concentration possibly due to other mechanical pathways.
As shown in Fig. 1c, LDPE films blended with various types and sizes of TiO2 showed high
elevation rate of carbonyl index after 48 hours of UV 254 nm irradiation while PP films showed
some increasing and then lowering back. At low TiO2 concentration, active particle sizes are 200nm
and 63µm. Furthermore, it appeared that anatase crystalline show slightly higher reactivity than
rutile crystalline in PE films.
Fig. 1 The thermal and photo oxidation of LDPE and PP films during processing and under
ultraviolet 254nm irradiation
As shown in Fig. 1d, LDPE films blended with various types and sizes of TiO2 showed high
elevation rate of carbonyl index after 48 hours of UV 254 nm irradiation. At low TiO2
concentration, active particle sizes are 200nm and 63µm. Furthermore, it appeared that anatase
crystalline show slightly higher reactivity than rutile crystalline in PE films. Moreover, the LDPE
film containing nanocrystalline TiO2–rutile (1%w/w) was able to reduce the film tensile strength by
32% within 72 hours and the anatase nanocrystalline TiO2 provided greater tensile strength
reduction by 55% within 96 hours. The LDPE film containing commercial TiO2 lowered their
tensile strength only by 7% while TiO2 with size sieving at 63µm reduced the tensile strength of
LDPE film up to 20 % within 72 hours. However, the tensile strength of PP films blended with
TiO2 tends to increase possibly due to cross linkage of hydrocarbon chains or recombination of free
radical intermediates via another mechanism. This explained the carbonyl index study results. The
investigation of the PP films degradation profile using weight loss technique also showed small
value only 2% with the highest TiO2 concentration at 5%, while LDPE films gave up to 4% weight
loss at 1% TiO2 concentration.
Summary
Most catalytic oxygenation under ultraviolet 254nm irradiation showed higher reactivity than
under ultraviolet 366nm irradiation. Among chosen metal oxides, only ZnO and TiO2 showed good
catalytic reactivity, especially both nanocrystalline TiO2 in both hexane and in plastic films. During
the plastics processing period, TiO2 with various particle sizes and concentrations showed
significant increasing of carbonyl index in both LDPE and PP films. However, the carbonyl
formation in PP films did not increase linearly according to additives concentration possibly due to
cross linkage of hydrocarbon chains or recombination of free radical intermediates via another
mechanism. Similar results also occurred in catalyzed photo-degradation of PP films. However,
nanocrystalline TiO2 showed great reactivity in both thermal oxygenation during the plastic
processing and the photo-degradation during the shortwave ultraviolet irradiation.
Acknowledgements
The authors would like to thank National Nanotechnology Center (NANOTEC), the National
Research Council of Thailand (NRCT) and the Faculty of Applied Science, King Mongkut’s
University of Technology North Bangkok for the financial support of this project.
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