Res. Chem. Intermed., Vol. 31, No. 7–8, pp.

661– 666 (2005)

 VSP 2005.
Also available online - www.vsppub.com

Long-term degradation of chemical structures

and mechanical properties in polyethylene induced
by ion-beam irradiation

TOSHITAKA OKA ∗ and YOSHIMASA HAMA

Advanced Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo,
Shinjuku, Tokyo, 169-8555, Japan

Received 31 March 2004; accepted 22 June 2004

Abstract—The long-term oxidative degradation of chemical structures and the mechanical properties
in different polyethylenes induced by ion-beam irradiation were investigated. They were measured
along the ion trace when the samples were stored in the atmosphere for a very long time. The
hydroperoxide group is very important in the degradation process. These degradation processes are
attributed to the mobility of oxygen molecule due to the density and the crystallinity of polyethylene.

Keywords: Long-term oxidative degeneration; ion-beam irradiation; polyethylene.

INTRODUCTION

We have investigated the relationship between the depth profile of the local
transformations and the mechanical properties for polyethylene irradiated with
various ion-beams [1, 2]. These results give very important information on the
distribution of mechanical properties in the bulk on ion-beam irradiation and on the
long-term oxidative degradation in high-density polyethylene.
In this work, we investigated the long-term oxidative degradation of chemical
structures and the mechanical properties in different polyethylenes induced by ion-
beam irradiation. We measured the changes in the chemical structure and the
mechanical properties along the ion trace for polyethylene when the samples were
stored for very long time. It is well-known that the hydroperoxide group is very
important for the degradation. We discuss the stabilization of radicals, the density
and the crystallinity of polyethylene, the mobility of oxygen and the flexibility of
the molecular chain to analyze the influence of the hydroperoxide group.

∗ To whom correspondence should be addressed. E-mail: kotobuki@mse.waseda.ac.jp

662 T. Oka and Y. Hama

EXPERIMENTAL
Samples
Single-site polyethylene (S-PE), low-density polyethylene (LDPE) and high-density
polyethylene (HDPE) were used (Table 1). They were additive-free films with
a thickness of 1 mm (S-PE) and 2 mm (LDPE, HDPE), respectively. S-PE was
obtained from DuPont Dow Elastomers (Japan), and LDPE and HDPE from Japan
Polyethylene.

Irradiation
A 1630 MeV Neon ion-beam was irradiated with Ring Cyclotron (RIKEN) in air,
at room temperature. The fluence was 3 × 1011 ions/cm2 . The injected ion-beam
dose not stop in a single sample sheet. Therefore, some samples were stacked up
to a thickness which corresponds to the ion-beam range calculated with SRIM2000.
The calculated ranges are 11.5 mm for S-PE, 10.94 mm for LDPE and 10.57 mm
for HDPE.

Measurements
The various properties of samples were measured 6 months and one year after irra-
diation. The micro-FT-IR system, gel-fraction measurement and tensile tests were
used. The samples were sliced by microtome into 100–150-µm-thick films along
the ion penetration for micro-FT-IR (JIR-6000, Jeol, Tokyo, Japan) measurement.
For the tensile test (STA-1225, Orientec, Tokyo, Japan) measurement, samples were
sliced into 200–300-µm-thick films, and then the maximum tensile strength and the
elongation-at-break were measured. For gel-fraction measurements, samples were
boiled with p-xylene at 140◦ C for 15 h and dried at 150◦ C for 4 h to obtain the
residual weight. From the residual weight, we can measure the gel fraction of poly-
ethylene.

RESULTS AND DISCUSSION

FT-IR spectrum
The depth profile of radiation-induced absorbance of carbonyl groups (at 1716 cm−1 )
of S-PE, LDPE and HDPE were measured with micro-FT-IR. The results of S-PE
Table 1.
Sample details

Density (g/cm3 ) MFR (g/10 min) Crystallinity (%)

S-PE 0.875 3 13
LDPE 0.920 1 44
HDPE 0.953 2.5 67
 Long-term oxidative degradation of chemical structures 663

(a)

(b)
Figure 1. Depth profiles of carbonyl groups: (a) S-PE, (b) HDPE.

and HDPE were shown in Fig. 1a and 1b, respectively. The result of LDPE was
similar to that of S-PE. In S-PE and LDPE, carbonyl groups increase hardly with
the time storage. In HDPE, however, carbonyl groups increase much with increas-
ing storage time. We have reported that the increase of carbonyl groups is attributed
to the hydroperoxide group induced by the reaction of the allyl radical with oxy-
gen [1, 2]. The hydroperoxide groups transform gradually to carbonyl groups by
means of a thermally- or optically-induced reaction. It is well-known that the pre-
dominant free radicals produced in polyethylene by irradiation are the alkyl and
allyl radicals [3]. These radicals are unstable in air/vacuum at room temperature,
but in HDPE the allyl radical is stable in vacuum at room temperature. Therefore,
the alkyl and allyl radicals induced in S-PE and LDPE by irradiation are so unstable
at room temperature that they disappear through a cross-linking or oxidation reac-
tion. At the surface of HDPE, the alkyl and allyl radicals are easy to react with
oxygen and produce carbonyl groups. On the other hand, the allyl radical is stable
664 T. Oka and Y. Hama

Figure 2. Depth profile of the gel fraction of LDPE.

in the inner region and reacts with oxygen diffusing into the inner region, and pro-
duces hydroperoxide groups. Because the concentration of the oxygen molecule in
the inner region is lower than on the surface, the allyl radical could survive during
the irradiation [1].

Gel fraction
Figure 2 shows the depth profiles of the gel fraction of LDPE measured 6 months
and 1 year after irradiation, respectively. The cross-linking of S-PE and HDPE
changes hardly with storage, but it increases about 10% in LDPE. The change of
the cross-linking should be attributed to the molecular motion. The amorphous
region in HDPE is so small that the flexibility of the molecular chain is low. On the
other hand, the amorphous regions in S-PE and LDPE are so large that the flexibility
is high. Therefore, the high flexibility of molecular in amorphous region leads to
the cross-linking by hydroperoxide in LDPE. However, the cross-linking in S-PE
dose not increase. Because of the very low density and crystallinity, the probability
of cross-linking in the amorphous region should be low. Moreover, the mobility
of molecules is higher than that in LDPE, so that the hydroperoxide will disappear
quickly as elastomer.

Tensile tests
Tensile tests of S-PE, LDPE and HDPE irradiated with ion-beam were carried out.
Figure 3 shows the depth profile of the elongation at break of LDPE (Fig. 3a)
and HDPE (Fig. 3b). The results for S-PE change hardly for the time storage,
because the molecules in the amorphous region of S-PE are very flexible and the
hydroperoxide which induces the long-term degradation disappears quickly. The
results for LDPE decrease with the time storage. The increase of the cross-linking
leads to the decrease of the elongation. The elongation of HDPE decreased near the
range of the ion because the LET was very high.
 Long-term oxidative degradation of chemical structures 665

(a)

(b)
Figure 3. Depth profile of elongations of (a) LDPE and (b) HDPE.

CONCLUSIONS

In this work, we investigated the changes of the chemical structure and the
mechanical properties along the ion trace for different polyethylene when the
irradiated samples were stored in the atmosphere for a very long time. The influence
of hydroperoxide groups is very important for the degradation. In S-PE, radicals
disappear quickly because the molecular flexibility is high. Therefore, the long-
term degradation is difficult to find in S-PE. This suggests that the S-PE has a good
resistance to long-term storage in air. In LDPE, hydroperoxide seems to have an
influence on cross-linking rather than on producing carbonyl groups. In HDPE,
hydroperoxide has an influence on producing carbonyl groups.
It is rather difficult to measure the behaviour of hydroperoxide groups by FT-IR.
Another probe will be used in the near future.
666 T. Oka and Y. Hama

Acknowledgements
This work was partially supported by Waseda University Grant for Special Research
Project (2002A-122, 2003A-128). The authors also acknowledge Dr. Yatagai
(RIKEN) for his support in the ion-beam irradiation experiments.

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(2001).
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3. M. Dole (Ed.), in: The Radiation Chemistry of Macromolecules, Vol. 1, p. 335. Academic Press,
New York, NY (1972).