Radiation Physics and Chemistry 56 (1999) 375±380

www.elsevier.com/locate/radphyschem

Short Survey
Irradiation of polyethylene: Some aspects of crosslinking
and oxidative degradation
p

Ajit Singh 1
Research Chemistry Branch, AECL, Whiteshell Laboratories, Pinawa, Manitoba, Canada, R0E 1L0

Abstract

Crosslinking is the dominant process when polyethylene is irradiated under inert atmosphere; however, when it is
irradiated in air, oxidative degradation becomes the dominant process, particularly at low-dose-rate gamma
irradiation. There have been suggestions in the literature that (i) crosslinking may still be an important process
during low-dose-rate gamma irradiation, and (ii) that peroxides can act as sensitizers for radiation-induced
crosslinking of polyethylene. A consideration of possible radiation e€ects in polyethylene, in the presence of oxygen,
suggests that there could be (i) an important role of cationic reactions leading to crosslinking; (ii) possible
crosslinking within the crystalline regions; and (iii) excitation energy transfer to the peroxides produced during
oxidative degradation to produce alkoxy radicals. # 1999 Published by Elsevier Science Ltd. All rights reserved.

1. Introduction becomes negligible, except on the surface, and cross-

linking is the dominant process (Dole, 1972, 1973;
E€ects of irradiation of polyethylene (PE) have been Feng and Ma, 1992; Singh et al., 1995). The products
studied extensively (Charlesby, 1960; Chapiro, 1962; of oxidative degradation of PE include water, carbon
Chappas and Silverman, 1980; Chappas et al., 1982; monoxide, carbon dioxide, alcohols, ketones, hydro-
Dole, 1972, 1973; Decker et al., 1973; Joshi et al., peroxides, peroxides and carboxylic acids (Dole, 1972,
1977; Patel and Keller, 1975; Lyons, 1983; Randall et 1973).
al., 1983; Seguchi and Yamamoto, 1986; Torikai et al., It is widely accepted that free-radical reactions, e.g.
1986; Brede et al., 1987; Sohma et al., 1991; Silverman, reaction (1), contribute to PE crosslinking, though
1992; Singh and Silverman, 1992; Feng and Ma, 1992; opinions on the precise details and the types of free
Osagawara, 1993). On gamma irradiation in vacuum, radicals involved vary (Charlesby, 1960; Chapiro,
or under inert atmosphere, PE undergoes crosslinking. 1962; Dole, 1972, 1973; Lyons, 1983; Randall et al.,
In air or in the presence of oxygen, oxidative degra- 1983; Tabata et al., 1990; Singh and Silverman, 1992).
dation becomes a major process during gamma ir-
radiation. In contrast, at the high dose rates obtained PE
‡PE
4 PE±PE 1†
with electron accelerators, oxidative degradation
In reaction (1), PE
represents the free radical formed
by the loss of a hydrogen atom from PE. On ir-
radiation in air at low dose rates, the peroxy radical
Based on a presentation at the RadTech Asia '95 at
p

Bangkok (14±16 December, 1995). formation dominates over the recombination reaction:
1
Present address: 822 Gulfview Place, Victoria, BC V8Y
2R6, Canada. PE
‡O2 4 PEO2
2†

0969-806X/99/$ - see front matter # 1999 Published by Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 9 - 8 0 6 X ( 9 9 ) 0 0 3 2 8 - X
376 A. Singh / Radiation Physics and Chemistry 56 (1999) 375±380

However, with increasing dose rates, there would be 2.1. Ionic species
increasing competition between these two reactions,
and the reaction of PE
with the peroxy radical would Work at low temperatures (<200 K) has demon-
be strated the formation and reactivity of the cation and
electron formed in PE (Willard, 1968; Ausloos, 1970;
PE
‡PEO2
4 PEOOPE 3† Dole, 1972, 1973; Iwasaki et al., 1983; Tagawa et al.,
1983, 1989; Brede et al., 1987; Jonah and Sauer, 1989;
At the high dose rates typically obtained with electron Le Motais and Jonah, 1989; Trifunac et al., 1989;
accelerators (e103 Gy sÿ1; Singh, 1991), the recombi- Ogasawara, 1993). These species have also been
nation reaction (reaction (1)) dominates in the compe- detected in room temperature and elevated temperature
tition between these reactions, primarily because the work. The reactions of the cations formed in polyethy-
dissolved oxygen gets rapidly consumed and the rate lene (reaction (4)) have not been studied in detail.
of the peroxy radical formation becomes dependent on However, based on the known or suggested reactions
the rate of di€usion of oxygen into the PE samples of the hydrocarbon cations, reaction (5) and the fol-
(Dole, 1972, 1973; Seguchi and Yamamoto, 1986). lowing reactions would be expected to occur on ir-
However, in addition to the expected crosslinking of radiation of polyethylene:
polyethylene on irradiation with electrons, some
workers have reported the occurrence of crosslinking Charge transfer:
of polyethylene even at the low-dose-rate gamma ir- PE ‡
‡ peCH ˆ CHpe 4 PE ‡ peCH±CHpe†‡
8†
radiations done in air (Torikai et al., 1986; Minkova
and Mihailov, 1990). There are also reports that per-
oxides can act as sensitizers for radiation-induced Dissociation: PE ‡
or PE ‡
4 peCH±CHpe†‡
‡ H2
crosslinking of polyethylenes (Yu et al., 1992, 1994; 9†
Kurian et al., 1993). A brief review of the mechanisms
of reactions in PE on irradiation has therefore been
undertaken to identify the processes that may lead to Condensation:
crosslinking of polyethylene in the presence of air. PE ‡
or PE ‡
‡ peCH ˆ CHpe 4 peCHPE±CH2 pe†‡

peCH±CHpe†‡
‡ PE 4 peCHPE±CH2 pe†‡
11†

2. Irradiation of polyethylene Recombination: PE ‡
‡ eÿ 4 PE  12†

Based on our understanding of the time-scale of
radiolytic events (Mozumder, 1969; Singh, 1972) ions PE ‡
‡ eÿ 4 PE
‡H
or H 
† 13†
and excited states would be formed initially, on ir-
radiation of polyethylene:
PE ‡
‡ eÿ 4 peCH ˆ CHpe ‡ H2 14†
‡
‡
ÿ  
PE9PE ‡ PE ‡ e ‡ PE ‡ PE 4†
PEH ‡ ‡ eÿ 4 PE ‡ H
15†
Neutral free radicals would be formed in subsequent
reactions of these species, e.g. reactions (5)±(7)
peCHPE±CH2 pe†‡
‡ eÿ 4 peCHPE±CH2 pe 16†
‡
‡
PE ‡ PE 4 PEH ‡ PE
5†
peCH±CHpe†‡
‡ eÿ 4 peCH ˆ CHpe and
PE  or PE  4 PE
‡H
and=or H 
6† =or peCH ˆ CHpe 17†

Lyons and Johnson (1993) quote Dole et al. (1958)

PE  or PE  4 pe
‡pe
: 7† for the suggestion that trans-vinylene formation on ir-
radiation of PE is a primary process, possibly invol-
In reactions (4)±(7), PE+
represents the polyethylene ving ionization followed by the detachment of a
cation, PE+
represents excited cation, PE represents molecule of hydrogen (presumably, reaction (9) fol-
electronically excited polyethylene, PE represents lowed by (17), and reaction (14)), with which they
superexcited polyethylene, H
represents hot hydrogen agree. The lack of a dose-rate e€ect on trans-vinylene
atom, and pe
represents a free radical formed by PE formation (J. Silverman, personal communication,
chain scission. 1995) is consistent with the occurrence of these reac-
 A. Singh / Radiation Physics and Chemistry 56 (1999) 375±380 377

tions, as is the lack of the e€ects of air, acetylene or 2.2. Excited states
temperature (Hagiwara et al., 1973; Mitsui et al., 1973;
Torikai et al., 1986). The fate of the PE excited states has not been fully
The reactions involving electrons, hydrogen atoms elucidated; though, based on the results of radiolysis
and other free radicals can only occur in the crystalline and photolysis of other hydrocarbons (Calvert and
regions, where oxygen is absent (Winslow et al., 1966). Pitts, 1966; Holroyd, 1968), reactions (6)±(7), and
In the amorphous regions where oxygen is present, (22)±(23) would be expected to occur:
oxygen would react with electrons, hydrogen atoms
and other free radicals, to give reactions (2), (18) and PE  or PE  4 H2 ‡ peCH ˆ CHpe 22†
(19) (Buxton et al., 1988):

eÿ ‡ O2 4 Oÿ

2 18† PE  4 PE ‡ hu† 23†

The loss of hydrogen with the formation of a double

H
‡O2 4 HO2
19† bond (reaction (22)) would be the dominant reaction
which could produce trans-vinylene, in addition to
reaction (9) followed by reaction (17), and reaction
Thus, there would be competition between reactions
(14). These reactions should occur both in the crystal-
(1) and (12)±(17), and reactions (2) and (18)±(19), with
line as well as in the amorphous regions. In the amor-
the latter reactions being strongly favoured on ir-
phous regions, there is the possibility of the lifetime of
radiation in air at low dose rates (gamma irradiation)
the excited states being reduced by oxygen:
in the amorphous regions of PE. As pointed out ear-
lier, the relative importance of reactions (2) and (18)±
(19) will decrease with increasing dose rates because PE  ‡ O2 4 PE ‡ O2 and=or 1 O2 † 24†
they are dependent on the availability of oxygen
through continued di€usion into the samples. However, because the lifetimes of excited aliphatic
The condensation reactions (10) and (11), followed hydrocarbons are typically in the nanosecond and sub-
by reaction (16), result in crosslinking. Reaction (11) nanosecond range (Hirayama and Lipsky, 1969;
can be followed by further condensation with PE, Katsumura et al., 1982, 1983), the extent of this
prior to reaction (16). PE contains some unsaturation; quenching reaction of oxygen is likely to be negligible.
also, the products of PE irradiation include unsatura-
tion (Dole, 1972, 1973; Lyons, 1983; Lyons and 2.3. Free radicals
Johnson, 1993), e.g. through reaction (14). This cat-
ionic crosslinking reaction should proceed even in the The free-radical species formed on irradiation of PE
presence of oxygen. Indeed, it would be expected that include hydrogen atoms, allyl radicals, alkyl radicals,
scavenging of the electrons by oxygen would increase superoxide anions, hydroperoxy radicals and peroxy
the lifetime of the cations, and thus the extent of the radicals. The formation of the hydrogen atoms, alkyl
cationic crosslinking. It has been reported that ir- radicals and allyl radicals within the crystalline regions
radiation of PE in the presence of nitrous oxide, a would depend on (i) the extent of charge recombina-
known electron scavenger, leads to enhanced cross- tion, and (ii) the extent of the decomposition of the
linking (BoÈhm, 1973), which supports the concept of excited species. The hydrogen atoms can react with
cationic crosslinking through reactions (10) and (11). PE, and with the sites of unsaturation, to produce
Though the formation of the superoxide anion can alkyl radicals (reactions (25) and (26)). The alkyl rad-
be inferred from the thermoluminescence and other icals formed within the crystalline regions can (i)
low temperature work (Dole, 1972, 1973), its for- migrate to the crystallite surfaces (Dole, 1972, 1973;
mation and reactions in PE do not seem to have Seguchi and Tamura, 1973), (ii) react with hydrogen
been studied directly by pulse radiolysis or other tech- atoms to produce trans-vinylene groups (reaction (27)),
niques. In the presence of oxygen, the cation-electron and (iii) react with the sites of unsaturation to give
recombination reactions given above could be replaced allyl radicals (reactions (28)±(29)).
by superoxide anion-cation reactions in the amorphous
PE ‡ H
4 PE
‡H2 25†
regions, and may include the following reactions:

PEH ‡ ‡ O2 ÿ
4 PE ‡ HO2
20† peCH ˆ CHpe ‡ H
4 PE
26†

PE ‡
‡ O2 ÿ
4 PE
‡HO2
21† PE
‡ H
4 peCH ˆ CHpe ‡ H2 27†

378 A. Singh / Radiation Physics and Chemistry 56 (1999) 375±380

PE
‡ peCH ˆ CH±CH2 pe 4 PE ‡ peCH ˆ CH±CH pe†
PE  ‡ PEOOPE 4 PEOOPE  † 4 2 PEO
39†

28†
PE  ‡ PEOOH 4 PEOOH  † 4 PEO
‡
OH 40†
H
‡ peCH ˆ CH±CH2 pe 4 H2 ‡ peCH
ˆ CH±CH pe†
: 29† PEOOPE ‡ eÿ 4 PEO
‡PEOÿ 41†

Although these reactions can also all occur in the

amorphous regions, at low dose rates the dominant PEOOH ‡ eÿ 4 PEO
‡OH ÿ 42†
reactions of the hydrogen atoms and the alkyl radicals
would be with the oxygen present to produce peroxy The
OH radicals formed (reaction (40) and analogous
radicals (reactions (2) and (19)). As the dose rate reaction of H2O2) should lead to the production of
increases, there would be competition between reac- water, as has been observed; however, the mechanism
tions (2) and (19), on the one hand, and reactions (1), suggested for its formation (Dole, 1972, 1973) is di€er-
(3), and (25)±(29), on the other. ent and does not include reaction (43).
The other free-radical reactions expected to occur on

OH ‡ PE 4 H2 O ‡ PE
43†
irradiation of polyethylene in air, in the amorphous
regions of PE, would include the following:
2.4. Crystalline regions
HO2
‡ PE
4 PEOOH 30†
Free-radical formation, and any decomposition of
HO2
‡ HO 4 H2 O2 ‡ O2 31† ions and excited states (including excited cations and
superexcited states) that normally take place within the
crystals, would be una€ected by the presence of oxygen
HO2
‡ PE 4 H2 O2 ‡ PE
32† because oxygen is excluded from the crystalline regions
(Winslow et al., 1966). Although the overwhelming
PEO ‡ PE 4 PEOOH ‡ PE
33† opinion is against crosslinking within the crystallites, it
has to be considered that one can get over 60% gel
Though hydrogen peroxide can be formed by reactions fraction in HDPE at doses of 100 to 500 kGy (Singh
(31) and (32), it does not seem to have been reported et al., 1995). In HDPE, the amorphous region is only
as a product of the irradiation of PE; it is possible that about 20±40%. Thus, there is likely to be crosslinking
it has not been sought or identi®ed as a product. within the crystals. It is possible that the double bonds
The peroxy radicals can also undergo recombina- already present in a crystal, or those formed within the
tion, with the formation of peroxides, alkoxy radicals, crystalline regions during irradiation (Dole, 1972,
ketones and alcohols (Ingold, 1969; Dole, 1972, 1973): 1973; Tabata et al., 1990), could become the sites of
crosslinking through reactions (10) and (11), particu-
PEOO
‡ PEOO
4 PEOO±OOPE 34† larly if an excited cation gets formed very close to the
double bonds; the energy of excitation of the cation
may increase the e€ective range or distance within
PEOO±OOPE 4 peOH ‡ pe2 CO ‡ O2 35†
which the cation can undergo ion-molecule reactions.
In any case, if there is crosslinking within the PE crys-
PEOO
‡ PEOO
4 PEO
‡ PEO
‡ O2 36† tals, it would take place even in the presence of oxygen
because oxygen is excluded from the crystalline regions
The reactions of the alkoxy radicals formed could (Winslow et al., 1966). Supporting evidence for cross-
include formation of ethers and alcohols, with the re- linking within the crystalline regions comes from the
generation of the alkyl radicals: work of Tabata et al. (1984) on n-eicosane and n-tetra-
cosane (as model compounds for crystalline PE), and
PEO
‡ PE
4 PEOPE 37† Sohma et al. (1991); the results of both of these
workers lead to the conclusion that the level of cross-
PEO
‡ PE 4 PEOH ‡ PE
: 38† linking within crystalline regions of HDPE would be
about one fourth of that in the amorphous regions.
In addition to these reactions, one could also get reac- On the other hand, Patel and Keller (1975) con-
tions following excited-state energy transfer to the per- cluded that in the case of PE crystals, crosslinking
oxides and hydroperoxides, as well as the following occurs at the chain ends, not within the crystal. They
reactions of peroxides and hydroperoxides with the used linear PE Marlex 6009, crystallized from xylene
radiolytically produced electrons: at 92.58C. These crystals were recrystallized from
 A. Singh / Radiation Physics and Chemistry 56 (1999) 375±380 379

xylene solutions at 708C, 858C and 908C. The self-seed- work on irradiation of polyethylene, it may be useful
ing method was used to ensure that the crystals were to focus on some of these processes, to obtain evidence
predominantly monolayers. All preparations were for or against them.
degraded by ozone at 608C to the stage where all folds
are cut and only COOH-capped single-traverse stems
remain. The samples were gamma irradiated (60 to Acknowledgements
6000 kGy) under vacuum. All samples remained fully
soluble (presumably in xylene); the gel dose varied Helpful comments by B. J. Lyons, T. Seguchi, J.
with the core thickness of the crystals, from 5910 kGy Silverman and A. Trifunac are gratefully acknowl-
for 75 AÊ to 2460 kGy for 180 AÊ (1 AÊ=0.1 nm). They edged.
argued that as the primary energy deposition must be
uniform throughout the crystal, excitations and sub-
sequent formation of radicals is expected throughout References
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