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-

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

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
increasing competition between these two reactions,
and the reaction of PE
with the peroxy radical would
be
PE
‡PEO2
4 PEOOPE
At the high dose rates typically obtained with electron
accelerators (e103 Gy sÿ1; Singh, 1991), the recombi-
nation reaction (reaction (1)) dominates in the compe-
tition between these reactions, primarily because the
dissolved oxygen gets rapidly consumed and the rate
of the peroxy radical formation becomes dependent on
the rate of di€usion of oxygen into the PE samples
(Dole, 1972, 1973; Seguchi and Yamamoto, 1986).
However, in addition to the expected crosslinking of
polyethylene on irradiation with electrons, some
workers have reported the occurrence of crosslinking
of polyethylene even at the low-dose-rate gamma ir-
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
crosslinking of polyethylenes (Yu et al., 1992, 1994;
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
crosslinking of polyethylene in the presence of air.
2. Irradiation of polyethylene
Based on our understanding of the time-scale of
radiolytic events (Mozumder, 1969; Singh, 1972) ions
and excited states would be formed initially, on ir-
radiation of polyethylene:
‡
‡
ÿ  
PE9PE ‡ PE ‡ e ‡ PE ‡ PE
Neutral free radicals would be formed in subsequent
reactions of these species, e.g. reactions (5)±(7)
‡
‡
PE ‡ PE 4 PEH ‡ PE

PE  or PE  4 PE
‡H
and=or H 

PE  or PE  4 pe
‡pe
:
In reactions (4)±(7), PE+
represents the polyethylene
cation, PE+
represents excited cation, PE represents
electronically excited polyethylene, PE represents
superexcited polyethylene, H
represents hot hydrogen
atom, and pe
represents a free radical formed by PE
chain scission.
2.1. Ionic species
Work at low temperatures (<200 K) has demon-
strated the formation and reactivity of the cation and
electron formed in PE (Willard, 1968; Ausloos, 1970;
3† Dole, 1972, 1973; Iwasaki et al., 1983; Tagawa et al.,
1983, 1989; Brede et al., 1987; Jonah and Sauer, 1989;
Le Motais and Jonah, 1989; Trifunac et al., 1989;
Ogasawara, 1993). These species have also been
detected in room temperature and elevated temperature
work. The reactions of the cations formed in polyethy-
lene (reaction (4)) have not been studied in detail.
However, based on the known or suggested reactions
of the hydrocarbon cations, reaction (5) and the fol-
lowing reactions would be expected to occur on ir-
radiation of polyethylene:
Charge transfer:
PE ‡
‡ peCH ˆ CHpe 4 PE ‡ peCH±CHpe†‡
8†
Dissociation: PE ‡
or PE ‡
4 peCH±CHpe†‡
‡ H2
9†
Condensation:
PE ‡
or PE ‡
‡ peCH ˆ CHpe 4 peCHPE±CH2 pe†‡

peCH±CHpe†‡
‡ PE 4 peCHPE±CH2 pe†‡
11†
Recombination: PE ‡
‡ eÿ 4 PE  12†
PE ‡
‡ eÿ 4 PE
‡H
or H 
† 13†
PE ‡
‡ eÿ 4 peCH ˆ CHpe ‡ H2 14†
4†
PEH ‡ ‡ eÿ 4 PE ‡ H
15†
peCHPE±CH2 pe†‡
‡ eÿ 4 peCHPE±CH2 pe 16†
5†
peCH±CHpe†‡
‡ eÿ 4 peCH ˆ CHpe and
6† =or peCH ˆ CHpe 17†
Lyons and Johnson (1993) quote Dole et al. (1958)
7† for the suggestion that trans-vinylene formation on ir-
radiation of PE is a primary process, possibly invol-
ving ionization followed by the detachment of a
molecule of hydrogen (presumably, reaction (9) fol-
lowed by (17), and reaction (14)), with which they
agree. The lack of a dose-rate e€ect on trans-vinylene
formation (J. Silverman, personal communication,
1995) is consistent with the occurrence of these reac-
 A. Singh / Radiation Physics and Chemistry 56 (1999) 375±380
tions, as is the lack of the e€ects of air, acetylene or
temperature (Hagiwara et al., 1973; Mitsui et al., 1973;
Torikai et al., 1986).
The reactions involving electrons, hydrogen atoms
and other free radicals can only occur in the crystalline
regions, where oxygen is absent (Winslow et al., 1966).
In the amorphous regions where oxygen is present,
oxygen would react with electrons, hydrogen atoms
and other free radicals, to give reactions (2), (18) and
(19) (Buxton et al., 1988):
eÿ ‡ O2 4 Oÿ

2 18†
H
‡O2 4 HO2
19†
Thus, there would be competition between reactions
(1) and (12)±(17), and reactions (2) and (18)±(19), with
the latter reactions being strongly favoured on ir-
radiation in air at low dose rates (gamma irradiation)
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
they are dependent on the availability of oxygen
through continued di€usion into the samples.
The condensation reactions (10) and (11), followed
by reaction (16), result in crosslinking. Reaction (11)
can be followed by further condensation with PE,
prior to reaction (16). PE contains some unsaturation;
also, the products of PE irradiation include unsatura-
tion (Dole, 1972, 1973; Lyons, 1983; Lyons and
Johnson, 1993), e.g. through reaction (14). This cat-
ionic crosslinking reaction should proceed even in the
presence of oxygen. Indeed, it would be expected that
scavenging of the electrons by oxygen would increase
the lifetime of the cations, and thus the extent of the
cationic crosslinking. It has been reported that ir-
radiation of PE in the presence of nitrous oxide, a
known electron scavenger, leads to enhanced cross-
linking (BoÈhm, 1973), which supports the concept of
cationic crosslinking through reactions (10) and (11).
Though the formation of the superoxide anion can
be inferred from the thermoluminescence and other
low temperature work (Dole, 1972, 1973), its for-
mation and reactions in PE do not seem to have
been studied directly by pulse radiolysis or other tech-
niques. In the presence of oxygen, the cation-electron
recombination reactions given above could be replaced
by superoxide anion-cation reactions in the amorphous
regions, and may include the following reactions:
PEH ‡ ‡ O2 ÿ
4 PE ‡ HO2
20†
PE ‡
‡ O2 ÿ
4 PE
‡HO2
21†
377
2.2. Excited states
The fate of the PE excited states has not been fully
elucidated; though, based on the results of radiolysis
and photolysis of other hydrocarbons (Calvert and
Pitts, 1966; Holroyd, 1968), reactions (6)±(7), and
(22)±(23) would be expected to occur:
PE  or PE  4 H2 ‡ peCH ˆ CHpe 22†
PE  4 PE ‡ hu† 23†
The loss of hydrogen with the formation of a double
bond (reaction (22)) would be the dominant reaction
which could produce trans-vinylene, in addition to
reaction (9) followed by reaction (17), and reaction
(14). These reactions should occur both in the crystal-
line as well as in the amorphous regions. In the amor-
phous regions, there is the possibility of the lifetime of
the excited states being reduced by oxygen:
PE  ‡ O2 4 PE ‡ O2 and=or 1 O2 † 24†
However, because the lifetimes of excited aliphatic
hydrocarbons are typically in the nanosecond and sub-
nanosecond range (Hirayama and Lipsky, 1969;
Katsumura et al., 1982, 1983), the extent of this
quenching reaction of oxygen is likely to be negligible.
2.3. Free radicals
The free-radical species formed on irradiation of PE
include hydrogen atoms, allyl radicals, alkyl radicals,
superoxide anions, hydroperoxy radicals and peroxy
radicals. The formation of the hydrogen atoms, alkyl
radicals and allyl radicals within the crystalline regions
would depend on (i) the extent of charge recombina-
tion, and (ii) the extent of the decomposition of the
excited species. The hydrogen atoms can react with
PE, and with the sites of unsaturation, to produce
alkyl radicals (reactions (25) and (26)). The alkyl rad-
icals formed within the crystalline regions can (i)
migrate to the crystallite surfaces (Dole, 1972, 1973;
Seguchi and Tamura, 1973), (ii) react with hydrogen
atoms to produce trans-vinylene groups (reaction (27)),
and (iii) react with the sites of unsaturation to give
allyl radicals (reactions (28)±(29)).
PE ‡ H
4 PE
‡H2 25†
peCH ˆ CHpe ‡ H
4 PE
26†
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†

28†
H
‡ peCH ˆ CH±CH2 pe 4 H2 ‡ peCH
ˆ CH±CH pe†
: 29†
Although these reactions can also all occur in the
amorphous regions, at low dose rates the dominant
reactions of the hydrogen atoms and the alkyl radicals
would be with the oxygen present to produce peroxy
radicals (reactions (2) and (19)). As the dose rate
increases, there would be competition between reac-
tions (2) and (19), on the one hand, and reactions (1),
(3), and (25)±(29), on the other.
The other free-radical reactions expected to occur on
irradiation of polyethylene in air, in the amorphous
regions of PE, would include the following:
HO2
‡ PE
4 PEOOH 30†
HO2
‡ HO 4 H2 O2 ‡ O2 31†
HO2
‡ PE 4 H2 O2 ‡ PE
32†
PEO ‡ PE 4 PEOOH ‡ PE
33†
Though hydrogen peroxide can be formed by reactions
(31) and (32), it does not seem to have been reported
as a product of the irradiation of PE; it is possible that
it has not been sought or identi®ed as a product.
The peroxy radicals can also undergo recombina-
tion, with the formation of peroxides, alkoxy radicals,
ketones and alcohols (Ingold, 1969; Dole, 1972, 1973):
PEOO
‡ PEOO
4 PEOO±OOPE 34†
PEOO±OOPE 4 peOH ‡ pe2 CO ‡ O2 35†
PEOO
‡ PEOO
4 PEO
‡ PEO
‡ O2 36†
The reactions of the alkoxy radicals formed could
include formation of ethers and alcohols, with the re-
generation of the alkyl radicals:
PEO
‡ PE
4 PEOPE 37†
PEO
‡ PE 4 PEOH ‡ PE
: 38†
In addition to these reactions, one could also get reac-
tions following excited-state energy transfer to the per-
oxides and hydroperoxides, as well as the following
reactions of peroxides and hydroperoxides with the
radiolytically produced electrons:
PE  ‡ PEOOPE 4 PEOOPE  † 4 2 PEO
39†
PE  ‡ PEOOH 4 PEOOH  † 4 PEO
‡
OH 40†
PEOOPE ‡ eÿ 4 PEO
‡PEOÿ 41†
PEOOH ‡ eÿ 4 PEO
‡OH ÿ 42†
The
OH radicals formed (reaction (40) and analogous
reaction of H2O2) should lead to the production of
water, as has been observed; however, the mechanism
suggested for its formation (Dole, 1972, 1973) is di€er-
ent and does not include reaction (43).

OH ‡ PE 4 H2 O ‡ PE
43†
2.4. Crystalline regions
Free-radical formation, and any decomposition of
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
because oxygen is excluded from the crystalline regions
(Winslow et al., 1966). Although the overwhelming
opinion is against crosslinking within the crystallites, it
has to be considered that one can get over 60% gel
fraction in HDPE at doses of 100 to 500 kGy (Singh
et al., 1995). In HDPE, the amorphous region is only
about 20±40%. Thus, there is likely to be crosslinking
within the crystals. It is possible that the double bonds
already present in a crystal, or those formed within the
crystalline regions during irradiation (Dole, 1972,
1973; Tabata et al., 1990), could become the sites of
crosslinking through reactions (10) and (11), particu-
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
which the cation can undergo ion-molecule reactions.
In any case, if there is crosslinking within the PE crys-
tals, it would take place even in the presence of oxygen
because oxygen is excluded from the crystalline regions
(Winslow et al., 1966). Supporting evidence for cross-
linking within the crystalline regions comes from the
work of Tabata et al. (1984) on n-eicosane and n-tetra-
cosane (as model compounds for crystalline PE), and
Sohma et al. (1991); the results of both of these
workers lead to the conclusion that the level of cross-
linking within crystalline regions of HDPE would be
about one fourth of that in the amorphous regions.
On the other hand, Patel and Keller (1975) con-
cluded that in the case of PE crystals, crosslinking
occurs at the chain ends, not within the crystal. They
used linear PE Marlex 6009, crystallized from xylene
at 92.58C. These crystals were recrystallized from
 A. Singh / Radiation Physics and Chemistry 56 (1999) 375±380
xylene solutions at 708C, 858C and 908C. The self-seed-
ing method was used to ensure that the crystals were
predominantly monolayers. All preparations were
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
6000 kGy) under vacuum. All samples remained fully
soluble (presumably in xylene); the gel dose varied
with the core thickness of the crystals, from 5910 kGy
for 75 AÊ to 2460 kGy for 180 AÊ (1 AÊ=0.1 nm). They
argued that as the primary energy deposition must be
uniform throughout the crystal, excitations and sub-
sequent formation of radicals is expected throughout
the crystal, and the observation that such radicals do
not lead to crosslinks within the lattice must be due to
the fact that the carbon atoms within the lattice are
too far apart and their position is too rigidly ®xed, to
allow a C±C bond to arise when two radicals in neigh-
bouring chains become adjacent. The length of a C±C
bond is 1.54 AÊ, whereas the closest distance between C
atoms of the adjacent chains is 4.1 AÊ. However, the
lack of crosslinking in Patel and Keller's (1975) work
could be due to the following factors: (i) the unsatura-
tion in their crystalline PE was probably completely
destroyed by the ozone treatment, thus eliminating the
possibility of crosslinking through the cationic reac-
tions (10) and (11); and (ii) energy and charge mi-
gration to the terminal carboxyl groups in their
samples may have been facilitated by the carboxyl
groups, reducing the probability of reactions occurring
within the crystals. Patel and Keller (1975) did report
loss of carboxyl groups on irradiation of the ozone-
treated PE crystals; this is consistent with the occur-
rence of charge and energy migration to the carboxyl
groups in their samples.
3. Conclusion
A consideration of the e€ects of irradiation of PE
leads to the identi®cation of several likely processes
that seem to have received inadequate consideration in
the past, namely: (i) on irradiation in air the formation
of superoxide anions, hydroperoxy radicals and hydro-
gen peroxide should occur in the amorphous regions;
(ii) cationic condensation reactions, which require par-
ticipation of the sites of unsaturation, can lead to
crosslinking in the crystalline and the amorphous
regions; (iii) excitation energy transfer to peroxides
and hydroperoxides, and their reactions with the radio-
lytically produced electrons, would lead to the for-
mation of alkoxy radicals, which, in turn, could lead
to the formation of ether linkages (PEOPE), and
which could also induce some crosslinking; and (iv)
cationic and excited molecule reactions are most likely
the dominant precursors of trans-vinylene. In future
379
work on irradiation of polyethylene, it may be useful
to focus on some of these processes, to obtain evidence
for or against them.
Acknowledgements
Helpful comments by B. J. Lyons, T. Seguchi, J.
Silverman and A. Trifunac are gratefully acknowl-
edged.
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