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Prog. Polym. Sci., Vol.

20, 1165-1199, 1995

0 1995 Eisevier Science Ltd
Pergamon Printed in Great Britain. All rights reserved.
0079-6700/95 $29.00



Polymer Institute, Slovak Academy of Sciences, 842 36 Bratislava, Slovakia


1. Introduction 1166
2. Properties of crosslinked polyolefins 1166
2.1. Polyethylene 1166
2.1.1. Crystallization 1166
2.1.2. Processing parameters 1170
2.1.3. Mechanical properties 1170
2.1.4. Mechanical properties above the melting temperature 1174
2.1.5. Aging, oxidation and effects of antioxidants 1175
2.1.6. Relaxation 1177
2.1.7. The effects of orientation 1177
2.1.8. Other properties 1178
2.1.9. Applications 1179
2.2. Polypropylene 1181
2.2.1. Crystallinity 1181
2.2.2. Mechanical properties 1182
2.2.3. Orientation 1183
2.2.4. Creep properties 1183
2.2.5. Thermal and thermooxidative stability and aging 1184
2.2.6. Other properties 1184
2.2.7. Applications 1185
2.3. Other polyolefins 1185
2.3.1. Mechanical properties 1185
2.3.2. Other properties 1186
3. Properties of blends with crosslinked polyolefins 1186
3.1. Control of blend morphology 1187
3.2. Crystallization 1188
3.3. Mechanical properties 1188
3.4. Applications 1190
3.5. Interpenetrating networks (IPN) and thermoplastic elastomers (TPE) 1190
4. Properties of composites with crosslinked polyolefin matrices 1190
4.1. Efficiency of crosslinking 1190
4.2. Mechanical properties 1191
4.3. Crystallization 1193
4.4. Other properties and applications 1193
5. Concluding remarks 1194
References 1195

1166 I. CHODAK

Crosslinking is a broadly used method for the modification of polymer properties.
This process involves the formation of tridimensional structures - gels - causing
substantial changes in material properties. The most common examples of cross-
linking applications involve the rubbers and thermosetting resins. However,
crosslinked polyolefins, especially polyethylene, are of significant interest as well.
Different procedures may be employed for the initiation of polyolefin crosslinking.
All commercially used processes are based on the formation of polyalkene macro-
radicals at some stage of the process. Common ways of initiating crosslinking involve
macroradical formation via thermal decomposition of organic peroxides,‘-3 high-
energy irradiation (gamma or electron beam),4-s and grafting of silane groups
which form crosslinks via hydrolysis of silanole moieties.’ Other procedures for
initiation of polyolefin crosslinking are less frequently used or have only been inves-
tigated in the laboratory. These include high-frequency heating,” initiation by thermal
decomposition of azo-esters or ethers,” UV irradiationI redox initiation13 and free-
radical-initiated grafting of various moieties onto polyalkene chains which can react
under various conditions leading to the formation of crosslinks often physical or
physico-chemical in nature.14’15 Several interesting modifications of peroxide-
initiated crosslinking were suggested.16 A detailed description of the various initiation
procedures together with mechanisms for these processes and specific features of each
procedure has been given recently in a comprehensive review by Lazar et ~1.‘~
Although an abundant number of scientific papers exists concerning polyolefin cross-
linking, most of these have been focused on the chemistry associated with the process of
polyethylene crosslinking. These reviews dedicated to polyolefin crosslinking discuss the
mechanism of initiation, efficiency and the overall chemistry of the process. The proper-
ties of these crosslinked materials are usually discussed only marginally. In this paper, we
review the changes in properties that are due crosslinking of polyolefins and multiphase
systems with the polyolefinic matrix. Details concerning chemistry will be only discussed
when they become important for an explanation of the properties of these materials.


The crosslinking of polyolefins may be initiated either in the melt (e.g., by thermal
decomposition of peroxides) or in the solid state (by high-energy irradiation - gamma
or electron beam). Crosslinking in the melt leads to a homogeneous distribution of
junctions while the process in the solid state proceeds mostly in the amorphous regions
or at the boundaries of crystallites. l8 This difference results in certain differences in the
ultimate behaviour of the crosslinked material.

2.1. Polyethylene

2.1.1. Crystallization
The morphology of polyethylene changes as a result of crosslinking. This is demon-
strated by changes in the melting and crystallization temperatures as well as in the rate

of crystallization and crystallized portion. The effects also depend on the molecular
weight of the particular polyethylene as indicated in Table 1. As mentioned above, a
principal difference exists between polyethylene (PE) crosslinked by thermal decom-
position of peroxides and by irradiation.” In the former case, crystallization proceeds
from a crosslinked melt, while in the latter crosslinking takes place in the solid state.
Therefore the degree of crystallinity in peroxide-crosslinked samples decreases and is
more or less constant after repeated melt-crystallization cycles, unlike in irradiation-
crosslinked PE where no change or even a slight increase in the crystallized portion
was observed after irradiation-induced crosslinking. However, after the first melt-
crystallization cycle of this crosslinked PE, a decrease in the crystallized portion was
observed, similar to peroxide-initiated crosslinking. This same tendency was also
observed when investigating the effects of crosslinking on the melting temperature
as shown in Table 1.19
The difference between crosslinking in the solid state and in the melt is sufficient to
explain most of the experimental data. However, an interesting hypothesis was sug-
gested by Nikolova et al.‘* Irradiation proceeds mainly in the amorphous regions and
on lamellar surfaces. Thus, a number of defects are formed on the surfaces of the
crystalline portion. This results in a change in the thermodynamic heat of fusion.
Experimentally observed decreases in the heat of fusion due to crosslinking are not
caused by a decrease of the crystalline portion but rather by an increase in the enthalpy
of the crystal surfaces. This hypothesis, although not generally recognized, is indirectly
supported by changes in densities on irradiation. It was found that the density of the
crystalline phase is almost constant with increasing doses, while the density of the
amorphous phase rises in both linear and branched polyethylene.20
A simple two-phase model including only crystalline and amorphous regions is not
valid for crosslinked polyethylene. Transient zones with linear density gradients have
to be introduced to describe the behaviour in irradiated PE. This transient zone might
be formed by defective lamellar surfaces as proposed in Ref. 18. However, it has to be
stressed that amorphization of the structure proceeds if the dose is rather high. A dose of
25 Mrad is sufficient for a drop in the crystalline portion from 51 %-6%.21 With increas-
ing temperature of irradiation, the dose required for amorphization tends to decrease.
Quantitatively, the effect of gamma irradiation on crystalline polymers involves
a dependence of the uncrosslinked sol content vs a difference in crystallization
temperatures for uncrosslinked ( Tco) and crosslinked ( TcR) polymer
S+S o.5= A + B/( Tco - TcR)
similar to the Charlesby-Pinner relation, where A and B are constants.22
The effect of irradiation on the crystallinity of polyethylene depends to a significant
extent on the molecular weight of the polymer. A much higher increase in density, heat
of fusion, and crystallinity degree was observed for ultra-high-molecular-weight
polyethylene with increasing irradiation dose as measured by X-ray, while the effect
was much smaller when high-density PE (HDPE) of normal molecular weight was
irradiated.23 The reason for this may involve a lower initial crystallinity in ultra-high
molecular weight PE (UHMWPE) due to a higher number of entanglements as
compared to HDPE. These entanglements behave as defects during crystallization.

Table 1. The changes in the melting temperature (Tm ) and crystallinity degree (C) for three polyethylenes differing in weight average molecular weight
(1.5 x 10 5 , PEl; 5 x 105 , PE2; 5 x 106 , PE3) as a function of the crosslinking degree determined by the concentration of peroxide [Px] or irradiation dose
(D) and characterized by gel content (g). Irradiated samples were analysed after irradiation before (suffix I) or after remelting (suffix 2)

g(%) g(%) Tm ('C) Tm1 ('C) Tm2 ('C) C(%) C1 (%) C2 (%)
[Px] D :-<
(wt.%) PEl PE2 PE3 (Mrad) PEl PE2 PE3 PEl PE2 PE3 PEl PE2 PE3 PEl PE2 PE3 PEl PE2 PE3 PEl PE2 PE3 PEl PE2 PE3 l.l
0 0 0 0 0 0 0 0 131 135 137 131 135 137 131 133.5 136 45 56 64 45 56 64 43 62 64 tl
0.1 23 97 2.5 0 63 80 132 136.5 138.5 127.5 133 136 39 58 50 56 67 42 48 57 ;J>.
0 135
0.2 2 73 99 5 53 83 90 128 127.5 132.5 134 54 56 69 43 46 52 ~
131 134 131 137 139 38 47 52
0.3 61 100 10 71 83 90 127 133 139 132 130.5 43 56 67 42 44 49
0.4 92 100 15 78 90 97 128 129 132 138.5 139.5 125.5 131 131 37 42 56 58 68 43 42 48
0.5 90 100 20 80 82 98 123 133 138.5 125 129.5 131 37 37 40 52 56 40 41 47
0.8 92 97 100 30 81 90 98 121 126 127 133 139.5 139.5 124 132 130 37 34 380 54 56 70 39 39 47

Many of them break during irradiation allowing for additional crystallization of part
of the material. In HDPE, the morphology is more ordered and the number of the tie
molecules present which can break during irradiation is substantially lower.
Moreover, it has been reported that this effect is time dependent to a significant
extent. Storage of irradiated samples at room temperature results in changes in both
the heat of fusion and melting temperature observed even after 31 months.24 The
extent of the effect depends on the irradiation dose. The dependences are more
complex in this case; either monotonous change, levelling off or a dependence with
a maximum are observed, depending on the length of storage. The molecular weight of
the polymer also plays a significant role.25 Recrystallization was suggested as an
explanation for the changes in the heat of fusion and melting temperature due to
irradiation. However, the mechanism for this process has not been explained in detail
regarding the persistent effect during several years. Considering the options proposed,
a retardation of crystallization due to the formation of crosslinks and a consequent
decrease in chain mobility is unlikely. A gradual crystallization of broken chains is
more probable especially if combined with possible gradual molecular fracture as a
rate controlling step.25 This might be an acceptable explanation considering the rather
long lifetime of macroradicals in irradiated polyethylene. When macroradicals are
trapped in crystalline regions, they can be detected by ESR spectroscopy even at tem-
peratures close to 400 K.26 It is of interest to mention that irradiated polyethylene was
found to be increasingly brittle with aging time.25 This may be attributed to oxidation
initiated by irradiation that slowly continues during storage. This process could also
contribute to recrystallization via breaking of additional macromolecules under stress.
As mentioned above, crosslinking initiated by thermal decomposition of peroxides
results in a decrease in the crystalline portion. This decrease is not extensive and
corresponds with the gel content.27 For example, the crystalline portion in low-
density PE (LDPE) was found to drop from the original value of 41% down to 36.5%
after crosslinking.
Crosslinking initiated by UV irradiation generally leads to similar changes in
crystallinity and melting temperatures compared to high-energy irradiation. No
changes in the melting temperature and heat of fusion have been observed when
crosslinking proceeds in the solid state at room temperature. A drop of both values
was observed when UV irradiation was carried out above the melting temperature or
solid-state-irradiated samples were melted and then recrystallized.29
Thermal properties are also influenced by silane crosslinking. A decrease in the
crystal size may be a reason for the lower melting temperature of crosslinked poly-
ethylene. However, alternative explanations have been suggested3’ including the
formation of irregularities in the structure. These defects will influence the melting
temperature according to the following equation:
--1 -
T, T,o Hi
where p is a probability factor equal to unity for an ideal polymer.
A fundamental concept, important for crystallization of semicrystalline polymers
like polyalkenes, involves an extension of the original theory for eutectoid copolymers3’
1170 I. CHODAK

to crystallizable networks.32 The crystallization abilities of networks should be

governed by the length distribution of the crystallizable chains. This approach can
help to rationalize the observed crystallization behaviour of crosslinked polyolefins
and was studied by Kilian32 with electron beam irradiated linear high molecular
weight PE.

2.1.2. Processing Parameters

An immediate and drastic reduction in polyethylene melt flow index (MFI) is
observed at rather small radiation doses. No flow generally occurs when the doses
are 10 Mrad or more.33 For other polymers, the melt flow index is almost zero even at
2 Mrad.34 The same phenomenon was observed when peroxide or trimethylolpropane
triacrylate (TMPTA) were employed. A thermal decomposition of 0.2wt.% of
peroxide in PE resulted in an almost zero value of MFI; the effect of TMPTA was
less pronounced but substantial as we11.35
In spite of this, attempts have been made to process partially peroxide-crosslinked
polyethylene. Substantial changes in structure and properties have been observed.36
Processing of gamma-irradiated HDPE pellets was also investigated.37 At doses up to
20 kGy, the molecular weight grows and the molecular weight distribution broadens.
Gels were formed at the highest doses used. Irradiated pellets could be processed by
compression. Injection moulding was only useful for materials devoid of any gel
Changes in rheological properties during peroxide-initiated silane grafting of poly-
ethylene were investigated by Ultsch and Fritz.38 Crosslinking reactions of silane-
modified LDPE during processing was also studied.39
The changes of the complex modulus after electron beam irradiation of HDPE were
found to be directly proportional to the radiation dose. On a semilogarithmic scale,
a straight line dependence was observed. According to this result, a more precise
measurement of the radiation dose was suggested, when compared to conventional
thin-film dosimeters placed inside the material.40

2.1.3. Mechanical Properties

The mechanical properties of irradiation-crosslinked polyethylene at ambient tem-
peratures depend very much on the type of polyethylene, molecular weight, processing
and crosslinking conditions, and other factors. Irradiation dose is a most important
parameter. At low doses, crosslinking proceeds mainly in amorphous regions. At
medium doses, crosslinks are formed on the lamellar surface and between individual
lamellae, resulting in a decrease in elasticity. Further increases in irradiation dose
results in crosslinking inside the crystallites leading to an amorphization of the struc-
ture and a loss of deformation properties.4’ Yield stress is reported to be only slightly
affected by irradiation-initiated crosslinking, while the tensile strength dependence on
the dose can be complicated in some cases.33 A significant drop in elongation at break
was observed; the value levels off at doses above 40 Mrad.

Small effects on mechanical properties such as tensile strength, elongation, stiffness,

tear strength and the density were observed for low-energy electron radiation initiated
crosslinking of both polyethylene and ethylene-co-vinylacetate copolymer. A substan-
tial increase in the yield stress was only observed for linear polyethylene of low
molecular weight. Hardly any than e was found if PEs with high and ultra-high
molecular weights were irradiated. 18 The role of crystallinity is demonstrated by
lower values for both yield and tensile strength at break after recrystallization of
irradiation-crosslinked PEs. On the other hand, tensile yield strength was shown to
decrease slightly and then increase with increasing electron beam irradiation dose for
HDPE. Even more distinct changes were found for compressive yield strength; an
increase of lo-20% was observed when the irradiation dose was raised from 20 to
500 kGy.42
A dramatic improvement was found for impact strength which was attributed a
similar effect as for an increase in molecular weight.43 Notch impact strength
increases were observed when the doses were above 10 Mrad. An increase by almost
one order of magnitude occurred at large doses, i.e., 50-75Mrad.33 The beneficial
effects of irradiation-induced crosslinking were also shown for the impact resistance of
foils.44 Crosslinking of LDPE by irradiation results in a small increase in tensile
strength. Important seems to be a higher tear resistance at repeated bending. Signiti-
cant improvements in stress corrosion were also reported.44 Results contradicting
ofther work have been obtained suggesting almost no changes in strain at break of
crosslinked LDPE? Apparently, under certain conditions, crosslinking is not neces-
sarily detrimental for this parameter. Avoiding oxidation during or after irradiation
might be a partial explanation for this result.
Gamma irradiation of HDPE slabs leads to changes in all of the mechanical
properties tested. Dependences of tensile strength at break, yield strength and
elongation at break on radiation dose show similar trends with a maximum at
about 20 Mrad; a linear increase of Young’s modulus was observed.34 A detrimental
decrease of elongation at break caused by gamma irradiation in air is attributed to
oxidation and scission of tie molecules, main-chain scission and inter- and intra-
molecular crosslinking at the crystalline region with simultaneous degradation of
the amorphous regions.45
Significant effects of various factors can be demonstrated by the data regarding
the crosslinking of drawn LDPE monofilaments. A dramatic increase in tensile
strength was observed with gamma irradiation up to doses of about 20 Mrad. Further
dose increase resulted in a sharp drop of tenacity and modulus. Continuous increases
in crosslink density with increasing dose are dominant until a significant decrease of
crystallinity, occurring at high doses, takes over to influence the structure and
properties of the material.
On the other hand, a decrease of both tensile strength and elongation at break
was observed for irradiation-crosslinked polyethylene of very high molecular
weight.47 This is attributed to the fact that the effect of the formation of crosslinks is
overlapped by substantial chain cleavage of long macromolecules from the very
beginning of irradiation, resulting in a decrease of rather high values of tensile
1172 1. CHODAK

strength. Apparently, tremendous decreases in ultimate elongation are also important

since this disables the mechanism of orientational strengthening which would other-
wise contribute significantly to high tensile strength values. The role of crystallinity
was demonstrated by a drop of strength at break after the recrystallization of radiation
crosslinked UHMWPE,19 although in this case, a decrease of initial strength due to
crosslinking was not confirmed.
Substantial changes have been observed when irradiating different types of poly-
ethylene under different conditions. More gel was formed in linear low-density PE
(LLDPE) than in HDPE if the irradiation proceeded in vacua. A higher portion of
fragmentation in LLDPE was found when irradiated in air. A higher mobility of
LLDPE chains which makes recombination easier was proposed as an explanation
for the former effect; tertiary carbons in LLDPE may be mainly responsible for the
latter. An increase of both elongation at break and tensile strength was found after
irradiation up to 5 Mrad, while a substantial decrease was observed when the dose was
higher. LLDPE maintains a certain level of ductility even when irradiated at 50 Mrad,
while other samples (HDPE, MDPE) were found to be brittle after irradiation at such
The effect of EB-initiated crosslinking on Vickers microhardness was also investi-
gated.42 Microhardness was shown to increase with increasing irradiation dose. The
dependence is similar to that for yield stress in compression.
Of particular interest is a tremendous increase of environmental stress cracking
resistance as a result of irradiation by a dose of 10 Mrad or more.33
The radiation crosslinking efficiency can be substantially increased by the presence
of various co-agents. A variety of compounds can serve as co-agents.49-51 The
presence of co-agents leads to an improvement in properties. The positive effect of a
co-agent on properties of crosslinked polyethylene may consist not only of an increase
in crosslink density but also partially in a different structure of the network. Crosslinks
are localized in regions of physical nodal points, i.e., in the neighbourhood of
lamellaes2 if no coagent is present, while in the presence of coagents, crosslinks are
formed as short chains.52
Interesting data have been published recently53 on the gamma irradiation of LLDPE
in the presence of carbon dioxide under supercritical conditions. The aim of the
investigation was to introduce carboxylic groups onto polyethylene chains but a
rather high degree of crosslinking was also observed. The gel content depends on
CO2 pressure. The changes in mechanical properties, i.e., a slight increase of tensile
strength and modulus and a decrease of elongation at break were attributed entirely to
the effect of crosslinking.
Rather contradictory data are reported in the literature when considering peroxide-
initiated crosslinking of polyethylene. An increase in tensile strength as well as elonga-
tion at break with increasing gel content was found after crosslinking initiated by
dicumyl peroxide. Both values are rather sensitive to the nature of the testing condi-
tions such as the rate of deformation.54 On the other hand, Bongart2* found no change
or even a slight drop in tensile strength and a decrease of elongation at break in
LDPE with an increasing degree of crosslinking initiated by peroxide. This apparent

discrepancy may be caused by differences in the molecular weight, molecular weight

distribution and morphological properties. The molecular weight of polyethylene was
found to play an essential role regarding tensile strength. A decrease in tensile strength
at break was reported for UHMWPE (Mw of 4.5 x 106) and for high MW HDPE
(Mw of 5 x 105), while an increase was observed for normal MW HDPE (Mw
1.5 x 105) with an increased peroxide concentration.” This behaviour was attributed
to the fact that tensile strength is substantially affected by the drawability of the
polymer prior to failure. UHMWPE and HMWPE undergo strain hardening at
high deformations, while LMWPE breaks at lower deformations without strain
hardening. Crosslinking results in a reduction of drawability, preventing strain
hardening. Therefore, for UHMWPE and HMWPE tensile strength at break
decreases, while in NMWPE, where stress hardening does not occur, a slight increase
in tensile strength is observed due to the formation of tie molecules.” It was suggested
that the products of peroxide decomposition can cause stress relaxation resulting in
changes of the long-term behaviour of crosslinked polyethylene.55
The effects of peroxide-initiated crosslinking on LDPE include a drop of Young’s
modulus, a slight decrease in yield stress, and an increase and subsequent decrease of
tensile strength with an increasing degree of crosslinking. All of these effects can be
explained by changes in morphology as discussed above (decrease of crystallinity and
crystallite size, increase in the number of tie molecules). A significant decrease of
elongation at break is similar to that observed for other modes of initiation or for
other types of PE. The drop in Young’s modulus was also examined by ultrasonic
The use of co-agents for crosslinking is beneficial for the peroxide-initiated process,
similar to irradiation initiation. Allylic, acrylic or methacrylic multifunctional com-
pounds are commonly used. The effect consists of an increase in the crossbond con-
centration. A slight increase in tensile strength, no change in yield strength, and a
decrease in the ultimate elongation values are consequences of the use of triallyl
cyanurate or polyfunctional methacrylates in crosslinking systems with peroxide
compared to peroxide-initiated crosslinking without these co-agents.58
Important changes in polyethylene properties have been observed when crosslinking
was initiated by peroxide within an extruder during extrusion.35 An almost two-fold
rise in yield strength was found along with an increase in impact strength. The increase
in modulus was somewhat surprising, indicating that a different morphology may be
formed under dynamic conditions. Nevertheless, it is questionable whether cross-
linking occurred in this case, since the amount of peroxide was only 0.3 wt. % (or
lower) and the decomposition of peroxide proceeded under dynamic conditions in
the extruder without any attempt to exclude oxygen. Unfortunately, data on gel
content were not provided.
Significant effects on mechanical properties were also observed when UV irradiation
crosslinking was applied for both HDPE and LDPE. Stress at break and modulus
increased approximately twice for both polyethylenes under question, while the
elongation at break decreased to one half in LDPE but eight times in HDPE.59 The
properties depended very much on the UV initiator used.
1174 I. CHODAK

It has been claimed6’ that irradiation of polyethylene pellets prior to processing

results in an improvement of certain mechanical properties. The yield stress and
modulus values appeared to correlate well with the melt flow index, indicating the
significance of molecular orientation of injection moulded samples with increasing
molecular weight.37 On the other hand, a certain drop in tensile strength was reported
when polyethylene powder was crosslinked by benzoyl peroxide.6’
Interesting conclusions can be drawn from data on silane crosslinking. The process
proceeds in two steps. First, silane is grafted onto the polyethylene chain by a radical
reaction initiated by peroxide and, in second step, crossbonds are formed by condensation
of silanole moieties. Comparison of silane-grafted polyethylene before and after cross-
linking can indicate the effects caused by introducing defects on the polyethylene chain
(grafting of silane) and what the effect of crosslinking itself is (condensation reaction). The
former effect should be related mainly to a decrease in crystallinity, while the latter is due
to the formation of a network and an increasing number of tie molecules. These con-
siderations correspond with experimental data where a drop in yield strength was
observed after silane grafting followed by certain recovery after crosslinking. Grafting
itself has no effect on tensile strength at break; an increase was found after crosslinking.
Both modulus and yield strength were found to be dependent on the crystallinity.30
When discussing the effect of crosslinking on mechanical properties, the concen-
tration of crosslinks is the most important parameter.62 In some cases even linear
dependences have been reported, e.g., elongation at break vs swelling degree
(proportional to crosslink density) for both LDPE and HDPE.63

2.1.4. Mechanical Properties Above the Melting Temperature

The main reason for the crosslinking of polyethylene in many cases is the retention
of a certain level of mechanical properties at temperatures over the melting point of the
material.64 The deformation behaviour of PE is improved by radiation crosslinking.
To maintain more than 60% of the original value of deformation, at least 70% of gel is
Lyons66 investigated the mechanical properties above melting temperature for
27 irradiation crosslinked polyethylenes (HDPE, LDPE and LLDPE) differing in
molecular weight, molecular weight distribution and initial vinyl concentrations.
The dependence of ultimate elongation at 160°C on the square root of irradiation
dose was found to be linear within a certain dose range, consistent with the behaviour
of a rubbery network. With increasing irradiation dose, the values of elongation at
break decrease and the elastic modulus increases.66
At 423 K the dependence of tensile strength on gel content goes through a maxi-
mum;28 at a high gel content, a decrease of strength is observed. Elongation at break
was found to be even more sensitive to the degree of crosslinking. At 423 K elongation
at break was found to be 200% or only 40% if the gel content was varied from 85 to
95 wt.%, respectively.28 The effect of increased crosslinking degree on the values of
elongation at break for various temperatures is shown in Fig. 1.
An improvement of thermomechanical properties was reported if crosslinking was
initiated by both decomposition of peroxides67 and gamma irradiation.t5 The effect

0.00 0.25 0.50 0.75 1 .oo

peroxide, %

Fig. 1. The dependence of elongation at break of LDPE on crossl~nking degree given by a

concentration of decomposed peroxide at 20°C (circles), 80°C (triangles) and 110°C

depends on the density of crosslinks. Even better thermomechanical properties were

reported for a physical network of polyethylene grafted with acrylic acid.‘5T68
The effect of UV initiated crosslinking on temperature resistance is similar to other
initiating systems. A substantial difference involves the fact that crosslinking is
efficient only in thin layers, The effect of UV irradiation on the behaviour of poly-
ethylene crosslinked by UV irradiation was reported by Oster et a1.69and Wilski et
~1.~’ as early as 1959. Films of LDPE irradiated with UV light in the presence of
benzophenone did not break under a load of 0.7 MPa for 15 minutes at 150°C.
The maintenance of mechanical properties above the melting temperature was also
found for silane-crosslinked polyethylene. A storage modulus of the order lo5 Pa was
reported at 180°C; the same value was very low when uncrosslinked polyethylene was

2.1.5. Aging, Oxidation and E@ects of Antioxidants

The effects of aging can be discussed from two points of view. First, the thermo- and
photooxidative stability of crosslinked polyolefins is usually diminished because of the
formation of defect structures (double bonds, tertiary carbons, long-lived macro-
radicals). On the other hand, a stabilization of morphology by crosslinking is
beneficial from the point of view of physical aging, Usually, fine crystalline structure
with good mechanical properties is formed after processing. This is thermo-
dynamically unstable and larger crystallites are formed during storage by slow
recrystallization resulting in a more brittle material. The recrystallization process is
retarded or partially hindered by crosslinking.
Storage of gamma-irradiated HDPE at room temperature up to 300 days results in a
decrease of the strength at break, but hardly any change of elongation at break was
1176 I. CHODAK




0 50 100 150 200 250 300

aging time, days

Fig. 2. A dependence of tensile strength (lower) and elongation at break (upper) of HDPE on
time of storage. Irradiation dose 0 (squares), 180 (circles) and 360 kGy (triangles).

observed (Fig. 2).34 A significant drop was found for samples irradiated by 18 Mrad
which is a dose causing a large increase of tensile properties measured immediately
after irradiation. However, a similar drop in tensile strength after storage was also
found for unirradiated HDPE. The oxidative stability of peroxide-crosslinked
polyethylene was also investigated by isothermal DTA.71
The yield of crosslinking initiated by a radical process is affected by the presence of
antioxidants. On the other hand, thermo- and photooxidative stability is influenced by
the extent of crosslinking. Although the formation of a crosslinked portion is influ-
enced by the presence of antioxidants, the effects of various antioxidants are not the
same. In Ref. 65 several different antioxidants were compared regarding gel formation
via EB irradiation. Mercapto benzoimidazole and 4,4-thio bis(6-t-butyl-3-methyl
phenol) were shown to have a small effect on the crosslinking degree. In contrast,
for N,N-dinaphthyl phenylenediamine and phenyl naphthylamine the drop in gel

content was substantial. It may be expected that the interference of an antioxidant

with crosslinking is caused by a consumption of the antioxidant with obvious con-
sequences on the thermal stability of the crosslinked material. 2,6-Di-t-butyl-p-benzo-
quinone diazide was found to be without effect on the mechanical properties of
crosslinked polyethylene while providing an efficient thermal stabilization.72
The radiation stability of crosslinked polyethylene is a major topic of recent interest.
The effect of antioxidants on the radiation stability of crosslinked polyethylene used
for cable insulation was investigated in Ref. 73. Thermal and a combination of thermal
and radiation aging of low-voltage polyethylene cable insulation was also studied.74 In
chemically crosslinked polyethylene, the combined effect consists of a superposition of
the individual phenomena.
The resistance of several insulating materials to long-term radiation effects was
compared by measuring the changes in mechanical properties after exposure of the
test specimens in high-level radiation areas within a Super Proton Synchrotron and in
a nuclear reactor. It was found that the relative decrease in both tensile strength and
elongation at break was lower for crosslinked polyethylenes (several grades) when
compared to uncrosslinked polyethylenes. The data scatter of the crosslinked
materials was also lower than that for the uncrosslinked PEs investigated.75

2.1.6. Relaxation
Dynamical-mechanical properties are sensitive to crosslinking. A shift in the
gamma relaxation peak is not observed but a decrease in intensity was found when
crosslinking was initiated either by peroxide decomposition or irradiation.
Nevertheless, the shape of the peak was different; peroxide crosslinking led to
symmetrical peaks, while asymmetric shapes were recorded for irradiation-
crosslinked polyethylene.76
The melt relaxation behaviour of LLDPE is dominated by power laws not only
directly at the gel point but in a rather broad region around the gel point. The
frequency window is broadest at the gel point. The power law exponent decreases
with increasing crosslinking degree, i.e., with radiation dose.77
Creep properties have been found to be the same for crosslinked and uncrosslinked
polyethylenes at room temperature, while a positive effect for crosslinking was
observed above RT. The differences between crosslinked and unmodified PE increase
with increasing temperature and load.54 The time dependence of the creep modulus at
low stress was shown to be related to the time dependence of microhardness data for
EB-crosslinked HDPE.42

2.1.7. The Efsects of Orientation

An increase in radiation dose results in an increase in tensile strength and shrinking
stress in foils which were first irradiated and then oriented. In contrast, a drop in both
parameters was observed when the procedures were applied in opposite order.78
Shrinking stress increases with irradiation dose as well as with the temperature of
shrinking. Obviously, crosslinking results in a fixation of the structure present in the
1178 I. CI-IODixK

material at the moment of irradiation.46 The dependence of tensile stress vs strain

(expressed in terms of the Mooney-Rivlin equation) was shown to have two linear
regions. The first was ascribed to affine deformation of crossbonds at low deformation,
while the second was attributed to ~ona~ne deformation due to slipping entangle-
ments at higher deformation.‘@
The memory effect and shrinking of crosslinked polyethylene are also of interest. It
was found that the shrinking force acts above the melting temperature in material
which was previously deformed. This is caused by the rubber elasticity of an expanded
network. Another, so-called ‘holding’ force, induced by thermal contraction, is also
active. The shrinking force is related to crosslinking density, while the ‘holding’ force is
determined by the nature of crystallinity and is independent of crosslinking.
Improved creep resistance was observed after gamma irradiation of HDPE tapes
oriented to a draw ratio of 6.5. Irradiation in an acetylene atmosphere results in a
decrease in the optimal dose to one tenth of that if irradiation proceeds in vices.
Irradiation leads to a suppression of plastic flow, i.e., yielding. The presence of
acetylene during irradiation results in a more effective reduction of creep rate
compared to irradiation in vacuo.*” This effect is most pronounced at higher tempera-
tures. The effect was observed to be even higher when post-irradiation crosslinking
(two-stage process, first irradiation, then exposure to acetylene) was applied.81
Crosslinking initiated by UV irradiation was shown to have similar effects as high-
energy radiation. Shrinking stresses are enhanced if crosslinking of either HDPE or
LDPE is applied before drawing, while very little effect was observed if drawn
materials were crosslinked.8z It is of interest that orientation has no influence on the
crosslinking degree of UV irradiated HDPE up to a drawing ratio near 10. Further
drawing results in a decrease of the gel content.83
It must be stressed that the irradiation of oriented polyethylene results in partial
degradation of the material. This phenomenon is more pronounced in oriented poly-
ethylenes than in the isotropic polymer. A greater number of tie molecules under
tension in the amorphous phase in oriented polyethylene compared to the isotropic
polymer seems to be a reasonable explanation for this observation.84
The effects of crosslinking on the properties of highly drawn high-modulus ultra-
high-molecular-weight polyethylene were also investigated (see e.g., Ref. 80). How-
ever, to understand the behaviour of this material, it is necessary to discuss the
properties in a broader extent in connection not only with the crosslinking procedure
but also with the peculiarities of morphology and processing. Although strictly poly-
ethylene in nature, this material is rather special from several points of view and a
discussion on its properties would need a thorough explanation of other aspects which
are not fully understood themselves. Therefore the topic is omitted, being too broad to
be adequately reviewed here.

Crosslinking results in a decrease of antioxidant migration at room temperature.

A temperature increase leads to a lowering of this effect.55 This may be partially

explained by the grafting of the antioxidant to polymer chains during peroxide-

initiated crosslinking as suggested in Ref. 85.
Diffusion coefficients are also affected by the formation of crossbonds. The diffusion
of antioxidants in peroxide-crosslinked polyethylene first increases with increasing
crosslinking due to a decrease in crystallinity but then a sharp decrease is
observed.86 The permeability of both gases and liquids is lower in irradiation-cross-
linked polyethylene compared to the uncrosslinked polymer. The separation factor
was also found to change when penetration of mixtures of various solvents through
crosslinked polyethylene was investigated.87
The temperature dependence of the coefficient of thermal conductivity for uncross-
linked polyethylene goes through a maximum at -50°C corresponding to the Tg.
Irradiation leads to a decrease of thermal conductivity with increasing dose in the
temperature interval -110 to 70°C. This behaviour is attributed to a decrease in
crystallinity with a dose increase. On the other hand, for samples with high
amorphous content, the reverse dependence was found; formation of crossbonds
due to irradiation results in an increase of thermal conductivity.*’ Irradiation also
leads to a lower thermal expansion coefficient,

2.1.9. Applications
Cable insulation is one of the most broadly used applications of crosslinked poly-
ethylene.88189It is claimed that approximately 12% of the insulation in Japan is made
from crosslinked polyethylene65 where crosslinking is performed by an electron beam
process. The main reason for the use of crosslinked insulation is thermal resistance,
i.e., maintaining a certain level of mechanical properties above the melting temperature.
Thus the cables can be used at higher temperatures. Short-term temperature increases
substantially above the melting point do not result in damage to the insulation. The
resistance of cable insulation toward water is also enhanced by crosslinking.
It must be stressed that the insulation efficiency of electron beam crosslinked poly-
ethylene falls remarkably with increasing temperature up to the melting temperature
where a recovery of the insulation effect almost to the level of uncrosslinked PE is
observed65 as shown in Fig. 3. An explanation for this behaviour involves electron
charge trapping and the formation of free macroradicals relatively stable under the
melting temperature but decaying rapidly in the melt. An increase in electrical
conductivity was also reported for LDPE irradiated by gamma rays.” Changes in
electrical behaviour were not reflected in breakdown voltage measurements, since no
significant effects on the dielectric strength were observed with radiation doses up to
5 x lo3 kGy.‘i The resistance against electric breakdown of crosslinked polyethylene
can be improved by the addition of aromatic aldehydes. 0.1-10 wt.% of dimethyl-
amino benzaldehyde led to a breakdown at 32.4 kV compared to 9.6 kV if no additive
was present.
Recently, silane crosslinking has been applied extensively for insulations in low-
voltage power cables.39 Regarding applications for cable insulation, the effect of
copper deactivators in irradiation-crosslinked polyethylene, as studied in Ref. 92, is
of interest.
1180 I. CHODAK

0 40 60 120 160


Fig. 3. A dependence of electrical resistance on temperature of non-irradiated (filled circles)

and irradiated PE at 1 (triangles), 10 (open circles) and 100 Mrad (squares).

A comparison of commercially applied technologies for the crosslinking of cable

and wire insulations has been made in Ref. 93. The industrial requirements, reliability,
and cost of electron beam irradiation, peroxide crosslinking, and silane technologies
have been reviewed.
Crosslinked polyethylene is also used as a shrinkable material since large deforma-
tions can be stored and later recovered by heating the material.79 This property is used
for the production of thermally shrinkable foils and pipes. The diameter of the pipe
can be expanded by air pressure above the melting temperature of the polymer, then
the product is rapidly cooled to RT and the expanded diameter is frozen in. When the
product is heated again above its melting temperature, a memory effect of the network
results in shrinkage of the pipe to its original diameter. The connection of individual
pipes can be performed by simply heating the joined ends of the pipes.
Crosslinking was suggested for heavy-duty polyethylene films which showed
enhanced sealability even after exposure to 15 Mrad radiation.43 Crosslinking can
result in cost savings when compared with uncrosslinked films employed in the
same application.
Irradiation-crosslinked UHMWPE was found to be superior to the non-irradiated
material when employed for the construction of hip prostheses. In spite of some
increase in the coefficient of friction, crosslinking resulted in a significant decrease
in wear.94 A high crosslinking level is present at the surface layer, while the core is
only slightly crosslinked. Thus, high-impact resistance together with good wear
resistance has been achieved in these materials.95

Photochemically initiated crosslinking of polyethylene using PC13 as a

photoinitiator resulted in an improved dyeability and lower flammability.96
An attempt was made to use elastic-strain grinding of crosslinked polyethylene for
the production of polymer powder.97 The powder based on crosslinked polyethylene
can be mixed in the polymer matrices in order to influence the properties of these

2.2. Polypropylene
Polypropylene crosslinking is complicated by an extensive portion of macroradicals
decaying by beta scission and disproportionation.17 Therefore, an effective co-agent
for crosslinking is required98 to suppress the fragmentation of polypropylene (PP)
macroradicals and to increase the efficiency of crosslinking.

2.2.1. Crystallinity
The effects of gamma irradiation of polypropylene on the crystallinity and melting
temperature was studied by several authors (e.g. Refs 99, 100). A drop in both melting
temperature and crystallinity was observed. No effects due to the presence of
antioxidants as well as different initial crystallinities were found. On the other
hand, it was reported”’ that irradiation up to 150 Mrad does not lead to substantial
changes of crystallinity measured by density and X-ray diffraction. Changes at the
molecular level due to gamma irradiation, such as conformational, destructive, cross-
linking, oxidation, and post-irradiation effects do not affect its supermolecular smectic
structure. lo2
Peroxide-initiated crosslinking results in a dramatic drop in crystallinity if no
co-agents are present. The size of spherulites is diminished to one third of their original
dimensions.36 DSC measurements showed that after crosslinking the crystallinity
dropped from 60% to near 10%.lo3 In the presence of an efficient co-agent, such as
hydroquinone, the decrease recorded was from 120 J/g for the original polypropylene
to about 100 J/g for the highly crosslinked PP.lo4 Obviously, in the absence of
co-agent, a decrease in crystallinity is caused mainly by defects formed by branching.
Crosslink formation plays only a minor role. In the presence of a co-agent, scission
and subsequent branching are suppressed and the network junctions are the prevailing
structural defects influencing the degree of crystallinity. The crystallinity drop in this
case is comparable with that of chemically crosslinked polyethylenes where almost no
scission is supposed to occur. It is of interest that with increasing crosslinking degree,
the crystalline form ratio is altered. As revealed by X-ray diffraction,105 the relative
content of the gamma form increases continuously with respect to the alpha form as
the gel fraction increases.
Electron beam irradiated PP was shown to act as an efficient nucleating agent.
Actual nucleation is supposed to proceed due to the presence of a PP network,
although no further details on the mechanism of action were given.lo6
1182 I. CHODAK

2.2.2. Mechanical Properties

The irradiation of PP leads to a greater degree of scission of macromolecules
compared to polyethylene unless an effective co-agent is present. Scission results in
a substantial drop in molecular weightlo and a consequent drop in tensile
strength.““‘08 At absorbed doses above 10 Mrad the material is extremely brittle.“’
Similar effects are caused by polypropylene macroradical reactions initiated via the
thermal decomposition of peroxides.’ lo The formation of internal stress was suggested
to be a reason.“’ Rather large differences were observed in the properties of annealed
monoclinic samples and unannealed monoclinic or smectic samples. The observed
phenomena have been attributed to an increased sensitivity of tie molecules to
scission in the unannealed material,“’ although nonhomogeneous oxidation was
suggested as an alternative explanation.“’ The mobility of oxidized core structures
is prevented by a crosslinked stiff internal layer. Therefore, internal stress is generated
resulting in crack formation in the oxidized layer.
Sawasaki and Nojiri1t2 have investigated PP crosslinking initiated by EB irradiation
using several polyfunctional monomers as co-agents for crosslinking. They suggested
that extremely efficient co-agents include those containing acryloyloxy moieities, e.g.,
tetramethylolmethane tetraacrylate or trimethylolpropane triacrylate. For cross-
linking of PP to high degrees, the required radiation dose is ten times lower than if
other co-agents (e.g., triallyl cyanurate) are used. Obviously, the necessity of using
lower doses for reaching the same gel content is important when considering the effects
of irradiation on properties. The decrease in elongation at break is
much lower with acryloyloxy monomers compared to allylic co-agents if a dependence
of gel content vs elongation is compared. However, at the same dose, the effect is
approximately the same for both co-agents investigated. With increasing gel content,
an increase of both moduli was observed.
It must be pointed out that a substantial number of free macroradicals remain in
the polymer after irradiation. These macroradicals, formed in crystalline regions,
contribute to the long-term degradation of mechanical properties.‘t3 The rate of
decay of residual radicals was found to depend strongly on the crystalline portion,
which can be influenced by processing and moulding procedures.l14 Kinetic models
for diffusion-controlled radical decay in two-phase systems have been proposed to
quantitatively explain this phenomenon.115
Peroxide-initiated crosslinking results in similar changes as caused by irradiation. In
the absence of co-agent a decrease of molecular weight was observed accompanied by
a decrease of both the modulus and yield strength.56 A vanishing of the yielding
phenomenon was observed at higher gel contents.56 The decrease in impact strength
can be substantial.36 Opposite tendencies were found in the presence of co-agents.l16
Again, the effect depends on the co-agent used; triacrylate monomers gave larger
effects compared to triallylcyanurate or benzoquinone. Nevertheless, in these experi-
ments, rather low amounts of peroxide were used and reactive extrusion was employed
for sample preparation.
Superior efficiency was reported for peroxide-initiatedcrosslinking if benzoquinone’ l7
or hydroquinone’18 were used as co-agents. Since the beta scission of polypropylene

macroradicals is suppressed significantly, mechanical properties are less affected by

degradation than if other crosslinking initiating systems are employed. An improve-
ment of impact resistance at low temperature and a decrease of the brittle point
by approximately 20°C was found.‘29 A significant enhancement of temperature
resistance even above 300°C was also demonstrated as shown in Table 2.119 Yield
strength was shown to depend on crystallinity as expected; somewhat surprisingly,
the same dependence was found for the tensile strength, although modulus and
elongation values drop steadily with increasing crosslinking degree.‘*’
Ultraviolet irradiation in the presence of PC& was reported to lead to an increase in
the thermal resistance of isotactic polypropylene,121 similar to other crosslinking
Ionic crosslinking of PP can also contribute to better properties. Polypropylene
with grafted maleic anhydride can be crosslinked by the addition of zinc diacetate or
sodium acetate. An increased softening point and better thermal stability result from
the crosslinking, while tensile strength is hardly affected.14 It is surprising that besides
bivalent zinc monovalent sodium can also act as a crosslinking agent suggesting that
crosslinking proceeds via a complex mechanism in this case.
An increase in tensile strength was also reported after crosslinking initiated by
polyacrylonitrile, polyarenes and polymeric Schiff bases at concentrations of
0.3-0.5 Wt.%.‘** However, no data are available to prove that crosslinking actually
occurred; physical modification may be a reason for the effects observed.

2.2.3. Orientation
The effect of UV-initiated crosslinking on the shrinking stress of oriented PP was
investigated by Zamotaev et aL8* Similar to PE, shrinking stress is enhanced if cross-
linking is applied before drawing, while a very small effect was observed if drawn
material was crosslinked. It is of some interest that no co-agent was used in this case.

2.2.4. Creep Properties

An improvement in the creep behaviour of PP tape irradiated in an acetylene
atmosphere was reported by Appleby and Busfield.’ This effect was investigated at

Table 2. Thermal resistance of uncrosslinked (0) vs crosslinked (XL) polypropylene given by time of
penetration (seconds) of a needle with an area 1 mm2 through a 1 mm thick slab at various temperatures.
Experiments up to 600 s

150 205 260 315

(kg) 0 XL 0 XL 0 XL 0 XL

2.5 >600 >600 11 >600 2 >600 2 40

5 >600 >600 3 >600 1 21 1 5
10 >600 >600 1 >600 1 2 1 2
20 >600 >600 1 40 I 2 1 1
1184 I. CHODAK

30 and 100°C and was found to be more pronounced at higher temperatures. A drop in
creep compliance was also reported as a result of gamma irradiation in the presence of
To explain his NMR experiments, Kunert et al.125 suggested that in peroxide-
initiated crosslinking in the presence of benzoquinone as a co-agent, the crosslinks
act as a plasticizer leading to an increase in the free volume.

2.2.5. Thermal and Thermooxidative Stability and Aging

Gamma irradiation leads to enhanced thermal degradation.“’ A pronounced effect
was observed with increasing irradiation dose. Considering two competing processes,
i.e., degradation and crosslinking, the former tends to prevail at doses above 3 Mrad.
Thermooxidative stability characterized by oxidation induction time depends
strongly on the irradiation dose or the concentration of initiator and is hardly
dependent on the gel content. Therefore, the use of an efficient co-agent for cross-
linking can be extremely beneficial allowing for a decrease in the irradiation dose to
achieve the required gel content and desired properties. This was demonstrated by
Sawasaki and Nojiri when using acryloyloxy-based polyfunctional monomers as PP
crosslinking co-agents.‘12
Ionically crosslinked maleic anhydride grafted PP was reported to possess increased
oxidative stability.14 Crosslinking of unstabilized PP with a peroxide-initiated process
in the presence of benzoquinone or hydroquinone as co-agents was reported to lead to
an extensive suppression of thermooxidation.‘26 This phenomenon was attributed to
the binding of hydroquinone to the PP network, preventing its sublimation out from
the system on the one hand and to a formation of bound semiquinoic radicals with
much higher thermooxidative efficiency on the other. This rather unique effect of
crosslinking on thermooxidative stability was enhanced by the addition of common
antioxidants. A clear synergism was observed in this case.127
The storage of gamma-irradiated polypropylenes was investigated12* by measuring
the flange break angle and energy to break. It was found that the brittleness increases
with the initial dose of irradiation and with storage time. The mobility of the chains is
decisive when considering the minimization of the irradiation effect on the mechanical
properties. In the presence of a mobilizing additive such as polypropylene wax,
atactic polypropylene or polypropylene oil, macroradical decay is faster and the effect of
storage on brittleness enhancement is smaller than in samples without any additive.12*
The primary reason involves an increase in the free volume due to the presence of the
additive. It was reported129 that the decomposition of peroxide results in an increase in
free volume in isotactic polypropylene, even in the absence of other additives. Local
changes in polypropylene tacticity could contribute to this effect.

2.2.6. Other Properties

No changes in the dielectric properties of gamma-irradiated PP have been reported
in an absence of additives. However, when allylmethacrylate was added as a cross-
linking co-agent, an increase in the dissipation factor was observed. The concentration

of the co-agent should not exceed 4 wt.%; in this case improvement of mechanical
properties can be reached without lowering the dielectric properties.‘24 Different data
are reported by Kita et al.13’ who observed an increase in electric strength after
irradiation of PP without any additive of doses up to 5 Mrad. Simultaneous cross-
linking, degradation and oxidation of PP are suggested as possible reasons for the
phenomena observed. The presence of the UV stabilizer Tinuvin 770 caused higher
conductivity at high electric fields and lower breakdown voltages. Gamma irradiation
was reported to reduce the conductivity of PP in this case,131 possibly by eliminating
the effect of the UV stabilizer due to its consumption or partial modification during
Atactic polypropylene was crosslinked to an elastomeric material by gamma
irradiation. Stress-optical behaviour was studied. It was found that birefringence
depends on the draw ratio and it is negative at low drawing while positive at draw
ratios higher than 1.8.132

2.2.7. Applications
Various applications for crosslinked PP have been suggested. Crosslinking to a gel
content of 55% was shown to be beneficial for cable insulation. Insulation with
crosslinked PP survived a high-voltage cut-through test (lOS’C, 30 kV) for 7 hours
without breakage, while the uncrosslinked material based insulation failed after 2.5
hours.l12 Both crosslinking via grafting of silanes initiated by peroxide decomposition
and radiation in the presence of polyfunctional monomers have been employed.
Maintaining a certain level of mechanical properties even above the melting
temperature can be useful for the production of foamed materials. Optimal values
of modulus and elongation are shown to be sufficient for the production of highly
foamed materials.l12 Twenty-fold foaming can be reached using common foaming
agents. The thermal stability of the foamed PP is higher than that of foamed PE.
This is understandable considering the differences in melting temperatures for both
Irradiation of PP fibres in the presence of co-agents such as acrylic acid or
vinylpyridine leads to an improvement in tenacity and dyeability.
Radiation degradation and stabilization of PP was extensively investigated because
of an application of radiation treatment for the sterilization of disposable syringes.lo8
It should be mentioned that the decomposition of peroxide during reactive
processing of PP is commonly used for the modification of rheological properties
via a decrease of the molecular weight and control of molecular weight distribution.
No co-agents for crosslinking are used in this case.134

2.3. Other Polyolefins

2.3.1. Mechanical Properties

An improvement of tensile properties as a result of peroxide-initiated crosslinking
was claimed to occur in ethylene-propylene copolymers. The properties depend on the
1186 I. CHODAK

type of peroxide used. Peroxides having a bis(phenolic) structure in the molecule were
found to give more beneficial effects than peroxides based on aliphatic structures.‘35
On the other hand, dicumyl peroxide decomposition was reported to lead to a
substantial decrease in tensile strength and elongation at break in both saturated
ethylene-propylene copolymers and, to a lesser extent, in EPDM (ethylene-
propylene-diene copolymer) indicating that besides crosslinking, degradation
processes take place.‘36 A comparison of three different curing systems for EPDM,
namely sulphur/accelerator, peroxide, and azide revealed a superior behaviour for
benzene-1,3-disulphonyl azide considering tensile and tear strength, elongation at
break, and modulus. 136
The presence of multifunctional unsaturated compounds as crosslinking co-agents
is beneficial for the properties of crosslinked EPM rubbers. Tensile strength is
substantially enhanced compared to peroxide-initiated crosslinking in the absence of
a co-agent.58 A significant drop of compression set was also observed. Generally these
changes can be ascribed to an increase in the crosslink density and to a suppression of
scission of the polypropylene segments within the copolymer.

2.3.2. Other Properties

Unfilled EP copolymers are claimed to have similar or better electrical properties
when compared to crosslinked PE. A comparison of ethylene-propylene-diene
copolymer with fully saturated EP leads to the conclusion that the former is more
resistant to deformation during compression but less suitable when aging is
considered. 137The viscoelastic and rheooptical behaviour of radiation crosslinked
ethylene-propylene copolymers was also investigated.138
Radiation,73 thermal and thermal/irradiation combined aging74 of chemically cross-
linked ethylene-propylene rubber were also investigated. Various antioxidants have
been evaluated but no particular antioxidant or combination of antioxidants was
found to be superior to the others.74
Crosslinking leads to changes in chlorinated polyethylenes. Crosslinking with 6% of
peroxide in the presence of 2% triallyl cyanurate results in excellent thermal resistance
and low permanent deformation, but to a lowering of tear resistance. A drawback may
be the formation of gaseous products resulting in porous structures.
The effect of irradiation resulting in antioxidant consumption and a decrease of
thermooxidative stability, described for polyethylene and polypropylene, was also
observed for ethylene-vinylacetate copolymers.139 Peroxide-initiated crosslinking of
EVA copolymer was also investigated.14’


Crosslinking may result in interesting changes when applied to blends of

incompatible polymers. Usually two objectives are mentioned for investigating cross-
linking in immiscible blends, namely an increase in the interaction between the two
phases and the stabilization of morphology. In the former case a certain degree of
crosslinking of both polymers is inevitable, while in the latter, the crosslinking of one

(preferably the dispersed phase) is sufficient for reaching the,desired effect. It has to be
stressed that both effects overlap when considering the properties of crosslinked

3.1. Control of Blend Morphology

The properties of a blend of immiscible polymers depend mainly on morphology. A
difficulty may consist of an intrinsic instability of such morphology, especially in the
molten state or when considering long-term behaviour. The morphology formed
during processing can be stabilized to a large extent by crosslinking of either the
dispersed phase or both components. This principle was examined by Van Gisbergen
and Meijer141 who investigated the effect of irradiation crosslinking on the coalescence
of polyethylene threads in a polystyrene matrix. Three types of interface were
considered, namely mobile, partially mobile and immobile. Equations for the kinetics
of coalescence have been derived and compared with experimental results.
The fine and uniform morphology of LDPE/PP blends was shown to be stabilized
by both peroxide-initiated crosslinking and EB irradiation. The effect is similar for a
continuous phase formed either by LDPE or by PP.142 Electron beam irradiation
was used to control both the morphology and rheology of blends of EPDM/
polypropylene. 143This procedure allowed for a balance of good processability with
high impact strength using high molecular weight polypropylene. Peroxide-initiated
crosslinking was investigated for LDPE/PP blends to enhance dispersive mixing of the
components by modifying their rheological properties.‘442145
A transesterification reaction was used for in situ crosslinking during reactive
extrusion of a dispersed phase comprised of a miscible blend of ethylene vinyl acetate
and ethylene methyl acrylate dispersed in a polypropylene matrix. With an increase in
the conversion of the reaction, the equilibrium between breakup and coalescence was
shifted to the formation of larger particles. However, after reaching a certain extent,
the mechanism was replaced by coagulation, leading to rather large particles, as
shown in Fig. 4.‘46 Microphase separation in crosslinked polymer mixtures has also
been theoretically treated. Crosslinking prevents complete segregation of the phases.

0 o”ooo
> Oe,OO
o”oo \
g g”
’ VQ

Fig. 4. A scheme for the development of coalescence and breakup processes under and above
the critical gel content g*.
1188 1. CHODAK

The size of domains was shown to be larger; the effect is temperature depe~dent.14’~14*

3.2. Crystallization
Crosslinking does not prevent two-phase-structure formation in blends of two
immiscible polymers, although the morphology of crosslinked blends is different
when compared to uncrosslinked analogues. Irradiation leads to a decrease of melting
temperature after remelting the blends of PP with either PE or EVA copolymer.‘4g~‘50
The effect is similar to the irradiation of individual polymers. Similar behaviour was
also observed for PP/LDPE blends crosslinked by peroxide in the presence of
hydroquinone as a co-agent for PP crosslinking.‘~ According to deviations from
linearity of the dependences of heats of fusion of both PP and PE parts on the
component concentration, the formation of a two-phase structure interconnected at
the interface was suggested.

The effects of crosslinking on the properties of PP-containing blends depends very

much on the extent of PP scission during crosslinking. A slight decrease of tensile
strength and an extensive drop of both elongation at break and modulus with
increasing dose of EB irradiation have been observed in blends of PP with either
HDPE or EVA copolymers. i49The mechanical properties depend on the composition
of the blends. These results are explained in terms of parallel effects of crosslinking of
the ethylene part and a prevailing scission of the polypropylene part. A comparison of
the properties of blends of LDPE and PP crosslinked either by peroxide or by
irradiation led to the same conclusion. Irradiation resulted in higher tensile strengths
as well as better elongation at break compared to the peroxide-initiated process.‘42
This was attributed to higher PP degradation initiated by peroxide compared to
irradiation. Attempts have been made to correlate the mechanical behaviour of
these blends with their microstructure. On the other hand, the irradiation of PP-
EPDM blends is claimed to result in the grafting of PP onto EPDM chains leading
to an improvement in mechanical properties.“’
The properties of peroxide-initiated crosslinking of PE-PP blends depend on both
the concentration of the initiator and the ratio of the blend components. Teh et ~1.,‘~’
recently reviewing the literature on PE-PP blends, came to the conclusion that at low
amounts of peroxide and/or in PE-rich blends, the yield and modulus values are
improved by crosslinking. An increase of peroxide and/or PP content resulted in
inferior mechanical properties. However, in most above-mentioned experiments, no
co-agent for PP crosslinking was present except for the paper by Borsig ef ~1.‘~~where
a tetrafunctional ally1 compound was used.
An improvement of the properties of crosslinked PP-containing blends can be
achieved with the use of co-agents. Efficient co-agents like hydroquinone prevent
scission in the PP component of the blend similar to the crosslinking of PP itself.‘17
The ductility of PP-LDPE blends increases after crosslinking resulting in a higher
elongation at break154 as well as better impact strength. The beneficial effect of

co-agent presence on the impact resistance of crosslinked LDPE-PP blends is demon-

strated in Table 3.‘18 It is seen that the impact strength of a 1 : 1 blend measured at
-20°C is very low for uncrosslinked blends. A significant increase was observed when
crosslinking to a high degree was applied in the presence of the co-agent. Hardly any
effect was achieved for a low degree of crosslinking. Crosslinking without a co-agent
leads to much lower impact strengths. Degradation of PP resulting in a brittle material
is an obvious explanation.“8
Crosslinking with the initiating system peroxide-hydroquinone was reported to
improve crack growth resistance of PP-LDPE blends by one order of magnitude
when compared to uncrosslinked blends.155
Crosslinking was also used for the modification of properties of blends of different
polyethylenes. Electron beam irradiation was used for the crosslinking of drawn
blends of ultra-high molecular weight and normal molecular weight polyethylenes.
Substantial improvements in high-temperature resistance were observed after irradia-
tion under nitrogen if the drawing ratio did not exceed 20 and the irradiation dose was
kept under 20 Mrad.‘56 Reactive extrusion and consequent silane crosslinking of
blends of LDPE and LLDPE was investigated in Ref. 38. The melting and crystal-
lization behaviour of HDPE-ultra-high molecular weight PE blends have been
investigated using DSC and thermomechanical measurements.157
The crosslinking of blends of PE with EPDM at different ethylene : propylene ratios
was investigated by Mukhopadhyay et a1.15* The modulus was found to be dependent
on the crystallinity as expected. Thermooxidative stability depends on the E : P ratio
and on the temperature of testing. Some complicated dependences have been reported.
A detrimental effect of the presence of PP on thermooxidative stability was demon-
strated in the irradiation crosslinked LDPE-PP blends. A temperature rise results in
an activation of the radicals trapped in the PP portion which is claimed to be the
decisive factor in the thermooxidative process.‘59
More sophisticated chemistry has to be applied if the crosslinking of polyolefins with
other polymers is desired. A triazine-type crosslinking agent containing both diallyl
and dithio moieties was used for a blend of PE with PVC. Improved compatibility was
obtained and this material was used as an adherent with high peel strength.16”
Crosslinking is also beneficial for the modification of ternary blends. It was demon-

Table 3. Impact strength (Wi) of uncrosslinked (0) and crosslinked (XL) blends of LDPE and PP
crosslinked by peroxide (P) and hydroquinone (HQ)

(wt.%) (Z%) Wi (kJ/m2) Wi (kJ/m’) Gel (%)

100 0 3 0.5 75 >llO 76

75 2.5 3 0.5 73 >llO 82
50 50 3 0.5 13 >llO 70
25 75 3 0.5 15 >llO 60
0 100 3 0.5 21 27 67
50 50 3 0 13 3 41
50 50 1 0.25 13 13 23
1190 I. CH0D.k

stratedi61 that the impact properties of EPDM-polystyrene blends can be improved

significantly by EB irradiation if a reactive compatibilizer, e.g., styrene-butadiene
block copolymer, is used. It was suggested that the impact properties were determined
by the interaction between the PS portion of the block copolymer and the PS matrix
since the interaction between the butadiene segments of the copolymer and EPDM is
sufficiently enhanced during irradiation.

3.4. Applications
One of the reasons for the crosslinking of polyolefin blends involves the recycling of
complex polymer mixtures. Major problems in the recycling of household plastic
waste arises from incompatibility of the major components, i.e., polyethylene, poly-
propylene, polystyrene and PVC. An economically acceptable process for
compatibilization is needed which does not depend significantly on the composition
of the blend and would lead to technically useful materials. Crosslinking of blends
should be seriously considered from this point of view. On the other hand, crosslinking
can also be beneficial for the modification of blends of industrial materials especially
when considering the strength-impact strength balance.

4.5. Interpenetrating Networks (IPN) and Thermoplastic Elastomers (TPE)

IPN and TPE materials are formed from crosslinked polymer blends. Numerous
examples of blends containing polyolefins are known when considering both IPNs’~~
and TPEs based on dynamic vulcanization of PP-EPDM blends,‘63 PP with other
elastomers’64 or other polyolefin combinations.‘65 IPNs have been discussed in several
earlier reviews (e.g. Ref. 166) and this topic is too extensive to be discussed in detail
here. Dynamically vulcanized TPE blends are also outside of the scope of this review
because the polyolefinic portion is not usually crosslinked in these materials.


Crosslinking results in substantial changes in morphology and properties of filled
semicrystalline polyolefins. The presence of filler also leads to a change in morphology,
especially by changing the ratio between amorphous and crystalline portions. This
results in changes in the effectiveness and kinetics of crosslinking. Both effects are
mutually influenced and rather surprising results can be expected in many cases.

4.1. Eficiency of Crosslinking

The presence of a filler can affect the efficiency of crosslinking. In some cases,
crosslinking is hindered (e.g., a protective effect of carbon fibres in polyethylene
matrices against EB radiation167). Other fillers, e.g., Si02, Ti02i6* or Zn0,‘69 can
activate the crosslinking process. The latter effect can be related to the fact that
although a higher concentration of stable radicals is formed by irradiation of PE
filled with Si02, these are thermally less stable as observed in Ref. 170. The

mechanism of the process is also influenced by the presence of carbon black.“r

On the other hand, the efficiency of crosslinking was found to depend on physical
factors, namely on the surface area of the filler in LDPE-silica mixtures (Fig. 5). This
phenomenon was attributed to an adsorption of peroxide on the filler surface prior to
crosslinking, resulting in microinhomogeneities of crosslinking distribution. This
effect was found to be more pronounced for samples with a filler having higher surface
areas. l’*

4.2. Mechanical Properties

The main advantage resulting from the crosslinking of the matrix in filled poly-
ethylene is the possibility of using higher amounts of filler without detrimental loss
of ductility. This phenomenon has been attributed to an increased amorphous portion
in the crosslinked matrix compared to uncrosslinked polymer,‘73 although the reason
is apparently more complex; obviously, a growth of molecular weight and an increased
number of tie molecules is a highly relevant explanation for the phenomenon
mentioned. The properties of crosslinked polyethylene filled with carbon black’74?175
and inorganic fillers1751176have been reported. Substantial increases in elongation
at break after crosslinking were demonstrated for silica-filled LDPE. The effect is
especially pronounced when mechanical tests were made close to the melting tempera-
ture”* as shown in Fig. 6. Significant improvements in crack growth resistance due to
crosslinking were reported for silica-filled LDPE,“’ similar to the effect of LDPE-PP
blends mentioned above.
Improved mechanical properties have also been obtained after crosslinking poly-
ethylene filled with organic fillers such as wood flour’77 or cellulose fibres.17* After
decomposition of the peroxide in the mixture, an increased degree of crosslinking was



filler, wt. %

Fig. 5. Insoluble portion formation in uncrosslinked (open symbols) and crosslinked 0.8% of
peroxide blends (filled symbols) LDPE with silica with surface areas 139 (circles), 109
(squares) and 21 m2/g (triangles).
1192 I. CHODAK

uncr 20°C 600

uncr 110°C

cr 20°C

cr 110°C

0 5 10 15 20


Fig. 6. The dependence of elongation at break on the filler content measured at 20 (circles) or
110°C (squares) for uncrosslinked (filled symbols) and peroxide-crosslinked (open symbols)
silica-filled LDPE.

achieved. This phenomenon was attributed to the formation of chemical bonds

between the filler surface and the polyethylene chains.177 An improvement in mechani-
cal properties due to crosslinking was claimed to be achieved for a mixture of PP with
lignin. 179Lignin was found to act as a co-agent for polypropylene crosslinking. A
modest antioxidative effect for various modifications of lignin was reported.“’
Peroxide-initiated crosslinking of silica-filled EPDM with a high content of ethylene
in the presence of a silane coupling agent was investigated in Ref. 18 1. An increase in
the network density was attributed to the presence of silane, resulting in interactions
between the filler surface and the polymer chains. Both static and dynamic properties
were found to improve due to crosslinking. However, at high filler contents, a steep
deterioration of properties, such as tensile strength, tear resistance and flex resistance,
was observed. Nevertheless, the concentration of the filler when the properties begin to
deteriorate was much higher for the crosslinked matrix compared to uncrosslinked
Crosslinking of a polyolefin matrix was also applied to a mixture with alumina
trihydrate. In this case, the aim of the introduction of the filler was to decrease the
flammability of cable insulation. The simple addition of the filler leads to a substantial
increase in stiffness and the resulting material was rather brittle. After crosslinking, a
recovery of the properties of the filled composite was observed.ls2
Crosslinking of polymer blends with a filler content is also of interest. The addition
of carbon black to a PP-EPDM blend and consequent irradiation leads to the
formation of a compound with an extremely high strength. The presence of a trifunc-
tional monomer acting as a co-agent for polypropylene crosslinking was necessary.lg3

4.3. Crystallization
When investigating crystallinity, two effects must always be considered. Namely the
presence of the filler and the crosslinking of the matrix. The effect of irradiation of
HDPE filled with silica or Ti02 is shown in Fig. 7. It is seen that low amounts of filler
result in an increase of the crystalline portion, while a decrease of crystallinity was
observed with increasing filler content. Irradiation does not have any effect until the
dose is lower than 50 Mrad. With increasing dose stabilizing activity of low filler
content but deteriorating effect of high amount of filler is obvious when compared
to unfilled PE.‘84
Different behaviour was observed when the crystallization of silica-filled LDPE was
investigated. Rather extensive studies185-‘87 showed that the crosslinking of unfilled
PE leads to a retardation of crystallization, while the presence of the filler in the
uncrosslinked matrix results in an increased crystallization initiation due to
nucleation but slower crystal growth because of the lower mobility of polymer chains
adsorbed on the filler surface. However, in a filled peroxide-crosslinked matrix, the
formation of a fixed pre-ordered structure was suggested, leading to a substantial
increase in the crystallization rate with increasing crosslinking degree, a behaviour
which is contradictory with the crystallization of unfilled polymer.

4.4. Other Properties and Applications

When considering the properties of filled polyolefins, it must be stressed that higher
filler contents are possible in the crosslinked matrix compared to the uncrosslinked
polymer. This was demonstrated for mechanical properties as shown above but other
properties have also been examined. Applications of crosslinked polyethylene for




D, Mrad

Fig. 7. A dependence of the degree of crystallinity on irradiation dose of unfilled HDPE

(crosses) and HDPE filled with 0.2 (filled triangles), 5.5% (filled circles) of silica or 0.9%
(open triangles), 6.7% (open circles) of Ti02.
1194 I. CHODAK

cable insulation may serve as an example. It was shown that although filled poly-
ethylene is more susceptible to water penetration, this effect is diminished after cross-
linking of the matrix. 50 wt.% of inorganic filler can be introduced into the PE matrix
without a substantial decrease in the break voltage value after storage in warm water
for up to more than one year.188 Peroxide-initiated crosslinking was also applied for
ethylene-propylene copolymer based mixtures for cable insulation.‘37 The effects of
various peroxides and the presence of different co-agents on the mechanical properties
and thermal aging were investigated.
The addition of conductive particles, e.g., carbon black, is a rather common way to
increase the electroconductivity of the material. Admixture of carbon black to poly-
ethylene is sometimes complicated by a large scattering of the electrical properties.
Substantial improvements in reproducibility can be achieved by crosslinking. A lower
mobility of the system and a lower degree of aggregation of the filler particles have
both been proposed as reasons for this result.189

Several decades of research and development with crosslinked polyolefins has shown
that these materials can be successfully applied in many areas. In the past, poly-
ethylene has occupied the greatest share of interest from the point of view of both
scientific research and industrial applications. Some open questions still exist, such as
the more or less unsuccessful and not fully understood attempts to improve the creep
behaviour of ultra-high modulus polyethylene fibres by radiation, peroxide, or UV
initiated crosslinking.
Crosslinking of polypropylene is a much more difficult task and, in fact, no signifi-
cant industrial applications exist to date. Beta scission of polypropylene macroradicals
is the main difficulty which must be overcome. The introduction of co-agents is only a
partial solution since generally used polyfunctional monomers do not improve the
crosslinking efficiency to the desired extent. Recently described quinones provide
rather high efficiencies but they are only active with peroxidic initiators and do not
respond positively to irradiation. Since the polypropylene melting temperature is
about 165X, a minimal processing temperature of the polymer must be above
190°C. At this temperature, the decomposition rate of peroxides is too high for safe
processing on large industrial scales. The technologies employed for crosslinkable
polyethylene cannot be used for polypropylene.
Another point which has to be mentioned is the toxicological problem of using
quinoic compounds as co-agents. These chemicals might themselves be potential
health threats. Moreover, during the reaction with peroxides they are transformed
into a range of poorly characterized species for which health effects are not known. It
is true that this is mainly a problem of production and not of utilization of the
products since once the crosslinking process is over, the co-agents are bound into
the polypropylene network and cannot diffuse out of the product. Therefore, poten-
tial application depends the development of proper technologies which would prevent
premature decomposition of the initiator during processing and undesirable health
effects of efficient co-agents during processing.

The difficulties related to crosslinking of ethylene-propylene copolymers are

between those for the PE and PP homopolymers. The efficiency of the process
depends on the ethylene : propylene ratio and can be increased by the introduction
of co-agents. Polyfunctional monomers are more effective than for polypropylene.
Bound co-agents can be also used, e.g., in the form of EPDM terpolymer, possessing
certain amounts of double bonds in the molecule. Problems with processing cross-
linkable mixtures containing peroxides do not exist since EP copolymers are usually
rubbery materials with low or no crystallinities and can be processed under 100°C by
technologies common in the rubber industry.
The investigation of two-phase materials, either blends or composites with cross-
linked polyolefinic matrices, has been less frequent. Some reasons for efforts in this
field have been mentioned above and these can be summarized as:
(1) stabilization of morphology;
(2) an increase in interfacial interactions between the phases;
(3) a possibility for an increase in filler content without a substantial loss of ductility;
(4) the possibility of utilizing mixtures of polymeric scrap eventually leading to useful
Crosslinking of blends and composites represents an alternative for properties
modification. This method broadens the opportunities for the preparation of
versatile tailor-made materials. A combination of physical, chemical and processing
modification may result in the control of:
(1) morphology, structure, viscosity, phase inversion;
(2) functional group content and quality, solubility; and
(3) processing conditions.

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