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Crosslinked polyethylene
S M Tamboli, S T Mhaske & D D Kale*
Institute of Chemical Technology, University of Mumbai, Matunga, Mumbai 400 019, India
Received 12 June 2003: revised received 22 July 2004; accepted 4 August 2004
Properties of polyolefins can be modified by crosslinking process. Different methods of crosslinking and effect of
process parameters, selection of crosslinking agents and applications are briefly discussed.
Polyethylenes are commodity plastics. They account several functional groups. These functional groups are
for more than 70% of total plastics market. capable of forming chemical bonds to convert
Polyethylene is easily available, at relatively low cost thermoplastics into thermosets9,10. McGrins11 has
and easily processable. It finds applications in described various commercially important crosslinked
household items, packaging, insulation, net ropes, thermoset materials and their curing reactions. These
fishing rods or medical applications, etc. Polyethylene are not of much relevance in the present study. For
is processed at temperature in the range 150-250°C1-3. thermoplastics, crosslinking is a process in which
Most polyethylene compounds contain reasonably high molecular weight thermoplastics are converted
good amount of fillers. Polyethylenes are into thermosets.
thermoplastic in nature and therefore they can be Crosslinked polyethylenes are either extruded or
reprocessed repeatedly. Polyethylene, however, will injection moulded. When degree of crosslinking is
soften and flow, and lose critical physical properties deliberately maintained very low, the resulting
at elevated temperature thereby limiting compound is termed as crosslinkable polymer.
its applications4,5. Therefore, crosslinking of Crosslinking can be combined with foaming also.
polyethylene is carried out to retain desirable Crosslinking of biopolymers and foaming is very
properties at high temperature. Crosslinking will common in food industry. Crosslinking for partially
change the nature of polymer from thermoplastic to crosslinked extruded profile is commonly employed
thermoset to yield a non melting, more durable in furniture. Although crosslinking of thermoplastics
polymer matrix. such as nylon, polypropylene and styrenics has
All types of important polyethylenes are received attention in literature. Present review is
crosslinked, like Linear low density polyethylene directed to the crosslinking of polyethylenes only.
(LLDPE), Low density polyethylene (LDPE), High Crosslinked polyethylene forms a dense network of
density polyethylene (HDPE) and Ethyl vinyl acetate high molecular weight, which improves impact
copolymer (EVA) and Polyolefinic elastomer (POE). strength, environmental stress crack resistance
Branched structure is more suitable for crosslinking. (ESCR), creep and abrasion resistance without
Therefore, crosslinking of LLDPE and HDPE requires influencing tensile strength and density to any
more attention. appreciable extent. Crosslinked polyethylene finds
Crosslinking leads to the formation of insoluble and wide applications in packaging and electrical
infusible polymers in which polymer chains are insulation applications and rotomoulding
joined together to form three-dimensional network 12,13
applications . The degree of crosslinking can
structure6-8. In thermoset, crosslinking (curing) takes change considerably from applications to
place through reaction between polymer chains with applications. Some aspects of crosslinking are
_________
*For correspondence (E-mail: ddkale@udct.org) reviewed here.
854 INDIAN J. CHEM. TECHNOL., NOVEMBER 2004
Crosslinking process
Crosslinking is a process in which carbon atoms of
same or different polyethylene chains are joined
together to form the three-dimensional network
structure14-16. The crosslinking process essentially
forms bonds between the polymer chains, which
could be directly between carbon to carbon or a
chemical bridge linking two or more carbon atoms18.
The main difference between thermoplastic and
crosslinked polymer is that, at temperature above the
crystalline melting point crosslinked polymer behaves
as a soft rubber while thermoplastic has no significant
strength above melting temperature. The changes in
the properties of polyethylene due to crosslinking
have been compared and documented in literature16,17.
Thus, crosslinking reduces the melt index and
elongation at break, while improves the impact
Fig.1⎯Schematic view of crosslinked and
strength, creep resistance, resistance to slow crack
uncrosslinked polyethylene
growth and also environmental stress crack resistance
(ESCR). The density and tensile strength of Branching
polyethylene are not influenced by crosslinking. POOH PO* + OH*
The crosslinking of polyethylene takes place in four PO* + PH POH + P*
stages: initiation, propagation, branching and
termination. The principal reaction involved in each When P* on two sites join, it leads to branching or
step is discussed below. network formation.
Initiation Termination
The first step in crosslinking process is generation Termination takes place by quenching of free
of free radicals, which can be through a chemical radicals due to presence of additives, impurities etc.
reaction or radiation energy. Decomposition of
initiators which are normally peroxides, or high- P* + P* P–P
energy radiations abstracts hydrogen atom from the POO* + POO* POOP + O2
backbone of polymer chain to produce free radicals. PO* + H* POH
α - particles Microwave
β - particles Infrared
High energy electron X-ray
Protons γ-ray
Deuterons Light energies (UV)
Neutron
Polyolefins and PVC Cross-linking with high-energy radiation Wire insulation for computers, and
sources in 0.4-3 Mev range. communication application
Polyolefins and PVC foams Cross-linking with high energy electron Improved thermal stability for insulating and
packaging application
Polytetra fluoroethylene (Teflon) Degradation by high energy electron or Conversions of waste Teflon material into easily
cobalt-60 in 0.2-0.4 May moldable powder or waxes of commercial value
Wood impregnated with acrylic Polymerization with cobalt-60 source No-wear high performance wood floors for
or methacrylic monomers high traffic areas
Low energy electron processing equipment in Adhesive products for modification of wood,
Curing of coating and adhesives
100-500 Kev range textiles, paper, film and metal substrates
Chemical crosslinking
Chemical crosslinking is a method, in which
chemicals or initiators are used to generate free
radicals, which in turns leads to crosslinking. In this
method, crosslinking takes place through direct
carbon-to-carbon bonds or through the chemical
bridges which connect different polyethylene
molecules34-36.
Degree of crosslinking in thermoplastic resin varies
according to crosslinking process. Chemical Fig. 3⎯Schematic representation of crosslinking of polyethylene
crosslinking by using peroxide gives highest and processing equipment operates at higher temperature.
uniform degree of crosslinking as compared to The compounding of polyethylene and peroxide must
physical crosslinking method. Kim and White have be carried out at low temperature, below the peroxide
reported the difference in degree of crosslinking decomposition temperature. Crosslinking is carried
between physical and chemical crosslinking out in the downstream equipment at significantly
processes37. Accordingly, radiation crosslinking yields higher temperature and pressure. The higher
between 34-75% degree of crosslinking. In chemical temperature decomposes the initiator and liberates a
crosslinking method, peroxide gives much high free radical that will abstract a hydrogen atom from
degree of crosslinking (up to 90%), while silane based polymer chain. This abstraction site then becomes
crosslinking can be 45-70% degree of crosslinking. reactive radical, forming a crosslinked bond with
Peroxide initiated crosslinking process depends on another reactive radical of same or different chain.
several variables, namely operating temperature, type This reaction occurs until all peroxide is consumed or
and concentration of peroxide, and molecular the temperature falls below the decomposition
characteristics of virgin resin such as, molecular point38,39. Schematic representation of this reaction is
weight, molecular weight distribution, branch shown in Fig. 3.
distribution and concentration of terminal vinyl Elimination of hydrogen atom converts tertiary
groups. hydrogen atoms of polypropylene and polyethylene to
The two main chemical crosslinking methods are, tertiary radical chain with low reactivity. Tertiary
(i) organic peroxide based and radical sites are not very reactive and are not
(ii) silane based (moisture cured). converted easily into more reactive secondary
radicals. The shifting of the radical site along
Crosslinking of thermoplastic by peroxide branched chain is hindered, and dimerization of chain
Peroxide crosslinking has been in use for more than radical becomes more difficult. Number of peroxides,
40 years and is the most common method for which are suitable for crosslinking of thermoplastic
crosslinking of thermoplastics especially and their dissociation temperatures, are listed in
polyethylenes. In this method, organic peroxide is Table 5.
used as initiator. Usually, organic peroxide is used in Dicumyl peroxide (DCP) is widely used for
its original unprocessed structure. Downstream crosslinking of thermoplastics, and crosslinking
858 INDIAN J. CHEM. TECHNOL., NOVEMBER 2004
efficiency of DCP is more than the other peroxides. Thermal decomposition of peroxide proceeds
During reaction of dicumyl peroxide with according to the following equation20,40,41,
polyethylene, gas generated in reaction contains 98%
methane. r = kd .[c] with kd = ko . e-E/RT … (4)
Where,
Kinetics of crosslinking by peroxide
Decomposition of peroxide, that is, generation of r = rate of decomposition
free radical is slowest reaction and it is the rate- kd = rate constant
determining step of crosslinking reaction of PE. ko = rate constant at base temp.[0°C]
TAMBOLI et al.: CROSSLINKED POLYETHYLENE 859
of PP onto PE could take place45. They have reported when exposed to excessive heat or light. Therefore,
that as PP content increased, the heat resistance of polyethylene compounds used for coating wire and
crosslinked compound decreased. cable application may contain anti-oxidants. Cables
Ethylene vinyl acetate (EVA) is blended with exposed to ultraviolet rays in sunlight must also
polyethylene quite widely. Ethylene vinyl acetate contain carbon black or other UV inhibitors. Such
copolymer is more rapidly crosslinked and accepts additives also assure that the electrical and
high filler loading, without significant loss of physical mechanical properties of the resin are preserved under
properties, making them well suited for lower voltage the high temperatures prevailing in the extruder50,51.
applications and in automobile etc. Carbon black of fine particle size can be used as a
thermal antioxidant. Carbon black is used as a
Peroxide coagent crosslinking method conducting filler for elastomer and plastics.
Coagents are low molecular weight molecules with Incorporation of carbon black increases brittle point
two or more reactive double bonds. Coagents work in and yields stress with concentration, without affecting
a free radical cure system. Free radicals are generated tensile strength52.
by using peroxide or high energy radiation sources,
coagent reacts with these free radicals to increase the Crosslinking by silane
efficiency of cure i.e. to give more crosslinks. The There are two types of processes for crosslinking of
presence or addition of a coagent in crosslinking polyethylene by silane grafting: two-step process and
provides more reactive sites where the crosslinking one-step process.
reaction can occur46. Addition of coagents reduces In two-step process, silane molecule such as vinyl
cure time, improves resistance to oils and fuels, trimethoxysilane (VTO) is grafted on polyethylene
improves heat aging, improves peroxide efficiency, chain. For grafting, the peroxide such as dicumyl
improves flexibility and gives higher tensile strength peroxide is mixed with the polyethylene in small
and hardness47,48. percentage. The peroxide initially generates free
radical on polyethylene chain. Grafting of silane takes
Advantages of peroxide-coagent system
The advantages of peroxide-coagent system are:
(i) excellent heat stability
(ii) simple compounding
(iii) better hot tear
(iv) good shelf life stability.
Applications
Peroxide-coagent systems are widely used in
automotive seals, automotive hoses, oil well packers,
swab cups, golf balls, butterfly valves, belts, mats,
shock absorber, cable, coating and foam packing.
place at the site where free radical is generated. The polyethylene. The degradation is mainly due to β-
grafted polyethylene is mixed with silanol chain scission. Crosslinking of polypropylene is
condensation catalyst such as dibutyltin dilauarate, possible only by silane grafting method.
and extruded or injection moulded profile is
produced. Up to this stage the polyethylene retains the Advantages of silane-grafted crosslinking
thermoplastic nature. Extruded or injection moulded Various advantages of silane-grafted crosslinking
article is crosslinked with the help of water or at are:
elevated temperature or at room temperature53,54. The (i) crosslinking can be done at room temperature
two-step silane crosslinking process is schematically (ii) low cost
represented in Fig. 4. (iii) higher gel percentage obtained as compared to
In one-step process, a copolymer of silane and physical crosslinking.
polyethylene may be formed or free radical generating
and grafting take place in single step only. The Disadvantage of silane-grafted crosslinking
chemical reaction of silane crosslinking is shown in Some disadvantages of silane-grafted crosslinking
Fig. 5. The reaction continues until all grafted are given below:
copolymer is converted into crosslink chains. In the
peroxide and irradiation cross-linking processes, the (i) curing time is very high as compared to peroxide
links between macromolecule consist of carbon- crosslinking
carbon bond. The silane process gives -Si-O-Si- (ii) extra downstream equipments are required (for
crosslinks. These siloxane bridges are weaker than condensation)
carbon-carbon bond, and this will have effect on the (iii) bond strength of crosslinking is weaker than
attainable strength and long term chemical bond strength in peroxide crosslinking system.
stability55,56.
Effects of crosslinking
Silane grafting of polyethylene Polyethylene is crosslinked to improve its
The most common silane used for cross-linking of dimensional stability at elevated temperature, to
polyethylene is vinyl trimethoxysilane (VTO). The
silane is introduced into polyethylene by melt grafting
using peroxide as an initiator. The silane-grafted
polyethylene is then crosslinked through
hydrolyzation of the methoxysilane group with water
followed by condensation of the hydroxyl group57,58.
Various types of silanes used in crosslinking are listed
in Table 7.
Crosslinking of grafted polyethylene is completed
only in presence of moisture. A catalyst is used to
activate and speed up the crosslinking process. The
crosslinking is also enhanced by high temperature, but
silane crosslinking is usually performed at 50 to 80oC
and at atmospheric pressure.
Polypropylene is degraded due to peroxide and
therefore, it cannot be crosslinked similar to Fig. 5⎯Silane grafted polyethylene crosslinking reaction
improve its impact resistance or to reduce its polyethylene prior to crosslinking is therefore, key
propensity to stress crack. Due to crosslinking function in processing.
polyethylene changes from ductile semi-crystalline Due to its thermoset nature recycling of crosslinked
solid to a non-crystalline elastomer59. polyethylene cannot carried out by melting it with
As crosslinked density increases, a degree of virgin polyethylene, since crosslinked polyethylene
crystallinity and crystallite thickness decreases. This does not melt. The crosslinking process decreased the
was studied by Badar60. Reduction in crystallinity crystallinity.
occurs because of crosslinking taking place in
amorphous phase. There is also some breakdown of Application of crosslinked polymers 63,64
crystallinity. Decrease in degree of crystallinity and Cable insulation
crystalline thickness, decreases Young’s modulus, The most advanced area of application for
yield stress, elongation at break and peak melting crosslinked polyethylene is in the electrical cable
temperature of polyethylene61. industry. Crosslinking, whilst not interfering with the
Harper62 studied the effect of crosslinking on melt dielectric properties of polyethylene, introduces
index and concluded that the melt flow index resistance to flow and permanent deformation above
decreases uniformly with increase in degree of the softening point. This permits higher conductor
crosslinking. operating temperature and reduces the level of short
Crosslinking increases the impact strength, circuit and overload protection required.
environmental stress crack resistance, creep resistance Flame retardant properties of pipe are also
without affecting tensile strength and flexural improved by irradiation (60% gel) by introducing
modulus. Comparison of different crosslinking double layer structure to the jacket, in which inner
methods is presented in Table 8. layer is adjacent to polyethylene insulation which is
crosslinked more densely than the outer layer. The
Disadvantages of crosslinking
wire exhibits markedly improved resistance to flame
As mentioned earlier, crosslinking of polyethylene
and heat deformation.
changes its nature from thermoplastic to thermoset.
This enhances the viscosity to a very high value. To Crosslinked polyethylene pipes
control the degree of crosslinking in a continuous The main applications for crosslinked polyethylene
process is very tricky. During extrusion of a profile, if hot water pipe are:
excessive crosslinking takes place stresses are
a) under floor or central heating
developed and, these do not get relaxed due to dense
b) domestic or portable water piping system.
network of polyethylene. Selection of proper
crosslinking agent is very critical. Blending uniformly The benefits of crosslinking become obvious above
crosslinking agents with polyethylene beds can lead to ambient temperatures where a reduction in the rate of
uneven distribution of crosslinking agent. Melting of creep for the corresponding hoop stress is observed.
TAMBOLI et al.: CROSSLINKED POLYETHYLENE 863
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