METHODS OF CROSS-LINKING OF
POLYETHYLENE
XLPE and PEX are the terms used in this review for
cross-linkable and cross-linked polyethylene, respectively.
Cross-links may comprise either direct
carbon-carbon bonds or bridging species such as
siloxanes [15]. Cross-links occur at random intervals
along the chains; in which the concentration can vary
widely, from an average of only one cross-link per
several thousand carbon atoms to one per few dozens
[16]. Several methods have been developed to
cross-link polyethylene including: azo, peroxide, and
silane as chemical methods and the radiation as a
physical method (Figure 1). Amongst these methods,
Figure 1. Polyethylene cross-linking methods.
cross-linking via silane grafting is a common and efficient
approach to cross-link polyethylene which per
se has no functional group or curing site for crosslinking
in a way similar to thermoset resins [17,18].
It is possible to quantify the degree of crosslinking
(i.e., a measurement of quality control) in any
of the aforementioned cross-linking methods by the
xylene extraction process set forth in ASTM D2765 or
DIN 16892 [19-22]. The measurement of gel content
is a direct way to assess the degree of cross-linking
[23].
Radiation Method
In 1948, Dole treated low density polyethylene with
high energy radiation [24]. Electron beam, gamma
rays, or ultraviolet radiation were used for radiation
cross-linking of polyethylene [25]. In radiation
method, the excited electrons are used to strike the
molecules at or near a carbon-hydrogen bond, and
thus, creating a free hydrogen atom to leave the parent
molecule in an excited state (free radical). Two
adjacent aforementioned sites can form a chemical
bond. Meanwhile, the two corresponding hydrogen
atoms also form a hydrogen molecule which diffuses
out of the structure. Radiation is carried out on the
already formed articles, i.e., in solid state and typically
in an inert atmosphere to prevent oxidative degradation.
The cross-linking density at a given irradiation
dose depends on the amorphous portions of the polymers,
as it occurs in the amorphous phase of the polymer
[11]. No temperature restriction in extrusion processing
and no residual peroxide or unwanted byproducts,
high cross-linking rates, and space savings for
the equipments are the advantages of radiation crosslinking
method [13]. However, there is an uneven
cross-linking which may occur as well as having a
limitation in cross-linking maximum thicknesses.
Meanwhile, the high initial investment and running
costs, high voltages needed for cross-linking thick
sections, and the necessity of protecting technicians
from radiation and the required governmental permission
are some of the other important drawbacks of this
method.