15 Cross-Linking
With the help of cross-linking agents, polyethyl-
ene (PE) is transformed from being a simple com-
modity thermoplastic into a more useful engineering
material. Cross-linking is often an unwanted result
of free-radical degradation processes—but inten-
tional, controlled cross-linking can be useful in
medical, foam, pipe, wire & cable, and other PE
applications for increasing heat resistance, physical
properties, and long-term durability. This chapter
will cover additives that cause cross-linking and
discuss related issues, addressing:
• What is the value of cross-linking PE?
(Section 15.1)
• What are the main types of agents and other
methods that cause cross-linking? (Section 15.2)
• How do these different agents and methods
compare? (Section 15.3)
15.1 Cross-Linked PE:
Advantages and Applications
The cross-linking of PE typically occurs during
the degradation of the polymer, but PE cross-
linked in a controlled way has useful properties.
Methods for intentionally cross-linking extruded
and molded PE have created an important niche of
applications. Cross-linked polyethylene (XLPE or
PEX) is used for more resilient foams, pipes, tubing,
film, sheet, cable coverings, and rotational moldings.
(Polypropylene (PP) is not normally cross-linked,
but cross-linked polypropylene (XLPP) is also
discussed briefly in this chapter.)
Cross-linking agents tie together carbon atoms
from different chains of the polymer, transforming
what were once viscous linear segments into an
insoluble gel network that no longer melts or flows
like a typical polyolefin. The degree of cross-linking
that occurs is determined by the percentage of
polymer chains interconnected in this network, or in
other words, the density or proportion of the gel
component. Higher cross-link density is the result of
Additives for Polyolefins. DOI: http://dx.doi.org/10.1016/B978-0-323-35884-2.00015-6
© 2015 Michael Tolinski, Published by Elsevier Inc.
more linkages per length of polymer chain, resulting
in larger property changes. Because cross-linking
prevents molecules from slipping by each other in
the amorphous regions of the resin, it particularly
affects temperature-dependent properties, giving the
XLPE more thermoset-like qualities, including:
• higher long-term service temperatures, includ-
ing better heat and dimensional stability (and as
little as 1% of the creep of the precrosslinked
polymer);
• improved impact resistance and environmental
stress-cracking resistance (ESCR);
• higher tensile strength and stiffness properties,
especially at high temperatures;
• better “shape memory” or “memory effect,” in
which a heated and deformed XL material
holds its shape when cooled, and then returns
to its original shape when reheated;
• improved cell formation in foams (stronger
cell walls limit the cell size distribution and
prevent cells from blowing open);
• improved chemical and solvent resistance
(though some solvents cause the XL material
to swell);
• better electrical resistance and dielectric
properties;
• and in some cases, improved weatherability.
Other properties may also be improved, depend-
ing on the degree of cross-linking in the polymer,
the cross-linking agent or process, and the initial
properties of the polyolefin [3-3, 15-2, 15-4].
These properties make XLPE useful especially
for extruded hot water pipe, foam insulation, large
containment tanks, and wire and cable coverings.
For power cable coverings or insulation, XLPE
withstands higher temperatures from electrical
overloads and short circuits than alternative materi-
als such as PVC can withstand. Its memory effect
can be exploited for joining together components
in these applications. Cross-linking properties are
159
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also useful for more durable, multilayer, silane-
crosslinked PE pipe, which has become more
competitive with copper and other pipes for water
and fluid transport [15-2, 15-5].
However, there are at least two general caveats
about crosslink-induced properties. One penalty for
the property improvements is that cross-linked
materials no longer truly melt at high temperatures,
limiting their recyclability. The other is that exces-
sive cross-linking initiated in the melted polymer
can result in brittle materials that lack crystalline
regions—regions that also contribute to valuable
mechanical properties. Thus ASTM pipe specifica-
tions (F 876-93) limit the degree of cross-linking in
XLPE pipes to between 65% and 89% [3-3, 15-5].
15.2 Cross-Linking Agents
The main commercially useful methods for
cross-linking use agents whose sole purpose is to
promote free-radical processes that essentially initi-
ate PE degradation. This ultimately creates bonds
directly between carbon atoms on adjacent polymer
chains. Some cross-linking agents, such as silanes,
integrate themselves between polymers to form
intermediate “bridging” links that connect one
chain to another.
15.2.1 Peroxide-Based Agents
Organic peroxide agents are the most common
agents used to initiate free radicals, and thus con-
trolled cross-linking, in PE (peroxide-created
XLPE is sometimes abbreviated “PEX-A”). The
peroxides (ROOR) decompose in the heat of pro-
cessing into peroxy radicals (RO•) that abstract
(remove) hydrogen atoms from the polymer chain.
This creates free radicals on the chain that can
bond with carbon radicals on another chain,
though the radicals can also react with other
species in the compound. A number of competing
mechanisms and factors can affect the efficiency
of this cross-linking process:
• Shorter, low molecular weight polymer chains
have less statistical chance of cross-linking
with other chains.
• Cross-linking agents have no effect within the
crystalline regions of a polymer.
ADDITIVES FOR POLYOLEFINS
• Because cross-linking encourages a mechanism
of polymer degradation, effective processes
must suppress unwanted oxidative degeneration
of the polymer (by keeping oxygen out of the
resin and process).
• Less-branched polymers and polymers with
methyl groups (such as PP) tend to be more
susceptible to degradation from unwanted chain
scission (breakage), rather than cross-linking.
• Primary antioxidant radical scavengers in a
compound, otherwise useful as heat stabili-
zers, can suppress the desired cross-linking
mechanism.
And perhaps most importantly is the timing of the
cross-linking in the process. Fast-acting peroxides
that decompose at lower temperatures may initiate
cross-linking prematurely in the process—before the
resin is fully formed into its final shape by extrusion
or molding. Thus a peroxide must be chosen that fits
the temperature/speed profile of the process. For
high-voltage XLPE cable coverings, for example,
peroxide cross-linkers are specifically chosen to fit
the production rates of high-output “continuous
vulcanizing” processes, which include a long curing
chamber several meters long [3-3, 15-2].
The appropriateness of a peroxide for a process
can be determined by its “half-life,” or the time
required for half of its mass to decompose at proces-
sing temperatures. A dicumyl peroxide cross-linking
initiator, for example, degrades relatively quickly
when compared with other peroxides, requiring only
a few minutes for half of its mass to decompose at
PE processing temperatures. Other peroxides with
longer half-lives take more time for decomposition/
initiation. Typically, a processing rate is timed to
allow a certain number of half-life periods to pass
before the polymer is considered to be sufficiently
cross-linked. The opposite problem is premature
cross-linking in the extruder when process tempera-
tures are too high (Case 15.1) [3-3, 15-1, 15-8].
15.2.2 Silane-Based Agents
Silane agents are composed of silicon bonded to
oxygen and various carbon groups. They use a mul-
tistep mechanism to form cross-linked networks
between polymer chains. They first must be grafted
onto a polymer’s backbone radical (using per-
oxides). Then they are available to form “siloxane
15: CROSS-LINKING 161

Case 15.1 Higher Temperature Peroxides for XLPE [15-10]

Problem: Premature cross-linking (“scorch”) and low outputs in peroxide-crosslinked XLPE extrusion.
Objective: Faster processing and higher processing temperatures without premature cross-linking in the
extruder.
Solution: A peroxide cross-linker with a decomposition temperature above the normal range.
Processing temperatures used for the production of peroxide-crosslinked high-density polyethylene
are limited by the decomposition temperatures of the peroxides used, in order to prevent premature
decomposition of the peroxides and cross-linking of PE in the extruder. Temperatures with typical
peroxides have to be limited to 160 170°C, limiting the output of the extruder because of the higher
viscosity of PE at these temperatures.
Addressing this issue, Akzo Nobel released a higher temperature peroxide (Trigonox 311) with a
20 30°C higher peroxide decomposition temperature. Cross-linking at higher temperatures results in a
less viscous, more homogeneous melt, the company says. This improves extruder output and the qualities
of the final product. The peroxide is targeted for where XLPE processing at 180 190°C is needed, as with
cross-linked pipe extrusion, rotational molding, and thermoplastic vulcanizate applications.

bridges” ( Si O Si ) by combining with grafted
agents on other polymer chains, with the aid of
moisture in hydrolysis/condensation reactions.
Silane/moisture-cured XLPE (sometimes abbre-
viated “PEX-B”) is commonly used for low-voltage
cable insulation, and it also can be used for thick
products. Improved cross-linking processes and
properties, along with new metallocene polyolefins,
have reportedly allowed its use in more rigorous
applications, such as under-the-floor hot water heat-
ing pipes, and more resilient foams [15-2, 15-4].
Traditional silane-XLPE processes used by
various manufacturers can differ, but they share the
following basic steps in common. First a prelimi-
nary mixing and compounding process is required
to graft vinyl silane onto PE, which, in the case
of two-step cross-linking, produces a pelletized
copolymer that must be kept dry to prevent prema-
ture cross-linking. Then, during melt processing/
compounding, this grafted material is mixed with a
masterbatch that contains a cross-linking catalyst to
speed up curing. This blend is processed into the
final product shape, which is cross-linked typically
in a process using steam or hot water (or it may be
allowed to cure simply using ambient conditions
over weeks of time) [3-3, 15-2, 15-4, 15-8].
Alternatively, as in Wacker Chemie’s Monosil
process, the extrusion steps can be combined into a
one-step process for creating a grafted, readily cross-
linkable compound. Other suppliers such as Dow
Corning and Momentive Performance Materials
have also tried to make one-step cross-linking easier
for processors by offering preblended masterbatches
that contain the cross-linking catalyst, peroxide, and
silane agent in one compound. Products like Evonik
Degussa’s Dynasylan Silfin liquid reportedly contain
vinyl silane, initiators, and catalysts—plus additives
such as antioxidants, processing aids, and metal
deactivators [14-30, 15-3, 15-4, 15-8].
No matter the process, care must also be taken to
avoid temperatures rising above the decomposition
temperatures of additives such as aluminum trihy-
drate and magnesium (di-)hydroxide mineral flame
retardants. As alternatives to mixers or twin-screw
compounders, new kneader designs have been devel-
oped for the safe integration of cross-linking agents
without over-heating or -shearing [15-8].
Cross-linked PP is difficult to make. Conventional
XLPE-type methods tend to produce more chain
scission in PP (as in controlled rheology PP appli-
cations) than the desired cross-linking reactions.
Thus molecular weight degradation predominates
over cross-linking. But some researchers have
made silane-crosslinked/moisture-cured XLPP,
using specific silane chemistries and/or coagent
grafting. They have determined ways to increase
gel content (cross-linking degree) in PP to over
50 60%, at which point the material’s dynamic
storage modulus increases markedly [15-9].
15.2.3 Radiation-Induced
Cross-Linking
High-energy electron beams (E-beams), X-rays, or
beta, gamma, and ultraviolet (UV) radiation can
also be used to form free radicals and initiate
162
radiation-crosslinked PE (“PEX-C”), in continuous
processes. Requiring no cross-linking additives, high-
energy radiation abstracts hydrogen atoms from
the polymer backbone, just as peroxides do. UV
cross-linking requires photoinitiator additives, or
sensitizers, and cross-linking bridge molecules in the
compound for efficient, controlled cross-linking.
However, both approaches depend on the penetration
of the electrons or light into the resin for uniform
cross-linking. Thus this radiation-induced cross-
linking is typically limited to thin, unfilled, low-
density resin applications, such as film, thin tubes,
fibers, wire insulation, and foam. X-rays and gamma
radiation penetrate deeper into the material and have
also been used to initiate cross-linking [3-3, 13-7].
E-beam cross-linking does provide some advan-
tages over chemical cross-linking agents, however. In
extruded pipe, researchers have found that radiation-
crosslinked PE has equal or better burst resistance
at high temperatures than silane-XLPE. And for
rotomolded linear low-density polyethylene gas
tanks, e-beam cross-linking reportedly enhances low
temperature impact strength and ESCR. Moreover,
e-beam cross-linking requires no additional chemical
agents and has fewer process variables to control.
However, e-beam equipment is extremely costly,
making contract service companies the only option
for many processors wanting to use it [15-7].
15.3 Factors in Choosing Cross-
Linking Agents
Given the differences in methods and materials
mentioned above, various factors influence the
choice of cross-linking approach:
• Costs: In terms of costs, cross-linking is often
more of an “equipment issue” than an “addi-
tives issue.” For example, considering the
equipment required and moisture-curing pro-
cessing steps, silane-XLPE processing is more
limited to manufacturers who supply or use
high volumes of grafted-silane material. But
more silane XL materials are being provided
ADDITIVES FOR POLYOLEFINS
by these companies that can be processed by
the end-user on standard extrusion equipment.
For continuous processes, irradiation processes
for cross-linking can be cost effective—but only
if the large initial investment for the equipment
can be justified and recovered. But despite its
own costs, cross-linking can help offset some
raw material costs—considering that cross-
linking increases a resin’s mechanical proper-
ties, the gauge or wall thickness of a product
may be reduced relative to its non-crosslinked
design, reducing raw material usage.
• Scrap reuse: Scrap XLPE coming from the
extruder may be recyclable only if it is reused
before cross-linking has progressed significantly.
Thus, slower curing, silane-based cross-linking
and in-line, radiation-induced cross-linking offer
more opportunities for scrap reuse. Recycling
after cross-linking is difficult if not impossible,
though at least one process has been developed
for using supercritical alcohol in an extruder
to decompose Si O Si cross-links in silane-
crosslinked PE. This reportedly allows the
XLPE to be reprocessed and reused for wire and
cable insulation.
• Processing flexibility: Overall, continuous
processes such as extrusion or slow molding
processes such as rotational molding are more
suited to cross-linking. High-volume, continu-
ous processes are more suited to peroxide and
radiation cross-linking. For easier handling
and dosing, peroxides and other agents are
available as free-flowing masterbatches.
• Part design: Radiation-induced cross-linking
is more limited to unfilled, thinner products
than chemical cross-linking. All part designs
and cross-linking methods—for both thick and
thin products—must ensure that cross-linking
is not simply limited to the surface of the part.
Other factors may be more specific to the
particular needs of wire and cable, foam, rotational
molding, or other sectors that depend on XLPE
[3-3, 15-1, 15-2, 15-6].