ARTICLE IN PRESS

Radiation Physics and Chemistry 71 (2004) 525–528

Business paper
Radiation cross-linked plastics: a versatile material solution for
packaging, automotive, Electrotechnic and Electronics
Sophie Rouif*
IONISOS, Z.I. Les Chartinières, Dagneux F-01120, France

Abstract

Used since the beginning of the 1970s for the production of halogen-free and heat-resistant cables and wires, for
conditioning polyethylene hot-water pipes or for the manufacture of heat shrinkable tubes and of tyres, radiation cross-
linking is developing fastly today on the scale of plastic-moulded parts, and not only by the mean of EB, but also under
gamma rays.
Indeed, it improves considerably the performances of a great number of plastics among thermoplastics, elastomers
and thermoplastic elastomers (TPE).
Radiation cross-linking reinforces the dimensional stability of polymers in chemically aggressive and high-
temperature conditions.
Radiation cross-linked-based engineering plastics offers OEM and end users in many branches of industry both
technical and economical advantages in comparison with high-performances plastics. They constitute a technical and
economical compromise between engineering plastics that failed and high-performances plastic, often over-tailored and
expensive.
This modern industrial technology gives way to new applications and perspectives in various sectors (packaging,
automotive, electrotechnic and electronics, including connectors, surface-mounted devices, integrated circuits, 3D-
MID, etc.) that are described in the paper.
Published by Elsevier Ltd.

Keywords: Radiation cross-linking; Plastics; Polymers; Applications

1. Introduction In this field, radiation cross-linked engineering plastics

are low-cost materials which can be tailored to suit
Today, industry and environment requirements are specific applications and can be readily adapted and
always asking for more and more performant materials. processed for use in mass production.
So during the last decade a great number of high- Up to nowadays, radiation cross-linking was limited
performance plastics have been emerging in addition to to only a few applications: the manufacture of rubber
more usual commodities and engineering plastics. for tyres, of cross-linked cable and pipe (pipe for
However, their consumption is increasing, they are underfloor heating systems), and of heat-shrinkable
still very expensive and their performances are some- tube.
times over-tailored compared to the requirements, and Cross-linking was then performed with electron
above all, in the case of thermoplastics, their tempera- accelerators of low energies (0.1 to 3 MeV), allowing
ture performances are directly related to very high only surface treatments (limited to a few millimetres of
processing temperatures. depth).
High-energy electron accelerators (10 MeV) and
*Tel.: +33-4-78-06-43-53. gamma plants (strong capacity of penetration of the
E-mail address: [email protected] (S. Rouif). radiation) developed since, allow today treatments of

0969-806X/$ - see front matter Published by Elsevier Ltd.

doi:10.1016/j.radphyschem.2004.03.050
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larger thicknesses of the size of a cardboard box (several ical characteristics, without any dimensional change.
centimetres) up to a pallet (1 m), so as to it enables the The following changes can thus be observed:
radiation cross-linking of moulded plastic parts, directly in
their packaging.
* increasing stress at break and increasing modulus,
* decreasing elongation,
2. Effects of radiation cross-linking and performances * improved impact resistance,
* improved creep resistance,
Radiation of plastics is a way to induce their cross- * improved resistance to stresscracking and to abra-
linking and to improve considerably their performances. sion.
As the cross-linking process changes a linear network
into a three-dimensional one, consequently it involves a
radical modification of the characteristics of the
2.2. Chemical properties
material:
* It produces an increase of the branching rate and of More generally, radiation cross-linked plastics present
the average molecular weight of the polymer. an improved resistance to:
* It also confers on plastics properties of insolubility,
infusibility and a significant improvement of their
dimensional stability in chemically aggressive and * their usual solvents (for example, acids in the case of
high-temperature conditions. polyamides, organic derivates in the case of poly-
ethylene or elastomers),
* hydrolysis (in the case of TPE or polyamides 6 and
Radiation cross-linking can be applied to a great 66, for example),
number of plastics (Table 1): thermoplastics, elastomers * to chemical aggressive agents like grease, oil, salt
and thermoplastic elastomers (TPE). haze, zinc dichloride (for certain automotive parts).
Some of them can cross-link on their own, some
others need to be formulated with a cross-linking agent
(promoter) or to be modified during their polymeriza-
tion. Commercial cross-linkable resins are available 2.3. Thermal properties
(several worldwide providers of polymers and com-
pounds). Of all properties, the thermal properties are affected
Radiation cross-linking has effects on the three main most strongly after radiation cross-linking. In particular,
characteristics of plastics, depending on the nature of significant improvements can be observed on:
the radiation cross-linkable resins:
* mechanical behavior, * dimensional stability, generally speaking (in all
* chemical stability, cases),
* thermal and flame resistance. * heat distortion temperature (in case of thermoplas-
tics),
2.1. Mechanical properties * creeping,
* glow wire resistance,
Radiation cross-linking can confer on certain plastics * flame resistance,
(PA, PE, but not PBT for example) improved mechan- * compression set (in case of elastomers and TPE).

Table 1
Radiation cross-linkable polymers

Thermoplastics
Polyolefins (HDPE, LDPE, PPa), EVA, PVCa, Polyamides (6, 66, 6 10 y), PBTa, PVDF, ETFE, ECTFE

Thermoplastic elastomers
TPOa (PP/EPDM/EVA, PP/PE/EPDM), TPE-S (i.e.: SBR), TPUa, PVC/NBR blends, TPE-E (ether–ester copolymers)

Elastomers
EPDM, EPR, chlorosulfonated polyethylene, nitrile rubbers (NBR, HNBR, NBR/PVC), Silicones (PDMS)
a
Cross-linking agent or modified structure is required.
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3. Advantages of radiation cross-linked plastics through have been emerging in fuel systems, especially because of
innovative applications improved barrier properties.

3.1. Packaging 3.3. Electrotechnic and electronics

In this field, radiation cross-linking of polyethylene In this field, the short-term thermal resistance of
presents various advantages because it involves: radiation cross-linked polyamides 6 and 66, especially in
case of electric arcs, have permitted the development in
* an improved impact resistance of polyethylene thermoplastic material of circuit breaker systems used to
(Table 2), be made of thermosets.
* a higher thermal stability, In the specific field of connectors, environment
* a good chemical compatibility towards aggressive pressures and new regulations have recently involved
chemicals and higher barrier properties towards the development of new SMD (surface mounted devices)
liquid and organic vapors migrating through the processes, such as lead-free welding wave processes and
packaging’s wall. reflow processes. In comparison with former technolo-
gies whose process temperatures were inferior to 200 C,
It enables the manufacturing of PE-based packaging
the new ones have involved a rise to a value above
with thinner wall, consequently lighter, according to the
250 C, even up to 300 C.
packaging manufacturing’s requirements, or without
Even if it consists of short-term high-temperature
barrier layer or coating.
conditions, standard PA and PBT, usually used before,
do not have a sufficient thermal resistance. That is why,
3.2. Automotive radiation cross-linked PA and PBT, that show a good
dimensional stability at very high temperature from
In the field of manufacturing of automotive parts, 250 C up to 350 C (Fig. 1) for a few minutes are
radiation cross-linked polyamides 6 and 66 are mainly developing today for such new applications.
used for two of their advantages: Always in the field of manufacturing of electronic
devices, radiation cross-linked PBT is tailored to suit the
* a higher service temperature (long-term stability) new three dimensional moulded interconnect device
showed by an improved heat distortion temperature
(HDT) of about 10 C (Table 3),
* an improved chemical resistance to zinc dichloride.

Because new engine technologies like direct injection

and the increasing use of soundproofing devices have
induced a rise of the temperature in the engine
environment, radiation cross-linked polyamide-based
parts have been developed in that place.
More recently, new radiation cross-linked material
applications (made of thermoplastics or elastomers)

Table 2
Izod impact resistance of HD PE (Hostalen GC 7260) versus
dose (source: Ionisos)

Dose (kGy) 0 100 300

Notched Izod impact resistance (kJ/m2) 6.7 11.2 27.7

Table 3
Heat distortion temperature HDT (load: 1.48 MPa) of radiation
cross-linked PA 6 filled with 30% glass fiber, versus dose
(source: Ionisos)
Fig. 1. Temperature resistance, 3 min at 280 C, of radiation
Dose (kGy) 0 75 100
cross-linked PBT (30% GF)-based connectors (Degussa and
HDT ( C) 183.5 188.7 191.7
Ionisos study) before (0) and after irradiation at 200 kGy.
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(3D-MID) technology. It consists of two-shot moulding Their development for the manufacturing of moulded
devices, made of both cross-linkable PBT and metalliz- parts requires an important technical and marketing
able cross-linkable PBT, followed by a radiation cross- involvement from contract radiation centers and cross-
linking treatment, and that can then withstand metalli- linkable resins’ producers.
zation or laser cutting processes. Such technology After a large prospecting of new applications,
presents two main advantages: fewer processing steps radiation cross-linked plastics are now emerging
and miniaturization of electronic components. among the other plastics, especially in the automotive
industry.
As an example, in France alone, the average part of
4. Perspectives plastics in a car is about 130 kg and 2,000,000 cars are
manufactured each year. Assuming that only 1% of this
Radiation cross-linked-based engineering plastics quantity of plastic is potentially cross-linkable by
offers OEM and end users in many branches of industry radiation, the induced yearly volume could represent
both technical and economical advantages in compar- 2600 T, only for the French automotive market. With
ison with high-performance plastics. They constitute a doses included in the range 50–150 kGy, it is an
technical and economical compromise between engineer- extensive prospect of development for both
ing plastics that failed and high-performance plastics, contract radiation centers and irradiation facilities’
often over-tailored and expensive. manufacturers.