Irradiated plastics: Applications and Perspectives for the

Automotive and Electrotechnic Industries

Sophie Rouif, IONISOS S.A., France

High penetration radiations

Radiation of plastics is a way to crosslink them and to improve considerably their properties.

Radiation crosslinking was limited up to nowadays to only a few applications: the manufacture of
rubber for tyres, of crosslinked cable and pipe (pipe for underfloor heating systems), and of heat-
shrinkable tube.

Crosslinking was then performed with electron accelerators of low energies (0.1 MeV to 3 MeV),
allowing only surface treatments (limited to a few millimetres of depth).

High-energy electron accelerators (10 MeV) and Gamma plants (strong capacity of penetration of the
radiation) developed since, allow today treatments of larger thicknesses of the size of a cardboard box
(several centimetres) up to a pallet (1 m), so as to it enables the radiation crosslinking of plastics parts
directly in their packaging.

2 types of ionizing radiations can be used to

crosslink plastic parts (finished parts) in depth :

BETA rays GAMMA rays

high-energy electron • photons emitted by a
• high-
beam (E.B) radioactive source (Co60 or
Cs137)
• post-
post-treatment
performed by • Processing without
cardboard boxes depalletizing : performed
directly by complete pallets
or big bags

Even after excessive periods of radiation, none of the two types of radiations used for crosslinking
plastics can produce radioactivity in the material. The radiation only triggers the chemical process of
ionization.
Effects of radiations and radiation crosslinking

Radiations induce the ionization of the polymer and create free radicals on carbon atoms. These ones
are then ready to give direct covalent bonding between the chains of polymer.

Thus, the crosslinking process changes a linear network into a three-dimensional one, and
consequently, it involves a radical modification of the characteristics of the material:

- It produces an increase of the branching rate and of the average molecular weight of the
polymer.
- It also confers on plastics properties of insolubility, infusibility and a significant
improvement of their mechanical behaviour with temperature.

Radiation crosslinking can be applied to a great number of plastics: thermoplastics, elastomers and
thermoplastic elastomers.

Some of them can crosslink on their own, some others need to be formulated with a crosslinking agent
or to be modified during their polymerization. Commercial crosslinkable resins are available (different
polymers’ and compounders’ manufacturers in Europe).

Suitable Polymers for Radiation Crosslinking :

THERMOPLASTICS ELASTOMERS (rubbers)
rubbers)
- Polyethylenes (HDPE, − EPDM, EPR
LDPE …) − HNBR, NBR
- Copolymers of ethylene : − NBR / PVC
EVA ... − silicones* … etc
- PVC*
- Polyamides* (PA 6, 6-6-6, 12 …)
THERMOPLASTIC
- PBT* ELASTOMERS (TPE)
- PVDF − TPE-
TPE-O* (EPDM-
(EPDM- or EVA-
EVA-
based)
based)
* : crosslinking agent or − TPE-
TPE-S* (ex : SBR)
modified structure is required − TPE-
TPE-U* (urethane
(urethane))
− PVC-
PVC-based TPE
− TPE-
TPE-E (copo
(copo ether-
ether-ester)

Properties of amorphous or semi-crystalline polymers can be improved considerably by crosslinking

under radiations. It turns them into materials that can be used over a large range of temperature above
their usual softening temperature, even above the melting point in the case of semi-crisatalline
polymers.
Thus, the applications of these materials at high temperatures are considerably extended.

That is why the applications of radiation crosslinking of plastics parts have been developping
considerably today in the automotive and electrotechnic sectors where high thermal performances are
required.

Radiation crosslinking has effects on the three main characterictics of plastics, depending on the
nature of the radiation crosslinkable resins:

- mechanical behavior
- chemical stability
- thermal resistance
 Mechanical properties

Radiation crosslinking can confer on certain plastics (PA, PE, but not PBT for example) improved
mechanical characteristics, without any dimensional change. The following changes can thus be
observed:

- increasing hardness
- increasing stress at break and increasing modulus
- decreasing elongation
- improved impact resistance
- improved creep resistance
- improved resistance to stresscracking and to abrasion

Chemical properties

More generally, radiation crosslinked plastics present an improved resistance to:

- their usual solvents (for example, acids in the case of polyamids, organic derivates in the case
of polyethylene or elastomers)
- hydrolysis (in the case of TPE or polyamides 6 and 6-6, for example)
- to chemical aggressive agents, like salt haze, grease, oil, for example

Thermal properties

Of all properties, the thermal properties are affected most strongly after radiation crosslinking. In
particular, significant improvements can be observed on:

- dimensional stability, generally speaking (in all cases)

- heat distortion temperature
- creeping
- glow wire resistance
- flame resistance
- compression set

Advantages

Radiation crosslinked plastics constitute an innovative material solution. They extend the choice of
materials because, in a great number of applications, they allow to reduce material or processing costs
and they can replace traditional materials or expensive ones.

Technical advantages:

- reduction of weight (for example, replacement of metal)

- to take advantage of plastics’ or thermoplastics’ processability (for example, replacement

of metals or thermosets by radiation crosslinked thermoplastics, replacement of rubbers
by crosslinked TPE)

Economical advantages:

- equivalent properties obtained with a lower quantity of material

- higher processing capacities related to thermoplastics’ processability

- low prices related to genaral use thermoplastics (commodities: PE, PP, PVC) or usual
engineering thermoplastics (PA, PBT, TPE …)

- radiation costs well below over-pricing related to high-performances engineering polymers

 Technico-
Technico-economical advantages of radiation crosslinked
thermoplastics for automotive applications
300°C 75
Thermal stability Approximative
materials’ price
PLAS TICS € / kg
fo r
220°C HIGH
TEMPERATURE
PAI LCP,PEEK
PI ,PEI
PSU , PES PA46 , PAA
PPA ,PPS,
150°C 8
PLASTECHNICAL PLASTICS
TIQUES TECHNIQUES
PC,PPO,PC/ABS PA6 , PA66, POM ,
6
130°C PA10 ,
SAN , ABS,
PBT , PET, PA11 ,
120°C PA amorphe PA12 2.5
COMMODITIES
PLAS TIQUES D’US AGE GENERAL
2
PS PP , PE
1
AMORPHES
AMORPHOUS SSEMICRISTALLINES
EMI CRIS TALLINS

Aera of thermal stabilty Aera of thermal stabilty

/ price of radiation / price of radiation
crosslinked PA and crosslinked PE and
PBT PVC

Industrial applications

Packaging: bottles, films, seals …

- improved chemical resistance

- improved barrier properties (impermeability, sealing)
- improved mechanical behavior (impact, strain …)

Electrotechnic & Electronics:

Crosslinked polyamide can replace thermosets for the manufacture of circuit breakers and contactors.
Without crosslinking, it can not withstand electric arcs.

Crosslinked PBT (polybutylene terephtalate) can be used for connectors entring in processes of
assembling like SMD or no-lead welding processes, including temperature treatment above the
melting temperature of virgin PBT.

Radiation crosslinked PBT can also withstand metallization or laser cutting directly on a support made
of it (3D-MID: Three Dimensional Moulded Interconnect Device).

The advantages are fewer processing steps and miniaturization of electronic components.
 Automotive:

Radiation crosslinked polyethylene, polypropylene, polyamides, PBT and elastomers (rubbers + TPE)
are today a new material solution for various applications in the engine environnement and in the fuel
or exhaust systems:

AUTOMOTIVE

Engine environment Fuel line

- Fixing - Tank
- Bellows - Pipes
- Pipes - Connections
- Inexpansion tank - Seals
- Air intake manifolds - Fixing …
- Valves
- Seals Exhaust line
- Gearbox’s parts Silencer
- Brake system’s parts …