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17 Crosslinked Thermoplastics

Rodney Patterson  , Andreas Kandelbauer , Uwe Müller † and Herfried Lammer †



Consultant, Fountain Valley, CA;  School of Applied Chemistry, Reutlingen University, Germany

Kompetenzzentrum Holz GmbH, Wood Carinthian Competence Center (W3C), Austria

O U T L I N E

Introduction 697 Cross-Linking of Thermoplastics Using Silane


Grafting Reagents 712
Radiation Cross-Linking of Thermoplastics 698
Effects of Silane Cross-Linking on
Effects of Radiation Cross-Linking on
Thermoplastic Polymers 715
Thermoplastic Polymers 703
Comparison of Cross-Linking Methods 715
Chemical Cross-Linking with Organic
Peroxides 708 Applications of Cross-Linked Thermoplastics 716
Effects of Peroxide Cross-Linking on References 734
Thermoplastic Polymers 708

Introduction coverings, cellular materials (foams), rotationally


molded articles, and piping. The cross-linked mate-
Enhancement of properties is an underlying rials display improved properties (Figure 17.1) [1].
incentive for the commercial development of cross- Applications of these materials are discussed in
linked thermoplastics. Cross-linking of polymers separate sections later in the chapter.
improves resistance to thermal degradation of phys- For crystalline olefin polymers, the structure of
ical properties and improves resistance to cracking the crystallite (regions where the long-chain mole-
effects by liquids and other harsh environments, as cules are closely aligned) and the connected/cross-
well as resistance to creep and cold flow, among linked noncrystalline regions contribute to polymer
other effects. This chapter deals with the cross- properties, including density. For example, poly-
linking of primarily aliphatic polymers (polyethy- ethylenes with densities in the range of 0.94 to
lenes, PE, and polypropylenes, PP) and acrylates. 0.96 g/cm3 may be expected to contain 65 to 90%
High-intensity radiation from electron beams or crystalline material (crystallite), while polyethylene
ultraviolet sources has been used to initiate poly- with a density of about 0.92 g/cm3 commonly con-
merization in thermoset systems of oligomers tains 50 to 60% crystalline material. The proportion
capped with reactive methacrylate (acrylic) groups of noncrystalline (amorphous) material is increased
or isocyanates. Using this cross-linking polymeriza- by high-energy radiation, an effect that is evidently
tion technique, films with low shrinkage and high due to the cross-linking of the molecules that
adhesion properties have been prepared for applica- occurs. Exposure on low-density polyethylene suffi-
tions as pressure-sensitive adhesives, glass coatings, cient to cause cross-linking of about 10% of the
and dental enamels. On the other hand, for thermo- carbon atoms gives a product that is entirely amor-
plastic systems such as polyethylene, chemical or phous at room temperature. This loss of crystalline
irradiation techniques have been used as the cross- structure toward being 100% cross-linked is quite
linking technology; this is the recognized standard easy to accomplish because it takes only a few of
for manufacturing industrial materials such as cable the hundreds of carbon atoms in each chain to be

Handbook of Thermoset Plastics. DOI: http://dx.doi.org/10.1016/B978-1-4557-3107-7.00017-8


© 2014 Elsevier Inc. All rights reserved. 697
698 HANDBOOK OF THERMOSET PLASTICS

~100°C Higher temperature Cross-linking of


Increased strength polyethylene
PE 50°C

PE-X
Chemical Physical

−15°C 1.000 h Peroxide Azo Silane Radiation


−40°C
>10.000 h Engle Sioplas

Low temperature Mechanical performance


Pont à Mousson Monosil
Fracture resistance Point loading resistance

Figure 17.1 Properties of cross-linked (PEX) and Daoplast Silane


uncross-linked PE [1].
UHF Dry silane

0.97 Figure 17.3 Methods available for polyethylene


cross-linking [2].

0.96 crystallinity and an understandably lower melting


point. The molecular weight spread in the molecular
weight of a specimen is not expected to influence
Density, g/cc

0.95 the final melting point or the melting range unless


there is an appreciable proportion of molecules of
molecular weight below 1500, which is not
0.94
expected in commercial processes. Thermoplastic
polymers, the most important in this context being
polyethylene, may be cross-linked by a number of
0.93
different process as illustrated in Figure 17.3 [2].
In the following sections, some basics of cross-
0.92 linking thermoplastics are discussed and the chemistry
100 110 120 130 140 150 of radiation-induced cross-linking is briefly presented.
Melting point, °C Subsequent sections cover the chemical cross-linking
Figure 17.2 Change of melting point with density of by peroxides and silane grafting reagents. Thereafter,
polyethylene homopolymers. (Data taken from some typical applications and important product clas-
reference [21a]. Reprinted with permission of ses are presented that illustrate the importance of
Phillips Chemical Co.) cross-linked thermoplastic materials.

cross-linked to an adjacent chain for the structure Radiation Cross-Linking of


to be all cross-linked. Thermoplastics
Polyethylene, like other non-cross-linked crystal-
line thermoplastic macromolecules, melts over a Thermoplastics may be cross-linked using irradia-
wide temperature range; as the temperature rises, tion techniques and chemical agents. Their effect is
the proportion of amorphous material increases until to interconnect the long-chain molecules of the ther-
all the crystalline regions are melted (disappear). moplastic by covalent bonds, with the results being
High-density polyethylenes (with a relatively high much the same as when thermoset resins are cured or
crystallite proportion) melt at 125° to 131°C, while hardened by curing agents. Radiation chemical stud-
lower density polyethylenes melt at 110° to 115°C ies [3a] on macromolecules (the word used originally
(Figure 17.2). These results are expected. The pres- to describe polymers) provided the first evidence for
ence of structural or stereochemical irregularities in the formation of cross-links, namely formation of
macromolecules makes for a lower degree of insoluble gel (due to cross-linking), production of
17: CROSSLINKED THERMOPLASTICS 699

main chain unsaturation (producing some double These enter into Coulomb interactions with the atoms
covalent bonds in the polymer macromolecules), per- or molecules of the absorber and produce ions, elec-
oxide formation, and changes in physical properties, trons, and excited molecules [4,6,8] that initiate dif-
among other effects. The state of the art up to 2012 is ferent chemical reactions. The two fundamental
well described in Ullmann’s Encyclopedia of actions of radiation are to ionize and to excite [4,6,8],
Industrial Chemistry [4,5], in several books such as and both ions and excited molecules can give free
[6], and papers of conference series on radiation radicals [4,6,9] that lead to cross-linking and degra-
chemistry such as RadTech Europe and IRAP dation. The first step [10] in the production of chemi-
(Ionizing Radiation and Polymers symposium). cal effects by high-energy radiation is the interaction
The energy carried by X-rays, γ-rays, and electron between the electromagnetic field of the γ-ray and
beams exceeds the energy required to break chemi- the electrons of the polymer to produce ionization or
cal bonds. Among the chemical processes that can electronic excitation. The γ-rays give rise to fast elec-
be induced by radiation, cross-linking of polymers trons that have appreciable energy. As the energy
and polymerization of monomers has found impor- required for producing chemical change is only a few
tant applications in industry [6]. Initially, the radia- electron volts per molecule, a fast electron is capable
tion chemical studies on crystalline olefin polymers of altering several thousand molecules and possibly
were carried out mostly on polyethylene [1,3]. producing a polymeric segment in an energy-rich
Today, studies on polypropylene, polyvinylchloride, state. The γ-ray photons lose part of their energy by
etc., are well known [6]. Nevertheless, cross-linked ejecting electrons from sites along the macromole-
polyethylene dominates the applications [6]. cule (Compton scattering).
When polyethylene is irradiated with X-rays, Interaction with outer electrons is the principal
γ-rays, or high-energy electrons, a considerable process that produces chemical change. As a result
change in physical properties can result from a of this photon absorption process, the outer elec-
limited degree of chemical change. Hydrogen gas is trons are excited to higher energy levels or are
liberated together with paraffins, such as methane, ejected, thereby leaving ions in their place. The
ethane, and propane, in smaller amounts. Physically, positive ions, being electron deficient, possess
the polymer becomes increasingly insoluble; at the properties of free radicals as well as of ions.
first, it becomes more flexible and transparent (as it The ionization should be considered as the removal
changes from crystalline to amorphous with cross- of an electron from the molecule as a whole rather
linking), but, after protracted radiation, it hardens and than from just one part. Consequently, the positive
becomes brittle. The structural changes involved in charges can be present anywhere in the molecule,
this transformation occur in the absence of heat and although it will tend to be localized at certain posi-
chemicals. These cross-linking reactions, induced by tions more than others, as, for example, at electron
radiation, can be closely controlled and cover an deficient sites such as double bonds. Nonetheless,
extremely wide range. the molecule is thereby ionized to act as an ion and
Although some property studies have been made so can give free radicals.
concerning the effect of irradiation at very high Excited molecules can also be formed just by the
doses, most studies have concerned themselves with high-energy particles themselves [10]. Fast particles
irradiation doses in the range of 0 to 150 Mrad. The excite molecules to the same levels as ultraviolet
reason for this is simply that the beneficial changes light, mainly the lowest allowed excited state, but
in properties occur at relatively low doses, and that slow electrons can excite to any level, and their
increasing doses serve only to degrade some of the excitation is of the whole molecule, not just one
properties of olefin polymers. From a technological part of it. In fact, it does not even tend to be local-
standpoint, therefore, the most importance dose ized, as is the case with gamma ray radiation. It
range is 0 to 60 Mrad. The radiation allows con- can occur at a site quite remote from the track of
trolled and limited cross-linking reactions to pro- the particle. The same phenomenon occurs in pho-
ceed in the solid state so that an object molded into tochemistry where energy is absorbed by the chro-
its final shape can be irradiated subsequently and mophore, and yet reaction or emission of
modified to give it the required properties [7]. fluorescence can occur elsewhere in the molecule.
When electrons, positrons, ions, γ-rays, or X-rays Excited molecules, if they do not phosphoresce
are absorbed, secondary electrons are produced. or fluoresce, can react in three ways. They can lose
700 HANDBOOK OF THERMOSET PLASTICS

their energy by internal conversion to give a polypropylene (all single bonds), a considerable
strongly vibrating lower electronic state. The energy amount of chain scissions is produced by the irradi-
of vibration may then be removed by collisions. ation. They would therefore not be good candidates
Excited molecules can also decompose into free for radiation cross-linking. Substances containing
radicals, but unless the decomposition is an ener- chlorine yield HCl, but chlorine or HCl cannot be
getic one, there is, in condensed phases at any rate, liberated as long as hydrogen atoms are present.
the possibility that the radicals may recombine Therefore, instead of the chlorine pendant to the
within the solvent cage (Franck-Rabinowitch chain being broken by irradiation, it is the carbon
effect), leading to no net reaction. This effect should bonds of the chain itself that are broken. This may
be especially marked with large molecules. Another explain why polyvinyl chloride is among the least
mode of decomposition may be noted: decomposi- resistant of all plastics to irradiation.
tion to yield molecular products either directly by a The irradiation of polyethylene leads to the for-
unimolecular process or by reaction with other mation of hydrogen and of alkyl free radicals of the
excited molecules. Finally, some excited molecules structure -CH2-•CH-CH2- (breaking the C-H bond
may react chemically like free radicals themselves. in polyethylene and not breaking a C-C bond in the
The role of ions and excited molecules in radia- backbone main chain [9,11]; see Figure 17.4). It
tion chemistry is reasonably well understood in gen- contains a now unshared electron where the hydro-
eral terms, but in specific instances, especially in the gen atom was previously connected. If two such free
irradiation of liquids and solids, it is very difficult to radicals are formed on neighboring or adjacent
sort out what is happening. Both ions and excited chains, a very probable reaction would be cross-
molecules can, however, give free radicals (as well linking by recombination of the free radicals. The
as stable molecular products). The nature and reac- evidence is that the cross-links occur primarily in
tions of the free radicals can be studied even though the amorphous phase of polyethylene, as well as in
it is rarely possible to decide exactly how they were the amorphous surface layers of the (nonamorphous)
formed [3a]. As mentioned, hydrogen gas is liber- single crystals of polyethylene. Nevertheless, the
ated by irradiation. In order to produce hydrogen -CH2-•CH-CH2- radicals can disproportionate and
from polyethylene, the C-H bond must be broken. produce unsaturation in the molecule [3a]. A further
Since the chemical bond strength of the C-H bond is change that occurs upon irradiation is the reduction
greater than the strength of the C-C bond, chain scis- of the pendant methylene groups present in the origi-
sion (of its C-C bonds) might be expected to occur nal polymer.
more frequently than scission of the C-H bond. The radiation of polymers results in both cross-
Despite this, experimental evidence [9] shows that linking and degradation. Which of both predomi-
chain scission is low for low-density polyethylene. nantly occurs is defined by the chemical structure
We know that if a C-C bond is broken, the sigma- of the vinyl unit BH2CaCR1R2B and the stability
bonding electrons are separated and the result is free of the resulting radical: [4,12]
radical formation. It would be expected, however,
that the two chain fragments produced by the C-C • Vinyl polymers with R1 and R2Qalkyl,
separation are held firmly in the solid matrix, and, COOR, OH, or halogen are predominantly
as a result, recombination of the two free radicals is degraded.
likely (cage effect). Therefore, polyethylene is, as
• In polymers R1QR2QH the cross-linking is
discussed later, a good candidate for radiation cross-
dominant.
linking.
When a polymer contains double covalent bonds • CO groups in the main chain favor the degra-
in its main chain, as does polybutadiene, no chain dation of the main chain [13].
scission upon irradiation is detected [9]. This is
obviously because only its CQC double bonds are Table 17.1 [17] lists polymers that are radiation
being attacked, and they can use up some of the cross-linkable. The table lists their G values for
energy by converting to a CaC single bond. In the cross-linking (GX) and scissioning (GS), overlook-
case of the polymer main chain containing carbon ing the subtle influences. Although some polymers
atoms, each of which is connected to four carbon may cross-link at a greater rate than scission, a low
atoms as in polyisobutylene or to three as in GX value would indicate a need for higher doses to
17: CROSSLINKED THERMOPLASTICS 701

Figure 17.4 Formation of cross-links via recombination of radicals in neighboring polymer chains [11].

achieve property improvements [17]. The following regions of polymers and can therefore oxidize only
polymers are mainly degraded as a result of the within the amorphous phase of the surface. Secondly,
irradiation: [4] polyisobutylene, butyl rubber, poly- the extent of oxidation per unit of radiation dose is
α-methylstyrene, poly(vinylidene chloride), poly- dependent on the dose rate. The lower the dose rate,
methacrylates, polymethacrylamides, cellulose and the more time the oxygen has to diffuse into the plas-
derivatives, polytetrafluorethylene, polytrifluorethy- tic per unit of dose so that the net amount of oxidation
lene, and polycarbonates. for the same dose is much greater at lower rates.
Another change occurs when irradiation of polyeth- Oxidation and cross-linking subsequent to irradi-
ylene is carried out in air. In this case, cross-linking is ation have been observed [9]. The phenomena have
inhibited and oxidation takes place mostly on or near been attributed to the persistence of free radicals in
the surfaces. This oxygen effect is attributed to the the polymers. Not only does oxidation occur during
formation of peroxides and hydroperoxides. The irradiation but it may continue for weeks after
mechanism may involve the combination of oxygen the irradiation if the alkyl free radicals are not
with a free radical to form a free radical of the type annealed out by heating (in the case of polyethyl-
RO2; this free radical can then abstract a hydrogen to ene, to 100°C or higher after irradiation). The post-
form hydroperoxide, which, in turn, can decompose irradiation oxidation of polyethylene has been
into two free radicals (other mechanisms are also pos- followed, using as a basis, the increase in the car-
sible). Two aspects of oxidation should be emphasized bonyl infrared absorption band at 1725/cm even after
[9]. Oxygen gas dissolves only in the amorphous 60 days of exposure to air at room temperature.
702 HANDBOOK OF THERMOSET PLASTICS

Table 17.1 Selected Radiation Cross-Linkable Polymers

GX GS
Polymer Irradiated in Air Irradiated in Vacuo GS/GX
Low-density polyethylene 0.81.25 [14] 0.40.5 [14].
Linear low-density polyethylene 0.71.1 [14] For Polyethylene
2.32.5 [14]
High-density polyethylene 0.31.25 [14]
Ethylenepropylene copolymer 0.41.1 [14] 0.10.38 [14]
Depends on composition of copolymer
Polyvinyl acetate 0.3 0.07
Irradiated in O2 [15] Irradiated in O2 [15]
Polyvinyl chloride 0.3 [14]
Polystyrene 0.020.05 [14] B0.010.02 [14]
Natural rubber 1.31.5 [14] 0.030.18
Purified rubber
irradiated in [15]
Polyamides (see also Table 17.2) 0.51.15 [14] 0.61 [14]
Nylon 6 0.67 [16] 0.6 [16]
Nylon 6,6 0.50 [16] 0.7 [16]
Nylon 6,10 0.62 [16] 0.76 [16]
Nylon 11 0.92 [16] 0.85 [16]
Nylon 12 0.92 [16] 0.85 [16]
Nylon 10,10 1.12 [16] 1.10 [16]
Nylon 12,10 1.14 [16] 1.10 [16]
Nylon MPD 10 0.07 [16] 0.07 [16]
Polybutadiene (cis-1,4) 5.3 [15] 0.1 [15]
Polybutadiene-styrene 2.9 [15]
(SBR; 16% styrene)
Polybutadiene-styrene 0.3 [15]
(SBR; 85% styrene)
Ethylene-propylene-diene- 2.18 [15] 0.26 [15]
monomer (EPDM; 57 mole%
ethylene 1 2.0 mole% EN)

Carbonyl formation may be accompanied by chain kinetics of irradiated polypropylene-ethylene copoly-


scission or increased cross-linking. A delayed cross- mers have been described by Koosha et al. [18].
linking reaction was observed when a high-density The result of irradiation will be different depend-
polyethylene was irradiated and then immediately ing on whether the polymeric material is irradiated
heated above its crystalline melting point. The before or after the molding process; the effect of
increased cross-linking was attributed to the migra- the process order has been studied in detail by
tion of free-radical centers through the polyethylene Sonnier et al. [19]. The authors conclude that the
(now amorphous) by random jumps of a hydrogen most efficient way to perform radiation treatments
atom from an adjacent site to the free-radical site. is to irradiate pellets prior to injection molding
Detailed recent studies describing the degradation since with this procedure all free radicals could
17: CROSSLINKED THERMOPLASTICS 703

readily react and lower doses are sufficient as com- Polypropylene


pared to post-injection molding irradiation [19].
One major technological improvement in proper-
ties of polypropylene brought about by applying radi-
ation cross-linking is the increase in melt strength of
Effects of Radiation Cross-Linking PP. The melt strength of polymers is a measure of the
on Thermoplastic Polymers melt resistance to external deformation; it influences
the thermoforming behavior and the tendency of
Polyethylene polymer sheets to sag [27]. The increase in melt
strength of polyolefins is basically due to an increase
The irradiation induced cross-linking of polyethyl- in the long-chain branching caused by the introduced
ene results in a cross-linking of the amorphous phase cross-linking sites [6]. However, in contrast to
of the polymer [20]; see Figure 17.5. The cross- polyethylene, radical formation in polypropylene is
linking results in a dramatic change of properties, predominantly accompanied by degradation, and
examples of which are given for high-density poly- cross-linking is not the main reaction. The mecha-
ethylene in Table 17.2 [21a]. The data indicate that nism of degradation reaction of polypropylene is
polymer cross-linking is accompanied by an increase generally explained by fragmentation of tertiary
in tensile strength and hardness and a decrease in sol- alkyl macroradicals, while the cross-linking is
ubility. Most of the properties depend on radiation explained by a combination of secondary alkyl
dose. Typically, radiation dosage affects crystallinity, macroradicals [28].
stiffness, yield strength, tensile strength, elongation at To avoid PP degradation, radiation cross-linking is
break, and crack propagation resistance [22]. Some typically employed with the exclusion of oxygen; for
effects of radiation dose on important technological instance, in the Himont process, to obtain high melt
properties of different types of polyethylenes are strength polypropylene (HMS PP), the oxygen levels
shown in Figures 17.517.8. are reduced to preferably ,0.004 % per volume [29].
The cross-linked structure improves the chemical Long-chain branching via electron beam cross-
resistance, solubility, and swelling decrease [26]. linking under nitrogen atmosphere and its effects on
Changes of Rockwell hardness and creep are shown the rheological properties was also studied more
in Figure 17.6. Irradiation also increases resistance recently [30] and it was found that the zero shear
to environmental stress cracking [26]. Interestingly viscosity of electron beam treated branched PP
the radiation effect on the electrical properties is decreased with increasing irradiation doses [6,30].
negligible [25]. A general comparison of different It is also possible to control the extent of chain
properties of cross-linked and thermoplastic poly- scission relative to cross-linking by performing the
ethylene is given in Table 17.3 [11]. irradiation in the presence of acetylene. As has been

Figure 17.5 Structural effects of cross-linking polyethylene [11].


Table 17.2 Effects of Gamma and Beta Irradiation on Properties of Marlex® High-Density Polyethylene

Beta Irradiation Dosage, Mrad


Typical Properties Temperature, °F (°C) 0 5 10 15 50
Tensile strength, psi (MPa) 82(28) 4110(28.3) 4210(29.1) 4293(30) 4400(30.3) 4560(31.4)
200(93) 1303(8.98) 1567(10.8) 1640(11.3) 1120(7.7) 1477(10.8)
270(132) — 180(1.2) 212(1.46) 455(3.13) 745(5.13)
Elongation, % 82(28) 20 18 22 20 20
200(93) 167 375 520 505 133
270(132) — 510 445 385 110
Hardness, Shore D 64 67 67 68 70
3
Density, g/cm 0.96 0.96 0.96 0.96 0.96
Solubility, tetralin, 266°F (130°C) Soluble Insoluble Insoluble Insoluble Insoluble
Color White White Ivory Ivory Tan
Gamma Irradiation Dosage, Mrad
Typical Properties Temperature, °F (°C) 0 1 10 100
Tensile strength, psi (MPa) 82(28) 5840(40.2) 7007(51.7) 7120(49.1) 8360(57.6)
82(28)
Elongation, % 13 15 15 1
Hardness, Shore D 64 68 70 70
3
Density, g/cm 0.952 0.955 0.955 0.967
Solubility, tetralin 266°F (130°C) Soluble Insoluble Insoluble Insoluble

Type of Irradiation F50 Values, h
Dosage, rad Gamma Beta
none 20 20
1 3 104 20 —
3 3 104 24 —
6 3 104 110 40
1 3 104 700 350
3 3 107 350 350
1 3 108 1 —

Measured by various laboratories.

Environmental stress cracking in Igepal CO-630 at 122°F (50°C).
Data taken from reference [21a]. Reprinted with permission of Phillips Chemical Company.
17: CROSSLINKED THERMOPLASTICS 705

Figure 17.6 Effect of irradiation dose on Rockwell


Figure 17.8 Effect of irradiation dose on dielectric
hardness and creep deformation of γ-irradiated
ultrahigh-molecular-weight polyethylene (UHMWPE) constant and dissipation factor of low-density
polyethylene (LDPE) [6,25].
[6,23].

[33,34]. The same authors also investigated the per-


formance of γ-irradiated PP films and found that the
radiation/acetylene treatment led to changes in tensile
properties like yield stress, rupture stress, and elonga-
tion strain, as well as in morphological properties and
crystallinity [35]. Thin films of isotactic PP have also
been irradiated in the presence of triallylisocyanurate
(TAIC), which leads to an increase in the micro-
hardness as measured by nanoindentation [36]. As
with acetylene, TAIC should again act as a cross-
linking agent, although the authors do not discuss the
chemistry involved in detail.
Figure 17.7 Effect of irradiation dose on wear rate Since the penetration depth of ionizing radiation
of γ-irradiated ultrahigh-molecular-weight is limited, radiation cross-linking of the surface-
polyethylene (UHMWPE) [6,24]. near regions in PP may selectively be targeted
for toughening the PP surfaces; this has been
shown for the radiation-induced cross-linking of done, for instance, in the presence of reactive
polyethylene [31], the cross-linking ratio of polypro- low-molecular-weight compounds like diallylphtha-
pylene can also significantly be increased when PP late (DAP), tetraallyloxyethane (TAE), and pen-
samples are irradiated with γ-beams in an acetylene taerithritoltriacrylate (PETA) [37]. However,
atmosphere [32]. The authors found that the draw- although the abrasion resistance of PP was sig-
ability and the melt strength of the irradiated isotactic nificantly increased upon photochemical surface
PP samples were significantly improved. While treatment, it was assumed that the observed
γ-irradiation in the presence of oxygen mainly leads improvement in surface performance in this case
to oxidative degradation, in an acetylene environment was mainly due to the photo-induced polymeriza-
radicals formed from PP may react with acetylene to tion and cross-linked film formation of the added
produce grafting. The graft radicals can in turn react co-monomers rather than to PP cross-linking.
with radicals in neighboring PP chains under forma- Although in principle radiation cross-linking of PP
tion of stable cross-linking bridges, leading eventu- is possible without any additional monomers, in
ally to an extended network [32]. Cross-linking of PP most cases multifunctional monomers are used in
under acetylene atmosphere is typically followed by combination with the radiation treatment to pre-
a thermal treatment to provide for radical recombina- vent deterioration in mechanical properties, to
tion and annihilation of the remaining radicals increase the yield in cross-linking, and to allow
706 HANDBOOK OF THERMOSET PLASTICS

Table 17.3 Comparison Cross-Linked vs. Thermoplastic Polyethylene [11]

Cross-Linked Cross-Linked
Property PE PE Property PE PE
Shape memory 1 2 Tensile strength 1 2
High and low 1 2 Crack propagation 1 2
temperature properties
Creep resistance 1 2 Elongation at break 2 1
Impact strength 1 2 Shrinkage 1 2
Chemical resistance 1 2 Shape recovery 1 2
Stress-cracking 1 2 Abrasion resistance 1 2
resistance

Table 17.4 Changes in Molecular Weight of Polypropylene and Polystrene


After Gamma Irradiation of 2.5 Megarads

Samples Unirradiated Irradiated



Polypropylene
Weight average molecular weight 4.0 3 105 9.4 3 104
Number average molecular weight 1.1 3 105 1.2 3 104
Molecular weight distribution 3.7 8.0

Polystyrene
Weight average molecular weight 2.6 3 105 2.6 3 105
Number average molecular weight 1.5 3 105 1.6 3 105
Molecular weight distribution 1.8 1.7

Hercules Pretax 6501.

Dow Styron 685D.

reduction of the applied radiation doses required data show the shift from high to low molecular
to produce a gel of given cross-link density weights for un-irradiated versus irradiated polyeth-
[33,38,39]. ylene, clearly indicating that severe chain scission
Another possibility to reduce radiation-induced has occurred. The use of stabilizers permitting ster-
degradation during electron-beam treatment of PP ilization of biomedical products by γ-irradiation
is the addition of radical scavengers (stabilizers) to significantly broadens the range of disposable pro-
the PP formulation. This strategy is often used ducts made from polypropylene.
when radiation treatments are applied for the sterili- During γ-irradiation of polypropylene in air, ran-
zation of objects made from PP in the biomedical dom free-radical formation is believed to occur, fol-
industry. Sterilization of PP-based biomedical pro- lowed by oxidative propagation of radicals [41].
ducts by γ-irradiation results in severe polymer The incorporation [40] of stabilizers into polypro-
degradation [40]. Table 17.4 shows the changes in pylene, such as a hindered amine or phenol, sup-
molecular weight of polypropylene and polystyrene presses oxidation and inhibits the deterioration of
samples after gamma irradiation was carried out by the polypropylene properties, thereby rendering it
a Cobalt-60 source at dosages to 2.5 Mrad at a more resistant to irradiation. This stabilizer action
0.5 Mrad/hr rate. The results show that for polysty- was accompanied by a reduction in stabilizer con-
rene, weight average and number average molecu- tent during irradiation and the subsequent storage
lar weights and molecular weight distribution were period. The reduction was attributed to the stabili-
nearly unchanged. For polypropylene, however, the zer’s possible mechanisms, namely that of radical
17: CROSSLINKED THERMOPLASTICS 707

scavenger, chain transfer agent, or peroxide decom- radiation, which produces free radical sites on the
poser. The conclusion was that, regardless of the polymer backbone [44] (i.e. the main chain). During
mechanism, stabilizers play a sacrificial role in pro- irradiation, these radicals initiate dehydrochlorination
tecting polypropylene from further degradation fol- and small amounts of main-chain scission and cross-
lowing irradiation. linking. This dehydrochlorination proceeds via chain
The use of stabilizers is not only useful to prevent reaction to produce conjugated double bonds. These
degradation of PP during radiation treatment, but also now-unsaturated structures absorb in the ultraviolet-
serve to reduce long-term radiation effects caused by visible region, thereby discoloring the polyvinyl chlo-
entrapment of reactive species within the material ride. This discoloration is of course accompanied by
which causes accelerated PP deterioration during some embrittlement (cross-linking) and cracking
storage. The progressive deterioration during storage (chain scission) of the PVC article.
of polypropylene articles following γ-irradiation has A number of insulations and coatings used in
been attributed to the presence of hydroperoxide high-temperature environments are produced by the
groups. These groups are known to be thermally radiation cross-linking of PVC resin [44]. A typical
unstable and are considered a potential source of stor- formulation for a radiation-curable coating includes a
age oxidation together with “trapped” peroxyl radi- base resin (a PVC), a cross-linking sensitizer (e.g.
cals. Trapped peroxyl radicals are thought to be in polyfunctional monomer), and a plasticizer. A typical
cross-linked (amorphous), solvent accessible (thereby resin cross-linking sensitizer must be capable of
not trapped) domains. It has been suggested [42] that being cross-linked by irradiation as well as incorpo-
incorporation of the stabilizer/additive increases the rating the PVC resin molecules into the network via
internal free volume in the amorphous phase of the grafting reactions. Polyfunctional monomers that
polymer, thus enhancing main chain mobility and have been shown to act as such for polyvinyl chloride
accelerating main chain recombination; this holds include allyl esters, dimethacrylates, trimethacrylates,
true both during and following irradiation. triallyl isocyanurate, divinyl benzene, and triacry-
Related to the cross-linking of polypropylene and lates. The polyfunctional methacrylates and acrylates
the improvement of its mechanical performance is were found to possess the greatest cross-linking sen-
the grafting of alien molecules/polymer chains onto sitivity. The plasticizer component is used to obtain
PP surfaces during radiation treatment. For example, the required physical properties for a specific coating
hydrophilic monomers or polymeric chains may be application. In one study, the system of polyvinyl
grafted onto PP via radiation-induced radical chemis- chloride blended with trimethylolpropane trimetha-
try. This strategy was recently used to improve the crylate (TMPTMA) and diundecylphthalate (DUP)
biocompatbility, and especially the hemocompatibil- was selected as a representative example of such
ity, of PP-based materials for biomedical applications radiation-curable coatings.
[43]. Other important radiation treatments have In the absence of a plasticizer, there was an ini-
focused on the activation (and ultimately, the hydro- tial preference for TMPTMA homopolymerization,
philization) of PP surfaces for improving the compat- after which PVC molecules were bound into the
ibility with matrix polymers when PP fibers are used network [44]. Increasing the irradiation temperature
as reinforcements for composites. primarily increased all the reaction rates equally.
Dehydrochlorination of the PVC did, however,
begin to compete with the grafting and cross-
Polyvinyl Chloride linking mechanisms at 80°C. Post-irradiation ther-
PVC cables for electrical insulations can be radia- mal treatment was shown to markedly alter the
tion cross-linked to significantly increase their tem- physical properties of the irradiated blends. This
perature stability. As with PP products, electron beam alteration was caused by the reactions of residual
treatments are also often used to sterilize biomedical monomer molecules and unreacted double bonds in
equipment. Although the mechanical properties of the cross-linked network. TMPTMA does not use
biomedicals are not seriously affected upon steriliza- all the available double bonds to form the network.
tion, discoloration can become a big problem [6]. Over a wide range of blend compositions, the
In polyvinyl chloride (PVC), carbonchlorine and cross-linking rate was found to be proportional to
carbonhydrogen bonds (both off the main-chain the TMPTMA concentration [44]. As the TMPTMA
carbon) are susceptible to cleavage by ionizing concentration decreased, soluble graft copolymers
708 HANDBOOK OF THERMOSET PLASTICS

were produced in addition to insoluble networks. In expected that the resultant recombination of adjacent
the blends, the free-radical sites are scavenged by free-radical sites (between adjacent polymer chains)
TMPTMA, which grafts to PVC and initiates incor- would produce a cross-linked material with enhanced
poration into the network via structures like PVC- thermal stability (Figure 17.9) [11]. Nevertheless,
(TMPTMA)x and PVC-(TMTMA)x-PVC. Blends during the free radical cross-linking, the same radical
with no TMPTMA (pure PVC or PVCDUP blends) intermediates are formed as with the radiation-
showed no significant gel formation. induced pathway. Therefore, the free radical-induced
The introduction of a DUP plasticizer component pathway in chemical treatment using organic perox-
into the mixtures enhanced (1) TMPTMA homopo- ides also results in both cross-linking and degradation.
lymerization, (2) TMPTMA grafting, (3) PVC The relative rates of degradation and cross-linking
cross-linking (at low dose), and (4) reactivity of strongly depend on the chemical structure of the vinyl
double bonds [44]. These effects are interrelated. unit BH2CaCR1R2B and the stability of the resulting
For example, TMPTMA grafting produced precur- radical [4,12]. Polyethylenes modified with organic
sors for PVC cross-linking. Among the parameters peroxides are used in such applications as rotational
that determine the chemical kinetics of the system molding [21b] and piping for hot water use [45]; these
are the concentration and mobility of the reactants. are discussed in more detail in subsequent sections.
The competition between reactions (1), (2), and Organic peroxides are useful as free-radical
(3) above are determined by the reactivity and initiators because they are stable compounds until
mobility of the double bonds. The ease with which heated and their decomposition rate (to free radi-
PVC, TMPTMA, and free radicals can diffuse cals) is temperature dependent [46]. Because in
through the matrix and react together constantly many instances peroxide decomposition follows
changes throughout the reaction. With PVC/ first-order kinetics, the decomposition rate at a par-
TMPTMA blends, the medium changes from a flex- ticular temperature is usually expressed as half-life.
ible PVC resin (plasticized by the monomer) to a Half-life is defined as the time necessary to decom-
three-dimensional network (strong and brittle). With pose one-half the amount of peroxide originally
DUP present, the blends remain flexible after irradi- present. For example, dicumyl peroxide, which can
ation; on a molecular level, this means that the be used to chemically cross-link polyethylene, has a
mobility of the reactive species remains high. Until half-life of 23 hours at 115°C, 1.8 hours at 130°C,
high conversions were reached, the mobility of the and 0.3 hour at 145°C. The melting point of low-
reactive sites was enhanced by the presence of DUP, density polyethylene ranges from 110° to 115°C.
and the double bonds were accessible for reaction. After mixing or milling of the polymer and perox-
These results show that, in the manufacture of ide, the mixture can be shaped and then heated to
cross-linked coatings, the inclusion of DUP would induce the decomposition of the peroxide initiator
result in energy efficiency, double-bond efficiency, with consequent cross-linking of the polymer in the
and a more stable product [44]. The increase in molten state (above the polymer’s melting point).
mobility (due to DUP) produced faster cross- Of course, the polymer is not molten for long as the
linking and therefore required less irradiation (less cross-linking begins to immediately solidify it.
energy). A typical dose was 4 Mrad. Bearing in mind the oxygen effect leading to carbon
groups in an oxidized state, the structure of the
chemically cross-linked polymer most probably is
Chemical Cross-Linking with more complex than simple cross-linked paraffin.
Organic Peroxides
Chemical cross-linking of saturated (all single
covalent bonds) polymers, such as polyethylene,
Effects of Peroxide Cross-Linking
polypropylene, and polyvinyl chloride, consists of on Thermoplastic Polymers
bond formation between the polymer chains using
organic peroxides (in general) as a free-radical Polyethylene
source. Cross-linking with free radicals involves Polyethylene cross-linked with dicumyl peroxide
hydrogen abstraction to produce a free-radical initia- exhibits two separate but overlapping regions
tor site on the polymer molecule. It would be of dielectric loss between 2150° and 250°C.
17: CROSSLINKED THERMOPLASTICS 709

Figure 17.9 Processes taking place during peroxide catalyzed cross-linking of polyethylene chains [11].

Polyethylene also shows three regions of dielectric be located in the amorphous phase, and hence to
loss centered around 60°, 0°, and 2100°C (alpha-, give rise to beta or gamma losses, but with activa-
beta-, and gamma-loss regions, respectively) [47]. tion energies different from those of oxidized poly-
These regions essentially result from carbonyl ethylene. The major loss effects that occur at the
dipoles produced by adventitious or deliberate oxi- lower temperatures are attributed to the individual
dation. Whereas both the beta and gamma losses loss peaks of these two major by-products of the
originate from the amorphous phase, the alpha cross-linking agent. Analog materials prepared by
region is associated with the crystalline phase. The Yang et al. [47] from linear low-density polyethyl-
dielectric loss regions can easily be located by ene, by blending in either the acetophenone or the
dielectric or capacitance measuring instruments. At 2-phenyl-2-propanol, confirm the hypothesis.
a relatively high dielectric loss, the dipoles present The concentration of dicumyl peroxide used to
become relatively slow and less able to move in modify a low-density polyethylene (number-aver-
response to an alternating current (AC) field being age molecular weight 5 32,000) affects the static
imposed. Obviously, the reason has to do with the and dynamic mechanical properties of the chemi-
contribution of the dipoles to cross-linking or other- cally cross-linked polymer. Kunert [48] reported on
wise to rigidizing the molecular structure. This studies carried out at levels of 0.5 to 2.5 weight
information contributes to how widespread the use percent to determine the changes in structure of
is of cross-linked polyethylene as insulation for cross-linked polyethylene. The results of his
underground electric cable and to its growing accep- dynamic mechanical property testing in shear, using
tance in foamed form as microwave insulation. a torsional pendulum, showed that the maximum
When dry cured, the polyethylene noted above value of the logarithmic shear decrement occurred
contains approximately equal amounts of the by- in the vicinity of 47°C (the so-called alpha relaxa-
products of the dicumyl peroxide initiators, namely tion point) in the uncross-linked and the cross-
acetophenone and 2-phenyl-2-propanol. Both of linked polyethylene. At 27°C, values for the storage
these molecules are polar and would be expected to modulus of cross-linked polyethylene were below
710 HANDBOOK OF THERMOSET PLASTICS

G1 = 107
(dyn/cm2)
20 Dicumyl peroxide

18 a = 0.005 Hz
b = 0.5 Hz
16 c = 5 Hz

Storage modulus 14
0% gel
c
12
0% gel

10 b

8
0% gel a
6
0 0.5 1.0 1.5 2.0 2.5 [%]
Concentration of peroxide

Figure 17.10 The storage modulus (G) of cross-linked polyethylene as a function of dicumyl peroxide
concentration as measured in a Weissenberg rheogoniometer. (Data taken from reference [48]. Reprinted
with permission of John Wiley & Sons, Inc.)

the values of the unmodified polymer; storage mod- for storage modulus occurring at peroxide concentra-
ulus decreased slightly as the peroxide concentra- tions of 0.5 and 2% (Figure 17.10). A resonance
tion decreased to about 2%. The same correlation method in the frequency range of 100 to 900 Hz gave
was observed at 80°C. At 87°C, however, the stor- similar results.
age modulus of the cross-linked polymer was The absence of any maximum of storage modulus
greater than for the non-cross-linked polyethylene; plotted against the peroxide concentration when
the storage modulus decreased slightly with testing with the torsion pendulum was attributed
increasing peroxide concentration. Kunert con- to the effect of a large deformation that probably
cluded that a storage modulus at 27°C is probably exceeded the range of linear viscoelasticity of this
affected mainly by crystallinity because this modu- material. Thus the storage modulus represents, in
lus exhibited higher values for the uncross-linked the torsional method, the averaged resultant proper-
polyethylene than for the cross-linked material ties of different phases in the cross-linked polyethyl-
where crystallinity is not a factor. At 87°C, ene specimen. On the other hand, the appearance of
however, which is near the melting point of poly- some maxima with the Weissenberg and resonance
ethylene crystallites, the storage modulus of the methods was taken to indicate that the deformations
uncross-linked polyethylene shows lower values are at least half those of the torsional method
than the cross-linked material. This is mainly due and are probably within the range of linear visco-
to an increased stiffness of the polyethylene net- elasticity. Thus the mechanical properties of differ-
work (cross-linking) at this temperature, as well as ent phases are not averaged. Two rigid structures in
near elimination of the crystallites. cross-linked polyethylene are proposed. The first
The Weissenberg rheogoniometer was used to test maximum is presumably related to the appearance
the cross-linked polyethylene as a function of fre- of crystallites (excessive crystallinity), and the sec-
quency over four decades at room temperature [48]. ond maximum is probably caused by a uniform rigid
The storage modulus increases as a function of fre- polyethylene network. The structure attributed to
quency between 0.005 and 5 Hz. A plot of storage excessive crystallinity is presumed to occur at a low
modulus as a function of peroxide concentration concentration of peroxide (B2%); the very regular
showed that, at constant frequency, the characteristic and perfect polyethylene network is presumed to
feature of the plot was the appearance of two maxima occur at the high peroxide concentration.
17: CROSSLINKED THERMOPLASTICS 711

The results of static mechanical property testing observed, compared to low-density polyethylene,
showed that, as the peroxide content increased, was explained by the fact that, when subjected to
Young’s modulus and stress at yield point dicumyl peroxide free radicals, the tertiary carbon
decreased while percent elongation at the yield atoms present in the long- and short-chain branch-
point increased. A plot of ultimate tensile strength ing of low-density polyethylene were very suscepti-
exhibited a maximum in the vicinity of 0.5% perox- ble to degradation compared to those in the straight
ide concentration. Elongation at break exhibited a chains.
similar maximum. Kunert’s conclusion was that The rheological properties of the modified poly-
Young’s modulus depends on the amount of rigid ethylene were determined with a Weissenberg rheo-
amorphous phase in cross-linked polyethylene. As goniometer. Plots of first normal stress difference
the amount of peroxide was increased, the amount versus shear stress for virgin and modified low-
of soft phase increased. Kunert considered that the density and high-density polyethylene showed that
soft phase may act as a plasticizer for the hard the resin became more elastic as the amount of
phase. He postulated that ultimate tensile strength dicumyl peroxide was increased. The results
depends on the amount of crystallites. Except for showed that if the concentration of dicumyl perox-
this, static mechanical properties (and especially ide was low enough not to yield insoluble gel parti-
Young’s modulus) depend on the amount of hard, cles, modified resins were obtained that could have
amorphous structures in the cross-linked resulted from chain extension rather than cross-
polyethylene. linking [49].
At the other end of the spectrum, Lem and Han
[49] reported on studies in which the highest perox-
ide concentration was 0.1 weight percent. In this Polypropylene
range, little if any insoluble gel particles were Radicals produced by peroxide decomposition
formed between the particular virgin resins and may abstract hydrogen at any site along the chain.
dicumyl peroxide. A comparison of the molecular If unsaturation is present, hydrogen abstraction will
weight distribution curves of a low-density polyeth- likely occur from a carbon group alpha to a double
ylene (number-average molecular weight 5 7,500) bond. In the absence of an allylic group, abstraction
before and after reacting with peroxide showed that is expected at the site of teritary hydrogen. Tertiary
the modified material had more high-molecular- hydrogen atoms characterize polypropylene and are
weight portions compared to the starting resin; both found at branch points in polyethylene. Hydrogen
number-average and weight-average molecular abstraction of a tertiary hydrogen forms free radi-
weight increased with increasing amounts of dicu- cals that tend to undergo chain scission at the
myl peroxide. In addition, the modified low-density expense of cross-linking. In contrast to polythylene,
polyethylene had more low-molecular-weight por- radical formation in polypropylene is accompanied
tions compared to the virgin resin. The results show by degradation and cross-linking. The mechanism
that, from a mechanistic viewpoint, dicumyl perox- of degradation reaction of polypropylene is gener-
ide added to the polymer and extended the polymer ally explained by fragmentation of tertiary alkyl
chains (especially the long-chain molecules) and macroradicals, while the cross-linking is explained
gave rise to larger molecules. There was also evi- by a combination of secondary alkyl macroradicals
dence that the degree of long-chain branching was [28]. The decreased efficiency of peroxide cross-
increased in the presence of dicumyl peroxide free linking of copolymers of ethylene and propylene
radicals. was accounted for in the same way.
The molecular weight distribution curve of a In order to counteract this inherent low cross-
high-density polyethylene (number-average molec- linking tendency of polypropylene, monomers con-
ular weight 5 15,300) showed that, after reacting taining several olefinic bonds may be incorporated
with dicumyl peroxide, the entire curve of the mod- into the polypropylene so that the overall system is
ified resin was shifted toward the right-hand side, provided with a significantly increased number of
indicating that polymer chains were extended in the cross-linked sites. In one study [28], pentaerythritol
presence of peroxide free radicals, and little disso- triallyl ether was evaluated as a “co-agent” in
ciation of C-C bonds had taken place [49]. The chemical cross-linking of isotactic polypropylene
little degradation of high-density polyethylene with the aid of organic peroxide. Looking at the
712 HANDBOOK OF THERMOSET PLASTICS

structure of the peroxides used in this study, it Cross-Linking of Thermoplastics


seems that the most efficient cross-linking initiators
Using Silane Grafting Reagents
formed benzoyloxy or phenyl radicals upon decom-
position. On the other hand, initiators giving alkyl Chemical cross-linking of polyolefins (and other
radicals were inefficient. A combination of dicumyl polymers) is also possible by grafting silanes onto
peroxide and sulfur was also used for the reversible the polymer chains as cross-linking agents that are
cross-linking of polypropylene [50], which lead to subsequently cured, typically under moist condi-
formation of semi-crystalline polyethylene chains. tions. A variety of processes have been devised to
An alternative to organic peroxide induced cross- perform silane cross-linking, the most important
linking for improving the melt resistance of being a two-step process (Sioplas) and a one-step
polypropylene-based thermoplastics has been dem- process (Monosil). The basic chemistry behind
onstrated by An et al. 2010 and An et al. 2012 silane cross-linking involves (a) grafting of alkoxy-
[27,51]. The authors used trimethylolpropane tria- silane cross-linkers onto the polymer chain via radi-
crylate (TMPTA) as a cross-linking agent to create cal chemistry, (b) subsequent hydrolysis of the
cross-linked propylene/1-butene copolymers in situ grafted alkoxy group, and (c) condensation of the
through heat induced reaction. Compared to radia- silanol entities of neighboring silanized polymer
tion and peroxide cross-linking, this approach is chains under formation of three-dimensionally
described as bearing several advantages such as ease cross-linked networks. Figure 17.11 illustrates the
of processing, low cost and capital investment, and principal chemical reactions taking place in silane
favorable properties of the processed materials [27]. cross-linking of polyethylene [2].

Figure 17.11 Principal chemical reactions involved in the silane cross-linking of polyolefins [2].
17: CROSSLINKED THERMOPLASTICS 713

H3C O
H3C
H2C CH3 CH2
O O Si
H3C Si CH3 O
O O O O
O CH2 O
H3C Si O
O
CH3 O H3C O
CH3
H3C
VTEO MEMO VTMOEO/TMEVS

CH3
CH3
H3C H3C CH3 CH3 NH2
CH3 O
N O
N O
O O H3C Si
O Si
CH3 O
Si O O
H2C
H2C N CH3 H3C
AMMO
VOS CH3 VTMO

CH3
H3C
O CH3 H3C O NH2
O O
Si NH Si
H3C O NH2 O
AMEO
DAMO H3C

Figure 17.12 Chemical structures of important examples of commercially available reactive vinylsilanes and
aminosilanes used for chemical grafting on polyethylene using the Sioplas process: vinyltriethoxysilane
(VTEO), 3-methacryloxypropyltrimethoxysilane (MEMO), vinyltris(2methoxyethoxy)silane (VTMOEO), vinyl-tris-
(2-butanonoximo)-silane (VOS), vinyltrimethoxysilane (VTMO), 3-aminopropyltrimethoxysilane (AMMO), N-(2-
aminoethyl)-3-aminopropyltrimethoxysilane (DAMO), and 3-aminopropyltriethoxysilane (AMEO). These
chemicals are available from Wacker (GENIOSIL product line).

The first step in silane cross-linking makes use structure of the alkoxysilane used, the nature of the
of peroxide catalysts that generate radicals that cross-linking bridges may vary a lot, and hence,
abstract electrons from the PE main chains in a cross-linked polyethylenes of tailored property pro-
similar way as occurs in the peroxide cross-linking files are accessible. Subsequent hydrolysis and
discussed in the previous section. However, the cross-linking of the silane bridges is performed
reaction conditions and formulations are tuned such using catalysts such as, for instance, dibutyl tin
that the radicals formed are mainly consumed by dilaurate.
grafting reaction with the alkoxysilane. Typical The grafting of silanes onto polyethylene and the
alkoxysilanes for cross-linking contain terminal silane cross-linking may be performed in two sepa-
vinyl groups that react readily with the secondary rate, subsequent steps. Grafting typically takes place
(PE) or tertiary (PP) radicals in the backbone. The in the polyolefin melt at temperatures of 140240°C;
molecular structures of a number of commercially for this, the silane and the organoperoxide radical ini-
available silanes for polyethylene cross-linking are tiator are compounded with the polyolefin and graft-
depicted in Figure 17.12. ing is readily performed via reactive extrusion on
One major advantage of the silane cross-linking conventional equipment. Thereafter, the grafted poly-
process is the flexibility in design of the resulting olefin is pelletized and may be stored until further
macromolecules. Depending on the molecular use in sealed vacuum bags for up to 6 to 9 months
714 HANDBOOK OF THERMOSET PLASTICS

Figure 17.13 Reaction scheme for the preparation of novel silane-modified polypropylene copolymers for
subsequent cross-linking reaction [57].

[2]. Longer storage times may result in undesired pre- developed during the past few decades to overcome
mature cross-linking of the grafted material. The final some of the limitations of these processes. For
product is then produced in a subsequent step by mix- instance, polyethylene may be functionalized with
ing the grafted polyolefin pellets with a masterbatch silanes using a cold plasma process [56]. Another
of polyolefin containing the cross-linking catalyst, important approach is to prepare silane/polyolefin
antioxidant, stabilizers, and a lubricant in a weight copolymers; the cross-linkable silane groups may
ratio of (typically) 5:95 [2,52], melting it, and extrud- be introduced into the polyolefin backbone directly at
ing it into the final product. Cross-linking takes place the stage of polyolefin synthesis. Special silane
by exposing the product to water or steam at approxi- ethylene copolymers have been developed for further
mately 7090°C. This process is known as the cross-linking purposes by Union Carbide, Borealis,
Sioplas process, developed in 1968 by Midland and Mitsubishi [55]. One recent development in this
Silicones Co. (Dow Corning Co.) [53]. It is character- field has been the copolymerization of di-tert-butoxy
ized by high output rates, low scrap, and most inter- (methyl)(oct-7-enyl)silane with propylene using a
estingly, by the possibility of using conventional zirconocene catalyst (Figure 17.13) [57].
extrusion equipment [2]. Since the silane is already built into the polyole-
Alternatively, the grafting and cross-linking can fin backbone, side reactions are not encountered
be performed in one step by using a specially during manufacturing; these reactions are typically
designed extruder with a high L:D ratio [2]. In this caused by the presence of free radicals and antioxi-
process, all components (polyethylene, alkoxysi- dants. Consequently, radical initiators are not
lane, peroxide catalyst, cross-linking catalyst, and required in the polymer formulation. Moreover, the
additives) are fed into the extruder and the final distribution of the incorporated silane bridges also
cross-linked product is formed directly. Originally, takes place more homogeneously across the material
this process was developed by BICC Limited and during copolymerization than with the Sioplas or
Establishments Maillefer SA in 1974 [54] and is Monosil grafting processes. Besides these advan-
known as the Monosil process (alternatively, the tages, another benefit of such co-polymers is the
Nokia-Maillefer process) [55]. Due to the special possibility of compounding them with high loads of
machinery required, this process is more capital filler materials. More recently, the so-called dry-
intensive, and since all the reactants are fed simul- silane process was introduced, which is quite similar
taneously into the extruder, the process is more dif- to the Monosil process but makes use of non-liquid
ficult to control and undesired premature or reactants; typically, catalysts, silanes, and initiators
excessive cross-linking may lead to comparatively are absorbed into porous resins, swellable carriers,
higher degrees of waste production [2]. or encapsulated masterbatches [2]. A comparison of
Besides the Sioplas and Monosil processes, vari- major technological issues encountered with silane
ous other manufacturing technologies have been cross-linking technologies for polyolefin cross-
17: CROSSLINKED THERMOPLASTICS 715

Table 17.5 Comparison of the Moist Cure Technologies Used in Silane Cross-Linking of Thermoplastics

Process Advantages Disadvantages


Main Processes
Sioplas • Fast curing • Two-step technology
• Versatility of base resin (LDPE, • Limited shelf life
EVA, EPR, DPE, etc.) • Higher raw material costs
• Low capital investment • Risk of pre-cross-linking on the surface
• No need for special equipment of pellets during storage
Monosil • Low material costs • Limited use of some additives
• Versatility of base resins • Handling of hazardous liquid chemicals
• Fast curing • High scrap rates
• Shelf life not an issue • High capital investment
• Specific equipment required
Alternatives to Main Processes
Reactor copolymer • Long shelf life • Slow curing
• Low capital investment • Low-density product only
• Higher raw material costs
Dry-silane • Potential low material costs • Use of additives limited or impossible
• Ease of storage • Moderate capital investment
• Improved safety and handling • Limited shelf life
• Versatility of base resins
• Fast curing
• Good homogeneity
• Less gels and fish eyes

linking is given in Table 17.5 [2]. For further details effects on the morphology, barrier, thermal, and
on the silane cross-linking of polyethylene, with rheological properties of high-density polyethylene
special emphasis on the Sioplas process, the reader reinforced with nanoclays and their polyamide
is referred to the excellent review by Morshedian blends was recently described [58,59]. It was found
et al. [2] (and the references cited therein). that due to the introduced hydrophilicity, the com-
patibility between the components of the compo-
Effects of Silane Cross-Linking on sites was greatly improved. The barrier effect
against oxygen migration in the material was sig-
Thermoplastic Polymers nificantly improved as well, and in the case of the
The overall performance of silane-cross-linked polyamide blends, synergetic effects of the silane
thermoplastics is improved compared to the unmod- treatment were found [59]. Silane cross-linking also
ified material and the effects are quite similar as turns out to improve the foamability of polyolefins,
obtained with the previously discussed cross- as shown for polypropylene [60].
linking methods. The major difference with using
silanes as cross-link bridges is that the technical Comparison of Cross-Linking
performance of the final cross-linked material can Methods
be tuned with respect to the desired end product
properties. The compatibility between thermoplastic In summary, thermoplastics are cross-linked
matrix systems and various types of fillers can sig- industrially by either irradiation or by application
nificantly be improved. Silane grafting and its of peroxide or silane grafting reagents. The product
716 HANDBOOK OF THERMOSET PLASTICS

Table 17.6 Comparison of Physical Properties of HDPE Cross-Linked by Different Cross-Linking Methods [6]

Cross-Linking Method
Peroxide Silane
Physical Property Radiation Catalysis Grafting
Max. gel content [%] 73 88 63
Physical properties at 60% gel
Elastic modulus [MPa] at 190°C 0.24 0.2 0.14
Crystallinity (as cross-linked) 69 60 69
Crystallinity (after re-melting) 61 58 67.5
Tenacity at break [MPa] at 150°C 0.75 0.7 0.9
Elongation at break [%] at 150°C 220 240 190
Max. elongation at break [%] at 150°C 330 300 270
Gel content [%] (at maximum elongation at break) 47 70 47
Elastic modulus [MPa] at 190°C (at maximum 0.14 0.3 0.07
elongation at break)

characteristics obtained by cross-linking thermo- as well as the potential safety hazards of the
plastic polymers depends to some extent on the employed chemicals (silanes, peroxides), into consid-
cross-linking method used. Makuuchi and Cheng eration. Table 17.7, compiled from the excellent
[6] compared the typical product characteristics of book by Makuuchi and Cheng [6] and the review by
high-density polyethylene (HDPE) after cross- Morshedian et al. [2], summarizes some of the major
linking by all three approaches. The authors technological differences and the application range of
extruded HDPE in sheet form and irradiated the the various cross-linking methods.
samples with electron beams with doses up to
50 kGy. While for the silane cross-linked PE
samples, similar sheets were used, the peroxide
Applications of Cross-Linked
cross-linked HDPE samples were pressed slabs.
In chemical cross-linking, among other parameters, Thermoplastics
the concentration of reagent and exposure time
were varied. Typical material characteristics are Polyolefin Foams
reproduced in Table 17.6. Polyolefin foams represent an important class of
Although the properties depend slightly on the industrial materials. Although most polymeric
method used, all three methods are applicable for foamed materials are either based on polyurethane,
producing hot water pipes, heat resistant wires, polystyrene, or poly(vinyl chloride), polyethylene
cables, and the like, and products meeting the foams are only ranked fourth in terms of sale, but
required specifications can be manufactured [6]. the growth rates of foams based on cross-linked PE
However, each method has its specific limitations. are impressive [61]. Polyolefins can be cross-linked
For instance, whereas radiation cross-linking due to by irradiation [62] as well as chemical means such
the limited penetration depth of the electron beam is as silane grafting [63]; the typical manufacturing
not suitable for bulk cross-linking of objects with process comprises three steps: (a) sheet formation,
greater thickness, chemical cross-linking methods are (b) cross-linking, and (c) foaming [61].
less suited for cross-linking thin films. Regarding Table 17.8 shows typical properties of a series of
end-products, quality monitoring and control mea- radiation cross-linked closed-cell polyethylene
sures are more important than the applied cross- foams [64a]. The foams, ranging in density from
linking method. For selection of the technology, the 1.5 to 15 lb/ft3, are characterized by excellent
manufacturer takes equipment and operational costs, mechanical, thermal, and chemical properties,
17: CROSSLINKED THERMOPLASTICS 717

Table 17.7 Technological Comparison of Polymer Cross-Linking Methods [2,6]

Radiation
Cross-Linking Method (Electron Beam) Peroxide Silane Ref.
Wire and cable,
tube, pipe, film Wire and cable,
Major products foam tube, pipe, foam Wire and cable, pipe MC2012
Plastic Polyethylene K K K MC2012
Polypropylene K x x MC2012
Polyvinylchloride K x x MC2012
Engineering plastics K 3 3 MC2012
Polytetrafluoroethylene K 3 3 MC2012
Fluoropolymer K K x MC2012
Capital investment High High Low M2009
Raw material costs Low Low Slightly high M2009
Cost of compounding Low Medium High MC2012
Cost of post-treatment High  Low M2009
Shelf life of compound Long Medium Short MC2012
Product thickness restriction ,10 cm . 0.3 mm . 0.3 mm MC2012
Limited by Difficult to achieve No limit, thickness M2009
penetration depth big diameters limited by speed of
of electron because of output cross-linking
Rate of cross-linking High Low Low MC2012
Degree of cross-linking Medium, High Low MC2012,
Probability of MC2009
variation
Process flexibility Very good Small Very good M2009
Operation Difficult Difficult Easy M2009
Extruder Standard Special Standard M2009
Production rate High as for PE Low High as for PE M2009
Scrap rates  High scrap Low M2009
Other Clean (pipe) Energy intensive Wider scope for M2009
because of fewer formulation through
additives broad processing
window, recyclability

K: In practical use; x: Technically possible, but no practical example; 3: Hard to apply.

together with a fine-cell structure and an excep- specially formulated to provide more flexibility and
tionally smooth surface; they are available in resilience than their standard grade of Type A desig-
thicknesses from 1/32 inch to more than 1 inch. nation. The science and technology of polyethylene
A cross-linked polyethylene foam sheet with an foams based on cross-linked PE was extensively
integral skin is also available in the same range of reviewed by Rodriguez-Pérez [61].
densities and thicknesses. The skin offers increased Polypropylene foam is also available, and cross-
abrasion resistance without reducing the foam’s flexi- linking has been shown to not only improve poly-
bility. Table 17.8 shows VOLARA foam products ethylene properties for foam-based materials, but
with a Type E designation; Voltek literature describes also to lead to improved foamability and material
them as cross-linked polyethylene copolymer foams performance of polypropylene. For instance, using
Table 17.8 Typical Properties of Closed-Cell, Radiation Cross-Linked Polyethylene Foams

Tensile Tear Thermal Water


Maximum Strength Elongation Resistance Stability % Absorption,
Compressive Compression (psi) ASTM (% to Break) (lb/in) Linear Shrink lb/ft3 Cut
Normal Strength (psi) Set (% Orig D-1564 ASTM D-1564 ASTMD-624 After 3 Hours Surface
Foam Density, at 50% Thick.) ASTM Max. ASTM
Product Ib/ft3 Deflection D-395 M C M C M C 180° 215° K-Factor D-1667
VOLARA 1.5A 1.5 1114 15 38 25 121 101 8 6 2.5 8.5
VOLARA 2A 2 1216 16 50 41 138 114 11 8 1.5 3.0 0.25 0.04
VOLARA 2MF 2 1216 30 48 36 78 62 13 8 1.5 2.2
VOLARA 2E 2 1115 21 60 48 250 250 11 10 3.6 20.0 0.25 0.04
VOLARA 2EE 2 1015 25 35 29 190 200 6 5 14.0 50.0
VOLARA 4A 4 1924 12 100 82 174 148 22 18 1.2 2.8 0.30 0.04
VOLARA 6A 6 2531 9 max. 148 124 220 176 35 28 1.0 2.2 0.32 0.04
VOLARA 6E 6 2227 8 max. 200 172 350 348 35 31 2.1 9.9 0.32 0.04
VOLARA 8M 8 6080 14 max. 250 200 165 120 65 50 0.2 0.5
VOLARA 12A 12 75100 15 max. 294 226 284 255 76 71 2.1 3.8
VOLAST A 3A 3 1823 20 max. 68 60 97 98 13 11 2.0 5.8

Available in formulation containing fire retardant additives.
Data taken from reference [64a]. Reprinted with permission from Voltek, Inc.
17: CROSSLINKED THERMOPLASTICS 719

materials) [64b]. However, the foams, like the poly-


olefin plastics, have a low-energy surface that is
not easily wet by laminating adhesives. The most
common way to improve wettability and adhesion
is corona ion plasma treatment. A similar effect can
be obtained by flame treating the polyolefin foam
prior to lamination/bonding. Then, using heat and
pressure, the foam may be laminated to itself, to
urethane foam, to polyolefin films, and to fabrics
made from natural fibers. Just before joining at the
laminating nip, each substrate is preheated using a
gas flame or electric heaters. To bond to a fabric,
film, or other substrate, a heat reactivation method
can be used. This technique employs a thermoplas-
tic film or pre-applied coating which, after heating
and applying pressure, bonds to another substrate
without the need to evaporate off water or carrier
solvent. Examples of adhesive films include low-
Figure 17.14 Car interior part made from radiation- density urethane foam, solid polyethylene, and
cross-linked, semirigid, closed-cell, long sheet foam ethylene-vinyl acetate films. These materials melt
(Reprinted by permission from Troy Industries Inc.) completely and become a solid continuous layer in
the final laminate. For substrates that cannot be
bonded using heat and/or pressure, adhesives may
a silane cross-linking one-step process based on be used. According to the manufacturer, adhesives
VTMS, the melt strength of PP was significantly are available which will bond polyolefin foam
improved and the properties of PP foams were stud- without pretreating the foam. Other adhesives
ied, including dependence on the preparation condi- require pretreatment.
tions, such as initiator concentration [60]. The Radiation cross-linked polyolefin foams can be
preparation of polypropylene foams and structure shaped by compression molding alone or in combi-
property relationships were recently studied by nation with other foams of different color and den-
Saiz-Arroyo et al. [65]. sity, fabrics, films, foils, non-wovens, solid plastics,
Cross-linked polyethylene and polypropylene and cellulosics [64c]. By combining the cross-
foams are resilient cushioning materials. In terms linked foams with other materials in whatever way,
of compression set resistance per ASTM D-395, a wide variety of products with desired properties
they even outperform the foam industry standard, and appearances can be tailored to specific end-use
silicone foam. Most applications are based on this requirements. While the combining is usually done
property together with some other quality such as by lamination prior to molding, materials can be
buoyancy, shock absorption, thermal or electrical bonded together in the mold. The choice is based
insulation, vibration dampening, and moisture pro- on the cost and ease of laminating various materi-
tection. Automotive applications include gasketing, als. For example, a two-way stretch nylon fabric
sun visors, and insulating liners for air-conditioner should be laminated before molding, whereas a
housing and carpet backing. Recreational and sport rigid high-density polyethylene plastic insert would
uses are based on protection against repeated shock be heated and then placed in the mold between
from relatively high stresses (Figure 17.14). The layers of hot foam.
foams also find uses in medical products because
they add comfort to orthopedic braces and cervical
collars, for example. Rotational Molding
Applications of the cross-linked polyolefin foams Powder process techniques, for making hollow
are diverse because these materials can be com- parts of polyethylene, evolved into rotational mold-
bined with others using proven plastics industry ing [21b]. In this method, a split metal mold is
methods (but with variations because of the foamed used. A cold mold is filled with a powdered resin,
720 HANDBOOK OF THERMOSET PLASTICS

then the mold is placed in an oven and rotated and slightly longer heating cycle times than nor-
simultaneously about two perpendicular axes. mally used with conventional high-density polyeth-
During this stage, a uniform layer of resin is depos- ylene resins [21b]. In most cases, an oven
ited on the mold. After sufficient time has elapsed temperature between 550°F and 625°F should be
to properly fuse the resin, and while it is still rotat- used. Temperatures below 550°F can be used quite
ing, the mold is cooled. After cooling, the part is satisfactorily, but longer cycle times are required.
removed from the mold and more resin is added to Temperatures above 625°F tend to generate too
start the cycle again. rapid a decomposition of the cross-linking agent.
The absence of positive pressure in the powder This can cause bubbles in the wall, blow holes
rotational process places certain limits on the type through the wall, pock marks on the surface, a
of resin that can be used. The higher molecular rough inside surface, or over-pressuring of the
weight resins used for blow molding (and some- mold if adequate venting is not provided.
times injection molding) cannot be rotationally Table 17.9 shows the nominal physical proper-
molded because they will not flow out in the ties of two rotational molding, cross-linkable, high-
absence of pressure to form a homogeneous, void- density polyethylene resins. When tested in a bent
free part. The polyethylene resins used in powder strip test (ASTM Dl 693), both Marlex® CL-100
processes generally range from as low as 3 to 5 to and CL-50 have outstanding environmental stress
as high as a 70 melt index. If molecular weight dis- cracking resistance (ESCR). The bent strip test is
tribution is considered constant, the lower the used for ESC characterization because it is pre-
molecular weight of the resin, the higher the melt sumed to be representative of the stresses and
index. The resins with the 3 melt index have better strains encountered in use. In this test, ten polymer
stress-cracking resistance, impact strength, and samples (1-1/2 in. 3 1/2 in. 3 1/8 in.) are bent 180°
resistance to creep than the high melt index resins, and immersed in a stress cracking agent. Each bar
but are also more difficult to mold. Recall that a contains a longitudinal slit 3/4 in. long 3 2/100 in.
low melt index polymer is one that has low flow deep down the center of the upper face. Resistance
rate at the test temperature. Parts with hard-to-fill is defined as the length of time needed for five of
areas would require a slightly higher melt index for the ten bars to show visible signs of cracking
good moldability. Because of the somewhat limited perpendicular to the slit. In the ASTM D1693 test,
stress cracking resistance and creep resistance of CL-100 has an F50 value greater than 1,000 hours.
the powdered polyethylene resins, parts fabricated With a properly cross-linked CL-100 sample, not
from these resins may be limited to the severity of a single specimen has failed in this test.
service to which they can be subjected. Marlex®CL-SO has a nominal ESCR F50 valve of
On the other hand, tanks made by the rotational 200 hours. When properly molded, most CL-50
molding process using cross-linkable high-density parts will have ESCR in excess of this. A more
resins have been used in a variety of applications, severe test under ASTM D1693 uses a 10% solu-
including the handling of corrosive chemicals. tion of the stress cracking agent; the cross-linkable
Tanks varying in sizes from a few to thousands of resins have similar values with this test as they do
gallons are being used in agriculture and industrial with less severe 100% solution.
applications [66]. Cross-linking gives products that Long-term hoop stress testing of the cross-
have excellent resistance to stress cracking and linkable resins indicates that they are superior to
chemical attack, excellent impact strength, weather- other rotational molding resins and equal to high-
ing characteristics, and overall toughness. Although density polyethylene extrusion grade pipe resins.
the cross-linked product goes through a crystalline Both CL-100 and CL-50 rotational molded samples
melt point at a temperature similar to uncross-linked of 2-in.-diameter pipe and 0.150-in. walls were
resin, it has sufficient melt strength to support itself used for long-term hoop stress testing at both 80°
at temperatures up to about 210°C. Smaller molded and 140°F. One set of CL-100 test samples at
products that are not subjected to a load will not 1,750 psi hoop stress and lower has gone more than
deform even at temperatures at which uncross- 50,000 hours without failure. Before testing, it was
linked high-density polyethylene will melt and flow. anticipated that the 1,700-psi sample would fail at
Cross-linkable resins (e.g. Marlex® CL-50 and approximately 100 hours. Because failure did not
CL-100) generally require lower oven temperatures occur, design hoop stress could not be determined;
17: CROSSLINKED THERMOPLASTICS 721

Table 17.9 Nominal Physical Properties of Marlex® CL-100 and CL-50 High-Density Polyethylene Resins

Natural, White,
and Standard
MARLEX® RESIN NUMBERS CL-50 Natural CL-100 Colors
ASTM D1248 Classification Type IV (1) Type IV (1)
Class A Class A
Category 1 Category 1
Meets Food and Drug Administration No No
Regulation 177.1520 for Food
Packaging
Nominal Physical Properties2
Density, ASTM D1505, g/cm3 0.93909423 0.9370.9403
Rotational Molded Properties
Environmental Stress Cracking .200 .1000
Resistance, ASTM D1693, 100% .175 .1000
Igepal
Condition A, F50, hr. 10% Igepal
Tensile Strength @ Yield, ASTM D63B 2600 (16) 2600 (16)
Type IV Specimen, 2 in. (50 mm)
per min, psi (MPa)
Elongation, ASTM D638 Type IV 400 450
Specimen, 2-in. (50 mm) per min., %
Flexural Modulus, ASTM D790, psi 110 M (758) 100 M (689)
(MPa)
Vicat Softening Temperature, ASTM B255 (B124) B260 (B127)
D1525, °F (°C)
Mesh Size 35 35

Available in either 35-mesh powder or pellets.

Available in 35-mesh powder only.
1. ASTM Classification for “Type” on base resin.
2. Specimens molded in accordance with Procedure C of ASTM D1928.
3. Density of natural cross-linked product.
4. Data obtained using a gas-operated extrusion plastometer based on a design by Canadian Industries Ltd. with a die having an orifice
diameter of 0.019925” (0.049 mm) and a land length of 0.176” (4.48 mm).
Data taken from reference [66]. Reprinted with permission of Philips Chemical Co.

however, it does indicate that a well cross-linked (220°F). A few non-cross-linked rotational molding
sample will have excellent long-term stress at both resins might have similar dart impact, but will not
80° and 140°F. The CL-50 data on the 0.150-in. give the part drop performance of the cross-linkable
wall part indicated its hoop stress would be superior resins. Another demonstration of the toughness of the
to conventional HDPE pipe resins [67]. cross-linked part is its ability to withstand repeated
When properly cured, the cross-linked part has drop impacts of 30 feet without failure. Even parts
exceptional impact and overall toughness at both that have been creased on previous drops can with-
room and low temperatures. Good impact can be stand repeated 30-foot drops [67].
developed even at 220° and 240°F. The impact trait With plastics in general, it is difficult to corre-
has been demonstrated both by dart impact and part late nominal physical properties with part perfor-
drop tests. Tanks filled with liquid have dropped 30 mances. This is even more difficult when comparing
feet without failure at room and low temperatures nominal physical properties and part performance of
722 HANDBOOK OF THERMOSET PLASTICS

cross-linkable to non-cross-linkable polyethylene. increasing degrees of cross-linking, the last prop-


With the exception of environmental stress cracking erty to reach maximum values is low-temperature
resistance (ESCR), the nominal properties of the impact strength. Room temperature impact strength
cross-linkable resins give little indication of the per- for cross-linkable resins can be misleading because
formance that cross-linked parts exhibit. In the early values are high even for poorly cross-linked parts.
development stage of cross-linkable HDPE, special Critical physical properties, such as stress crack
tests [67] were developed to illustrate and give a bet- resistance, and percent elongation, develop their
ter understanding of what could be expected of cross- maximum values when low-temperature impact
linked parts. These tests illustrated such properties as strength of the molded part is equivalent to its
ESCR, long-term hoop stress, gasoline resistance, room temperature impact strength. According to the
impact resistance, and overall toughness. For one manufacturer, particular attention should be given
test, a 2-gallon jerry can (portable gasoline container) to failure patterns of impacted samples. Improperly
was 75% filled with gasoline, sealed, and placed in a cross-linked parts will crack or shatter when
130°F room. At 130°F, the fuel has a vapor pressure impacted. Such brittle type failures at 220°F have
of 7.25 psi. The cross-linked jerry can had a nominal consistently been an indication of improper curing.
wall thickness of 1/8-in. and weighed 800 grams. When properly cross-linked specimens do fail, they
This container underwent testing for 3 years and did exhibit ductile failures at temperatures of 220°F or
not fail. Similar tests run on the same container higher. Ductile failures appear as a puncture
molded from non-cross-linked resins available at that through the specimen and show that the tensile
time had failures which varied from less than 1 hour strength of the material was exceeded. Should
to a maximum of 4 days. Some currently available impact properties be poor, a progressive increase in
resins would be expected to give better performance, heating time and/or oven temperature is needed
but still would not equal the cross-linkable resins. until impact properties improve.
Drop impact tests of molded containers were The percent gel test is another method to indi-
used to evaluate part impact strength and overall cate cross-linking levels in molded CL-100 and
toughness. Containers varying in size from 2 to CL-50 parts [21c]. Refluxing ethylbenzene extracts
3,000 gallons have been drop tested. Containers up the non-cross-linked portion of a specimen. The
to 80 gallons and filled with water or antifreeze remaining gel insolubles are largely cross-linked
solutions have been dropped from 30 feet at tem- polyethylene yielding a quantitative measure for
peratures of 80°F. Larger containers containing degree of cure. Normally a high degree of cross-
only 50 gallons of water have been dropped 30 feet linking (optimum cross-linking) is indicated by gel
without failure. The capacity of the lift used for levels of 85 to 90%, but this can vary by
drop tests limited the volume of water used in the 1 / 2 10% depending on wall thickness and mold-
larger containers. A 1/2-in. wall, 3,000-gallon tank ing conditions. The effect of wall thickness on per-
filled with water was dropped 10 feet without fail- cent gel is a phenomenon contrary to expected
ure. This same tank filled with sand passed a simi- values. Wall thickness of less than 1/8 in. can pro-
lar drop impact test. For another drop, a 50-gallon duce 80 to 85% gel and be well cross-linked, while
tractor fuel tank was filled with water and dropped a part in a 1/4-in. wall may produce percent gels
30 feet. The part had a nominal wall thickness of consistently above 90%. When wall thickness
0.200 in. and weighed 30 pounds. The part and exceeds 1/4 in., percent gel should be tested in the
water had a total weight of 450 pounds. After the inner surface of the wall to ensure that the results
drop, no evidence of the deformation which are not unrealistically high and misleading as to
occurred on impact could be detected [67]. whether there was good cross-linking throughout
Low-temperature impact testing is one of three the wall. Other variations observed in this test are
quality control procedures for indicating the level caused by the amount of surface area of the gel
of cross-linking in production parts. The others are sample exposed to the refluxing ethylbenzene.
percent gel and the bent strip test. These two tests Another consideration in interpreting percent gel
are discussed later. Dart impact at 220°F is consid- data is its relationship to impact properties. A high
ered to be the most critical and comprehensive percent gel is usually achieved before full develop-
quality control test for parts molded from CL-100 ment of maximum low-temperature dart impact.
and CL-50 [21c]. As the compounds reach Because low-temperature dart impact is the last
17: CROSSLINKED THERMOPLASTICS 723

property to be improved in CL-100 and CL-50, it deformed state (having been cooled below its crys-
should be included with a gel test for the best qual- talline melting range) until the material is heated
ity control of production. above the crystalline melting range, whereupon it
A bend test is a quick test for a rough estimate will return precisely to its cross-linked geometry.
of the degree of cure [21c]. This method of deter- The action of this heat to relax the deformed (e.g.
mining whether the interior surface of rotational stretched) material is what makes it able to return
molded CL-100 parts is properly cured provides a to its original, undeformed, or unstretched state.
means of checking for degree of cross-linking This phenomenon can be illustrated by simply tak-
shortly after the part is molded. Due to the heat dif- ing a rubber band (cross-linked, of course), hanging
ferential between the interior and exterior surfaces a weight on it to stretch/deform it, and then heating
of a rotational molded part, the interior surface it until it returns to its original unstretched/unde-
cures later than the exterior surface. The difference formed geometry. A further explanation of the
in cure means the interior portion of the part cross- forces involved is as follows.
links last, so that stressing the interior portion pro- When a cross-linked polyethylene structure is
vides some indication of cross-linking. Conclusions heated above its crystalline melting point, the crys-
from this test should be verified periodically by talline structure is destroyed and a rubbery (still
low-temperature impact tests. cross-linked) amorphous material results [3b]. In
The producer [21c] concludes that the best produc- this state the material can be deformed by a force
®
tion quality control test for cross-linking in Marlex and will return to its original dimensions upon
CL-100 and CL-50 is low-temperature dart impact at removal of the force. If the material is deformed
220°F or lower. Percent gel is also a good method while hot, the molecules will distort elastically. If
but requires more time and expense than low- the force is removed, the molecules will return to
temperature impact testing. The bend test may also their original, lower free energy state. If, however,
be used but should be related to percent gel or dart the polymer (i.e. cross-linked molecules) is cooled
impact testing. During initial molding trials for a new in the elastically distorted state, the material will
production part, low-temperature impact levels and/ crystallize (below the crystalline region) and remain
or percent gel of proposed test areas should be corre- in the deformed/distorted state. The molecules
lated with acceptable performance of the overall part. remain in this distorted state because the total crys-
talline forces have greater strength than the forces
due to the relatively few cross-links, and the mole-
cules cannot relax to any extent until the crystallites
Heat-Shrinkable Tubing are re-melted. The deformed condition is the form
One of the main applications of cross-linked in which heat-shrinkable tubing is supplied to users
thermoplastics is in the manufacture of tubings and [68]. The user/render is referred to the following
cables (e.g. for drinking water and heating sys- summary of engineering considerations to take
tems). Heat shrinkable systems are of special when using heat-shrinkable tubing: [68]
importance with regards to the interesting post-
irradiation effects they display upon cross-linking.
One of the most interesting and novel features of 1. All heat-shrink tubing changes dimension
crystalline olefin polymers is the irradiation- longitudinally as well as diametrically when
induced elastic memory phenomenon [3b]. When shrunk. This may affect one’s selection of
these polymers are cross-linked into heat shrinkable material and/or shrink ratio offered. When
tubing products, for example, they behave as typi- shrinking over long cables, it might help to
cal thermoplastics below their crystalline melting shrink both ends in place before proceeding
range and as elastomers (i.e. cross-linked rubbers) to prevent/restrict longitudinal shrinkage.
above their crystalline melting range. This is possi- 2. The more relatively noncrystalline (amor-
ble only because of their cross-linked structure. It is phous) tubings tend to shrink over a wide
therefore possible to deform (e.g. stretch) such a temperature range, starting as low as 100°F.
product in its amorphous state (above the crystal- The more crystalline materials such as the
line melting range) and freeze/cool the product in polyolefins exhibit a narrow shrink tempera-
the deformed state. It will then remain in the ture range based on the crystalline melt
724 HANDBOOK OF THERMOSET PLASTICS

points; they shrink quickly when raised to adhere well to polyolefins and other materi-
the necessary temperature. als. These tubings offer excellent moisture
3. The wall thickness on heat-shrinkable tubing seals.
increases when the tubing is shrunk. The 7. When covering rollers, the best method is to
wall thickness at any stage of recovered use a hot air gun, and, starting at one end,
inside diameter (e.g. at the inside diameter rotate the roll while the tubing shrinks, chas-
needed to tightly shrink down to and encir- ing the “shrink shoulder” down the roll to
cle a particular diameter cable) can be cal- the other end.
culated as follows (Equation 17.1): 8. When shrinking any tubing, care must be
d1 5 I.D. with/at unrestricted/full recovery taken to heat it uniformly around the cir-
w1 5 wall thickness with/at unrestricted/full cumference. If a localized area becomes
recovery completely shrunk before the remainder, it
d2 5 I.D. at which the wall thickness is to be will leave a chill mark (which is nearly
determined impossible to remove) spoiling the looks of
w2 5 wall thickness at the recovered I.D. to the job. Raychem Corp. recommends the
be determined use of a proper reflector to help avoid this
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi problem.
ðd1 12w1 Þ2 2 d1 1 d22 2 d2 9. Hot air is the most commonly used method
w2 5 (17.1) of shrinking tubing, especially thin tubing
2
over non-metallic parts. Care must be exer-
For thin-wall tubing, this can be approxi- cised to see that the air blast does not move
mated by Equation 17.2: the tubing out of place.
10. Oven heating is a very good method of
d1
w2 5 w1 (17.2) batch processing. It usually provides a tight
d2 covering. In the case of electrical compo-
nents being covered, oven heating also tends
Neither formula takes longitudinal change to drive out moisture.
into account. Note that a shrinkable tubing’s
unrestricted/fully recovered inside diameter 11. A gas torch is often used when the tubing is
and wall thickness are always given by the large and has a heavy wall. It can be used
tubing manufacturer and in the applicable very successfully in production for small
MIL specification. parts in lieu of a hot air blast. A soft flame
should be used to avoid burn or soot depos-
4. Most plastics are notch sensitive, so care its on the parts.
should be exercised to have smooth cut ends
(because irregular edges may induce split- 12. Infrared heat is a favorite production method
ting during the shrinking process). because it can be easily controlled, is very
fast, and has no air blast to disturb the tub-
5. Flame retardant properties tends to make ing’s location on the part. Since it can be
polyolefins opaque. Therefore, clear polyo- too fast, care must be exercised to not dam-
®
lefins are not flame retardant. Kynar is a age the assembly. Color will have a marked
good substitute when clear non-flammable effect: the darker colors absorb more heat
tubing is needed. (The MIL spec slash than the light (i.e. clear tubing over black
®
sheet for Kynar shrink sleeving is MIL-1- cable is nearly impossible to shrink with
23053/8.) infrared heat).
6. Dual-wall tubings offer some interesting
design possibilities. The inner wall melts Although initial work in the field of elastic mem-
and flows around the encased part. The ory was carried out with polyethylene, other poly-
inner wall can be supplied adhesive lined so mers exhibit this phenomenon after aeration.
it not only encases but also adheres to the Table 17.10 provides a listing of various heat-
part. There are adhesives available that shrinkable tubing products and their typical
Table 17.10 Heat-Shrinkable Insulation and Encapsulation Tubings

Product Description
Flexible Polyolefins RNF-100 General purpose, flame retarded, polyolefin
Type 1
RNF-100 General purpose, flexible, transparent polyolefin, not flame retarded
Type 2
RT-876 Highly flame retarded, very flexible polyolefin with low shrink temperature
RT-102 Highly flexible, flame retarded, polyolefin with very low shrink temperature
RP-4800 Flame retarded, flexible polyolefin with high shrink ratio and high mechanical strength
Semirigid Polyolefins CRN High strength, flame retarded, semirigid polyolefin
Type 1 and Type 2
RT-3 Semirigid flame retarded opaque polyolefin
Duel Wall Polyolefins SCL Meltable inner wall, selectively cross-linked, semirigid polyolefin
TAT-125 Flexible dual wall adhesive tubing, flame retarded jacket thin wall
Type 1 and Type 2
ATUM Semi-flexible, high expansion, (3:1) heavy dual wall, adhesive tubing, flame retarded jacket

Fluoroplastics Kynar High temperature, flame resistant, clear, semirigid polyvinylidene fluoride
Convulex Convoluted, flexible irradiated polyvinylidene fluoride
RT-218 Semi-rigid, white, high temperature, low-outgassing fluoroplastic tubing
Vinyl PVC Flexible, flame resistant, polyvinylchloride, glossy

Elastomers NT (Neoprone) Heavy duty, flexible, abrasion resistant, flame retarded elastomer
SFR (Silicone) Highly flexible, flame retarded, heat or cold shock resistant

Viton Flexible, flame retarded, heat and chemical resistant fluoroelastomer
(Fluoroelastomer)
Product Typical Applications
Flexible Polyolefins RNF-100 Insulation of wire bundles; cable and wire identification (terminal and component insulation, protection and
Type 1 identification).
RNF-100 Transparent coverings for components such as resistors, capacitors, and cables where markings must be
Type 2 protected and remain legible.
RT-876 Coverings for cables and components where excellent flexibility and outstanding flame retardance are
needed.
RT-102 Flexible material for general purpose protection and insulation. Especially effective for low temperature
use.
RP-4800 Repair sleeving for harness jackets; high shrink ratio to fit over connector and recover tightly on cable.

(Continued )
Table 17.10 (Continued)

Product Description
Semi-rigid Polyolefins CRN Insulation and strain relief of soldered or crimped termination; protection of delicate components; cable
Type 1 and Type 2 and component identification.
RT-3 Particularly suited for automated application systems to insulate and strain relieve crimped or soldered
terminals. Furnished in cut pieces.
Dual Wall Polyolefins SCL Encapsulation of components, splices, terminations, requiring moisture resistance. Mechanical protection
and shrink ratios as high as 6 to 1.
TAT-125 Insulates and seals electrical splices, bi-metallic joints, and components from moisture and corrosion.
Type 1 and Type 2 Tough covering for delicate components.
ATUM Environmental protection for a wide variety of electrical components, including wire splices and harness
breakouts.
Fluoroplastics Kynar Transparent insulation, mechanical protection of wires, solder joints, terminals, connections, and
component coverings.
Convulex Mechanical protection of cable harnesses. Excellent flexibility and chemical resistance. Good high
temperature performance.
RT-218 Insulation of splices and terminations in aircraft and mass transit markets; cable and wire identification.
Vinyl PVC Insulation and coverings of cables, components, terminals, handles.
Elastomers NT (Neoprone) Insulation and abrasion protection of wire bundles and cable harnesses.
SFR (Silicone) Cable and harness protection requiring maximum flexibility and resistance to extreme temperatures;
ablative protection for cables in rocket blast.
Viton Insulation and protection of cables exposed to high temperature and/or solvents such as jet fuel.
(Fluoroelastomer)
Typical Values°
Product Operating Size/Range, Shrink Standard
Temp. Range Expanded Ratio Colors
Continuous, °C Diameter, (approx.)
(°F) inches (mm)
Flexible Polyolefins RNF-100 255 to 135 3=64 to 5 2:1 Black, white,
Type 1 (2 67 to 275) (1.2 to 127.0) red, yellow,
blue
RNF-100 255 to 135 3=64 to 5 2:1 Clear
Type 2 (2 67 to 275)
RT-876 255 to 135 3=64 to 4 2:1 Black, white,
(2 67 to 275) (1.2 to 127.0) red, yellow,
blue
RT-102 275 to 125 3=64 to 4 2:1 Black
(2 103 to 257) (1.2 to 101.6)
RP-4800 255 to 135 3/4 to 4 4:1 Black
(2 67 to 275) (19.2 to 101.6)
Semirigid Polyolefins CRN 255 to 135 3=64 to 1 2:1 Type 1: Black
Type 1 and Type 2 (2 67 to 275) (1.2 to 25.4) Type 2: Clear
RT-3 255 to 135 .220 to .460 2.3:1 Black
(2 67 to 275) (0.6 to 1.2)
Dual Wall Polyolefins SCL 255 to 110 1/5 to 1 3:1 Black
(2 67 to 230) (3.2 to 25.4)
TAT-125 Type 1 and 255 to 110 1/8 to 4 2:1 Type I: Black
Type 2 (2 67 to 230) (3.2 to 101.6) Type 2: Clear
ATUM 255 to 110 1/8 to 11/2 3:1 Black
(2 67 to 230) (3.2 to 38.1)
Fluoroplastics Kynar 255 to 175 3=64 to 1 2:1 Clear
(2 67 to 347) (1.2 to 25.4)
Convolex 255 to 150 9/32 to 1 5/8 n/a Black
(2 67 to 302) (7.1 to 41.3)
RT-218 255 to 200 3=64 to 4 2:1 White
(2 67 to 392) (1.2 to 101.6)
Vinyl PVC 235 to 105 3=64 to 2 2:1 Black
(2 31 to 221) (1.2 to 50.8)
Elastomers NT 270 to 121 /4 to 4
1
1.75:1 Black
(Neoprone) (2 94 to 250) (6.4 to 101.6)
SFR 75 to 180 /4 to 2
1
1.75:1 Black
(Silicone) (2 103 to 356) (6.4 to 50.8)
Viton 240 to 200 3=64 to 2 2:1 Black
(Flouroelastomer (2 40 to 392) (4.7 to 50.8)
Product Minimum Tensile Elongation, Dielectric Flame
Shrink Strength, % Strength, Resistance
Temperature, psi (kPa) Volts/mil
°C (°F) (Volts/mm)
Flexible Polyolefins RNF-100 121(250) 1800 400 800 Flame-
Type 1 (12,410) (32,000) retarded
RNF-100 121 (250) 1800 400 1000 Not flame-
Type 2 (12,410) (40,000) retarded

(Continued )
Table 17.10 (Continued)

Product Description
RT-876 100 2000 450 800 Highly
(212) (13,790) (32,000) flame-
retarded
RT-102 90 2500 400 800 Flame-
(194) (17,420) (32,000) retarded
RP-4800 121 1800 300 700 Highly
(250) (12,410) (28,000) flame-
retarded
Semi-Rigid Polyolefins CRN Type 1 and 135 (275) 2500 300 800 Flame-
Type 2 (17,240) (32,000) retarded
RT-3 135 2500 (17,240) 300 1000 (40,000) Flame-
(275) retarded
Dual Wall Polyolefins SCL 135 (275) 2500 (17,240) 400 1000 (40,000) Non flame-
retarded
TAT-125 121 (250) 1800 (12,410) 300 700 (28,000) Flame-
Type 1 and Type 2 retarded
jacket
ATUM 125 (257) 2500 (17,240) 400 350 (14,000) Flame-
retarded
jacket
Fluoro-plastics Kynar 175 (347) 6000 (41,370) 300 900 (36,000) Highly
flame-
retarded
  
Convolex n/a Highly
flame-
retarded
RT-218 175 6000 (41,370) 300 900 (36,000) Highly
(347) flame-
retarded
Vinyl PVC 175 (347) 2500 (17,240) 300 700 (28,000) Highly
flame-
retarded
Elastomers NT 175 (347) 1800 350 350 Flame-
(Neoprene) (12,410) (14,000) retarded
SFR (Silicone) 175 (347) 600 300 500 Flame-
(4,140) (20,000) retarded
Viton 175 (347) 1500 300 400 Flame-
(Flouroelastomer) (10,340) (16,000) retarded
Fluid Resistance‡ (room temp.) Specification Reference Guide
MIL-I-23053 MIL-R-46846
Aqueous
Hydrocarbon Solutions Acids,
Product Solvents Bases /Sheet Class Type Class
Flexible Polyolefins RNF-100 Type 1 Good Excellent /5 1
RNF-100 Type 2 Good Excellent /5 2
RT-876 Good Excellent V I
RT-102 Good Excellent
RP-4800 Good Excellent /5 1
Semirigid Polyolefins CRN Type 1 Type 2 Good Excellent /6 /6 12
Good Excellent
RT-3 Good Excellent
Dual Wall Polyolefins SCL Good Excellent /4 1
TAT-125 Type 1 and Good Excellent /4 2
Type 2
ATOM Good Excellent /4 3
Flouro-plastics Kynar Excellent Excellent /8
Convolex Excellent Excellent
RT-218 Excellent Excellent
Vinyl PVC Excellent Excellent /2 1
Elastomers NT (Neoprone) Good Good /1 1,2 I I
SFR (Silicone) Good Good /10
Viton (Flouro- Excellent Excellent /13 III I
elastomer)
Caps PD Good Excellent

Geometry of product precludes these test values

Trademark Pennwalt

Trademark DuPont.
°
Specific minimum requirements and test methods are given in applicable Thermofit specifications.

Fluid resistance is presented only in general terms and is based on room temperature immersion of commonly encountered solvents.
Data taken from reference [68]. Permission to reprint from Raychem Corp.
730 HANDBOOK OF THERMOSET PLASTICS

a rectangular, multi-cavity, heat-shrinkable device


is available for permanent splicing of flat conduc-
tor cable to flat conductor cable or round wires.

Cross-Linked Acrylates
Cross-linking of thermoplastics by irradiation or
with the aid of free radicals also extends to acry-
lates. Cross-linked acrylics (polymethylmethacry-
lates, PMMA) are used as coatings or in sheets in
the instrument, aircraft, and optical industries. Cell
cast acrylic sheets are an optically clear, transparent
material that is available in a variety of sheet sizes
and thicknesses starting at about 0.06 in.; final
thickness may depend on the supplier and the sheet
Figure 17.15 Soldertact contact prior to and after size. The material is used in both outdoor and
heating. (Data taken from reference 69; reprinted indoor applications and can be obtained in clear
with permission from Raychem Corp.) and transparent colors; general-purpose sheets are
also available in selected opaque colors.
Table 17.11 shows some of the property differences
between a thermoplastic acrylic (e.g. “Plexiglas” or
applications and properties after shrinking [68]. “Lucite”) and its cross-linked counterpart; the
The applications include the insulation of a variety cross-linked acrylate exhibits superior solvent and
of electrical and electronic components including craze resistance, higher impact strength, as well as
wires, lugs, terminals, and connectors. In practice resistance to deformation at 122°F. While solvent
the tubing is supplied in the form of an expanded cementing can be used to join the thermoplastic
diameter ranging from 3/64 in. to 5 in. The user part or sheet to itself, special purpose cements are
heats the tubing, which melts the crystallites in the needed for the cross-linked material.
molecular structure. This allows the cross-linked Cross-linkable coating systems are usually sup-
material to return to its original shape, thus demon- plied as a combination of resins, cross-linking
strating its elastic memory. Table 17.10 shows that agents (oligomers), catalysts, and various types of
the shrink ratio varies among the products approxi- additives dissolved or dispersed in organic or aque-
mately from 1.75:1 to 3:1. After cooling, the crys- ous solvents. Commercial processing of these for-
tallites reform and hold the tubing in the original/ mulations includes provisions for the safe and
recovered form. Upon subsequent reheating, no fur- complete removal of the volatile solvents, usually
ther change in shape will take place unless a with the application of heat. Spurred by govern-
mechanical force is applied. ment regulations to substantially reduce the amount
The heat needed to melt the crystallites of a of pollutants in the air, coating formulations that
heat-shrinkable cross-linked thermoplastic is, in contain no solvent are becoming available. In lieu
certain instances, also sufficient to melt solder. of the solvent, the formulation consists of an oligo-
This has led to the development of solder-sleeve mer containing unsaturation. The oligomer is used
devices consisting of fluxed solder and thermoplas- either by itself, or more often, in combination with
tic inserts at each end [69]. When placed over a a monomer that contains unsaturation either along
cable shield and heated, the solder melts and the side chain or in the backbone. The system is
flows, connecting the ground lead and shield cured by the application of high-energy radiation
(Figure 17.15). The outer sleeve shrinks and the with the monomer and all other organic compo-
thermoplastic inserts melt, encasing the termination nents copolymerizing with the oligomer through a
to provide a sealed termination. Other devices are free radical mechanism. The so-called high solids
available for a connector that takes removable con- systems make it easier to meet the nonpolluting
tacts. The contacts may terminate coaxial cables, requirements since there are no volatile, small
shielded wires, and twisted wire pairs. In addition, organic molecule constituents. The low viscosity
17: CROSSLINKED THERMOPLASTICS 731

Table 17.11 Nominal Properties of Cell Cast and Cross-Linked Acrylic Materials

Cross-Linked
Property ASTM Method Acrylic Sheet Acrylic
Specific Gravity D-792 1.19 1.19
Refraction Index D-542 1.49 1.49
Transmission & Haze Measurement D-1003
Parallel (%) 91 92
Total (%) 92 93
Haze (%) 1 1
Tensile Strength, Rupture, p.s.i. D-638 10,500 8,190
Flexural Strength, Rupture, p.s.i. D-790 16,000 13,900
Compressive Strength, Yield, p.s.i. D-695 8,000 18,200
Impact Strength-Izod Notched Ft. Lbs/in D-256 3.5 4.2
of Notch
Abrasion Resistance Falling Emery Test D-673 3 3
(x-methacrylate)
Deformation Under Load D-621-485
2000 p.s.i. 122°F, 24 Hrs. 0.2 0.4
4000 p.s.i. 122°F, 24 Hrs. 0.5 2.2
Rockwell Hardness D-785 M-104 M-94
Resistance to Stress MIL-P-6997
Critical Crazing Stress ARTC MOD.
Isopropyl Alcohol p.s.i. 1700 4000
Toluene p.s.i. 1300 4000
Solvent Resistance, 7 days D-543
Immersion at 77°F Dissolved Soft-Swollen
Acetone Dissolved Soft-Swollen
Ethyl Acetate Dissolved Soft-Swollen
Ethylene Dichloride
Coefficient of Linear Thermal D-696-44
25
Expansion 3 10 per °F 2.9 2.8
240°F to 220°F 3.1 3.0
220°F to 0°F 3.3 3.3
0°F to 20°F 3.6 3.8
20°F to 40°F 3.9 4.2
40°F to 60°F 4.2 5.3
60°F to 80°F 4.6 6.0
80°F to 100°F 3.6 4.0
Average 240°F to 100°F
(Continued )
732 HANDBOOK OF THERMOSET PLASTICS

Table 17.11 (Continued)

Cross-Linked
Property ASTM Method Acrylic Sheet Acrylic
Coefficient of Thermal Conductivity in (Cenco-Fitch) 1.3 1.8
BTU
ðHr:ÞðSq:Ft:Þð°F=In:Þ
Dielectric Constant D-150
60 Cycles 3.7 3.5
1 Kilocycle 3.3 3.2
1 Megacycle 2.5 2.7
Power Factor D-150
60 Cycles 0.050 0.002
1 Kilocycle 0.040 0.001
1 Megacycle 0.030 0.004
Loss Factor D-150
60 Cycles 0.19 0.006
1 Kilocycle 0.13 0.004
1 Megacycle 0.08 0.001
Arc Resistance D-495 No Tracking No Tracking
Surface Resistivity (ohm/square inch) D-257 2.00 3 10 18
1.02 3 1016
Flammability (Burning Rate) inches per D-635 Range 0.60 to 0.89
minute 1.1
Ignition Temperature D-1929-62T
Flash Temperature 620°F 620°F
Self Ignition Temperature 878°F 878°F
Water Absorption 24 hrs, 25°C D-570
Water Absorbed—% 0.20 0.035
Soluble Matter Lost—% 0.00 0.00
Odor — None None
Taste — None None
Ultra-Violet Transmittance 320 nm — None None

(twin consistency) of the formulation is obtained by formulations using as oligomers high-molecular-


selecting the oligomers and monomers from those weight polystyryl polymers which are capped with
candidates with the lowest viscosity. methacrylate groups; these are Chemlink® 4545B
An oligomer that contains groups that undergo a and Chemlink® 4500B with molecular weights of
free radical polymerization reaction on exposure 4,500 and 13,000, respectively [70]. 1,6-Hexanediol
to electron beam or ultraviolet radiation is an diacrylate reportedly yields a clear, compatible
important component of the formulation for a solution with Chemlink® 4545B, and with
cross-linkable acrylic. One system involves the use Chemlink® 4500B, up to concentrations of 60%
of oligomers capped at both ends with highly active and 50%, respectively; it is classified as a high-
acrylate groups, usually in combination with acry- solvency monomer. Trimethylolpropane triacrylate
late monomers. Table 17.12 shows examples of two dissolves Chemlink® 4500B to provide a clear
17: CROSSLINKED THERMOPLASTICS 733

Table 17.12 Typical Formulations Containing breaking strength and Young’s modulus decreased.
MACROMERt Monomers as Oligomers The polyacrylourethane films have a one-phase
morphology in which the hard urethane segments and
Weight
the soft polyester segments are homogeneously
Component Percent
mixed [73]. The films obtained from 1,000-molecu-
Chemlink® 4545B 50 lar-weight oligomers are hard and somewhat brittle
Tetrahydrofurfuryl acrylate 37 due to their one-phase morphology in which hard
Trimethylolpropane triacrylate 5 glassy segments play a dominate role. The films

obtained from 4,600- and 6,000-molecular weight oli-
Ganex V-516 Wetting agent 1
gomers are soft and tough, once again due to their

Irgacure 184 Photoinitiator 2 one-phase morphology in which soft rubbery seg-
® ments are more effective. The original crystalline
Chemlink 4500B 40
1,6-Hexanediol diacrylate 47
structure of pure 6,000-molecular-weight oligomer is
retained in the pre-crystallized γ-irradiated film, but
Tetrahydrofurfuryl acrylate 5 the electron beam irradiated films show partial melt-
Trimethylolpropane triacrylate 5 ing of the crystallites that was attributed to the heat
Ganex V-516 Wetting agent 1 of polymerization. The solid-state polymerized,
γ-irradiated films have lower elongation, a higher
Irgacure 184 Photoinitiator 2
modulus, and a higher breaking strength due to their

GAF Corp. much higher crystallinity.

Ciba-Geigy Corp.
Data taken from reference [70]. Reprinted with permission from
Sartomer Company.

Fluoride-Containing Polymers
Fluorinated polymers exhibit very interesting
compatible solution up to a concentration level of properties with respect to their chemical, thermal,
40%; it is categorized as a medium-solvency mono- and electric stabilities; their inertness to acids,
mer. The radiation-cured systems offer clear, hard bases, solvents, and oils; their low dielectric con-
films. Acrylamide-functional oligomers are under stant and refractive indexes; their high resistance to
evaluation [71]. They are derived from alkenyl aging and oxidation; and their low surface tension,
azlactones and amine-terminated oligomers in what which makes them very hydrophobic in nature.
is described as a one-step, facile reaction at room Furthermore, they are typically not flammable,
temperature. In comparison with the isocyanate and which is an especially interesting characteristic.
epoxide groups, the polymeric amines react with Since fluorinated polymers comprise a wide range
azlactones at controlled and predictable rates that of thermoplastic and elastomeric compounds rang-
are intermediate between the very reactive isocya- ing from semi-crystalline to totally amorphous,
nate and the slow reacting epoxide moieties. they find numerous applications in building and
Electron beam (EB)-cured coatings based on oli- construction, automotive, petrochemical, aeronau-
gomers capped with acrylate groups have been used tics and aerospace, photonics, and the electronics
for coating metal, wood, and paper where film exten- industries. The performance of fluoropolymers can
sibility is not generally required. In textile applica- be further enhanced by cross-linking [74].
tions, however, elongation at break of greater than For instance, polyvinylidene fluoride (PVDF) is a
200% is needed for practically all end uses [72]. semi-crystalline thermoplastic polymer with interest-
Elastomeric EB-cured coatings were obtained in ing thermal, chemical, and physical properties that
films cast from polyesterurethane oligomers (based can be modified by copolymerization with co-
on toluene diisocyanates) that were capped by acry- monomers or ter-monomers such as tetrafluoroethy-
late groups at both ends of the chain and monomer lene, hexafluoroprolene, trifluoroethylene, and many
diluent. Increasing the chain length between the two others [74]. However, PVDF is relatively
acrylate groups resulted in an increase in ultimate unstable towards attack by bases, which leads to
elongation from 20% to 210% and a decrease in degradation via fluoride elimination and results in
glass transition temperature from 50° to 225°C; oxidizable CQC double bonds. Whereas the
734 HANDBOOK OF THERMOSET PLASTICS

Table 17.13 Trade Names

Trade Name Product Company


®
Chemlink Macromert Series High-molecular-weight monomers Sartomer Corp.
® ®
Lucite , Plexiglas Acrylic sheet DuPont, Rohm and Haas
®
Marlex Cross-linkable high-density PE Philips Chemical Corp.
®
Minicel Cross-linked polyolefin foam Voltek Corp.
®
Photoglaze UV and EB curable coatings Lord Corp.
®
Thermofit Cross-linked, heat shrinkable Raychem Corp.
tubing
®
Solder Tacts Solder perform encased in a Raychem Corp.
cross-linked, heat shrinkable
insulation sleeve
®
Volara Closed-cell, radiation cross-linked Voltek Corp.
polyethylene foam
®
Penntube Cross-linked, heat shrinkable Penntube Plastics Co., Inc.
tubing
®
Markel Cross-linked, heat shrinkable Markel Corp.
tubing

homopolymer PVDF (due to its high degree of crys- [2] Morshedian J, Hoseinpour PM. Polyethylene
tallinity) is not suitable for stabilization via cross- cross-linking by two-step silane method: a
linking reactions, copolymerization with functional review. Iran Polym J 2009;18(2):10328.
fluoromonomers bearing reactive groups such as [3] Raff RAV, Doak KW, editors. Crystalline ole-
hydroxyl, carboxyl, or trialkoxysilyl functions, pro- fin polymers. New York: Inter-science
duces PVDF-based copolymers that are readily cross- Publishers, John Wiley & Sons; 1965 (a) Dole
linkable and display much improved stability. M, Mechanism and chemical effects in irradi-
A number of different cross-linking agents have ated polymers; (b) Lanza V.L, Irradiation-
been successfully used for cross-linking fluoropoly- properties changes.
mers. For example, besides radiation curing, cross- [4] Mehnert R, Bögl KW, Helle N, Schreiber GA.
linking using peroxide catalysts, diamines, dithiols Radiation chemistry. In: Ullmann’s encyclope-
in combination with diamines, aromatic polyhy- dia of industrial chemistry, 7th ed., vol. 31;
droxy compounds, and others, have been used. A 2011. p. 2149. doi:http://dx.doi.org/10.1002/
detailed review of the cross-linking chemistry and 14356007.
technology of this important class of materials is [5] Allonas X, Croutxé-Barghorn C, Bögl KW,
given by Taguet et al. [74]. Helle N, Schreiber GA. Radiation Chemistry.
Table 17.13 lists commercial information for the Ullmann’s Encyclopedia Industrial Chemistry
trade names of popular products. 2012;vol 31:131. doi:http://dx.doi.org/10.1002/
14356007.a22_471.pub2.
[6] Makuuchi K, Cheng S. Radiation processing of
References polymer materials and its industrial applica-
tions. Hoboken New Jersey: John Wiley &
[1] Beech S. PE-X, not just a material for plumb- Sons; 2012.
ing applications, TEPPFA/PPG Conference [7] Renfrew A, Morgan P, editors. Polyethylene-
Edinburgh March 2005. Source: ,http://www. the technology and uses of ethylene polymers.
pexassociation.net/uploads/files/PEX%20not% 2nd ed. London: Diffe & Sons Ltd.; 1960.
20just%20a%20material%20for%20plumbing% [8] Henglein A, Schnabel W. Einführung in die
20applications.pdf.; 2005 [accessed 10.07.13]. Strahlenchemie. Berlin: Akademie Verlag; 1969.
17: CROSSLINKED THERMOPLASTICS 735

[9] Dole M. Effect of radiation environments on melted UHMWPE. Biomaterials 2006;27:


plastics. In: Garner DP, Stahl GA, editors. 91725.
The effects of hostile environment on coatings [23] Ikada Y, Nakamura K, Ogata S, Makino K,
and plastics. Washington, D.C.: American Tajima K, Endoh N, et al. Characterization of
Chemical Society; 1983. ultrahigh molecular weight polyethylene irra-
[10] Swallow AJ. Radiation chemistry of organic diated with -rays and electron beams to high
compounds, vol. 2. New York: Pergamon doses. J Polym Sci Part A: Polym Chem
Press; 1960. 1999;37(2):15968.
[11] Stubenrauch K. PEX: cross-linked PE, pipe [24] Muratoglu OK, Bragdon CR, O’Connor DO,
training. Borealis A/S 2005. Jasty M, Harris WH, Gul R. Unified wear
[12] Becker HGO, editor. Einführung in die model for highly cross-linked ultra-high
Photochemie, Thieme Stuttgart, 21.03.2013, molecular weight polyethylene (UHMWPE).
1989. Biomaterials 1999;20:146370.
[13] Timpe HJ, Bauman H. Photopolymere [25] Dadbin S, Frounchi M, Saeid MH, Gangi F.
Prinzipien und Anwendugen. Leipzig: VEB Molecular structure and physical properties of
Deutscher Verlag für die Grundstoffindustrie; e-beam cross-linked low-density polyethyle
1988. for wire and cable insulation applications.
[14] Woods RJ, Pikaev AK. Applied radiation J Appl Polym Sci 2002;86:195969.
chemistry: radiation processing. New York: [26] Oda E. Wire and cable. Radiat Phys Chem
John Wiley & Sons, Inc.; 1994. p. 351, 355 1981;18:24152.
and references therein. [27] An Y, Xing H, Wang Y, Tang T. Characterization
[15] Dawes K, Glover LC. In: James EM, editor. of high melt strength propylene/1-butene
Physical properties of polymers handbook. copolymer synthesized by in situ heat induc-
Woodbury, NY: American Institute of Physics tion melt reaction. J Appl Polym Sci
Press; 1996. p. 563, 574. 2012;125:272431.
[16] Makaucchi K, Asano M, Abe T. Nippon [28] Borsig E, Fiedlerova A, Lazar M. J Macroml
Kagaku Kaishi, 686; 1976. Sci Chem 1981;A16(2):513.
[17] Parks LA. Radiation Cross-linking of [29] Sheve BJ, Mayfield JW, DeNicola AJ.
Polymers. Source: ,http://www.sterigenics. Polypropylene with free-end long chain
com/cross-linking/cross-linking.htm.; 2011 branching, process for making it and use
[accessed 10.07.13]. thereof, European Patent EP 0190889, 1986.
[18] Koosha M, Ebrahimi N, Jahani Y, Sajjadi [30] Auhl D, Stange J, Münstedt H, Krause B,
SAS. Radiat Chem Phys 2011;80:8106. Voigt D, Lederer A, et al. Long-chain
[19] Sonnier R, Massardier V, Clerc L, Lopez- branched polypropylenes by electron beam
Cuesta JM, Bergeret A. Reactive compatibili- irradiation and their rheological properties.
zation of polymer blends by g-irradiation: Macromolecules 2004;37(25):946572.
Influence of the order of processing steps. J [31] Jones RA, Salmon mGA Ward IM.
Appl Polym Sci 2010;115:17107. Radiation-induced cross-linking of polyethyl-
[20] Keller A, Ungar G. Radiation effects and crys- ene in the presence of acetylene  a gel frac-
tallinity in polyethylene. Radiat Phys Chem tion, UV-visble and ESR spectroscopy study.
1983;22:15581. J Polym Sci Part B Polym Phys 1993;31:
[21] Phillips Chemical Co., Plastics Technical 80719.
Center (a) Technical Service Memorandum [32] Yoshiga A, Otaguro H, Parra DF, Lima
#243, Engineering Properties of Marlex® LFCP, Lugao AB. Controlled degradation and
Polyolefins; (b) Technical Information Bulletin cross-linking of polypropylene induced by
#17, Rotational Molding. r Technical Service gamma radiation and acetylene. Polym Bull
Memorandum #291, Quality Control Tests for 2009;63:397409.
Cross-linking Marlex® CL-100 and CL-50. [33] Oliani WL, Parra DF, Fermino DM, Riella
[22] Oral E, Malhi AS, Muratoglu OK. HG, Lima LFCP, Lugao AB. Study of gel for-
Mechanisms of decrease in fatigue crack mation by ionizing radiation in polypropylene.
propagation resistance in irradiated and Radiat Phys Chem 2013;84:205.
736 HANDBOOK OF THERMOSET PLASTICS

[34] Oliani WL, Parr DF, Riella HG, Lima LFCP, chemical cross-linking of isotactic polypropyl-
Lugao AB. Polypropylene nanogel: “Myth or ene. J Appl Polym Sci 2010;116:394403.
reality”. Radiat Phys Chem 2012;81:14604. [51] An Y, Zhang Z, Wang Y, Qiu J, Tang T.
[35] Oliani WL, Lima LFCP, Parra DF, Dias DB, Structure and Properties of high melt strength
Lugao AB. Study of the morphology, thermal polypropylene prepared by combined method
and mechanical properties of irradiated isotac- of blending and cross-linking. J Appl Polym
tic polypropylene films. Radiat Phys Chem Sci 2010;116:173946.
2010;79:3258. [52] Micropol Limited, ISOPLAS crosslinkable
[36] Manas D, Hribova M, Manas M, Ovsik M, polyethylene. ,http://www.isoplas.co.uk/
Stanek M, Samek D. The effect of beta irradi- download/Isoplas-Crosslinkable-Polyethylene.
ation on morphology and micro hardness of pdf. [accessed October 30.10.13].
polypropylene thin layers. Thin Solid Films [53] Scott HG. Cross-linking of a polyolefin with a
2013;530:4952. silane, U.S. Patent 3,646,155, 1972.
[37] Bahners T, Häßler R, Gao SL, Mäder E, [54] Swarbrick P, Green WJ, Maillefer C, GB-
Wego A, Schollmeyer E. Photochemical sur- Patent 1526 398, 1978.
afce modification of PP for abrasion resis- [55] Panzer LM, Bisang W. Silane crosslinmking
tance. Appl Surf Sci 2009;255:913945. of polyethylene for improving product quality
[38] Ulanski P, Rosiak JM. Encyclopedia of and simplfying the production process. Int
nanoscience and nanotechnology. In: Nalwa Polym Sci Technol 1998;25:516.
HS, editor. Polymeric nano/microgels, 8. [56] Novak I, Popelka A, Krupa I, Chodak I,
California-USA: ASC; 2004. p. 84571. Janigova I, Nedelcev T, et al. High-density
[39] Rosiak JM, Ulanksi P, Kadlubowski S. polyethylene functionalized by cold plasma
Emerging applications of radiation in nanotech- and silanes. Vacuum 2012;86:208994.
nology. Conventional and radiation synthesis of [57] Zimmer S, Schöbel A, Halbach T, Stohrer J,
polymeric nano and microgels and their possi- Rieger B. New curable propylene copolymers
ble applications. The proceeding of a technical containing tert-butoxysilane side groups.
meeting IAEA-TECDOC-1438, 2225 March, Macromol Rapid Commun 2013;34:
Bologna, Italy, 2005. p. 99120. 2216.
[40] Horng P, Klemchuk P. Plast Eng 1984;40(4):35. [58] Sharif-Pakdaman A, Morshedian J, Jahani Y.
[41] Carlsson DJ, Torborg Jense JP, Wiles DM. Influence of the silane grafting of polyethyl-
Polym Preprints 1984;25(1):85. ene on the morphology, barrier, thermal, and
[42] Williams JL. Polym Preprints 1984;25(1):87. rheological properties of high-density polyeth-
[43] Jin J, Zhang C, Jiang W, Luan S, Yang H, ylene/organoclay nanocomposites. J Appl
Yin J, et al. Colloids Surf A: Physicochem Polym Sci 2012;125:E30513.
Eng Asp 2012;407:1419. [59] Sharif-Pakdaman A, Jahani Y, Morshedian J.
[44] Bowmer TN, Vroom WI, Hellman MY. J Effect of organoclay and silane grafting of
Appl Polym Sci 1983;28:2553. (See refer- polyethylene on morphology, barrierity, and
ences for previous papers by these authors and rheological properties of HDPE/PA6 blends. J
their associates.) Appl Polym Sci 2013;127:121120.
[45] Narkis M. Mod Plast 1980;57:68. [60] Liu H, Chuai C, Iqbal M, Wang H, Kalsoom
[46] Kolezynski JR. Mod Plast Encyclopedia BB, Khattak M, et al. Improving foam ability
1969;46(10A):316. of polypropylene by cross-linking. J Appl
[47] Yang YT, Phillips PJ. Appl Polym Sci Polym Sci 2011;122:97380.
1983;28:1137. [61] Rodriguez-Pérez MA. Cross-linked polyolefin
[48] Kunert KA. J Macromol Sci Chem 1982;A17 foams: Production, structure, properties, and
(9):1469. applications. Adv Polym Sci 2005;184:
[49] Lem KW, Han CD. J Appl Polym Sci 97126.
1982;27:1367. [62] Cardoso ECL, Scagliusi SR, Parra DF, Lugao
[50] Bouhelal S, Cagio ME, Bartolotta A, Di AB. Gamma-irradiated cross-linked LDPE
Marco G, Garrido L, Benachour D, et al. On foams: Characteristics and properties. Radiat
polyethylene chain generation through Phys Chem 2013;84:1705.
17: CROSSLINKED THERMOPLASTICS 737

®
[63] Chaudhary BI, Sengupta SS, Cogen JM, Curto [68] Raychem Corp. Technical Bulletin, Thermofit
M. Silane grafting and moisture cross-linking of Heat-shrinkable Tubing. Selection Guide.
polypropylene. Polym Eng Sci 2011;51:23746. [69] Raychem Corp. Technical Bulletin, Solder
[64] Voltek Inc., (a) Technical Bulletin, Closed Tacts Contacts.
Cell Foam Properties; (b) Bulletin TB2 August [70] Sartomer Company Technical Bulletin,
1983, Laminating Guide; r Bulletin TB3 Chemlink® 4545B/4500B High Energy
January 1984, Compression Molding Guide. Curable Macromolecular Monomers.
[65] Saiz-Arroyo C, Rodriguez-Pérez MA, Tirado J, [71] Heilmann SM, Rasmussen JK, Krepski LR,
López-Gil A, de Saja JA. Structure-property Smith II HK. Polym Preprints 1984;2:35.
relationships of medium-density polypropylene [72] Oraby W, Walsh JK. J Appl Polym Sci
foams. Polym. Int. 2013; http://dx.doi.org/ 1979;23:3227.
10.1002/pi.4424 [published online]. [73] Wadhwa LH, Walsh JK. J Appl Polym Sci
[66] Phillips Chemical Co., Bulletin 842-84 TF, 1982;27:591.
Best Resins for Rotational Molding. [74] Taguet A, Ameduri B, Boutevin B. Cross-
[67] Carrow GE. Cross-linkable polyethylene, the linking of vinyliden fluoride containing fluor-
proven plastic for handling corrosive chemi- opolymers (2005). Adv Polym Sci
cals. Corrosion/82. 2005;184:127212.