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Report 143

Adhesion and
Bonding to
Polyolefins

D.M. Brewis and I. Mathieson

Volume 12, Number 11, 2002

 RAPRA REVIEW REPORTS
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Item 1
Source of
Macromolecules
original article
33, No.6, 21st March 2000, p.2171-83
Title EFFECT OF THERMAL HISTORY ON THE RHEOLOGICAL
BEHAVIOR OF THERMOPLASTIC POLYURETHANES
Authors and
Pil Joong Yoon; Chang Dae Han affiliation
Akron,University
The effect of thermal history on the rheological behaviour of ester- and
ether-based commercial thermoplastic PUs (Estane 5701, 5707 and 5714
from B.F.Goodrich) was investigated. It was found that the injection
moulding temp. used for specimen preparation had a marked effect on the
variations of dynamic storage and loss moduli of specimens with time
observed during isothermal annealing. Analysis of FTIR spectra indicated
that variations in hydrogen bonding with time during isothermal annealing Abstract
very much resembled variations of dynamic storage modulus with time
during isothermal annealing. Isochronal dynamic temp. sweep experiments
indicated that the thermoplastic PUs exhibited a hysteresis effect in the
heating and cooling processes. It was concluded that the microphase
separation transition or order-disorder transition in thermoplastic PUs could
not be determined from the isochronal dynamic temp. sweep experiment.
The plots of log dynamic storage modulus versus log loss modulus varied
with temp. over the entire range of temps. (110-190C) investigated. 57 refs. Companies or
GOODRICH B.F. organisations
Location USA mentioned
Accession no.771897

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 Adhesion and Bonding to
Polyolefins

D.M. Brewis and I. Mathieson

(Institute of Surface Science & Technology, Loughborough University)

ISBN 1-85957-323-1
 Adhesion and Bonding to Polyolefins

Contents
Abstract ............................................................................................................................................................ 3

1. Introduction .............................................................................................................................................. 3

2. Principles .................................................................................................................................................. 4
2.1 Theories of Adhesion ...................................................................................................................... 4
2.2 Wettability ....................................................................................................................................... 4
2.3 Diffusion ......................................................................................................................................... 5

3. Methods Used to Study Surfaces ............................................................................................................ 6

3.1 Introduction ..................................................................................................................................... 6
3.2 X-Ray Photoelectron Spectroscopy XPS ....................................................................................... 6
3.3 Static Secondary Ion Mass Spectrometry ....................................................................................... 9
3.4 Reflection IR ................................................................................................................................... 9

4. Pretreatments and Primers for Polyolefin Plastics ............................................................................ 10

4.1 Introduction ................................................................................................................................... 10
4.2 Flame Treatment ............................................................................................................................11
4.3 Corona Treatment ......................................................................................................................... 13
4.4 Low Pressure Plasma Treatment ................................................................................................... 13
4.5 Chromic Acid Treatment ............................................................................................................... 14

5. Pretreatments and Primers for Polyolefin Elastomers ...................................................................... 15

5.1 Introduction ................................................................................................................................... 15
5.2 Ethylene-Propylene Copolymers .................................................................................................. 15
5.3 Butyl Rubber ................................................................................................................................. 16
5.4 Unsaturated Hydrocarbon Elastomers .......................................................................................... 16
5.4.1 Natural Rubber ................................................................................................................. 16
5.4.2 Styrene-Butadiene Copolymers ........................................................................................ 18
6. Discussion ............................................................................................................................................... 19

7. Conclusions ............................................................................................................................................. 23

References ...................................................................................................................................................... 23

Abbreviations and Acronyms ....................................................................................................................... 25

Abstracts from the Polymer Library Database .......................................................................................... 27

Subject Index ............................................................................................................................................... 121

1
 Adhesion and Bonding to Polyolefins

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Rapra Technology Limited or the editor. The series is published on the basis that no responsibility or
liability of any nature shall attach to Rapra Technology Limited arising out of or in connection with any
utilisation in any form of any material contained therein.

2
 Adhesion and Bonding to Polyolefins

Abstract 1 Introduction

Polyolefins have many applications. Polyethylene is Polyolefins are among the most widely used of all
the most widely used plastic and in tonnage terms polymers finding many applications in packaging,
olefinic elastomers such as styrene-butadiene building, transport and other industries. It is often
copolymers, dominate applications such as tyres. necessary to join polyolefins to other substrates,
including metals and other polymers in order to
It is often necessary to join a polyolefinic substrate to combine the properties of the two materials. An
another substrate. A pretreatment will normally be example is a laminate of polyethylene and aluminium
required unless a diffusion mechanism operates. foil used in the food and drinks industries; the
Diffusion mechanisms operate during welding together polyethylene provides heat-sealing properties while the
of two pieces of polyolefin, bonding a polyethylene aluminium provides excellent barrier properties. While
with a hot melt adhesive based on ethylene-vinyl some applications require joining polyolefins to other
acetate copolymers, and using an ethylene-acrylic acid substrates, other applications require the polyolefins
copolymer as a tie layer when extruding two to be painted, printed upon or metallised. The
incompatible polymers. polyolefins that must be bonded may be in the form of
plastics, elastomers (EPDM, styrene-butadiene-styrene
A wide range of pretreatments for polymers exists. (SBS), etc.) and fibres (especially polypropylene).
However, there are usually preferred methods for Important examples where it is necessary to paint
plastics and elastomers. The most common methods polyolefins include car bumpers and other automotive
for pretreating plastics are corona discharge, flame, and components. Good print adhesion to film, bottles and
low pressure plasma treatments whereas the most jars is clearly essential. Likewise, good adhesion of
common method for olefinic elastomers is the use of metal, deposited via solution or vacuum, to polyolefins
an organic chlorine donor. is often required.

It is now possible to determine the surface chemical Adhesion failures occurring in service can be very
changes caused by pretreatments. X-ray photoelectron expensive to rectify. For example poor paint adhesion
spectroscopy is especially useful in this respect to polypropylene bumpers could involve recall of many
providing quantitative information on the first few thousands of cars. Even when identified at the
nanometres on the surface of a material. Much research production stage, poor adhesion can be very expensive
has been carried out on pretreatments for plastics where to rectify. It is not uncommon for several days’
changes in surface chemistry have been determined and production to be lost while an adhesion problem is
in some cases related to adhesion performance. being solved.
However, few such studies have been carried out with
elastomers partly because of the complexity of their When it is necessary to join two pieces of the same
formulations. Several compounding ingredients polyolefin, heat sealing can be used; several welding
migrate to the surfaces of elastomers making it difficult options exist, including electrofusion, ultrasonic, hot
to differentiate between changes to these additives and gas, hot plate and infrared techniques (a.1). If it is
changes to the underlying polymer chains. necessary to join a polyolefin to another substrate,
options include coextrusion, adhesive bonding and
There has been considerable controversy on whether mechanical fastening. To achieve satisfactory adhesion
pretreatments for polyolefins are effective by removing when bonding with an adhesive, printing, painting or
potential weak boundary layers or by introducing metallising it is usually necessary to pretreat the
functionality in the form of carbonyl and other groups. polyolefin. Pretreatments of polyolefins have been the
The present authors believe that if a diffusion mechanism subject of a great amount of research and development
is not operating then such groups are necessary to (377) and these treatments form a major part of this
improve wetting and increase interaction across review. Exceptions where a pretreatment is not required
interfaces. That is not to say that ‘small molecules’ do are noted in Section 2.3.
not sometimes affect adhesion. If these small molecules
are not absorbed, for example by the adhesive, then a This review explores the joining of polyolefins to a
weak boundary layer will exist with resulting poor variety of substrates especially by means of adhesive
adhesion. Also, additives on polyolefins will affect bonding and the coating of polyolefins with printing
pretreatments such as the corona discharge method as inks, paints and metals. The use of mechanical fasteners
there will be a tendency to chemically modify the is not covered and the use of thermal methods is only
additive rather than the underlying polymer chains. briefly discussed (see Section 2.3). The various types

3
 Adhesion and Bonding to Polyolefins

of polyethylene (PE), polypropylene (PP) and ethylene- The weak boundary theory received considerable
propylene (EP) polymers, together with elastomers support from other research work and some of this is
based on dienes, will be examined. outlined below. It is certainly easy to envisage various
possible sources of weak boundary layers on polyolefin
Our understanding of adhesion to polyolefins has been surfaces, namely:
greatly helped by the development of techniques which
provide information on surface chemistry. These • impurities arising from the polymerisation process;
include X-ray photoelectron spectroscopy (XPS), static • the low molecular weight tail of a polymer;
secondary ion mass spectrometry (SSIMS) and
reflection infrared (IR) analysis. The principles of these • additives, e.g., antioxidants and slip agents;
techniques are outlined in Section 3 and examples of
• external processing aids, e.g., mould release agents;
their use are given in Sections 4 and 5 which cover
plastics and elastomers respectively. • contamination after processing.

Schonhorn and co-workers have put forward evidence

in favour of the weak boundary concept using
polyethylene as the substrate. In 1966, Hansen and
2 Principles Schonhorn (a.3) reported work in which they
bombarded polyethylene and certain other polymers
2.1 Theories of Adhesion with activated inert gases and found that the adhesion
of an epoxide adhesive to the polymers greatly
It is first necessary to consider why materials adhere increased, although the critical surface tensions of the
to each other. There are four main theories of polymers were unchanged. Also, using reflection
adhesion, namely adsorption, electrostatic, diffusion infrared analysis they were unable to detect any
and mechanical keying. According to the adsorption chemical changes in the surface. They therefore
theory, macromolecules of the mobile phase proposed that regions of low molecular weight on the
(adhesive, printing ink, etc.) are adsorbed onto the surface had been crosslinked to the long polymer chains
substrate and held there by forces ranging from weak thereby eliminating weak boundary layers. In fact,
dispersion forces to chemical bonds; an interface Hansen and Schonhorn suggested that surface
exists. In the electrostatic theory there is a transfer of treatments in general act primarily by eliminating weak
charge between the mobile phase and the substrate boundary layers.
such that they are held together by electrostatic forces.
The third theory requires the diffusion of In some later work Schonhorn and Ryan (401) exposed
macromolecules of the mobile phase into the polyethylene to ultraviolet (UV) radiation. They found
substrate, thereby eliminating an interface. With the joint strengths with an epoxide adhesive much
mechanical keying theory, the mobile phase flows into increased, but there was no evidence of oxidation using
the irregularities (pits and troughs) of the substrate reflection IR and contact angle measurements. They
surface and after hardening, a keying action occurs. concluded that crosslinking at the surface occurred
thereby eliminating a potential weak boundary layer.
These theories will each be important with particular The work of Schonhorn and co-workers will be
systems, but the adsorption theory is likely to be the discussed further in Section 6.
most generally applicable. Aspects of joining
polyolefins by a diffusion mechanism are briefly Before any adhesion mechanism can operate, good
discussed in Section 2.3. contact between the two materials is necessary. The
question of wettability is therefore of crucial
importance and this topic will now be briefly
To these four theories should be added a theory of non-
considered.
adhesion, due to the existence of regions of low
cohesive strength in the interfacial region. Bikerman
(a.2) first suggested that adhesion problems associated
with polyethylene are due to weak boundary layers. 2.2 Wettability
He suggested that molecules of low molecular weight,
that are normally present in commercial polyethylenes A satisfactory level of contact between the mobile
separate from the melt and create a region of low phase, for example an adhesive, and the substrate is
strength on the surface. essential for good adhesion.

4
 Adhesion and Bonding to Polyolefins

A direct measure of wettability may be carried out via γs is the SFE of the solid
a contact angle measurement (θ).
γsp is the polar component of the solid SFE
This is the tangent a drop of liquid makes when placed
on a substrate surface. Viz: γsd is the dispersion component of the
solid SFE

This is the equation of a straight line where

(1+Cos θ) /2γl (γld)1/2 is plotted against (γlp/γld)1/2. Hence
the square of the gradient is γs p , i.e., the polar
component of the surface free energy of the solid and
the square of the γ intercept is γsd, i.e., the dispersion
component of the surface free energy of the solid.

Although the greatest contribution to the surface free

energy of a polymer comes from the dispersion
When there is a strong attraction between the liquid component, the polarity of the surface is more easily
and the solid, θ will be small (or zero for perfect altered with a pretreatment. For example, an untreated
wetting). Conversely when the attraction between low density polyethylene (LDPE) sample with a zero
liquid and solid is poor a large contact angle is obtained, polar component and a 31.9 mJ m -2 dispersion
possibly greater than 90° as illustrated below. component, shows an increase in the polar component
to 8.0 mJ m-2 after a flame treatment. The dispersion
component stayed fairly constant at 30.7 mJ m-2 (a.4).

Typically a ten-fold increase in adhesion may be

observed from such a treatment. Adhesion
improvement comes from better wetting and stronger
interfacial attraction due to the new functionality.
Hence surface free energy estimation can be a useful
tool to assess adhesion performance.

Such is the case with polyolefins; the water contact angle

on high density polyethylene (HDPE) is around 104°. 2.3 Diffusion
The poor wetting is due to relatively low attractive forces
between water, which is a very polar molecule, and PE If two pieces of the same polymer are heated to a
that has no polarity within its molecule. sufficiently high temperature and brought together
under pressure, then chain segments from the two
Contact angle values from various pure liquids may be pieces will interpenetrate and the interface will be
used to estimate the surface free energy of a substrate eliminated. This process is often termed autohesion.
via various thermodynamic theories; a review of which There is no dispute that this process will occur when
is given elsewhere (378). One example is the Owens, two pieces of the same polymer are involved as in heat
Wendt and Kaelble approach which enables the polar sealing, although ethylene-propylene copolymers are
and dispersion components of the surface free energy known to exhibit relatively poor autohesion.
(SFE) to be evaluated from a knowledge of the contact
angle of various liquids of known polar and dispersion Whether diffusion between two different polymers
values. The equation employed is as follows: occurs will depend on a number of factors including
temperature, time available and chemical compatibility.
(1+ cos θ) γl/2(γld)1/2 = (γsp)1/2 (γlp/γld)1/2 + (γsd)1/2 It is often desirable to combine the properties of two
or more polymers and this can be achieved by
where: γl is the SFE of the liquid coextrusion. If two polymers A and B are insufficiently
compatible to achieve good adhesion, then a tie-layer,
γlp is the polar component of the liquid SFE
often a copolymer, may be used. This is a polymer that
γld is the dispersion component of the is compatible with both A and B. A tie-layer may also
liquid SFE be used to join a polyolefin to a metal; for example,

5
 Adhesion and Bonding to Polyolefins

ethylene-carboxylic acid copolymers have been used 3.2 X-Ray Photoelectron Spectroscopy XPS
to bond LDPE to aluminium (391).
In this technique a solid, e.g., a plastic film, is
There is evidence that chlorinated polypropylene (CPP) bombarded with X-rays of known energy under high
primers diffuse into polypropylene; for example vacuum.
Tomasetti and co-workers (91) used radioactive
labelling to demonstrate the diffusion of CPP into PP Photoelectrons from different core levels are ejected.
and PP/EP blends. Other primers used in conjunction
Photoelectrons from the first few atomic layers have a
with cyanoacrylates also diffuse into polyolefins (see
characteristic kinetic energy depending on the elements
for example (384)).
present in the surface regions. The binding energy of a
photoelectron from a particular core level is given by
Hot melt adhesives may be used to bond untreated
the following equation.
polyolefins apparently by a diffusion mechanism. The
most common type of hot melt is based on ethylene-
vinyl acetate copolymers and these may be used to bond EK = hν – EB – φ
polyethylenes (for an example see (325)). Such hot
melts have been commercially available for nearly forty where: EK is the kinetic energy of the photoelectron
years. More recently a number of reaction-setting
EB is the binding energy of the photoelectron
adhesives which can bond untreated polyolefins have
been developed. For example, Fields and co-workers hν is the X-ray energy
(375) using an acrylic resin with an anaerobic curing
system achieved good adhesion to untreated LDPE. φ is the constant for a given instrument

The joining of PE, PP and other plastics in pipelines A schematic diagram of the equipment used is shown
has been described (127); both fusion and in Figure 1.
electrofusion welding are included. Details of fusion
methods to join polyolefins and other plastics are By scanning different energies, a spectrum is obtained;
given in reference (a.1). an example is given in Figure 2.

The elements present in the first few atomic layers can

be readily identified from their characteristic binding
3 Methods Used to Study Surfaces energies. The percentage concentration of each element
can be calculated from the following equation.
3.1 Introduction
Ix
A knowledge of the surface chemistry of substrates is Sx
important in our understanding of adhesion. There are Cx = × 100
a number of techniques which provide information on ∑ ⎛ In ⎞
⎝ Sn ⎠
the surface chemistry of plastics of which the following
are the most important:
where: Cx = percentage concentration of element X
X-ray photoelectron spectroscopy XPS Ix = quantity of photoelectrons from element X
(or electron spectroscopy for
chemical analysis) (ESCA) Sx = sensitivity factor for element X

Σ(In/Sn) = summation of I/S for all elements

Static secondary ion mass spectrometry SSIMS

Reflection infrared analysis reflection IR It is thus a routine matter to obtain a quantitative

elemental analysis of the surface regions of a solid.
As far as polyolefins are concerned these techniques are
especially useful for determining the chemical changes For a given element, there are small differences in
that have occurred after a pretreatment, revealing the binding energies depending on the chemical
true locus of failure of a structure and identifying small environment of the element. Thus for carbon the
molecules, including contaminants, on surfaces. The bonding energy for C1s varies depending on the
three techniques listed above are now outlined. neighbouring atoms (see Table 1).

6
 Adhesion and Bonding to Polyolefins

Figure 1
Schematic diagram of an XPS instrument

Figure 2
Broad scan XPS spectrum of treated polypropylene

Table 1 Binding energies for the C1s peak in It is therefore possible, by obtaining a high resolution
spectrum, to determine which chemical groups are
various chemical environments
present in the surface regions of a polymer. In
Structure Binding energy eV Figure 3, the C1s peak for corona treated
C-C, C-H 285.0
polypropylene is shown (a.5).

C-O 286.5 The concentrations of the various chemical groups

present are given in Table 2.
C-O-O 287.1
C=O 288.1 The concentration of different chemical groups in the
surface of a polymer may also be determined using
COOH 288.9
derivitisation reactions. These are reactions specific

7
 Adhesion and Bonding to Polyolefins

Figure 3
High resolution C1s spectrum of corona-treated PP showing separation of the ‘shoulder’ into component contributions

Table 2 Assignment of peaks for Table 3 Concentration of different chemical

corona-treated polypropylene (a.5) groups after CD treatment of polyethylene (393)
Position (eV) Area (%) Assignment Concentration*
285.0 91.7 C-C, C-H Group Initial Water-washed
286.5 1.2 C-O Peroxide 1.2 0.9
287.1 2.3 C-O-O Hydroxyl 1.7 1.1
288.1 2.3 C=O Carbonyl 1.8 0.9
288.9 1.2 COOH Epoxide 2.3 1.1
289.5 1.3 O=C-O-C=O ? Carboxylic acid 1.6 0.8
-NO3 0.8 0.4
* Moles of functional species per initial unreacted
to a particular group and which introduce a new carbon atom (x102)
element to the surface. Such reactions are illustrated Reprinted from L.J. Gerenser, J.F. Elman, M.G. Mason and J.M.
in Figure 4. Some results for corona treated Pochan, E.s.c.a. studies of corona-discharge-treated polyethylene
polyethylene (393) are given in Table 3. surfaces by use of gas-phase derivatization, Polymer, 1985, 26,
1162, with permission from Elsevier Science.

In an earlier study (395), Briggs and Kendall used

derivitisation reactions to study the discharge
treatment of LDPE. They converted keto groups in autoadhesion between two pieces of the treated PE
corona treated polyethylene to the corresponding was very low, thus confirming the mechanism for
pentafluorophenylhydrazone. They found that the autoadhesion in terms of keto-enol interactions.

8
 Adhesion and Bonding to Polyolefins

Figure 4
Derivatisation reactions used to quantify the groups introduced into a polyolefin by a corona discharge (CD) treatment
(Reprinted from L.J. Gerenser, J.F. Elman, M.G. Mason and J.M. Pochan, E.s.c.a. studies of corona-discharge-treated polyethylene
surfaces by use of gas-phase derivatization, Polymer, 1985, 26, 1162, with permission from Elsevier Science.)

3.3 Static Secondary Ion Mass Spectrometry ketone, absorbs in the region 5.80-5.86 μm. The location
of the absorption is usually expressed as a wave number,
XPS is limited in the molecular information it provides i.e., waves per centimetre, in this case 1725-1715 cm-1.
and its surface sensitivity. Static SIMS is especially
good in these respects. However, it does not normally Most modern instruments use Fourier transform
give quantitative information. analysis and are termed FTIR. Information on plastic
surfaces can be obtained by using reflection techniques.
The basic principles of SSIMS are as follows. The sample The sample, typically in the form of a plastic film, is
is bombarded under high vacuum by a beam of ions, placed in close contact with a prism of either
causing the ejection of ions and neutrals from the surface. germanium or KRS-5 (a mixed TlBr-TlI crystal). The
The ions may be due to elemental species (e.g., Cu+, O-) sampling depth is given by the Harrick equation.
or to ‘cluster’ ions (e.g., MgO+, C6H5O-). The positive
and negative ions may be separated and two mass spectra
obtained. By carefully limiting the ion beam current λo
dp = 1
n2
density, the information obtained can be limited to the 2 πn1[sin θ − (
2 2
n1 ) ]
2

first 2-3 atomic layers; this is the basis of static SIMS.

From the fragment pattern of ions it is often possible where: dp is the distance below the surface at which
to determine the chemical nature of the surface. For the amplitude of the electric field is 1/e of its
example, polydimethylsiloxane (dimethysilicone) is initial value
readily identified from the fragment pattern (73, 133,
147, 207, 221) from the positive SSIMS spectrum. θ is the angle of incidence between the IR
beam and the surface normal

3.4 Reflection IR n1 and n2 are the refractive indices of the

reflection element and sample
Infrared spectroscopy is a method of detecting chemical
groups. It depends on the fact that different chemical λo is the wavelength of the radiation
groups absorb radiation at characteristic wavelengths.
For examples, a C=O group in a saturated aliphatic Some typical values of dp are given in Table 4.

9
 Adhesion and Bonding to Polyolefins

Table 4 Multiple reflection infrared (MIR) conditions and depths of penetration (a.6)
dp at 1723 cm-1
Reflection element n2/n1a Angle of incidence dp/λo
(μm)

Ge 0.378 45 0.067 0.39

KRS-5 0.631 60 0.122 0.65

KRS-5 0.631 45 0.208 1.21

a Ratio of refractive index of PE (1.515) to that of reflection element (Ge=4.0, KRS-5=2.4)
D. Briggs, V.J.I. Zichy, D.M. Brewis, J. Comyn, R.H. Dahm, M.A. Green and M.B. Konieczko, Surface and Interface Analysis, 1980,
2, 3, 107. ©John Wiley and Sons Limited. Reproduced with permission.

Figure 5
The reflection IR spectra of low density polyethylene treated with chromic acid at 70 °C for various times (a.7)

The use of reflection IR is illustrated by the results will be examined separately; plastics will be examined
shown in Figure 5. The spectra show that various in this section and elastomers in Section 5. Over the
functional groups are introduced into polyethylene on last 50 years a number of pretreatments have been
treatment for the different times with chromic acid. developed to improve adhesion to polyolefins. Much
of the early work was directed towards improving the
printability of polyethylene. Around 1950, the
methods that were developed included treatment with
4 Pretreatments and Primers for corona discharge, flame, chromic acid immersion and
Polyolefin Plastics chlorine gas activated by UV. The first three methods
became firmly established for the treatment of
4.1 Introduction polyethylene and later polypropylene. Corona
discharge, which involves breaking down air into
The pretreatments used for plastics and elastomers active species including oxygen atoms, ozone and
are generally different and the two groups of materials ions, by the application of a high voltage, is still the

10
 Adhesion and Bonding to Polyolefins

preferred method for treating film. Flame treatment, These include organic peroxides (a.8), ammonium
which involves exposing the plastic to a flame for peroxydisulphate (a.9), sodium hypochlorite (388) and
less than one second, is still favoured for treating an electrochemical method (74). Some of the important
cylindrical objects such as bottles. Chromic acid is pretreatments are now described in more detail.
very effective for treating three-dimensional objects
but is being phased out for environmental reasons.
4.2 Flame Treatment
Around 1960, a number of workers studied the effect
of low pressure plasmas on polyolefins and other
plastics. Workers at Bell Laboratories found that large The object to be treated, e.g., a bottle, is passed over
improvements in bondability were achieved if one or more burners, each of which possesses a large
polyethylene and other plastics were exposed to a number of closely-spaced jets. The burners are fed
radiofrequency (RF) plasma, they termed this process with an air-hydrocarbon gas mixture, whose
CASING (Crosslinking by Activated Species of INert proportions are controlled within definite limits. The
Gases) as they believed the process was effective by treatment time is usually in the region of 0.04-0.1
crosslinking low molecular weight material to long seconds (Figure 6).
polymer chains rather than introducing new functional
groups. This work has led to considerable controversy The ratio of air-to-hydrocarbon for complete
(see Section 6). combustion is known as the stoichiometric ratio. For
example, the complete combustion of one volume of
In the 1980s interest was renewed in the use of halogen methane requires 9.55 volumes of air, so the
gases to pretreat polyolefins and there is significant stoichiometric ratio for an air: methane flame is 9.55:1.
commercial interest in this approach; treatment of
polyolefins for a few seconds with mixtures of fluorine In one of the first detailed studies of the flame
and inert gases gives large improvements in treatment Ayers and Shofner (402) examined most of
bondability. Chlorinated polypropylene primers are the key variables namely: the nature of the gas, the
sometimes used commercially instead of a air-to-gas ratio, the effect of contact time and the
pretreatment, e.g., they are applied to polypropylene distance of the polymer from the flame. The nature
bumpers prior to painting. of the polyolefin used was not stated. The
effectiveness of the treatments was assessed using a
A number of other pretreatments have been examined tape peel-test and the adsorption of a dye. The authors
although they have not found widespread industrial use. found that higher levels of treatment were achieved

Figure 6
Schematic representation of flame treatment

11
 Adhesion and Bonding to Polyolefins

with an excess of air over the stoichiometric Sutherland and co-workers carried out a detailed study
requirements to burn all the propane; this was also of the pretreatment of various PP types (see for
true with methane and butane. The authors concluded example a.10). Improvements in adhesion were
that the optimum treatment time was about 0.02 s and assessed by means of a butt test. In some cases the
that the optimum distance between the polymer and adhesion to an epoxide adhesive was assessed, but in
the top of the inner cone was about 10 mm. many cases the PPs were first coated with a
polyurethane paint so that improvements in paint
The study of Ayres and Shofner (402) was carried out adhesion could be determined. Changes in adhesion
without access to X-ray photoelectron spectroscopy to a PP homopolymer after flame treatment under a
XPS, a technique which, as stated earlier, enables a variety of conditions are given in Table 5. It can be
quantitative elemental analysis of the surface regions of seen that good adhesion is obtained under a broad
a polymer to be carried out. range of conditions.

Garbassi and co-workers (390) found that the flame For comparison the tensile strength of the control
treatment of polypropylene resulted in large increases involving PP wiped with trichloroethane was 2 MPa.
in the adhesion of polyurethane and acrylic paints to the
polymer. Curve fitting of the C1s spectra indicated that A study of the flame treatment of low-density
hydroxyl and carbonyl were the predominant groups polyethylene showed very high levels of oxidation
formed, although some carboxyl groups were formed (Table 6), although the oxidised layer was less than
after repeated flame treatment. 10 nm thick.

Table 5 Adhesion tests of polyurethane-painted flame-treated polypropylene (a.10)

Tensile strength
Locus of failure
(MPa)
Air-to-gas ratioa 8:1 24.7 C
9:1 25.4 C
11:1 26.4 C
13:1 26.7 C
14:1 25.8 C
Total flow rateb (l min-1) 12 26.0 I
18 25.6 C
24 26.4 C
36 27.2 C
48 24.0 C
Distance of polymer surface from inner 2.5 22.8 C
cone tipc (mm)
10 26.4 C
20 22.1 C
40 6.5 I
60 4.2 I
I interfacial between paint and polymer
C complex failure including cohesive within PP
a Total flow rate 24 l min-1; distance 10 mm
b Air-to-gas ratio 11:l; distance 10 mm
c Air-to-gas ratio 11:l; total flow rate 24 l min-1

12
 Adhesion and Bonding to Polyolefins

Table 6 XPS and joint strength data for flame treated low density polyethylene (397)
Polymera Time (s)b O:C (atom %) Lap shear strengthc (MPa)
X 0 0.25 0.6
X 0.1 16.9 6.6
X 0.4 31.0 7.2
Y 0 <0.25 0.4
Y 0.1 20.5 5.6
Y 0.4 33.4 7.2
aX is a polymer with no additives whereas Y contains 10 times the normal level of antioxidant. It is clear that the
antioxidant does not diminish the effectiveness of the treatment.
b The abnormally high treatment time increases the surface oxygen concentration, but does not cause a further
increase in adhesion because material failure within the PE had already occurred at 0.1 s.
cA composite lap shear test was used in which PE film was bonded to two strips of aluminium with an epoxide adhesive.

4.3 Corona Treatment Factors which determine the effectiveness of the treatment
include the power input, line speed, the magnitude of the
The main application of corona treatment is film for the air gap, the relative humidity, the chemical nature of the
packaging industry. Film is passed, typically at 2 m s-1 polymer, the additives used and the time between
over an earthed metal electrode (Figure 7). The distance processing the polymer and the treatment. Adhesion is
between the electrode and the film is usually 1-2 mm. A also affected by the time between the treatment and the
high frequency (10-20 kHz) generator and step-up bonding, printing or painting operation.
transformer produce a high voltage, which causes the
electrical breakdown of the air with the formation of Surface analysis has shown that the corona discharge
atoms, ions, electrons and other active species. treatment introduces various groups, such as carbonyl,
into the polymer surface. Typically 5 atomic percent
Practical aspects of corona treatment have been of oxygen is introduced into a polyolefin film.
discussed by Lawson and Greig (259).
Many studies have been carried out on the corona
treatment of polyolefins . These include studies on
corona treatment of four different polyethylene films
for effects on wettability and adhesion (392), and post-
treatment with a silane which was claimed to further
enhance adhesion (112).

It is known that additives such as slip agents and

antioxidants can adversely affect corona treatment if
this is not done in-line, i.e., immediately after
processing. If the additives migrate to the surface before
the treatment is carried out, then inferior adhesion may
result. This is because there will be a tendency to
chemically modify the additives rather than the
underlying polymer chains.

4.4 Low Pressure Plasma Treatment

Figure 7
In this method, power is applied to a gas or a monomer
Schematic representation of corona discharge treatment at low pressure (typically 1 torr) and a plasma

13
 Adhesion and Bonding to Polyolefins

consisting of ions, electrons, atoms and free radicals Many studies on plasma treatment of polyolefinic
is formed. plastics have been carried out, often involving surface
analysis. These studies include:
There are several parameters which control the effect
of a plasma on a polymer including: • the treatment of PP in a nitrogen or ammonia
plasma to improve the adhesion of vacuum-
• the nature of the gas deposited aluminium (385)

• the gas pressure and flow rate • improved epoxide-PP adhesion attributed to CO
functionalities introduced by air, oxygen or
• the discharge power nitrogen plasma treatments (383)
• the excitation frequency
• halogenation of PP with a chlorotrifluoromethane
• the nature of the polymer plasma (381) and

• the temperature of the polymer. • the treatment of PE fibres with an oxygen plasma
(380).
Improved adhesion may be due to a variety of
mechanisms:
4.5 Chromic Acid Treatment
• removal of contaminants by ablation
For complex shapes, or if etching is required,
• crosslinking
oxidative solutions may be used to treat polymers.
• grafting of monomers to a polymer surface Chromic acid has been the most commonly-used
reagent, but for environmental reasons it is avoided
• introduction of functional groups. where possible.

The last effect can take place during exposure to a X-ray photoelectron spectroscopy (XPS) has been used
plasma or upon exposure to the atmosphere when free to study the chemical changes caused by chromic acid
radicals can react with oxygen or water. treatments (see Table 8). Even very mild treatment
conditions (e.g., 5 s at room temperature) result in
The improvements in adhesion for a wide variety of substantial oxidation of polyolefins and large increases
polymers are shown in Table 7. in adhesion.

Table 7 Effect of plasma treatment on the lap shear strengths of polymers (386)
Polymer Lap shear strength (MPa)
Before treatment After treatment
Polyimide 2.9 17.9
HDPE 2.2 21.6
LDPE 2.5 10.0
PP 2.5 21.3
Polycarbonate 2.8 6.4
Nylon 5.9 27.6
Polystyrene 3.9 27.6
Polyvinylidene fluoride 1.9 9.0
Polytetrafluoroethylene 0.5 5.0

14
 Adhesion and Bonding to Polyolefins

Table 8 XPS data for polyolefins treated with chromic acid (398)
Polymer Treatment Surface composition (atom %)
C O S
LDPE None 99.8 0.2 -
1 min / 20 °C 94.4 5.2 0.4
6 h / 70 °C 85.8 13.1 1.1
PP None 99.8 0.2 -
1 min / 20 °C 93.4 6.3 0.3
6 h / 70 °C 94.0 5.7 0.3

5 Pretreatments and Primers for Over the last 50 years many methods have been developed
to pretreat plastics and elastomers. Partly because of the
Polyolefin Elastomers much simpler formulations, pretreatments for plastics have
been the subject of much greater scientific interest. Our
5.1 Introduction understanding of pretreatments for plastics is therefore
much greater than that for elastomers. Pretreatments for
In many cases, elastomers are joined to other materials elastomers have been developed on an empirical basis
during the process of vulcanisation. However, in other but some scientific studies of successful pretreatments
cases, elastomers are joined to other materials after have been undertaken. Different olefinic elastomers vary
vulcanisation. With this second group, it is often much more than olefinic plastics in their response to
necessary to pretreat the elastomers before bonding. various pretreatments and different types are therefore
Pretreatments range from physical methods such as a treated separately here.
solvent wipe or abrasion to chemical methods such
as treatment with trichloroisocyanuric acid. Physical
methods can be used to remove cohesively weak 5.2 Ethylene-Propylene Copolymers
layers from the polymer. This is essential to good
bonding unless these layers can be absorbed by the Ethylene-propylene elastomers (EP) have low total
adhesive. However, physical methods will only be surface energies with small polar components. As
effective if the underlying elastomer possesses would be expected, the adhesion of paints and
suitable functional groups or if a diffusion mechanism adhesives to untreated EP is poor. To achieve good
operates in a subsequent adhesion operation, e.g., adhesion to EP, the introduction of suitable functional
bonding. Chemical methods may also remove weak groups is required unless a diffusion mechanism can
layers or chemically modify them so that they are operate. Bragole (399) found that UV treatment of
more compatible with the adhesive; in addition EPDM coated with a thin layer of benzophenone
chemical methods may roughen a surface. However, resulted in large increases in the adhesion of acrylic,
an effective chemical method will also modify the epoxy and urethane paints to the polymer.
chemistry of the elastomer so that the interaction with
the adhesive is increased. This will usually be essential Ellul and Hazelton (376) subjected EPDM,
with olefinic elastomers. polypropylene and natural rubber/polypropylene
blends to various halogenation treatments, namely
In general, elastomers contain a greater variety and fluorine/carbon dioxide, sodium hypochlorite/acetic
quantity of additives than plastics; fifteen or more acid and bromine water. With the natural rubber blend,
components in a particular formulation is quite there was a substantial uptake of fluorine, chlorine
common. These additives, or compounding and bromine in the surface regions as indicated by
ingredients as they are often called, may well create energy dispersive X-ray analysis and with all three
a cohesively weak layer on the elastomer surface. On pretreatments the adhesion to an acrylic tape was
the other hand, plastics usually contain a small number greatly enhanced. In contrast, with the EPDM blend,
of additives and in relatively low concentration. fluorine was the only reagent which reacted with the

15
 Adhesion and Bonding to Polyolefins

polymer and only this treatment resulted in a significant permanganate. Most of the treatments had little effect
increase in adhesion to the acrylic tape. The above on the adhesion to an epoxide. It was concluded that
results can be explained in terms of the different much chain scission occurred with the result that
concentrations of carbon-carbon double bonds in the suitable functional groups were not introduced in
two blends. Substantial incorporation of chlorine and sufficient quantity into long polymer chains. Such
bromine could occur with the natural rubber- chemical modification is necessary for good adhesion
polypropylene blend but not with the EPDM blend. unless a diffusion mechanism is operating.
However, fluorine gas will readily react with saturated
hydrocarbon (a.11) and therefore the incorporation of
fluorine into the EPDM blend is not surprising.
5.4 Unsaturated Hydrocarbon Elastomers
Lawson and co-workers (349) using X-ray
5.4.1 Natural Rubber
photoelectron spectroscopy (XPS) found that
trichloroisocyanuric acid (TCICA) in ethyl acetate did
not chemically modify EPDM. Natural rubber (NR), being essentially a hydrocarbon,
has a low surface energy. Some of the components in a
Lawson (a.12) found that a corona treatment improved formulated elastomer, such as zinc oxide and carbon
the wettability of EPDM as indicated by glycerol black, may substantially increase the surface energy
contact angles and the use of a series of formamide/2- whereas organic additives such as extender oil and
ethoxyethanol mixtures (ASTM D2578 (a.13)). antioxidants may migrate to the surface and create a
However, the contact angles increased significantly potentially weak boundary layer.
over a period of one hour, indicating molecular
Pettit and Carter (400) found that chlorine gas, acidic
rearrangement, with the polar groups introduced by the
sodium hypochlorite and an organic chlorine donor in
pretreatment tending to move to the bulk of the
an organic solvent, all much improved the peel strengths
elastomer. No improvement in a peel test involving a
of joints involving natural rubber and a polyurethane
polyurethane coating was observed.
adhesive. Oldfield and Symes (379, 394) found that
aqueous or organic-based chlorination gave much higher
Minagura and co-workers (324) treated an EP elastomer
joint strengths than a solvent-wipe, abrasion or treatment
with UV and sputter etching. Large increases in adhesion
with concentrated sulphuric acid (Table 9).
were reported. However, the treatment times were long,
being 10 minutes for ion etching and one hour for the Oldfield and Symes used X-ray fluorescence, infrared
UV treatment. Scanning electron microscopy (SEM) analysis and contact angle measurement to study the
indicated that the two methods caused considerable TCICA treatment. X-ray fluorescence showed the
roughening of the surface. X-ray photoelectron amount of chlorine introduced into the polymer increased
spectroscopy (XPS) and Fourier transform infrared with the TCICA concentration; with a 3% TCICA
analysis (FTIR) indicated the introduction of substantial solution, they estimated the chlorine content in the NR
quantities of oxygen-containing functional groups. was 16.7% w/w. Reflection infrared analysis indicated
Kondyurin and Klyachtin (343) noted only modest
that chlorine substituted at allylic positions in the
improvements, at best, after treating EPDM with UV,
polymer backbone. Substantial improvements in
despite clear infrared evidence for the formation of
wettability were achieved, especially if the concentration
hydroxyl and carbonyl groups after treatment.
of trichloroisocyanuric acid was at least 0.8%.

Lawson and co-workers (349) pretreated various

5.3 Butyl Rubber elastomers including natural rubber with a 3% w/v
solution of TCICA in ethyl acetate. They used X-ray
Butyl rubber consists of ≥95% of isobutylene units with photoelectron spectroscopy (XPS) to study the chemical
a small quantity of isoprene which permits crosslinking changes caused by the pretreatment. In agreement with
via sulphur vulcanisation. Butyl rubber has a low Oldfield and Symes, they concluded that the chemical
surface energy and in addition organic components with modification was mainly substitution rather than addition
a low cohesive strength may exist on the surface. In at the carbon-carbon double bond. The basis of this
one study (389), butyl rubber was subjected to several conclusion is as follows: TCICA may either add to the
treatments which normally cause substantial chemical double bond in natural rubber or cause substitution in
modification to polymer surfaces. The treatments the allylic position. Consider the structure of
included chromic acid etching, corona discharges, trichloroisocyanuric acid (TCICA) in Figure 8, i.e.,
flames, bromination, UV radiation and potassium equal quantities of chlorine, nitrogen and oxygen would

16
 Adhesion and Bonding to Polyolefins

Table 9 Effect of pretreatment on the peel strengths (N mm-1) of NR-epoxide-NR (394)

Pretreatment Peel strength Locus of failure
Toluene wipe 0.1 I
Abrasion on grinding wheel 1 I
Acidified hypochlorite 10 R
Concentrated sulphuric acid 1 I
TCICA in ethyl acetate 18 R
I - apparent interfacial
R - cohesive in rubber

if the structure is represented simply by

TCICA

then with addition +

Figure 8
Addition reaction of TCICA with natural rubber

be introduced into the elastomers. With substitution, only and used contact angle measurements and reflection
chlorine is introduced. By determining the quantities of FTIR to study the changes caused by the
these elements by XPS it is possible to deduce whether chlorination. They studied ‘pure’ natural rubber, a
substitution or addition has occurred. peroxide cured formulation and a conventionally
cured formulation. Contact angles of glycerol on the
Extrand and Gent (387) treated natural rubber rubber surfaces reduced after chlorination as shown
surfaces in an acidified sodium hypochlorite solution in Table 10.

Table 10 Effect of chlorination on the contact angles between ethylene glycol and various rubber
surfaces (387)
Substrate Contact angle (°)
Before treatment After treatment
‘Pure’ rubber 64 11
Peroxide cured 46 30
Conventionally cured 82 30

17
 Adhesion and Bonding to Polyolefins

With regard to the infrared study, bands occurring Oldfield and Symes (394) found that physical
at 660, 750 and 1260 cm -1 were assigned to the treatments were inferior to three chemical methods
effects of chlorination. In addition, bands at 780, 916 (Table 11).
and 1410 cm -1 are almost certainly also due to
chlorination. Using X-ray fluorescence, they estimated the chlorine
concentration in the first few microns of the SBR after
Kusano and co-workers (362) found that neither corona treatment with TCICA at various concentrations. With
nor plasma treatments improved peel strength with a a 3% solution, the resulting chlorine concentration was
polyurethane adhesive despite improved wettability as 16.1% w/w.
indicated by water contact angles. FTIR indicated
substantial oxidation after the corona treatment but only Pastor-Blas and co-workers (a.14) found that physical
minor oxidation after the plasma treatment. treatments such as abrasion did not result in significant
increases in the peel strengths obtained with a
polyurethane adhesive. On the other hand, treatment
5.4.2 Styrene-Butadiene Copolymers with TCICA in ethyl acetate resulted in large increases
in peel strength.
Styrene-butadiene rubber (SBR) has a low surface
energy, but this may be considerably increased by the On the basis of the relative amounts of chlorine and
incorporation of various components. Organic additives nitrogen introduced into SBR, Lawson and co-
such as antioxidants will tend to migrate to the surface workers (349) concluded that both substitution and
thus creating a potential weak boundary layer. addition reactions were significant when this
elastomer was treated with TCICA in ethyl acetate.
Pettit and Carter (400) found that treatment of SBR Similar results were obtained with polybutadiene
with chlorine gas, acidified sodium hypochlorite or an (see Section 5.4.1).
organic chlorine donor in an organic solvent resulted
in large increases in peel strength for SBR- Pastor-Blas and co-workers (302) studied the effect of
polyurethane-SBR joints. the TCICA concentration in ethyl acetate. For solutions

Table 11 Effect of pretreatments on the peel strengths (N mm-1) of SBR-epoxide-SBR joints (394)
Pretreatment Peel strength Locus of failure
Toluene wipe 0.2 I
Abrasion on grinding wheel 1 I
Acidified hypochlorite 12 R
Treatment with conc H2SO4 12 R
TCICA in ethyl acetate 11 R
I - apparent interfacial
R - cohesive within rubber

Table 12 XPS studies of SBR treated with solutions of TCICA in ethyl acetate (310)
Concentration of TCICA Surface analysis (atom %)
(wt%)
C O Si N Cl S
0 95.7 2.8 1.5 - - -
2 92.7 4.3 1.0 1.0 0.8 0.2
7 91.5 4.6 0.7 1.9 0.9 0.4

18
 Adhesion and Bonding to Polyolefins

up to 2% w/w mainly chlorinated hydrocarbon and C- Other methods have been shown to considerably
O species were reported. At between 2 and 5% w/w an improve the bondability of SBR materials. Aqueous
excess of unreacted TCICA was indicated while above solutions of an organic chlorine donor or the use of an
5% w/w there was a detrimental effect on adhesion electrochemical method resulted in large increases in
due to a weak boundary layer forming consisting of peel strength with a water-based polyurethane adhesive
isocyanuric acid. (a.15). Kusano and co-workers (362) found that corona
and plasma treatments resulted in large increases in
Pastor-Blas and co-workers (310) treated an SBR peel strength with a polyurethane adhesive. Lawson
formulation with TCICA solutions in ethyl acetate (a.12) reported that a 10 s corona treatment improved
having concentrations ranging from 0.5-7% by weight. the water wettability of an SBR. He also reported
The chemical changes caused by the pretreatments are cracking of the elastomer which he ascribed to the
shown in Table 12. ozone generated in the discharge.

Rubber strips were bonded with a solvent-based Styrene-butadiene block copolymers (SBS
polyurethane (PU) and the joint strengths determined thermoplastic elastomers) have a low surface energy.
in a T-peel test. After peeling, the test pieces were Therefore, to achieve good adhesion to SBS a
examined using a variety of techniques; XPS and FTIR chemical pretreatment may be necessary. A
confirmed that the treatment introduced various complicating factor is that migratory organic additives
chemical groups. The peel strengths were obtained after may lead to a weak layer. Pettit and Carter (400) found
treatments with 0.5, 2 and 7% w/w. The highest peel that treatment of SBS with chlorine gas, acidified
strength was obtained with the 2% solution. sodium hypochlorite or an organic donor in an organic
solvent resulted in large increases in peel strength with
In a related publication, treatment with fumaric acid in a polyurethane adhesive.
a butan-2-ol/ethanol mixture and TCICA in butan-2-ol
were compared (352). In general, the TCICA was more As with SBR, aqueous solutions of an organic chlorine
effective at enhancing the peel strength achieved with donor and an electrochemical method were also
a solvent-based PU adhesive. Infrared analysis effective with SBS (a.15).
indicated that the treatments were probably effective
by removing zinc stearate (reduction in peak at Pastor-Blas and co-workers (304) treated SBS with
1540 cm -1 ) and by introducing carbon-oxide
TCICA solutions (0.5, 2 and 7 wt%) in ethyl acetate.
functionalities (seen as peaks at 1704 cm-1 and 1670
The SBS was bonded with a polyurethane and the joint
cm-1 for the TCICA and fumaric acid respectively).
strengths determined in a T-peel test. The failed
With TCICA, C-Cl bonds were also observed.
surfaces, after peeling, were examined by a variety of
techniques including XPS and FTIR. The highest
Pastor-Sempere and co-workers (373) treated two strength (3.3 N mm-1) was obtained with the 0.5%
styrene-butadiene rubbers with fumaric acid in a butan- solution. It was concluded that the stronger solutions
2-ol/ethanol mixture. This resulted in improved weakened the surface regions. FTIR and XPS showed
adhesion in both cases, but the improvement with one that the treatment introduced chlorine and oxygen
formulation was significantly greater than with the functionalities.
other. The lower peel strength was attributed to the
presence of paraffin wax and zinc stearate. Roughening
prior to treatment with fumaric acid resulted in
additional improvements with both rubbers. Infrared
analysis indicated that the fumaric acid was effective 6 Discussion
by introducing C=O bonds and by reducing the
concentration of zinc stearate. In addition, the fumaric Polyolefins usually require pretreatment to achieve
acid caused a roughening of both rubbers. satisfactory adhesion. Physical methods such as
solvent wiping are normally ineffective, one exception
A later publication (313) demonstrated that high is described below (a.16). However, pretreatments can
concentrations of TCICA could lead to the formation be avoided if a diffusion mechanism operates. Thus,
of weak boundary layers. Treatment of two SBR polyolefins can be bonded to other substrates with
materials with a 7 wt% solution of TCICA in ethyl hot-melt adhesives such as those based on ethylene-
acetate resulted in poor peel strengths unless the vinyl acetate co-polymers (325) or with certain
treated surfaces were vacuum dried for one hour at reaction setting adhesives based on acrylics (374). If
10-2 Torr. two pieces of the same polyolefin are to be joined

19
 Adhesion and Bonding to Polyolefins

then fusion methods may be used (see for example, This may lead to a substantially higher degree of
(127)). Another exception, which is likely to be rare, wetting. Also, the intermolecular forces will be stronger
is where surface topography is dominant, e.g., the and stress concentrations due to voids will be reduced.
large increase in adhesion resulting from the Although reflection IR has failed to detect any chemical
trichloroethylene vapour treatment of PP (a.16) is changes with several different treatments of
probably due to mechanical keying. However, changes polyolefins, XPS has detected substantial surface
in topography caused by commercial pretreatments oxidation in all cases examined. In the CASING
of polyolefins are likely to be of secondary process Hansen and Schonhorn claimed no chemical
importance. Large increases in adhesion can be changes occurred but this has been disputed by Sowell
obtained, using for example a corona discharge, and co-workers (403) and by Malpass and Bright (a.17).
without any noticeable changes in topography.
Using reflection IR, Blais and co-workers (382) could
The remaining discussion centres on pretreatments of detect no changes in surface chemistry after treating
polyolefins, in particular the options available and the PP with chromic acid. They concluded that a weak layer
mechanisms by which the treatments operate. The had been washed away by the chromic acid and that
effects of additives are also considered. this was the reason for the improved adhesion that they
had observed. However, Briggs and co-workers (398)
There has been considerable debate over the last 40 using XPS clearly showed that chromic acid introduced
years regarding the mechanism by which substantial quantities of functional groups into PP.
pretreatments enhance adhesion. Some workers have
favoured the view that improved wetting caused by The introduction of polar groups into a polyolefin
the introduction of functional groups is vital whereas surface will lead to improved wetting which should
others believe that pretreatments remove potential result in improved adhesion provided no weak
weak boundary layers. boundary layers are present. Functionalisation can
sometimes lead to improved adhesion with increasing
Hansen and Schonhorn (a.3) have argued that the main surface energy. When Schonhorn and Hansen (a.3) used
function of surface treatments is to eliminate potential the CASING process with fluorine a decrease in the
weak boundary layers and that any oxidation is of critical surface tension of LDPE occurred, although
secondary importance. It is certainly true that some adhesion increased and this was taken as evidence in
pretreatments, e.g., CASING (a.3) can cause favour of the weak boundary concept. However, it is
crosslinking, and in principle any small molecules on possible to explain this result because when the PE
a surface may be incorporated into a network by surfaces are fluorinated the hydrogen bonding
crosslinking or alternatively they may be ablated. Also capability is increased. The polar component of the
with an etching treatment, such as chromic acid, small surface energy of poly(vinyl fluoride) is similar to that
molecules could be washed away from the surface. One of a typical flame treated PP surface.
key question is, therefore, whether it is necessary to
introduce chemical functionality into a polyolefin The present authors suggest that the balance of evidence
surface to achieve good adhesion. favours the following general view. Perfect wetting of
a polyolefin surface would lead to high levels of
It can be calculated that provided wetting is complete, adhesion even if only dispersion forces were involved.
dispersion forces are more than sufficient to account Therefore, wetting with untreated polyolefins must be
for the highest adhesion levels that have been observed inadequate and surface pretreatments which result in
in direct tension. However, on a sub-microscopic level chemical modifications will either increase the degree
real surfaces may be highly irregular and the degree of of wetting and/or lead to interactions across the
wetting may be far from complete. This will certainly interface that are stronger than dispersion forces.
be true if the viscosity of the ‘mobile phase’ is high Usually, both processes will occur due to the
and the ‘setting time’ is low. It is unknown what degree introduction of polar functions, some of which are
of wetting is required to give satisfactory adhesion. The capable of participating in relatively strong specific
overall interaction between the polyolefin surface and hydrogen bonding interactions. Much more work is
the ‘mobile phase’ will depend on the degree of contact required to identify the role of strong interactions, but
achieved and the magnitude of the intermolecular the importance of such interactions has been
forces involved. demonstrated directly by the interaction of discharge
treated PE with a nitrocellulose ink (396) and directly
The commercial pretreatments for polyolefins will by the adhesion levels between partially fluorinated
certainly increase the surface energies of polyolefins. but untreated polyolefins and epoxide adhesives (a.18).

20
 Adhesion and Bonding to Polyolefins

Another piece of evidence in favour of the need to Case C represents the weak boundary explanation for
introduce functional groups into polyolefins, is the lack of adhesion to polyolefins. However, Briggs and
fact that polymers already possessing functional co-workers (398) showed that this mechanism did not
groups, such as poly(vinyl chloride) and nitrile operate for the LDPE they studied. They followed the
rubber (394) are easy to adhere to in their untreated chromic acid etching of LDPE under very mild
state provided that ‘small molecules’ are not present conditions and did not observe the expected
on the surface. discontinuity in either oxidation level or adhesion at
low etching time. The joint strength between untreated
Weak boundary layers (WBLs) will be important in LDPE and an epoxide adhesive was low but there was
some cases but much evidence has been presented no evidence of transfer of hydrocarbon to the epoxide.
against the idea that WBLs are the main reason for
adhesion problems involving polyolefins. However, it Case D has been studied by Brewis (a.8). The chromic
is important to understand the role of low molecular acid etching of HDPE increased the joint strength from
weight species on polyolefin surfaces. In the context 1.8 to 17.6 MPa in a lap shear test. Spreading a layer
of this review we can distinguish 6 possible cases as of petroleum jelly (approx 2 x 103 nm thick) over the
shown in Figure 9. etched surface prior to bonding only reduced the bond
strength to 12.7 MPa, as all or most of the petroleum
Examples of these cases include: jelly was absorbed by the adhesive. This indicates the
importance of a displacement or absorption mechanism.
(A) this represents the view of those who believe that
the poor adhesion of polyolefins is due to the lack Case E is well known to PE converters. Migration of
of functional groups polar additives required for surface properties such as
low friction or low static charging cause problems in
discharge treating for printing or laminating. In
(B) chromic acid etched and washed PE
particular, the additive rather than the underlying
polymer chains tend to be chemically modified.
(C) untreated PE with low molecular weight polymer
on surface
Case F is relevant to several situations. It well known
that printing or bonding discharge treated LDPE or PP
(D) chromic acid etched PE contaminated with a film containing some additives (particularly slip and
hydrocarbon oil or grease anti-static) becomes more difficult as the film ages due
to additive bloom. Overtreatment of polyolefin surfaces
(E) untreated PE with a high level of slip agent by discharge treatment (and probably some other
treatments) causes low molecular weight oxidised
(F) discharged treated PE with anti-static or slip agent. material to be produced by degradation. This may or

A B
N N N P P P

n n n n n n
C D
N N N P P P

p p p p p p
E F
N N N P P P

Figure 9
Simplified cases of low molecular weight species on polyolefin surfaces where N and P refer to non-polar
and polar high molecular weight (strong) material, and n and p refer to the corresponding low molecular
weight (weak) material

21
 Adhesion and Bonding to Polyolefins

may not affect subsequent adhesion. Some systems are the same way to these pretreatments. However, this is
tolerant to high levels of such material, presumably not always the case. Thus, Lawson (a.12), found that a
because it can be incorporated into the ink or adhesive corona treatment of an EPDM did not improve the peel
layer. However, lamination or heat sealing operations strength to a polyurethane coating. It is probable that
may be hindered. the reason for the poor adhesion is a layer of low
molecular weight material on the EPDM. During
The existence of small molecules on the polyolefin surface corona treatment this layer, rather than the underlying
is probably common, but, low molecular weight material polymer, would be oxidised. Hence, the polyurethane
will not behave as a WBL if the interaction between coating would not be able to interact strongly with the
substrate and adhesive (etc.) is sufficiently strong to cause EPDM. Even if the EPDM was oxidised by the corona
displacement or if an absorption mechanism occurs as treatment, there would still be a cohesively weak layer
noted by Brewis (a.8). It is also important to remember on its surface.
that a potential WBL can be created by a pretreatment,
e.g., the corona discharge method. Where elastomers possess carbon-carbon double bonds
there is the possibility that pretreatment may be effective
As noted in Section 4, there have been many detailed by addition or substitution reactions. Thus some reagents
studies relating to the pretreatment of plastics. Much may be effective with unsaturated hydrocarbons such
is now known about these pretreatments including the as SBR and SBS but not with EP elastomers. This is
chemical groups introduced, their concentrations and demonstrated by the work of Lawson and co-workers
the depth of chemical modification. In contrast, the (349) who found that treatment with trichloroisocyanuric
number of studies involving elastomers is much lower acid in ethyl acetate resulted in the introduction of
and in general the studies have been much less substantial quantities of chlorine into SBR,
informative. One of the reasons for this is that polybutadiene and natural rubber, but not into EPDM.
elastomers usually contain several additives often in
relatively high concentrations. These additives make Several methods have been shown to be effective at
an understanding of the pretreatments much more pretreating unsaturated hydrocarbon elastomers. These
difficult. Because of the wide range of formulations include treatment with concentrated sulphuric acid,
for a particular elastomer, it is also more difficult to acidified sodium hypochlorite and trichloroisocyanuric
generalise about pretreatments than it is with plastics. acid in ethyl acetate. The last method is the most
For example, it is known that some formulations of commonly used commercially but in many countries
SBR are considerably easier to pretreat than others.
legislation is being introduced to reduce the use of
organic solvents. Promising results have been obtained
Another important difference between olefinic plastics with new solvent-free methods (a.15). An
and olefinic elastomers is that most elastomers possess electrochemical method involving the highly reactive
carbon-carbon double bonds whereas the plastics complex ion AgNO3+ has been found to be effective
(LDPE, HDPE, LLDPE and PP) do not. With with polyolefins (PP, SBS, SBR); Ag2+ is continuously
elastomers reagents which react with carbon-carbon regenerated electrochemically and in principle only
double bonds are used whereas with plastics the
electricity and water are consumed (a.15). Another
pretreatments must break C-C and C-H bonds.
method involving the use of an aqueous acidified
suspension of N-chloroparatoluene sulphonamide, has
Hydrocarbon materials with few carbon-carbon double been found to greatly enhance adhesion to SBS (a.19).
bonds will first be considered. The most important
examples in this group are ethylene-propylene
The preferred commercial methods for pretreating
elastomers which may be crosslinked with peroxides
different polyolefins can be summarised as follows:
or sulphur systems; in the latter case small quantities
of dienes are polymerised with ethylene and propylene
(EPDM). As EP rubbers contain no polar groups it will Polymer Pretreatment Method
normally be necessary to chemically modify the
polymers to enable them to interact strongly with polar Film (PE, PP) Corona
adhesives such as epoxides and polyurethanes. In the Bottles (PE) Flame
case of plastics such as polyethylene and
polypropylene, large increases in adhesion can be Mouldings (PE, PP) Flame, plasma, primers
achieved by treating with a flame, corona, plasma, EPDM Grafting, primers
reactive gases such as fluorine or etching solutions. It
SBS, SBR TCICA
would be expected that EP rubbers would respond in

22
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