Polymer International Polym Int 50:11151123 (2001)

DOI: 10.1002/pi.753

Blends of maleic-anhydride-grafted
polyethylene with polyethylene for improved
cathodic disbondment performance
Debashis Roy, George P Simon* and Maria Forsyth
School of Physics and Materials Engineering, Monash University, PO Box 69M, Victoria 3800, Australia

Abstract: Buried metal structures such as pipes are usually protected by a coating, often in conjunction
with cathodic protection (CP). Whilst this minimizes corrosion, it can also lead to the loss of adhesion
between the protective coating and metal structure by a phenomenon called cathodic disbondment
(CD). In this study, various medium-density polyethylene (MDPE) compositions with maleic-
anhydride-grafted-polyethylene (MAH-g-PE) have been formulated to investigate the effect on CD
performance, as well as both wet and dry bond strength. The results indicate an improvement in both
CD performance and bond strength for all compositions. Differential scanning calorimetry (DSC) and
pressure-volume-temperature (PVT) experiments are used to characterize the polymer formulations
developed and to aid in the understanding of the reasons for such improvement. Energy dispersive
X-ray spectroscopy (EDXS) has been used to obtain surface analysis data on disbonded materials in
order to evaluate the failure mode during the CD process. It is found that there may be an optimum
loading of the polar functional groups in MDPE necessary for the best CD performance, and that wet
adhesion strength (rather than dry) is an important parameter to assess and understand the CD
performance of coatings.
# 2001 Society of Chemical Industry

Keywords: polyethylene blends; steel plate; cathodic disbondment; adhesion; 90 peel test; PVT diagram

INTRODUCTION polyethylene coating on steel pipe generates carbonyl

Buried steel structures are often protected physically
from the environment by a coating in conjunction with
cathodic protection (CP) by way of an impressed
current. Cathodic disbondment (CD) is one of the
main failure processes for organic coatings on steel
structures under CP, and may lead to the loss of
corrosion protection for the metal at the tip of crevice
that forms under the disbonded coating. CD may be
dened as the loss of adhesion between a protective
coating and the metal substrate. This usually emanates
from a aw (often termed a `holiday') in the coating,
and is proposed to be due to the generation of hydroxyl
ions formed from oxygen reduction due to a cathodic
potential on the metal substrate.1 High-performance
coatings used in conjunction with cathodic protection
are required to have the ability to resist such
disbondment to ensure a long, useful service life.
Polyethylene is one of the most widely used corrosion
protection thermoplastic coating materials which
protects steel from corrosion by providing a barrier
to oxygen, water and corrosive ions.
Generally, for good adhesion of polyethylene to
steel, conditions are required which permit oxidation
of the polymer.2 It is believed that the contact thermal
oxidation which takes place at the high temperatures of
and other oxygen-containing groups, which can result
in Lewis acid/base interactions with a high surface
energy substrate like steel.3,4 The use of plastics which
already contain polar functional groups, such as
methacrylic-acid-modied-polyethylenes, applied by
ame technology in the study of Sugama et al,5 have
shown an improvement of the interfacial bond
strength of the copolymer to steel with a low rate of
delamination in 0.50 M NaCl solution at an applied
potential of 1.5 V versus the saturated calomel
electrode (SCE). The open literature in this area is,
however, limited in extent.
Another important feature of polyethylene that may
affect its CD properties is the relatively large coef-
cient of thermal expansion (contraction) of the coat-
ing, which is about 1214 times larger than that of
mild steel6 and may result in residual shrinkage
stresses. The high thermal contraction differential on
cooling occurs because the coating crystallizes and
densies further as temperature is reduced, in addition
to any bulk contraction on cooling. For a semi-
crystalline thermoplastic bonding to metals, its crystal-
linity plays an important role in the residual stress
development7 which may develop an internal strain
with a possibility of inducing/promoting interfacial

* Correspondence to: George P Simon, School of Physics and Materials Engineering, Monash University, PO Box 69M, Victoria 3800,
Australia
E-mail: George.Simon@eng.monash.edu.au
(Received 23 January 2001; revised version received 3 May 2001; accepted 22 May 2001)

# 2001 Society of Chemical Industry. Polym Int 09598103/2001/$30.00 1115

D Roy, GP Simon, M Forsyth

failure. Finally, an important consideration in for-

mulating a coating for corrosion protection is to ensure
that adhesion is maintained in the presence of water
and hydroxyl ions.8
In this study, we investigate the hypothesis that CD
performance and bond strength can be signicantly
improved by blending maleic-anhydride-grafted-poly-
ethylene (MAH-g-PE) with more traditional medium-
density polyethylene (MDPE) coatings. To verify the
hypothesis, various polyethylene samples blended with
MAH-g-PE at a range of concentrations were applied
to steel plates by compression moulding to allow CD
and various peel tests to be conducted to assess their
ability to produce improved CD performance.

EXPERIMENTAL
Materials
The main polymer used in this work was medium-
density polyethylene (MDPE, Experimental Grade,
provided by Qenos). This MDPE was modied by Figure 1. Schematic diagram of the 90 peel-test rig.
blending with a maleic-anhydride-grafted high-density
polyethylene (MAH-g-PE) at a range of concentra-
tions. A master batch (MB) containing carbon black min 1 and for 0.01 mm min 1 speed samples an
(CB) and heat stabilizer was used in all samples, Instron 4505 was used, as shown in Fig 1. The 1-kN
leading to the incorporation of 2.5  0.5% carbon load cell was used to measure the peel force (Newton)
black and standard heat stabilizer content into each of the coating having 25-mm width, and was subse-
sample. quently converted into N mm 1 for peel strength by
dividing measured peel force by width. When a coating
Blend preparation is peeled from the substrate at a constant rate, the
The MDPE, MB and MAH-g-PE components were measured force should ideally be constant. In practice
blended in a melt mixer (Rheocord 90 of HAAKE Inc) this is not so, as shown in the curve in Fig 2. When the
at 170 C and 60 rpm for 68 min. The mixing ratios of results are reported, the mean values of such curves are
MDPE (including MB)/MAH-g-PE (wt/wt) were presented.11
100/0, 97.5/2.5, 95/5, 90/10 and 80/20.
Method of peel-test sample preparation (various
Calorimetric measurements failure initiation techniques)
One of the most widely used methods for estimating A variety of methods of initiating the peel tests were
the degree of crystallinity uses heat of fusion measure- used, depending on the nature of test (wet or dry). The
ments from differential scanning calorimetry (DSC). following techniques were followed: (a) mechanical
Percentage crystallinity9 is given by: peel initiation by chisel for dry peel testing, (b)
% Crystallinity DHf =DHc  100 1
where DHf = heat of fusion of a test sample, as
measured by the area under the main peak of the
DSC curve. DHc = heat of fusion of the 100% crystal-
line material. The crystallinity of the blends and base
polymer were investigated using a Perkin Elmer
DSC-7. The samples (about 510 mg) were heated
from 40 C to 170 C at a scanning rate of 10 C min 1.
To determine the percentage crystallinity of neat
polymers and other blends, we have considered DHc
(heat of fusion of pure crystalline polyethylene) to be
293 J g 1.10

Peel-test set-up
A 90 peel-test rig was designed and built, and was
mounted with the lower frame supported by the cross-
arm of a tensile tester. A Hounseld tensile tester was Figure 2. Typical curve trace (dry) from 90 peel test for blend 1 at a cross-
used for samples tested at a cross-head speed of 1 mm head speed of 1 mm min 1 at room temperature.

1116 Polym Int 50:11151123 (2001)


mechanical peeling by chisel, followed by immersion
in 1 M NaOH solution for at least 1 h without
impressed current, and (c) initiation of failure by
cathodically disbonding the sample (polarization
potential 1.5 VSCE in 0.51 M NaCl) (The latter two
methods for wet peel testing). It should be noted that
the methods (b) and (c) for wet peel testing were tried
in an attempt to induce as much adhesive failure as
possible in order to simulate the largely adhesive
failure of the CD test itself. Dry adhesion testing
(initiated as described in (a)) is in any event largely
cohesive, leaving behind a thin layer of polymer on the
steel surface and is performed to allow comparison of
dry bond strength of various coating samples, rather
than for any mechanistic study of the CD process, and
allows comparison with the wet adhesion strength of
respective samples.
For peel-test specimens, a 2-mm thick coating was
applied on sand-blasted steel strip (190 mm 
10 mm  25 mm) with a mould cavity (190 mm 
12 mm  25 mm) at 320 C for 34 min in a heated
press at 10 MPa, and was subsequently quenched in
the cold press. The difference in testing applies to the
manner in which the failure locus is commenced. In
the case of dry peel tests, the compression-moulded
sample was chiselled off at about 50 mm from one edge
to mount on the 90 peel-test rig and subsequently
clamped by the tensile tester grip. Method (b) for wet
peel testing involved chiselling off approximately
50 mm of polymer from one edge and leaving the
sample in 1 M NaOH solution (pH underneath coating
measured from XPS analysis, not shown here, was
between 13.7 and 13.9 at the end of 28 days of CD test
under normal conditions, which is about 1 M NaOH)
without any impressed current for at least 1 h before
the peel test was conducted. For method (c), in an
attempt to initiate true adhesive failure, cathodically
disbonded peel-test specimens (Fig 3) were prepared
by placing them in 3 wt% NaCl solution under 3 mA
current for seven days (c 1 M NaOH measured by pH
meter, as well as titration), after initially peeling 50 mm
of coating from one end of the coated steel plate with a
chisel.
CD test sample preparation
A 2-mm thick coating of blended material was applied
Figure 3. Schematic representation of the CD induced peel-test sample
preparation.
Polym Int 50:11151123 (2001)
Blends of maleic-anhydride-grafted polyethylene with polyethylene
by compression moulding on sand-blasted to near
white nish (AS 1627.4Class 2 12)12 steel plate
(230 mm  230 mm  4 mm) with a mould cavity
(190 mm  190 mm  2 mm) at 320 C for 34 min at
a pressure of 10 MPa, using glass-reinforced Teon as
a mould-release agent. The sample was quenched in
the cold press at a cooling rate of approximately 80 C
min 1, immediately after being removed from the hot
press.
CD test set-up
The basic experimental set-up required in the Aus-
tralian Standard AS 4321199513 (similar to ASTM
G8-95) was followed for the evaluation of the CD
performance of various coating samples. In accor-
dance with this test method, a 6-mm diameter aw was
drilled through the compression-moulded coating
sample to the metal surface in the centre of each CD
cell location using a at-end mill bit. Rigid PVC cells
having a diameter of 80 mm and approximately 90 mm
long were xed centrally over the holiday using silicone
adhesive. A PVC weathering apron (80 mm nominal
diameter) was attached to the PVC pipe with PVC
solvent adhesive. Both compartments were lled with
3 wt% NaCl solution, ie 0.52 M NaCl solution, and an
impressed current (3  0.02 mA) was applied using a
platinum anode which is kept at about 1.5 V versus
SCE to the steel/solution interface. At intervals not
exceeding 3 days, the circuit current was recorded and
adjusted to 3 mA if necessary. The test temperature
was maintained at 23  2 C throughout the test which
was run for 28 days. After 28 days the coating was
removed to measure the extent of disbondment. This
is reported as an average radial disbondment (RD).
Pressure-volume-temperature (PVT) experiments
PVT data14 record the specic volume of a material as
a function of pressure and temperature. The PVT data
was obtained on a Gnomix device where the conning
uid used was mercury. Since mercury is almost an
incompressible uid over a wide range of temperatures
and pressure, its volume change is very small and can
be subtracted via a mercury calibration run. The
advantage of this type of PVT device is that the sample
is under hydrostatic pressure at all times and there are
neither friction nor leakage problems. Each sample
was heated to 250 C and cooled to 50 C at a scanning
rate of 3 Cmin 1, at a lowest positive pressure of
10 MPa so as to generate PVT data.
The following equation15 was used for the calcula-
tion of the coefcient of thermal expansion,
a 1=V V =T P 2
where a is the coefcient of thermal expansion of the
specimen, V is the volume of the specimen, and
(dV/dT)P is the change in volume with respect to
change in temperature at a constant pressure, P, in the
PVT plot.
1117
D Roy, GP Simon, M Forsyth
Figure 4. DSC thermograms for MDPE, MAH-g-PE and MDPE/MAH-g-PE
blends.
Energy-dispersive X-ray spectroscopy
After removing the disbonded polyethylene surfaces
on completion of the 28 days of CD test, they were
gold-coated to make them conductive; and energy-
dispersive X-ray spectroscopy (EDXS) utilizing
Moran Scientic Software was employed in conjunc-
tion with a Joel JSM-840A, scanning electron micro-
scopy (SEM) to analyze the disbonded surfaces
qualitatively, to detect the presence of iron and other
elements on the PE surface. EDXS was also performed
on the matching, cathodically disbonded steel surface.
RESULTS AND DISCUSSION
Effect of blending on degree of crystallinity
DSC experiments were performed to determine the
effect of crystallinity on making various blends. Degree
of crystallinity was determined from DSC experiments
and the traces for the various blend compositions are
shown in Fig 4. The heat of fusion of the respective
material was obtained from the area under endothermic
peak of the curve and converted to percentage crystal-
linity using eqn (1). The degree of crystallinity is shown
in Fig 5 as a function of wt% addition of MAH-g-PE into
MDPE and it can be seen that the loading of very low
crystallinity material such as MAH-g-PE (crystallinity
about 16%) into a more highly crystalline material such
as MDPE (crystallinity of about 46%) slightly decreases
the total degree of blend crystallinity. The full results
obtained are summarized in Table 1, which shows that
the values of the percentage crystallinity in the blend are
slightly greater than predicted by the rule of mixtures, so
Heat of fusion Degree of crystallinity
Sample
MDPE
97.5/2.5
95/5
90/10
80/20
Table 1. Degree of crystallinity of neat polymers
MAH-g-PE
and blends
1118
Figure 5. Plot of degree of crystallinity versus addition of MAH-g-PE (wt%).
that high crystallinity is maintained. Even though the
more crystalline MDPE is slightly diluted, the minority
phase of MAH-g-PE appears to nucleate additional
crystallinity in the MDPE phase. It can also be observed
in the DSC thermograms in Fig 4 that the melting peaks
of MDPE and MAH-g-PE were at 128 C and 122 C
respectively, whilst the melting peak of blends ranged
between 128 C and 122 C. From these results, we
would suggest that any changes observed in CD
performance will not be a result of morphological/
crystallinity changes, ie shrinkage stresses, due only to
minor changes in coating crystallinity upon blending.
Effect of blend composition on dry bond strength
The dry bond strength was plotted as a function of
composition of the MDPE blends modied with
MAH-g-PE at a range of concentrations and is shown
in Fig 6. It is evident that blends yield higher dry bond
strength compared to unmodied MDPE, although
sufciently high dry bond strength (from a practical
perspective) was clearly obtained even with unmodi-
ed MDPE and the high-energy steel substrate. In all
the blends, an improvement in dry bond strength is
observed and it is seen that for loading of greater than
5 wt% MAH-g-PE, bond strength does not improve
further. It was observed in all dry post-peel test
samples that the failure mode is entirely cohesive,
leaving behind a residual trace of polymer on the steel
substrate. Thus, the polarity of the blend may have
produced toughness in the bulk material rather than
simply promoting greater bonding with the substrate.
% crystallinity
(DHf ; J g 1) (%) (according to rule of mixtures)
134.8  2.0 46.0  1.0 46.0  1.0
132.7  0.8 45.3  0.5 45.2  0.5
130.6  0.9 44.6  0.5 44.5  0.4
129.6  1.0 44.2  0.5 43.0  0.4
124.3  0.5 42.4  0.2 40.0  0.1
47.0  2.0 16.0  1.0 16.0  1.0
Polym Int 50:11151123 (2001)

Figure 6. Plot of dry bond strength (N mm 1) versus the addition of MAH-g-
PE (wt%).
Effect of blend composition on CD performance
The results of CD performance as RD (mm) are
plotted against the percentage of MAH-g-PE into
blend as shown in Fig 7. For all the blends, an
improvement in CD performance is observed which
suggests that the introduction of a polar functional
group into polyethylene matrix improves CD perfor-
mance. It can be noted that there is a shallow
minimum with 2.5 wt% blend, indicating that even
the addition of 2.5 wt% added polar functionality is
required to cause a signicant improvement in CD
properties. Indeed, there is a slight decrease in CD
resistance for higher loadings (20 wt%) due to the
possibility of degradation of the polar moieties in the
presence of alkali generated during CD reactions. This
result, therefore, veries our hypothesis that the
introduction of a lower amount of functionalized
polyethylene containing a polar functional group such
as anhydride into the backbone of polyethylene does
improve CD performance. When CD performance of
these materials is compared against the dry bond
strength, a lack of correlation is observed between
Figure 7. Plot of radial disbondment (mm) versus the addition of MAH-g-
PE (wt%).
Polym Int 50:11151123 (2001)
Blends of maleic-anhydride-grafted polyethylene with polyethylene
these two properties. This is reasonable, as both are
quite different phenomena, dry adhesion tests showing
cohesive failure due to fracture of the bulk polymer,
whereas (as expected) an interfacial failure mode was
clearly observed in case of the CD processes. The
similar observation, ie lack of correlation between CD
performance and dry bond strength, was also found in
the study of Smith et al 16 in an epoxy/steel coating
system.
Time dependence of CD process
The radial disbondment was determined as a function
of time in order to investigate the temporal depen-
dence of MDPE coated steel substrate and the results
are shown in Fig 8. Rather than a simple linear
dependence, it was possible to distinguish three
distinct stages of disbondment: 07 days, 714 days
and 1428 days, being represented as AB, BC and
CD, respectively. The study of Steismo and Skar17
found the time dependence of the cathodic disbonding
of epoxy/steel system to comprise an initial delay,
followed by a linear increase in the disbonded area
with time. The study of Hinton and Charlton18 in a
polyamide-cured epoxy/steel system showed the dela-
mination area increased with time according to a
second-order polynomial. Watts and Castle19 have
predicted a logarithmic dependence of disbondment
area with time in the initial stages of the disbondment.
The study of Luo et al 20 on polyurethane/steel coating
system found a slow rate of disbonding at the
beginning after which the disbonding is linearly related
to time. Higgins et al 21, however, have found the
`three-phase' disbondment, ie the disbondment in
three stages. It can be observed in Fig 8 that the RD is
greater during the rst week of the test (1.2 mm day),
after which the rate decreases in the second week to
0.77 mm day 1 and is effectively constant in weeks 24
at 0.74 mm day 1. In order to determine how the
different blends inuence such behaviour, a more
limited series of temporal tests at 14 and 28 days were
undertaken.
Figure 8. Plot of radial disbondment (mm) of unmodified MDPE as a
function of time, showing three distinct stages of disbondment during 28
days CD test.
1119
D Roy, GP Simon, M Forsyth
Figure 9. Disbonded area versus test time (days) as a function of
composition for unmodified MDPE, 5 wt% MAH-g-PE loaded MDPE and
20wt% MAH-g-PE loaded MDPE.
The effect of addition of MAH-g-PE to MDPE for
the improvement of CD performance by way of a
disbonded area is presented in Fig 9. The result
indicates that there is a higher CD initially for blends,
but with a lesser slope, whereas MDPE starts from a
lower level and develops at a faster rate compared to
blends. The disbonded area is found to increase
linearly with time during the 1428 days of the CD
test. Thus it appears that blending with polar func-
tional groups results in a decreased rate of disbonding
at later stages of the process. This could indicate an
increased resistance to the aggressive species under the
coating at longer times. It should be noted that, with
increased disbondment, a larger potential drop is
expected such that the potential at the crevice will be
signicantly more positive than at the holiday. This
change in potential is likely to result in a changing CD
mechanism with time.
Wet and dry peel tests at a slow speed
The mechanism22 of dry adhesion of polyethylene to a
high-surface-energy substrate like steel is associated
with the deection of the peeling path away from the
interface into the bulk of the polymer. This is probably
inuenced by the formation of polar functional groups
such as carbonyl and other oxygen-containing groups
during thermal oxidation of non-polar polyethylene,
resulting in dipolar adhesive bonds with steel suf-
ciently strong to encourage the crack to move into the
bulk coating, where a larger volume of polymer is
mechanical peeling
Sample
Blend 1a
Blend 2b
Table 2. Peel strength (N mm 1) for different pre-
a
experiment crack initiations at a cross-head speed MDPE MB.
b
0.01 mm min 1 MDPE 2.5 wt% MAH-g-PE.
1120
deformed during fracture. At a lower strain rate/peel
rate, the deformation can be minimized to a greater
extent which would give a smaller value of peel
strength, as well as being likely to induce adhesive
failure, and it has been attempted more closely to
replicate these conditions by performing the wet peel
test at a lower cross-head speed. The rate of disbond-
ment (disbondment speed) during CD is approxi-
mately 0.0005 mm min 1, considering a disbondment
of 20 mm in 28 days, which is much lower than the
cross-head speed of 1 mm min 1 commonly used to
measure dry peel strength.
To allow further understanding of the mechanisms
affecting CD performance, peel tests were carried out
at a slow strain rate of 0.01 mm min 1 on the Instron
4505 instrument under both dry and wet conditions
for the base MDPE/CB blend (Blend 1) and that
modied with 2.5 wt% MAH-g-PE (Blend 2). In the
case of wet peel tests, using the slow strain rate, two
different failure initiation procedures were followed in
an attempt to encourage interfacial failure. The results
of peel tests at a slow strain rate are presented in Table
2. It can be seen that there is an improvement of 40%
of dry bond strength upon modication with 2.5 wt%
MAH-g-PE. It is clear from the results that wet
adhesion strength has improved for both methods of
initiation for the 2.5 wt% MAH-g-PE loaded sample,
compared to the unmodied MDPE. As can be seen
from Table 2, when CD-induced wet adhesion
strength is compared with the respective dry bond
strength, the magnitude of the reduction of bond
strength in the case of unmodied MDPE is about
70%, compared to 55% of reduction in bond strength
in the case of 2.5 wt% MAH-g-PE loaded blend, all
measured at the same cross-head speed. It can also be
seen that the mode of failure in dry, as well as wet, peel
tests in 1 M NaOH without impressed current, follows
predominantly cohesive failure compared to adhesive/
interfacial failure in case of wet peel test initiated under
CD conditions. This study indicates that the factors
that inuence wet adhesion strength are also impor-
tant parameters for improving CD performance,
although what the specic factors are is unclear.
However, what is apparent is that wet adhesion tests
may well be good predictors of CD behaviour and are
quite useful as they can generate data much more
rapidly than normal CD test. Thus wet peel tests could
be used as a screening test to assess the CD
performance of various coating samples.
Wet (0.51 M NaCl) with
Dry with Wet (1 M NaOH) with mechanical peeling &
mechanical peeling impressed current CD
(Chisel) (Chisel) initiation/3 mA
2.7  0.2 1.0  0.4 0.8  0.1
3.8  0.6 3.2  0.5 1.7  0.1
Polym Int 50:11151123 (2001)

Figure 10. Experimental specific volume curve for MDPE showing the
volume changes in two stages (crystallization and shrinkage).
Thermal expansion coefficient and CD performance
As well as adhesion in wet conditions, other properties
of coatings may affect their CD performance. For
thermoplastic adhesive bonding to metals, different
thermal properties between the polymer coating and
metal substrate may generate residual stresses during
the cooling process, which may inuence CD proper-
ties. One important aspect of organic coatings is their
relatively high coefcient of thermal expansion com-
pared to the mild steel substrate, about 1214 times
higher in the case of PE. The large difference in
thermal expansion coefcients may manifest itself
during cooling and so develop internal strains within
the material. This can weaken the effective adhesion
strength of the coating and this might promote the
probability of an interfacial failure.23 As well as
differential shrinkage on cooling, the crystallization
of semi-crystalline polyethylene itself leads to stresses
that result in strain at the interface between coating
and steel. Note that we have already observed that
blending at the concentrations used in this work does
not signicantly modify the crystallinity of the coating.
PVT experiments were performed in order to
determine the effect of thermal expansion coefcient
and change in volume shrinkage of the primary
polymer and other blend samples on CD perfor-
mance. The volume changes during crystallization
(DVcrystallization) and shrinkage (DVshrinkage) can be
determined from isobaric PVT plot in a manner
illustrated in Fig 10 for the base polymer. Table 3
quanties the change in volume on cooling, the initial
Sample
MDPE
Blend 1a
Blend 2b
a
Table 3. Change in specific volume and thermal MDPE MB.
b
expansion coefficients of polymers MDPE 2.5 wt% MAH-g-PE.
Polym Int 50:11151123 (2001)
Blends of maleic-anhydride-grafted polyethylene with polyethylene
Figure 11. PVT plot as a function of composition of MDPE, Blend 1 and
Blend 2.
change due to crystallization and further thermal
contraction occurring following crystallization, as the
sample is cooled to room temperature, largely due to
further shrinkage of the amorphous region and to a
lesser degree of the crystalline phase. DV due to
crystallization is found to be similar for base polymer
and blends, as expected from the similar degree of
crystallinity determined from DSC. The linear
thermal expansion coefcient (a) of each sample
was calculated in the region between room tempera-
ture and the melting point from an isobaric plot of the
specic volume and temperature using the eqn (2).
The PVT experiment shows very similar thermal
expansion coefcients, as seen in the slopes of the
curves in Fig 11, which are plots for the main polymer
and the blends. Thus, the coefcient of thermal
expansion does not change appreciably for such low
additions of MAH-g-PE into the base polymer. It is
evident from the Table 3 that specic volume does
not change markedly as a function of composition in
PVT experiment. It is also clear that the thermal
expansion coefcient of modied materials containing
low amounts of additive plays a minor role in
modifying CD performance. Therefore we can con-
clude that any improvements seen in this work are not
as a result of any major change in shrinkage stresses.
Surface analysis: interface between the polymer and
steel
In order to further identify the mode of failure, the
cathodically disbonded polymer and steel sides of
Change in specic Change in specic Thermal expansion
volume during volume during coefcient (1/ V(d V/ d T)P
crystallization shrinkage DVshrinkage (during shrinkage)
DVcrystallization (cm3 g 1) (cm3 g 1) ( C)
4
0.09 0.06 10.8  10
0.08 0.07 11.0  10 4
0.09 0.08 13.7  10 4
1121
D Roy, GP Simon, M Forsyth
sample Blend 2 (after the completion of 28 days CD
test), taken from the region of 23 mm around the
initial holiday, were examined using EDXS. The EDX
spectra are shown in Fig 12 and the surface analysis of
polymer demonstrates the presence of iron on the
polymer surface, suggesting that the failure in this
region close to the holiday occurred due to dissolution
of iron oxide at the holiday. It is also clear from EDX
spectrum obtained from surface analysis of cathodi-
cally disbonded steel surface, that there is no trace of
carbon/polymer indicating the fact that disbondment
mode is truly interfacial failure. EDXS was also
performed on disbonded polymer surface at the
completion of 28-day CD test, at varying length from
the holiday and a general trend of decreasing iron level
could be observed on disbonded polymer surface with
distance from the holiday. The cathodic-disbonding
process is a complex and multi-stage phenomenon. A
plausible explanation of this phenomenon was offered
by Watts and Castle,19 who suggested a two-stage
theory of disbondment. The rst stage is dissolution of
metal oxide following a logarithmic rate and the
second stage is due to the failure at metal oxide/
polymer interface with a linear rate. The third stage
seen in this work and reported by Higgins et al 21
suggests a change in failure kinetics, the reasons for
which are not clear. There is other evidence in the
literature,19,24 which also reports that reduction of
interfacial oxide is the prime cause of the earlier stage
of disbonding.
CONCLUSIONS
This work has indicated that the discussion of
adhesion strength and its effect on CD performance
necessitates measurement of wet adhesion strength,
using tests which encourage interfacial failure. No
correlation was found between CD performance and
Figure 12. Energy-dispersive X-ray
Spectroscopy (EDXS) of cathodically-
disbonded polymer surface (dotted
line) and cathodically-disbonded steel
surface (solid line) for blend 2, near
holiday.
1122
dry bond strength, which is reasonable as the mode of
failure in CD is observed to be an interfacial/adhesive
failure whereas dry bond strength corresponds to the
cohesive failure mode. It appears that wet adhesion
strength is thus an important indicator of the im-
provement of CD performance: the higher the value,
the better the CD performance of the coating material.
This study also indicates that quite low loading of
polar functional groups can lead to signicant im-
provement in CD performance. It is shown that degree
of crystallinity and thermal expansion coefcient do
not change appreciably for the low addition of 2.5 wt%
MAH-g-PE and this plays a minor role in modifying
CD performance of a semi-crystalline thermoplastic
polymer, such as polyethylene, due to factors such as
internal stresses or shrinkage. EDXS suggests that iron
oxide is involved in the disbondment process of
polyethylene/steel system at the holiday, in presence
of cathodic protection. The improvement of CD
performance is due to the improvement of wet
adhesion strength upon introduction of polar func-
tional group such as MAH-g-PE into MDPE due to
the improved adhesion between polymer/metal oxide
layer, reecting a lower disbondment rate in the slope
of the blends compared to unmodied base polymer
MDPE. These two parameters appear to be corre-
lated, as can be seen in the strong correlations between
results in the CD-induced wet adhesion test and the
CD test. Such wet adhesion tests are much more rapid
to perform than waiting the 28 days for CD results and
thus may prove to be a rapid and effective screening
test for new samples.
ACKNOWLEDGEMENTS
DR gratefully acknowledges the support of the CRC
for Polymers throughout this project. The authors
would like to thank Mr Ashley Fletcher and Mr Lex
Polym Int 50:11151123 (2001)

Edmond, Tyco Water Pipelines Research, for their
valuable help in this work; and Mr John Thomas and
Mr Robert Brown, Moldow Ltd, for PVT experi-
ments. The authors would like to thank Dr James
Mardel, CSIRO Molecular Science for helping with
XPS experiments.
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