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


Blends of maleic-anhydride-grafted polyethylene with polyethylene

mechanical peeling by chisel, followed by immersion by compression moulding on sand-blasted to near


in 1 M NaOH solution for at least 1 h without white nish (AS 1627.4Class 2 12)12 steel plate
impressed current, and (c) initiation of failure by (230 mm  230 mm  4 mm) with a mould cavity
cathodically disbonding the sample (polarization (190 mm  190 mm  2 mm) at 320 C for 34 min at
potential 1.5 VSCE in 0.51 M NaCl) (The latter two a pressure of 10 MPa, using glass-reinforced Teon as
methods for wet peel testing). It should be noted that a mould-release agent. The sample was quenched in
the methods (b) and (c) for wet peel testing were tried the cold press at a cooling rate of approximately 80 C
in an attempt to induce as much adhesive failure as min 1, immediately after being removed from the hot
possible in order to simulate the largely adhesive press.
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 CD test set-up
steel surface and is performed to allow comparison of The basic experimental set-up required in the Aus-
dry bond strength of various coating samples, rather tralian Standard AS 4321199513 (similar to ASTM
than for any mechanistic study of the CD process, and G8-95) was followed for the evaluation of the CD
allows comparison with the wet adhesion strength of performance of various coating samples. In accor-
respective samples. dance with this test method, a 6-mm diameter aw was
For peel-test specimens, a 2-mm thick coating was drilled through the compression-moulded coating
applied on sand-blasted steel strip (190 mm  sample to the metal surface in the centre of each CD
10 mm  25 mm) with a mould cavity (190 mm  cell location using a at-end mill bit. Rigid PVC cells
12 mm  25 mm) at 320 C for 34 min in a heated having a diameter of 80 mm and approximately 90 mm
press at 10 MPa, and was subsequently quenched in long were xed centrally over the holiday using silicone
the cold press. The difference in testing applies to the adhesive. A PVC weathering apron (80 mm nominal
manner in which the failure locus is commenced. In diameter) was attached to the PVC pipe with PVC
the case of dry peel tests, the compression-moulded solvent adhesive. Both compartments were lled with
sample was chiselled off at about 50 mm from one edge 3 wt% NaCl solution, ie 0.52 M NaCl solution, and an
to mount on the 90 peel-test rig and subsequently impressed current (3  0.02 mA) was applied using a
clamped by the tensile tester grip. Method (b) for wet platinum anode which is kept at about 1.5 V versus
peel testing involved chiselling off approximately SCE to the steel/solution interface. At intervals not
50 mm of polymer from one edge and leaving the exceeding 3 days, the circuit current was recorded and
sample in 1 M NaOH solution (pH underneath coating adjusted to 3 mA if necessary. The test temperature
measured from XPS analysis, not shown here, was was maintained at 23  2 C throughout the test which
between 13.7 and 13.9 at the end of 28 days of CD test was run for 28 days. After 28 days the coating was
under normal conditions, which is about 1 M NaOH) removed to measure the extent of disbondment. This
without any impressed current for at least 1 h before is reported as an average radial disbondment (RD).
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 Pressure-volume-temperature (PVT) experiments
by placing them in 3 wt% NaCl solution under 3 mA PVT data14 record the specic volume of a material as
current for seven days (c 1 M NaOH measured by pH a function of pressure and temperature. The PVT data
meter, as well as titration), after initially peeling 50 mm was obtained on a Gnomix device where the conning
of coating from one end of the coated steel plate with a uid used was mercury. Since mercury is almost an
chisel. incompressible uid over a wide range of temperatures
and pressure, its volume change is very small and can
CD test sample preparation be subtracted via a mercury calibration run. The
A 2-mm thick coating of blended material was applied 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
Figure 3. Schematic representation of the CD induced peel-test sample change in temperature at a constant pressure, P, in the
preparation. PVT plot.

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D Roy, GP Simon, M Forsyth

Figure 4. DSC thermograms for MDPE, MAH-g-PE and MDPE/MAH-g-PE


Figure 5. Plot of degree of crystallinity versus addition of MAH-g-PE (wt%).
blends.

Energy-dispersive X-ray spectroscopy that high crystallinity is maintained. Even though the
After removing the disbonded polyethylene surfaces more crystalline MDPE is slightly diluted, the minority
on completion of the 28 days of CD test, they were phase of MAH-g-PE appears to nucleate additional
gold-coated to make them conductive; and energy- crystallinity in the MDPE phase. It can also be observed
dispersive X-ray spectroscopy (EDXS) utilizing in the DSC thermograms in Fig 4 that the melting peaks
Moran Scientic Software was employed in conjunc- of MDPE and MAH-g-PE were at 128 C and 122 C
tion with a Joel JSM-840A, scanning electron micro- respectively, whilst the melting peak of blends ranged
scopy (SEM) to analyze the disbonded surfaces between 128 C and 122 C. From these results, we
qualitatively, to detect the presence of iron and other would suggest that any changes observed in CD
elements on the PE surface. EDXS was also performed performance will not be a result of morphological/
on the matching, cathodically disbonded steel surface. crystallinity changes, ie shrinkage stresses, due only to
minor changes in coating crystallinity upon blending.

RESULTS AND DISCUSSION


Effect of blending on degree of crystallinity Effect of blend composition on dry bond strength
DSC experiments were performed to determine the The dry bond strength was plotted as a function of
effect of crystallinity on making various blends. Degree composition of the MDPE blends modied with
of crystallinity was determined from DSC experiments MAH-g-PE at a range of concentrations and is shown
and the traces for the various blend compositions are in Fig 6. It is evident that blends yield higher dry bond
shown in Fig 4. The heat of fusion of the respective strength compared to unmodied MDPE, although
material was obtained from the area under endothermic sufciently high dry bond strength (from a practical
peak of the curve and converted to percentage crystal- perspective) was clearly obtained even with unmodi-
linity using eqn (1). The degree of crystallinity is shown ed MDPE and the high-energy steel substrate. In all
in Fig 5 as a function of wt% addition of MAH-g-PE into the blends, an improvement in dry bond strength is
MDPE and it can be seen that the loading of very low observed and it is seen that for loading of greater than
crystallinity material such as MAH-g-PE (crystallinity 5 wt% MAH-g-PE, bond strength does not improve
about 16%) into a more highly crystalline material such further. It was observed in all dry post-peel test
as MDPE (crystallinity of about 46%) slightly decreases samples that the failure mode is entirely cohesive,
the total degree of blend crystallinity. The full results leaving behind a residual trace of polymer on the steel
obtained are summarized in Table 1, which shows that substrate. Thus, the polarity of the blend may have
the values of the percentage crystallinity in the blend are produced toughness in the bulk material rather than
slightly greater than predicted by the rule of mixtures, so simply promoting greater bonding with the substrate.

Heat of fusion Degree of crystallinity % crystallinity


Sample (DHf ; J g 1) (%) (according to rule of mixtures)
MDPE 134.8  2.0 46.0  1.0 46.0  1.0
97.5/2.5 132.7  0.8 45.3  0.5 45.2  0.5
95/5 130.6  0.9 44.6  0.5 44.5  0.4
90/10 129.6  1.0 44.2  0.5 43.0  0.4
80/20 124.3  0.5 42.4  0.2 40.0  0.1
Table 1. Degree of crystallinity of neat polymers
MAH-g-PE 47.0  2.0 16.0  1.0 16.0  1.0
and blends

1118 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
Figure 6. Plot of dry bond strength (N mm 1) versus the addition of MAH-g- distinct stages of disbondment: 07 days, 714 days
PE (wt%). 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
Effect of blend composition on CD performance of epoxy/steel system to comprise an initial delay,
The results of CD performance as RD (mm) are followed by a linear increase in the disbonded area
plotted against the percentage of MAH-g-PE into with time. The study of Hinton and Charlton18 in a
blend as shown in Fig 7. For all the blends, an polyamide-cured epoxy/steel system showed the dela-
improvement in CD performance is observed which mination area increased with time according to a
suggests that the introduction of a polar functional second-order polynomial. Watts and Castle19 have
group into polyethylene matrix improves CD perfor- predicted a logarithmic dependence of disbondment
mance. It can be noted that there is a shallow area with time in the initial stages of the disbondment.
minimum with 2.5 wt% blend, indicating that even The study of Luo et al 20 on polyurethane/steel coating
the addition of 2.5 wt% added polar functionality is system found a slow rate of disbonding at the
required to cause a signicant improvement in CD beginning after which the disbonding is linearly related
properties. Indeed, there is a slight decrease in CD to time. Higgins et al 21, however, have found the
resistance for higher loadings (20 wt%) due to the `three-phase' disbondment, ie the disbondment in
possibility of degradation of the polar moieties in the three stages. It can be observed in Fig 8 that the RD is
presence of alkali generated during CD reactions. This greater during the rst week of the test (1.2 mm day),
result, therefore, veries our hypothesis that the after which the rate decreases in the second week to
introduction of a lower amount of functionalized 0.77 mm day 1 and is effectively constant in weeks 24
polyethylene containing a polar functional group such at 0.74 mm day 1. In order to determine how the
as anhydride into the backbone of polyethylene does different blends inuence such behaviour, a more
improve CD performance. When CD performance of limited series of temporal tests at 14 and 28 days were
these materials is compared against the dry bond undertaken.
strength, a lack of correlation is observed between

Figure 8. Plot of radial disbondment (mm) of unmodified MDPE as a


Figure 7. Plot of radial disbondment (mm) versus the addition of MAH-g- function of time, showing three distinct stages of disbondment during 28
PE (wt%). days CD test.

Polym Int 50:11151123 (2001) 1119


D Roy, GP Simon, M Forsyth

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
Figure 9. Disbonded area versus test time (days) as a function of 4505 instrument under both dry and wet conditions
composition for unmodified MDPE, 5 wt% MAH-g-PE loaded MDPE and for the base MDPE/CB blend (Blend 1) and that
20wt% MAH-g-PE loaded MDPE.
modied with 2.5 wt% MAH-g-PE (Blend 2). In the
case of wet peel tests, using the slow strain rate, two
The effect of addition of MAH-g-PE to MDPE for different failure initiation procedures were followed in
the improvement of CD performance by way of a an attempt to encourage interfacial failure. The results
disbonded area is presented in Fig 9. The result of peel tests at a slow strain rate are presented in Table
indicates that there is a higher CD initially for blends, 2. It can be seen that there is an improvement of 40%
but with a lesser slope, whereas MDPE starts from a of dry bond strength upon modication with 2.5 wt%
lower level and develops at a faster rate compared to MAH-g-PE. It is clear from the results that wet
blends. The disbonded area is found to increase adhesion strength has improved for both methods of
linearly with time during the 1428 days of the CD initiation for the 2.5 wt% MAH-g-PE loaded sample,
test. Thus it appears that blending with polar func- compared to the unmodied MDPE. As can be seen
tional groups results in a decreased rate of disbonding from Table 2, when CD-induced wet adhesion
at later stages of the process. This could indicate an strength is compared with the respective dry bond
increased resistance to the aggressive species under the strength, the magnitude of the reduction of bond
coating at longer times. It should be noted that, with strength in the case of unmodied MDPE is about
increased disbondment, a larger potential drop is 70%, compared to 55% of reduction in bond strength
expected such that the potential at the crevice will be in the case of 2.5 wt% MAH-g-PE loaded blend, all
signicantly more positive than at the holiday. This measured at the same cross-head speed. It can also be
change in potential is likely to result in a changing CD seen that the mode of failure in dry, as well as wet, peel
mechanism with time. tests in 1 M NaOH without impressed current, follows
predominantly cohesive failure compared to adhesive/
Wet and dry peel tests at a slow speed interfacial failure in case of wet peel test initiated under
The mechanism22 of dry adhesion of polyethylene to a CD conditions. This study indicates that the factors
high-surface-energy substrate like steel is associated that inuence wet adhesion strength are also impor-
with the deection of the peeling path away from the tant parameters for improving CD performance,
interface into the bulk of the polymer. This is probably although what the specic factors are is unclear.
inuenced by the formation of polar functional groups However, what is apparent is that wet adhesion tests
such as carbonyl and other oxygen-containing groups may well be good predictors of CD behaviour and are
during thermal oxidation of non-polar polyethylene, quite useful as they can generate data much more
resulting in dipolar adhesive bonds with steel suf- rapidly than normal CD test. Thus wet peel tests could
ciently strong to encourage the crack to move into the be used as a screening test to assess the CD
bulk coating, where a larger volume of polymer is performance of various coating samples.

Wet (0.51 M NaCl) with


Dry with Wet (1 M NaOH) with mechanical peeling &
mechanical peeling mechanical peeling impressed current CD
Sample (Chisel) (Chisel) initiation/3 mA
Blend 1a 2.7  0.2 1.0  0.4 0.8  0.1
Blend 2b 3.8  0.6 3.2  0.5 1.7  0.1
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 Polym Int 50:11151123 (2001)


Blends of maleic-anhydride-grafted polyethylene with polyethylene

Figure 10. Experimental specific volume curve for MDPE showing the
Figure 11. PVT plot as a function of composition of MDPE, Blend 1 and
volume changes in two stages (crystallization and shrinkage).
Blend 2.

Thermal expansion coefficient and CD performance change due to crystallization and further thermal
As well as adhesion in wet conditions, other properties contraction occurring following crystallization, as the
of coatings may affect their CD performance. For sample is cooled to room temperature, largely due to
thermoplastic adhesive bonding to metals, different further shrinkage of the amorphous region and to a
thermal properties between the polymer coating and lesser degree of the crystalline phase. DV due to
metal substrate may generate residual stresses during crystallization is found to be similar for base polymer
the cooling process, which may inuence CD proper- and blends, as expected from the similar degree of
ties. One important aspect of organic coatings is their crystallinity determined from DSC. The linear
relatively high coefcient of thermal expansion com- thermal expansion coefcient (a) of each sample
pared to the mild steel substrate, about 1214 times was calculated in the region between room tempera-
higher in the case of PE. The large difference in ture and the melting point from an isobaric plot of the
thermal expansion coefcients may manifest itself specic volume and temperature using the eqn (2).
during cooling and so develop internal strains within The PVT experiment shows very similar thermal
the material. This can weaken the effective adhesion expansion coefcients, as seen in the slopes of the
strength of the coating and this might promote the curves in Fig 11, which are plots for the main polymer
probability of an interfacial failure.23 As well as and the blends. Thus, the coefcient of thermal
differential shrinkage on cooling, the crystallization expansion does not change appreciably for such low
of semi-crystalline polyethylene itself leads to stresses additions of MAH-g-PE into the base polymer. It is
that result in strain at the interface between coating evident from the Table 3 that specic volume does
and steel. Note that we have already observed that not change markedly as a function of composition in
blending at the concentrations used in this work does PVT experiment. It is also clear that the thermal
not signicantly modify the crystallinity of the coating. expansion coefcient of modied materials containing
PVT experiments were performed in order to low amounts of additive plays a minor role in
determine the effect of thermal expansion coefcient modifying CD performance. Therefore we can con-
and change in volume shrinkage of the primary clude that any improvements seen in this work are not
polymer and other blend samples on CD perfor- as a result of any major change in shrinkage stresses.
mance. The volume changes during crystallization
(DVcrystallization) and shrinkage (DVshrinkage) can be Surface analysis: interface between the polymer and
determined from isobaric PVT plot in a manner steel
illustrated in Fig 10 for the base polymer. Table 3 In order to further identify the mode of failure, the
quanties the change in volume on cooling, the initial 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)
Sample DVcrystallization (cm3 g 1) (cm3 g 1) ( C)
4
MDPE 0.09 0.06 10.8  10
Blend 1a 0.08 0.07 11.0  10 4

Blend 2b 0.09 0.08 13.7  10 4

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) 1121


D Roy, GP Simon, M Forsyth

sample Blend 2 (after the completion of 28 days CD dry bond strength, which is reasonable as the mode of
test), taken from the region of 23 mm around the failure in CD is observed to be an interfacial/adhesive
initial holiday, were examined using EDXS. The EDX failure whereas dry bond strength corresponds to the
spectra are shown in Fig 12 and the surface analysis of cohesive failure mode. It appears that wet adhesion
polymer demonstrates the presence of iron on the strength is thus an important indicator of the im-
polymer surface, suggesting that the failure in this provement of CD performance: the higher the value,
region close to the holiday occurred due to dissolution the better the CD performance of the coating material.
of iron oxide at the holiday. It is also clear from EDX This study also indicates that quite low loading of
spectrum obtained from surface analysis of cathodi- polar functional groups can lead to signicant im-
cally disbonded steel surface, that there is no trace of provement in CD performance. It is shown that degree
carbon/polymer indicating the fact that disbondment of crystallinity and thermal expansion coefcient do
mode is truly interfacial failure. EDXS was also not change appreciably for the low addition of 2.5 wt%
performed on disbonded polymer surface at the MAH-g-PE and this plays a minor role in modifying
completion of 28-day CD test, at varying length from CD performance of a semi-crystalline thermoplastic
the holiday and a general trend of decreasing iron level polymer, such as polyethylene, due to factors such as
could be observed on disbonded polymer surface with internal stresses or shrinkage. EDXS suggests that iron
distance from the holiday. The cathodic-disbonding oxide is involved in the disbondment process of
process is a complex and multi-stage phenomenon. A polyethylene/steel system at the holiday, in presence
plausible explanation of this phenomenon was offered of cathodic protection. The improvement of CD
by Watts and Castle,19 who suggested a two-stage performance is due to the improvement of wet
theory of disbondment. The rst stage is dissolution of adhesion strength upon introduction of polar func-
metal oxide following a logarithmic rate and the tional group such as MAH-g-PE into MDPE due to
second stage is due to the failure at metal oxide/ the improved adhesion between polymer/metal oxide
polymer interface with a linear rate. The third stage layer, reecting a lower disbondment rate in the slope
seen in this work and reported by Higgins et al 21 of the blends compared to unmodied base polymer
suggests a change in failure kinetics, the reasons for MDPE. These two parameters appear to be corre-
which are not clear. There is other evidence in the lated, as can be seen in the strong correlations between
literature,19,24 which also reports that reduction of results in the CD-induced wet adhesion test and the
interfacial oxide is the prime cause of the earlier stage CD test. Such wet adhesion tests are much more rapid
of disbonding. 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.
CONCLUSIONS
This work has indicated that the discussion of
adhesion strength and its effect on CD performance ACKNOWLEDGEMENTS
necessitates measurement of wet adhesion strength, DR gratefully acknowledges the support of the CRC
using tests which encourage interfacial failure. No for Polymers throughout this project. The authors
correlation was found between CD performance and would like to thank Mr Ashley Fletcher and Mr Lex

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 Polym Int 50:11151123 (2001)


Blends of maleic-anhydride-grafted polyethylene with polyethylene

Edmond, Tyco Water Pipelines Research, for their Encyclopedia of Polymer Science and Engineering, vol 4, 2nd
valuable help in this work; and Mr John Thomas and edn, John Wiley & Sons Inc, 487488 (1986).
11 Gardon JL, Treatise on Adhesion and Adhesives, ed by Patrick RL,
Mr Robert Brown, Moldow Ltd, for PVT experi-
Marcel Dekker, New York, p 293 (1967).
ments. The authors would like to thank Dr James 12 AS 1627.41989: Metal FinishingPreparation and Pretreat-
Mardel, CSIRO Molecular Science for helping with ment of Surfaces, Part 4: Abrasive blast cleaning, Australian
XPS experiments. Standards.
13 AS 43211995: Cathodic Disbonding Resistance Test, Fusion-
bonded medium-density polyethylene coating and lining for
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