materials

Article
Degradation Monitoring of HDPE Material in CO2-Saturated
NaCl Environment through Electrochemical Impedance
Spectroscopy Technique
Hafiz Usman Khalid * , Mokhtar Che Ismail and Norlin Nosbi

Department of Mechanical Engineering, Universiti Teknologi PETRONAS, Perak 32610, Malaysia;

[email protected] (M.C.I.); [email protected] (N.N.)
* Correspondence: [email protected]

Abstract: Extensive damage due to saturated seawater and CO2 exposure under high temperature
and pressure in high-density polyethylene (HDPE) has been studied by Infrared Spectroscopy
(FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), Field Emission
Scanning Electron Microscope (FESEM), and Electrochemical Impedance Spectroscopy (EIS). The
degradation of square-shaped HDPE samples having 1 mm thickness was investigated at 70 bars
with 60, 75, and 90 ◦ C separately for three weeks in an autoclave chamber. A clear indication of
aging was observed in terms of chain scission by the formation of the methyl group (1262 cm−1 ),
and the appearance of degradation products, including the alcohol and hydroxyl groups. The
decline in glass transition temperature (Tg ), melting point (Tm ), and crystallinity (Xc ) result from
branching and formation of degradation products in the aged samples. TGA results reveal that the





 degradation shifts the characteristic temperatures (T5% and T10% ) to lower values compared to virgin
Citation: Khalid, H.U.; Ismail, M.C.;
HDPE. FESEM images show clear surface cracks and rough patches after 3 weeks. The Xc value
Nosbi, N. Degradation Monitoring of increased due to chain mobility at higher temperatures (90 ◦ C). The impedance is relatively high
HDPE Material in CO2 -Saturated 1011 ohms.cm−2 for a virgin sample, but it drops down to 109 and 106 after degradation. Impedance
NaCl Environment through and dielectric loss were correlated, and the significance of dielectric loss was observed at lower
Electrochemical Impedance frequencies. These characterizations will contribute to more efficient and detailed evaluation criteria
Spectroscopy Technique. Materials for degradation monitoring.
2021, 14, 2823. https://doi.org/
10.3390/ma14112823 Keywords: HDPE; CO2 exposure; EIS; dielectric; degradation monitoring

Academic Editor: Francesca Lionetto

Received: 21 April 2021

1. Introduction
Accepted: 21 May 2021
Published: 25 May 2021
Pipelines are used for the transportation of crude oil and natural gas in the oil and
gas industries. In upstream production, pipeline integrity is affected by corrosion due to
Publisher’s Note: MDPI stays neutral
contaminants in the process fluid such as CO2 , H2 S, and microbes. CO2 corrosion (sweet
with regard to jurisdictional claims in
corrosion) and H2 S (sour corrosion) are the most prevalent forms of corrosion, influenced
published maps and institutional affil- by many factors such as CO2 and H2 S content, water chemistry, temperature, flow velocity,
iations. and material surface condition [1,2].
Typical industrial practices employ cost-effective mitigation methods of material
selection, corrosion inhibition and chemical treatments, metallic and non-metallic linings,
and other appropriate options [3,4]. Recently, a potential option of non-metallic pipe (NMP)
Copyright: © 2021 by the authors.
for combating internal pipeline corrosion is assessed. The use of non-metallic pipes (NMP)
Licensee MDPI, Basel, Switzerland.
in oil and gas production and transportation is deemed to be promising based on the
This article is an open access article
improved material properties that are accepted as viable and reliable solutions to reduce
distributed under the terms and corrosion [5]. However, as a part of monitoring and maintenance management, continuous
conditions of the Creative Commons monitoring of the installation is required.
Attribution (CC BY) license (https:// NMP liners provide a potential corrosion management solution in cases where the
creativecommons.org/licenses/by/ long-term reliability of chemical corrosion inhibition systems is not suitable. Sometimes,
4.0/). the inhibitor consumption rate is so high that it becomes more expensive than a liner over

Materials 2021, 14, 2823. https://doi.org/10.3390/ma14112823 https://www.mdpi.com/journal/materials

Materials 2021, 14, x FOR PEER REVIEW 2 of 19

Materials 2021, 14, 2823 2 of 19

the inhibitor consumption rate is so high that it becomes more expensive than a liner over
the pipeline’s lifetime [2,6]. NMP has been implemented in pipelines mainly due to its
the pipeline’s
corrosion lifetime
resistance [2,6].
to the NMP environment
process has been implemented in pipelines
[7–9]. However, mainly due
these materials to its
degrade
corrosion resistance to the process environment [7–9]. However, these materials degrade
as a result of their interaction with the process environment [10,11]. The most common
as a result of their interaction with the process environment [10,11]. The most common
polymer material used in the pipeline industry includes high-density polyethylene
polymer material used in the pipeline industry includes high-density polyethylene (HDPE),
(HDPE), polyamide (PA11, PA12), and polyvinylidene fluoride (PVDF) [8,12,13].
polyamide (PA11, PA12), and polyvinylidene fluoride (PVDF) [8,12,13].
Thermoplastic-lined pipes have been proved to be commercially viable in one of the
Thermoplastic-lined pipes have been proved to be commercially viable in one of the
reports given by Atkins Boreas [13]. Thermoplastic liners (TPL) have been used effectively
reports given by Atkins Boreas [13]. Thermoplastic liners (TPL) have been used effectively
to control downhole failures in oil and gas production compared to other mitigation strat-
to control downhole failures in oil and gas production compared to other mitigation
egies, including coatings and chemical treatment. The usage of TPL was cost-effective, as
strategies, including coatings and chemical treatment. The usage of TPL was cost-effective,
proved by the case studies in Canada, Basin, and Bahrain [8].
as proved by the case studies in Canada, Basin, and Bahrain [8].
The degradation or aging susceptibility of thermoplastics depends on the environ-
The degradation or aging susceptibility of thermoplastics depends on the environ-
mental
mental factors
factorsand
andpolymer
polymerchemical
chemicalstructure
structure(molecular
(molecular weight,
weight, type
typeof of
bonds,
bonds,crystal-
crys-
linity) [14,15]. Thermoplastics have an inherent property to allow
tallinity) [14,15]. Thermoplastics have an inherent property to allow gases, vapors, and gases, vapors, and liq-
uids to pass through them. The environmental and temperature factors
liquids to pass through them. The environmental and temperature factors radically influ- radically influence
them [16,17].
ence them In general,
[16,17]. degradation
In general, of polymers
degradation of polymersoccurs due to
occurs due permeation,
to permeation, absorption,
absorp-
and
tion,oxidation, particularly
and oxidation, in the in
particularly immersed condition
the immersed of the internal
condition pipeline
of the internal [9,18]. How-
pipeline [9,18].
ever, the degradation is a time-dependent and
However, the degradation is a time-dependent and slow process.slow process.
Aging
Aging studies
studies areare intended
intended to to accelerate
accelerate thethe degradation
degradation chemistry,
chemistry, and and the
the resulting
resulting
degradation stage is often monitored with supporting chemical
degradation stage is often monitored with supporting chemical analysis such analysis such as as
IR IR
signa-
sig-
tures, discoloration, crosslink state, melting behavior, crystallinity,
natures, discoloration, crosslink state, melting behavior, crystallinity, and morphological and morphological
characterization
characterization [19–22].
[19–22]. ItIt is
is well
well known
known thatthat the
the degradation
degradation proceeds
proceeds through chain
through chain
scission,
scission, degree
degree ofof branching,
branching, and andcrosslinking,
crosslinking,as asevident
evidentby bythe
thedecrease
decreaseininthe themolecular
molecu-
lar weight
weight [15].
[15].
Permeation
Permeation is is the
the prominent
prominent aspect
aspect of of the
the degradation
degradation of of pipelines
pipelines due due to
to the
the expo-
expo-
sure
sure of acidic gases and immersion in hydrocarbons, including acids
including acids in the presence of
temperature
temperature and and pressure
pressure [23–27]. In the presence of hydrocarbons, polyolefins swell as
they
they both
both have a similar chemical structure. Polyamide Polyamide degrades
degrades due due to the presence of
water at higher temperatures [28].
Permeation
Permeation underunder highhigh temperature-pressure
temperature-pressure working working conditions
conditions containing
containing hydro-
hydro-
carbons
carbons and acidic gases limits the NMP’s operational envelopes. Thus, condition-based
monitoring through
through systematic
systematicevaluation
evaluationofofdegradation
degradation phases
phases is critical
is critical for for success-
successfully
usingusing
fully NMPNMP materials. Furthermore,
materials. Furthermore, permeation
permeation is a slow process
is a slow and requires
process sensitive
and requires sen-
monitoring
sitive methods.
monitoring methods.Currently, test test
Currently, coupons
couponsare are
used for for
used monitoring
monitoring NMPNMP degrada-
degra-
tion asas
dation shown
shown ininFigure
Figure1.1.These
Thesecoupons
couponsare areinserted
insertedin in pipelines
pipelines andand then retrieved
and evaluated
and evaluated using molecular weight change as a measuring measuring indicator
indicator [25,29,30].
[25,29,30]. The
coupon
coupon method provides a qualitative measurement of the degradation
provides a qualitative measurement of the degradation mechanism mechanism and is
and
incapable of monitoring the progression of damage
is incapable of monitoring the progression of damage [31,32]. [31,32].

(a) (b)

Figure 1. (a) Polymer coupon in the pipeline, (b) coupon and holder.
Materials 2021, 14, 2823 3 of 19

The EIS technique is proposed in this research article to evaluate HDPE performance
after the degradation in terms of impedance property. It can be used for corrosion rate
measurements, corrosivity monitoring, coating integrity measurements, and reaction mech-
anism investigations based on impedance property. Due to immersion in the HCl and
chloride solution, coatings degrade, which is illustrated by the formation of a capacitive
loop in the Nyquist diagram, and the electrolyte has penetrated through the coating and
reached the metal surface [33,34]. Corrosion pitting was seen in the embedded steel rein-
forcement due to the presence of different chloride concentrations [35]. Similar studies have
been carried out to study the corrosion and aging behavior of X65 steel, KOH electrolyte,
and hard metals [36–38].
For the life prediction of the NMP, a quantitative correlation of the damage phases
is indispensable. There is a research gap in on-field evaluation, such as post-installation
(in-service) degradation modes for NMP due to permeation. Our objective is to establish
a correlation between degradation chemistry with the HDPE polymer’s critical physi-
cal and dielectric properties. It can be useful for quantitative measures to identify the
degradation stages in the material after permeation damage. Hence, there is a need to
provide an evaluation criterion that can contribute to a more systematic and detailed
assessment process.

2. Materials and Methods

2.1. Sample Preparation
The commercial HDPE polymeric sheet of 1 mm thickness has been provided by
ARJ Development Sdn Bhd, Perak, Malaysia. It has been cut into square samples with
dimensions of 23 mm. CO2 gas cylinders were provided by AGS Sdn Bhd, Penang, Malaysia
while NaCl was taken from the Materials lab of CCR in UTP, Perak, Malaysia. Five samples
were used as a reference for different characterizations, and the remaining ones were
used for degradation purposes. The HDPE sheet and CO2 gas which were used in the
experiment with the following properties are shown below in Tables 1 and 2.

Table 1. Physical properties of CO2 .

Density Melting Temperature Glass Transition Dielectric Strength

Material Dielectric Constant
(g/cm3 ) (◦ C) (◦ C) (MV/m)
HDPE 0.95 125–130 −78 2.3–2.4 18.9–160

Table 2. Properties of HDPE material.

Gas MW (g/mol) Density (kg/m3 ) Critical Temperature (◦ C) Crystal Structure Purity (%)
CO2 44.01 1.977 31.1 Trigonal 99.9

2.2. Degradation/Aging of HDPE

The aging of the HDPE was carried out in the HPHT (high-pressure, high temperature)
autoclave containing the 3.5% NaCl solution pressurized with CO2 gas. The parameters
are shown in Table 3.
The experiment was designed so that the virgin samples were immersed in CO2 -
saturated 3.5 wt% NaCl solution in the high-temperature, high-pressure autoclave. The
evaluation of polymeric properties includes chemical structure, crystallinity, thermal stability,
microstructure, and dielectric property using FTIR, DSC, TGA, FESEM, and EIS techniques.
Materials 2021, 14, 2823 4 of 19

Table 3. Experimental Design Parameters.

Material Parameters Characterization

FTIR
- - Evaluation of the chemical changes within the
structure
DSC
Pressure 70 bars
Evaluation of crystallinity and melting temperature
HDPE TGA
Temperature 60, 75, 90 ◦ C
Evaluation of thermal stability and mass loss
FESEM
Duration 21 days
Evaluation of morphological properties
EIS
- -
Evaluation of impedance and dielectric properties

2.3. Characterization Techniques

2.3.1. Fourier Transform Infrared Spectroscopy (FTIR)
FTIR was performed using a PerkinElmer frontier model spectrometer installed in
the Universiti Teknologi Petronas, Seri Iskandar, Malaysia, equipped with attenuated total
reflectance (ATR) at the scanning range of 500–4000 cm−1 frequency and resolution of
4 cm−1 . Based on the spectral recordings, the variations that occurred were analyzed:
formation/disappearance, increase/decrease, and displacement of various bands. The
virgin samples of HDPE usually contain five spectral bands [39,40].

2.3.2. Differential Scanning Calorimetry (DSC)

DSC is a thermoanalytical technique and examines heat effects associated with phase
transitions and chemical reactions as a function of temperature. Thermal analysis was
carried out to measure the glass transition temperature (Tg ), melting temperature (Tm ),
melting enthalpy, and % crystallinity (Xc ). Around 10.08 mg sample mass was taken for the
analysis. The sample was heated twice from −80 to 170 ◦ C with a heating and cooling rate
of 10 ◦ C/min rate in a nitrogen gas atmosphere. The thermal route consists of two cycles.
The first cycle eliminates the thermal history and residual solvents, while the second one
is for getting sharp Tg . The Tg is calculated using the TA analysis software, and it is in
sub-ambient temperatures [41].
Equation (1) was used to carry out the Xc (% crystallinity) measurement for the
reference sample:
∆Hm (cal )
Xc = × 100 (1)
∆Hs
where ∆Hm (cal ) is the calculated heat (J/g) of fusion values and ∆Hm (s) is the standard
heat of fusion values for 100% crystalline HDPE. The given value for crystalline HDPE in
the literature is 293 J/g [42–44].

2.3.3. Thermogravimetric Analysis (TGA)

The thermal stability of HDPE samples was studied using TGA analysis. PerkinElmer
STA 6000 simultaneous thermal analyzer installed in the Universiti Teknologi Petronas, Seri
Iskandar, Malaysia, was employed at a temperature range of 450–500 ◦ C with 10 ◦ C/min
heating rate under nitrogen atmosphere.

2.3.4. Field Emission Scanning Electron Microscopy (FESEM)

A Zeiss SUPRA 55 VP microscope installed in the Universiti Teknologi Petronas, Seri
Iskandar, Malaysia, was employed to investigate the morphological properties of virgin
and aged polymers after being coated with gold using a sputter coater (Emitech K550X).
 A Zeiss SUPRA 55 VP microscope installed in the Universiti Teknologi Petron
Iskandar, Malaysia, was employed to investigate the morphological properties of
and aged polymers after being coated with gold using a sputter coater (Emitech K
Materials 2021, 14, 2823 5 of 19
2.3.5. Electrochemical Impedance Spectroscopy (EIS)
A potentiostat/galvanostatic Autolab model PGSTAT30 was used for the EIS
urements. It is employed
2.3.5. Electrochemical Impedanceby the 3-electrode
Spectroscopy (EIS)arrangement cell with 3.5 wt% NaCl so
Stainless steel, Ag/AgCl, and Autolab
A potentiostat/galvanostatic the coated model polymer
PGSTAT30 were
wasused
used as
for athe
counter,
EIS mea-referen
working electrode, respectively. The measurement frequencies rangesolution.
surements. It is employed by the 3-electrode arrangement cell with 3.5 wt% NaCl from 10 MHz
Stainless steel, Ag/AgCl, and the coated polymer were used as a counter, reference, and
kHz with 10 mV amplitude.
working electrode, respectively. The measurement frequencies range from 10 MHz to
There
100 kHz withare twoamplitude.
10 mV main ways to plot impedance spectra, Bode and Nyquist. Ny
sensitive
Theretoarechanges;
two mainimaginary
ways to plotimpedance was plotted
impedance spectra, Bode andversus the Nyquist
Nyquist. real partis of impe
sensitive
while fortoBode,
changes; imaginary
the impedance was
total impedance plotted versus
is plotted versusthefrequency
real part of and
impedance,
the phase sh
while for Bode, the total impedance is plotted versus frequency and
the EIS test, we use our samples as a coating. Therefore, four carbon steel the phase shift. For theplates h
EIS test, we use our samples as a coating. Therefore, four carbon steel plates have the exact
exact dimensions as the HDPE samples that were used for this purpose. The epoxy
dimensions as the HDPE samples that were used for this purpose. The epoxy adhesive
sive
was was
appliedapplied
on theon theofsides
sides of thesample
the HDPE HDPEand sample and metal
metal plate makingplate making
a 10–15 micronsa 10–15 m
thick layer.The
thick layer. The prepared
prepared samplesample
for thefor
EISthe
testEIS
and test and
the EIS the isEIS
setup setup
shown is shown
in Figure 2a,b.in Figu

(a) (b)
Figure 2.(a)
Figure 2. (a)Assembly
Assembly of setup,
of EIS EIS setup, (b) prepared
(b) prepared sample. sample.

3. Results and Discussion

3. Results and Discussion
3.1. Structural Modifications and Chemical Composition
3.1. Structural Modifications
The evaluation of chemicaland
andChemical
structuralComposition
changes was based on the comparison
of theThe
pre-and post-exposure
evaluation spectra. and
of chemical The peaks around
structural 2915 andwas
changes cm−1 show
2848based thecompar
on the
asymmetric and symmetric vibration of CH2 [45], CH2 (methylene) bending observed at
the pre-and post-exposure spectra. The peaks around 2915 and 2848 cm show the −1
1462 cm−1 . The virgin sample of HDPE always contains a strong peak at 1462 cm−1 because
metric and symmetric
it is associated vibration
with methylene and CHof CH2 [45], CH2 (methylene) bending observed
2 scissoring. Vibration in the amorphous part and
deformation in the crystalline phase was observed at 718 cm−1 and 729 cm−1 [19,46].
Figure 3 represents five different peaks in the spectra of 1 mm-thick HDPE material. The
difference in absorbance bands occurred after the exposure experiments in the autoclave
chamber, shown in Figures 4a,b, and 5a,b.
As expected, the extent of the observed variations is stronger at higher tempera-
tures. The sample degradation occurred largely through chain scissions in the soft amor-
phous phase and was usually reflected through an increase in the chain mobility of this
region. There are four regions 550–600, 1000–1400, 1600–1700, and 3100–3700 cm−1 in
which polymer aging was shown in terms of different absorption bands as shown in
Figures 4a,b, and 5a,b. The appearance of different functional groups and their assigned
spectral bands are shown in Table 4.
 associated
associatedwith methylene
with methylene and
andCHCH2 scissoring. Vibration in the amorphous part an
2 scissoring. Vibration in the amorphous part
formation in the crystalline phase was
formation in the crystalline phase was observed
observed at at
718 cmcm
718
−1 and 729 cm−1 [19,46]. Fig
−1 and 729 cm−1 [19,46].
represents five different peaks in the spectra of 1 mm-thick
represents five different peaks in the spectra of 1 mm-thick HDPEHDPE material.
material.The diffe
The di
inin
absorbance bands occurred after the exposure experiments in the
absorbance bands occurred after the exposure experiments in the autoclave autoclave cha
c
Materials 2021, 14, 2823 6 of 19
shown in Figure 4a,b, and Figure 5a,b.
shown in Figure 4a,b, and Figure 5a,b.

Exp 3 T = 90°C °
Exp 3 T = 90 C

Exp 2 T = 75°C °
%T Exp 2 T = 75 C
%T

Exp 1 T = 60°C °
Exp 1 T = 60 C

Ref
Ref

1462
727 1462
719 727
719
2916
2848 2916
2848

500 1000 1500 2000 2500 3000 3500 4000

500 1000 1500 2000 2500 3000 3500 4000
-1
Wavenumber
Wavenumber(cm
(cm) -1)
FTIR spectra
Figure3.3.FTIR
Figure spectra forfor
virgin and and
virgin aged aged
samples.
samples.
Figure 3. FTIR spectra for virgin and aged samples.

558 1089
558 1089 1262
1262 1368
1368
Transmittance (%)
Transmittance (%)

Transmittance (%)
Transmittance (%)

556 1042
556 1042
1086 1105 1262 1368
1086 1105 1262 1368

1082 1100
1041 1082 1100
1041 1262 1368
1262 1368

550 600 1000 1100 1200 1300 1400

550 600 1000 1100 1200 1300 1400
Wavemuber (cm-1) -1 -1
Wavemuber (cm ) -1
Wavemuber (cm ) Wavemuber (cm )
(a)(a) (b)(b)
Figure
Figure
Figure4.4.FTIR
4.FTIR spectra
spectra
FTIR (a)(a)
spectra 550–600,
550–600,
(a) (b)(b)
1000–1400.
(b) 1000–1400.
550–600, 1000–1400.
MaterialsMaterials
2021, 14, x FOR
2021, PEER REVIEW
14, 2823 7 of 19

3448

Transmittance (%)
Transmittance (%)

3443
1647

3431

3100 3200 3300 3400 3500 3600 3700

1600 1650 1700
Wavemuber (cm-1) Wavemuber (cm-1)

(a) (b)
Figure
Figure5.
5. FTIR spectra
FTIR spectra (a)(a) 1600–1700,
1600–1700, (b) 3100–3700.
(b) 3100–3700.

4. Spectral bands for virgin and aged samples.

AsTable
expected, the extent of the observed variations is stronger at higher tempera
The(cm
Wavenumber sample
−1 ) degradation occurred largely through chain scissions in the soft amor
Reference Exp 1 phaseExpand 2 was usually
Exp 3 reflectedAssigned
through Vibrational Bands/Functional Groups
an increase in the chain mobility of this r
There 556
are four regions
558 550–600, 1000–1400, C-Cl1600–1700, and[47]
bending vibration 3100–3700 cm−1 in which
719 719 719 was shown
mer aging 719 in terms of CHdifferent
2 rocking vibration (amorphous
absorption bands phase) [19,48] in Figure 4a,
as shown
727 728 729 729 CH2 rocking vibration (crystalline phase) [49,50]
1041 Figure1042
5a,b. The appearanceC-O of stretching
different functionaldeformation
(alcohol)/O-H groups in and their
alcohol [51]assigned sp
1082 bands1086
are shown 1089 in Table 4. C-O stretching (alcohol) [52]
1100 1105 C-O stretching vibration (alcohol) [53,54]
1262 1262 1262 CH3 vibration [52,53]
1368 Table
1368 4. Spectral
1368 bands for virgin and
CHaged samples.
2 wagging (amorphous) [55]
1463 1463 1463 1463 CH2 scissoring (amorphous phase) 45,46]
Wavenumber (cm−1) 1647 O-H bending (water absorption) [48]
2848 Exp 1 2848 2848 2848 Assigned Vibrational
CH2 symmetricBands/Functional
stretching [51] Groups
Reference Exp 2 Exp 3
2916 2916 2916 2916 Asymmetric stretching of CH2 [51]
556
3431 558
3443 3448 C-Cl bending vibration
Hydroxyl group [19,20] [47]
719 719 719 719 CH2 rocking vibration (amorphous phase) [19,48]
727 728 729 729
3.1.1. Chain Scission CH2 rocking vibration (crystalline phase) [49,50]
1041 1042 The bands around C-O stretching
and 720 and 1468 (alcohol)/O-H deformation
are due to the vibrational in alcohol
deformation [51]
band of
1082 1086 the1089
methylene group. The peaks aroundC-O 725–730 demonstrate connected
stretching (alcohol) [52] methylene; as
the exposure temperature increases, the wavenumber shifted from lower to higher values
1100 1105 C-O stretching vibration (alcohol) [53,54]
(729 cm−1 ), showing the decline of molecular chain length [47,48]. The chain-breaking
1262 1262 1262 the aging of HDPE with the characteristic
de-fines CH3 vibration [52,53]
group including 1368 cm−1 [49]. The
peak − 1
around 1368 cm is due to external
1368 1368 1368 CHhydrogen
2 wagging vibrations of CH2 [19,34]
(amorphous) [55] or wagging
deformation of methylene groups. The appearance of peaks in these bands can be attributed
1463 1463 1463 1463 CH2 scissoring (amorphous phase) 45,46]
to the presence of side-chain branches of PE [45,50]. The band around 1262 cm−1 (methyl)
1647 O-H bending
shows the process of chain scission because (water
it appears absorption)
in all the experiments[48]
since methyl
2848 2848 2848 2848as the end group in molecular chains
served CH2 [46,47].
symmetric stretching [51]
2916 2916 2916 2916 Asymmetric stretching of CH2 [51]
3431 3443 3448 Hydroxyl group [19,20]

3.1.1. Chain Scission

The bands around and 720 and 1468 are due to the vibrational deformation ba
the methylene group. The peaks around 725–730 demonstrate connected methyle
Materials 2021, 14, 2823 8 of 19

3.1.2. Degradation Products

The formation of degradation products after the high temperature and pressure expo-
sure has been shown in different absorption bands. The appearance of bands around 1041
and 1042 shows the C-O stretching in primary alcohol or O-H deformation in alcohol [51].
The absorption bands appear around 1082, 1086, and 1089, respectively, are associated
with C-O stretching in alcohol, and this is due to the presence of saturated seawater under
high temperature in the surroundings [52]. The bands around 1100 and 1105 are due to
C-O vibration within the alcohol as a degradation product [53,54]. The appearance of the
bands around 556 cm−1 and 558 cm−1 are due to the contact of the process medium with
the polymer surface as the solution contains chlorides, and it is also evident by the rough
surface patches and cracks in FESEM images [55]. The band around 1647 cm−1 in experi-
ment 2 shows the formation of unsaturation groups in the polymer and demonstrates that
O-H bending is due to water absorption [42]. The peaks that appeared between 3100 and
3700 are associated with the presence of liquid water within the sample or hydroxyl group
and intramolecular hydrogen bonding [19,20]. As the temperature increases within the
experiments, the hydroxyl group shows increased thermal degradation [19,20,44,56]. As
the temperature increases from 60 to 75 ◦ C, the water is absorbed into the polymer surface
with cracks, as shown by the bands. The hydroxyl group shows the acidic functional group
due to acidic gas (CO2 ) [57].
The change in the peak values of almost all functional groups supports the conforma-
tional change on the polymer surface. The pressure and the NaCl solution degrade the
material by leaving the characteristic signature of oxygen, chlorine, and hydroxyl; this also
causes breakage of tie molecules followed by the chain layering and crystalline content as
well as the formation of microcracks [42].

3.2. Thermal and Crystallinity Analysis

The Tm of the virgin sample is 132.01 ◦ C. The step between 80 and 100 ◦ C is typically
due to smaller crystals, and probably they were made due to some processing. It can be
due to the inclusion of additives, pigments, or simple thermal or physical processing [58]
of the material before being tested in the DSC, as shown in Figure 6. Figures A1–A4 have
Materials 2021, 14, x FOR PEER REVIEW 9 of 19
been shown in Appendix A for representing Tg values. The experimental values for Tm , Tg,
and Xc were in Table 5.

Exp 3

Exp 2
Heat Flow (W/g)

Exp 1

Ref
Tm =132.01

0 20 40 60 80 100 120 140

o
Temp ( C)
DSCheating
Figure6.6.DSC
Figure heating curves
curves forfor virgin
virgin andand
agedaged samples.
samples.

The decrease in crystallinity is mainly due to the formation of degradation products

(alcohol, hydroxyl) and branching [59–61]. Branched polyethylenes have lower crystallin-
ity and melting temperature as compared to linear ones [62]. Furthermore, chain scission
increases the HDPE chain mobility, which increases the Xc at high temperatures [59]. The
Materials 2021, 14, 2823 9 of 19

Table 5. Thermal properties for virgin and aged samples.

Sample Melting Temp (Tm ) Melting Enthalpy Glass Transition (Tg ) Crystallinity (%Xc ) a
Ref 132.01 177.6 −75.82 60.6
Exp 1 130.24 173.8 −76.67 59.3
Exp 2 129.01 168.6 −77.13 57.5
Exp 3 129.85 170.9 −76.39 58.3
a Observed heat of fusion divided by 293 J/g.

The decrease in crystallinity is mainly due to the formation of degradation products

(alcohol, hydroxyl) and branching [59–61]. Branched polyethylenes have lower crystallinity
and melting temperature as compared to linear ones [62]. Furthermore, chain scission
increases the HDPE chain mobility, which increases the Xc at high temperatures [59].
The increase in crystallinity was observed at high temperatures (90 ◦ C) and is attributed
to the enhanced chain mobility in the amorphous phase, which favors morphological
rearrangements [63,64].
The absorption of CO2 in HDPE is greater in experiments 1 and 2 [23]. The small
amount of decrease in Tg is due to CO2 absorption at 60 and 75 ◦ C, and it is evident by the
reduction in crystallinity. Due to induced aging, the crystallinity values become higher, and
it restricts the diffusion of CO2 , also evident by the slight increase in Tg [65]. The increase
in CO2 diffusion followed by the rise in temperature as pressure is constant throughout
the experiments [66]. Tm and Tg both show the decreasing trend due to branching that
occurred in the HDPE samples after the degradation.
The neat HDPE crystallizes at 119 ◦ C, and in our case, it is 117 ◦ C [52]. Branching
within the polymer relates to density and further with the crystallinity of the polymer.
After thermal treatment and CO2 exposure, chain scission occurred, and the sample lost
its crystallinity which can also be seen by the decrease in Tm . Chain mobility increases at
higher temperatures which tends to enhance the crystallinity values [51].
More side chain branches decrease the crystallinity as well as the melting temperature.
The crystallinity of the polymer directly relates to the density; an increase in density induces
higher crystallinity values [67]. DSC results are affected by the branching, which lowers the
T5% and T10% . The formation of new degradation products plays the role of defect centers,
disturbing the reorganization and chain folding during the crystallization process [59,61].
This fact produces imperfect crystallites as reflected by Xc , T5%, and T10% values.

3.3. Thermal Stability Analysis

Representative TGA curves for virgin and aged samples after the CO2 exposure at 60,
75, and 90 ◦ C have been shown in Figure 7. We will use T5% and T10% (temperature for 5%
and 10% weight loss) to demonstrate the aging within the samples. The respective values
for weight loss against temperature are shown in Table 6. All the curves exhibit only one
degradation step attributed to the chain scission mechanism of polyolefin material thermal
degradation [59]. HDPE dissociation at lower temperatures follows C-C bond breakage,
while C-H dissociation occurred at high temperatures [53].

Table 6. Thermal degradation temperatures for virgin and aged samples.

Characteristic Temperatures Ref Exp 1 Exp 2 Exp 3

T5% (◦ C) 446.86 444.36 432.95 439.59
T10% (◦ C) 455.32 452.82 448.41 451.71

The weight loss in terms of T5% and T10% is more significant in experiments 1 and
2; this is due to the chain breaking and scission in the aged sample supported by the
DSC thermograms. The values for T5% and T10% decreased in the first two experiments
due to a drop in crystallinity factor [44]. Alcohol and hydroxyl groups appeared as a
degradation product, as seen by the FTIR spectrum. As soon the branching disappears at a
 Table 6. Thermal degradation temperatures for virgin and aged samples.

Characteristic
Ref Exp 1 Exp 2 Exp 3
Temperatures
T5% (°C) 446.86 444.36 432.95 439.59
T10% (°C) 455.32 452.82 448.41 451.71
Materials 2021, 14, 2823 10 of 19
The weight loss in terms of T5% and T10% is more significant in experiments 1 and 2;
this is due to the chain breaking and scission in the aged sample supported by the DSC
thermograms. The values for T5% and T10% decreased in the first two experiments due to a
drop in crystallinity factor [44]. Alcohol and hydroxyl groups appeared as a degradation
high temperature, the temperature drops down, as shown in Table 6 and Figure 7 [59,68].
product, as seen by the FTIR spectrum. As soon the branching disappears at a high tem-
The material
perature, got thermally
the temperature drops down,stable due in
as shown toTable
higher
6 andcrystallinity
Figure 7 [59,68].values
The ma-at higher temperatures
in experiment
terial got thermally 3. The
stable duechanges
to higher in the thermal
crystallinity values decomposition
at higher temperatures temperatures
in ex- show the clear
periment
effect of3.polymer
The changesstructure
in the thermal decomposition
(branch content) temperatures show the clear effect curve.
on a thermogravimetric
of polymer structure (branch content) on a thermogravimetric curve.

100

Ref
Exp 1
80 Exp 2
Exp 3
Weight (%)

60

40

20

100 200 300 400 500

Temp (oC)
Materials 2021, 14, x FOR PEER REVIEW
Figure 7. Thermograms for virgin and aged samples. 11 of 19
Figure 7. Thermograms for virgin and aged samples.

3.4. Morphological Properties

3.4. Morphological Properties
Figure 8a–d shows the micrograph taken from the virgin sample and aged samples
afterFigure
three8a–d shows
weeks the micrograph
of aging taken from
in the autoclave the virgin sample and aged samples
chamber.
after three weeks of aging in the autoclave chamber.

(a) (b)

(c) (d)
Figure 8. FESEM micrographs for virgin and aged samples. (a) Reference, (b) Experiment 1, (c)
Figure 8. FESEM micrographs for virgin and aged samples.(a) Reference, (b) Experiment 1, (c) Exper-
Experiment 2, (d) Experiment 3.
iment 2, (d) Experiment 3.
The material loses its strength due to aging in the aggressive environment with an
acidic gas (CO2) under high temperature and pressure. Microcracks and surface damage
were identified due to thermal degradation and the presence of chlorides in the autoclave
chamber [44]. The appearance of roughness in experiment 1, while surface cracks in ex-
periments 2 and 3 illustrate the attack of NaCl solution and CO2 in the autoclave chamber
 Materials 2021, 14, 2823 11 of 19

The material loses its strength due to aging in the aggressive environment with an
acidic gas (CO2 ) under high temperature and pressure. Microcracks and surface damage
were identified due to thermal degradation and the presence of chlorides in the autoclave
chamber [44]. The appearance of roughness in experiment 1, while surface cracks in
experiments 2 and 3 illustrate the attack of NaCl solution and CO2 in the autoclave chamber
under high temperature and pressure [69,70].

3.5. Impedance Analysis

Materials 2021, 14, x FOR PEER REVIEW EIS investigation was carried out to study the effect of CO2 exposure and simulated
seawater solution on virgin and aged HDPE samples. Figure 9 shows the corresponding
Bode plot for virgin and aged samples.

Figure 9. Bode plot for virgin and aged samples.

Figure 9. Bode plot for virgin and aged samples.
The impedance decreased in experiments 1 and 2 due to the chain scission, which
The due
occurred impedance decreased
to CO2 exposure and in experiments
saturated seawater1in andthe 2autoclave,
due to the chain inscission,
as shown
Figure 9. The
occurred dueagedto COmaterial loses itsand
2 exposure strength as compared
saturated seawater to theinvirgin sample. Initially,
the autoclave, as shown in
the virgin sample indicates very high resistance (10 11 ) at low frequency. The impedance
9. The aged material loses its strength as compared to the virgin sample. Initially,
values higher than 107 illustrate excellent surface protection of the sample [33]. The half
gin sample
semicircle indicates
at high very
frequency washigh resistance
ascribed (10protection
to coating
11) at low frequency. The impedance
performance. The coating
higher
impedancethandecreases
107 illustrate
when the excellent
materialsurface
degradesprotection of theand
in the autoclave, sample [33]. The half s
the capacitance
cle at can
loop highbefrequency
seen in the was
Nyquistascribed to coating
plot. Coating protection
impedance startsperformance.
decreasing from 1011coating
The
9
to 10decreases 6
then 10 ohms.cm − 2 ◦
ance when the for samples
material aged at 60
degrades inandthe 75 C temperatures.
autoclave, and the Coating
capacitance lo
resistance (Rc ) decreases while the capacitance increased, as shown in the Nyquist plot.
be seen in the Nyquist plot. Coating◦impedance starts decreasing from 1011 to 109 t
However, the resistance gets higher at 90 C, and this behavior also shows us the loss in
ohms.cm
capacitance. for
−2 samples aged
Zw represents at 60 impedance,
the Warburg and 75 °Cwhich temperatures.
resulted from Coating resistance (
the diffusion
creases while
of ions from thethe capacitance
electrolyte to the increased, as shown
electrode interface. Thein the Nyquist
modeling of EIS plot. However,
data was
sistance gets higher at 90 °C, and this behavior also shows us the loss in to
carried out using the NOVA software, an equivalent electrical circuits (EEC) were used capacita
analyze the degradation of coatings quantitatively. Nyquist plots and the EEC circuits have
represents the Warburg impedance, which resulted from the diffusion of ions fr
been shown in Figures 10 and 11, while their respective circuit element values are shown
electrolyte
in Table 7. to the electrode interface. The modeling of EIS data was carried out us
NOVA software, an equivalent electrical circuits (EEC) were used to analyze the
dation of coatings quantitatively. Nyquist plots and the EEC circuits have been sh
Figures 10 and 11, while their respective circuit element values are shown in Table
 sistance gets higher at 90 °C, and this behavior also shows us the loss in capacitance. Zw
represents the Warburg impedance, which resulted from the diffusion of ions from the
electrolyte to the electrode interface. The modeling of EIS data was carried out using the
NOVA software, an equivalent electrical circuits (EEC) were used to analyze the degra-
Materials 2021, 14, 2823 12 of 19
dation of coatings quantitatively. Nyquist plots and the EEC circuits have been shown in
Figures 10 and 11, while their respective circuit element values are shown in Table 7.

Materials 2021, 14, x FOR PEER REVIEW

Materials 2021, 14, x FOR PEER REVIEW 13 of 19

(a) (b)

(c)(c) (d) (d)

Figure
Figure 10.
Figure10. Modeled
10.Modeled Nyquist
ModeledNyquist
Nyquist plots
plots
plots forfor
for virgin
virgin
virgin andand
and aged
aged
aged samples
samples
samples (a)(a) (a) Reference,
Reference,
Reference, (b) (b) (b) Experiment
Experiment
Experiment 1, 1, (c)
Experiment
Experiment 2,2,(d)
(c) Experiment (d) Experiment
Experiment3.3.3.
Experiment
2, (d)

(a) (b)
(a) (b)

(c) (d)
(c) (d)
Figure 11. EEC of virgin and aged samples. (a) Reference (b) Experiment 1 (c) Experiment 2 (d)
Experiment
Figure
Figure11. 3.
11. EEC
EECof
of virgin andaged
virgin and agedsamples.
samples.(a)(a) Reference
Reference (b) Experiment
(b) Experiment 1 (c) Experiment
1 (c) Experiment 2 2
Experiment 3. 3.
(d) Experiment
Table 7. EEC values for virgin and aged samples.
Table 7.Samples
EEC values for virgin and aged−2samples.
Rp (MΩ.cm ) Cc (pF.cm−2) Zw (μΩ.cm−2)
Ref
Samples Rp 95.5
(MΩ.cm−2) C17.4
c (pF.cm−2) Zw (μΩ.cm−
Exp 1 16.7 32.9
Ref 95.5 17.4
Exp 2 3.83 78.7 1.62
Exp 1 16.7 32.9
Materials 2021, 14, 2823 13 of 19

Table 7. EEC values for virgin and aged samples.

Samples Rp (MΩ.cm−2 ) Cc (pF.cm−2 ) Zw (µΩ.cm−2 )

Ref 95.5 17.4
Exp 1 16.7 32.9
Exp 2 3.83 78.7 1.62
Exp 3 12.8 23.6 1.68

After CO2 exposure, the crystallinity decreases, indicating aging within the sample
as well as the occurrence of roughness and microcracks. Nyquist plots show us the
diffusion mechanism within the sample at lower frequencies as illustrated by the Warburg
diffusion mechanism. The data points are dispersed as seen in the Nyquist plot and this
electrochemical noise is probably due to high sample thickness. Thick and high-quality
coatings have almost infinite resistance with low capacitance [71,72]. Due to this feature,
we get minimal current values, and resistive elements in the model dominate [72]. The
difference in impedance values is quite prominent in lower frequencies. We have seen the
diffusion mechanism in experiments 2 and 3, while the Zw increases at higher temperatures.
The EEC values for virgin and aged samples are shown in Table 7.

Dielectric Properties
The real and imaginary parts of impedance have been gathered from the Nyquist plot.
Our aim here is to relate the impedance with the dielectric property of the HDPE material.
HDPE has an ordered structure and has less free volume for polarizability. We can calculate
the dielectric loss from Equations (2–4) and hope to see what changes before and after the
CO2 exposure experiment within the HDPE material.
We will calculate the real and imaginary permittivity from complex impedance, which
in turn gives us dielectric loss [73]. Table 8 is showing the dielectric factor at different
low frequencies.
εo εr A
·C = , (2)
t
t Z 00
·ε0 = × , (3)
ωAε o ( Z 0 )2 + ( Z00 )2
t Z0
ε00 = × , (4)
ωAε o ( Z 0 )2 + ( Z00 )2 .
where ε o (vacuum permittivity) = 8.85 × 10−12 , ε r (material‘s permittivity) = 2.4,

Table 8. Dielectric loss of virgin and aged sample at lower frequencies.

Parameters Ref Exp 1 Exp 2 Exp 3

Frequency (Hz) (ε00 ) (ε00 ) (ε00 ) (ε00 )
34.3043 0.0025 0.0075 5.67 0.157
6.73416 2.27 × 10−18 3.23 × 10−17 28.12 8.72 × 10−16
1.32193 2.80 × 10−18 8.34 × 10−17 142.25 4.21 × 10−15
0.00999989 0.567 12.845 12811 1.215× 10−5

Area (A) = 0.023 m2 , thickness (t) = 0.001 m, ε0 (real permittivity), ε00 (imaginary
permittivity or dielectric loss), tan δ (loss tangent or dissipation factor), Z 0 (real impedance),
Z00 (imaginary impedance).
The decrease in dielectric loss factor with gradually increasing frequency is the com-
mon characteristic of dielectric material. The analysis with temperature shows that the
dielectric loss of HDPE increases in the low-frequency region until 75 ◦ C; after that, it
decreases at much higher temperatures [74,75]. In dielectric materials, the dielectric losses
Materials 2021, 14, 2823 14 of 19

occur due to the dipolar molecules. Dielectric loss increases followed by the rise in ag-
ing temperature.
The relation between impedance and dielectric loss is contrary. Higher values of
dielectric loss have been seen in experiments 1 and 2 to explain the aging of HDPE after the
CO2 exposure and thermal treatment. The hydroxyl group (-OH) in non-polar polymers
increases the dielectric loss factor and is associated with the size and dipole orientation
for small molecules [76]. The mobility of segments in the amorphous phase and within
the small portions of macromolecules are affected by polymer crystallization. The values
of dielectric loss increase as the polymer crystallization occurs. This is mainly due to the
transition of polar portions of macromolecules into crystallites [77].

4. Conclusions
Our investigation aimed to monitor the influence of temperature and CO2 exposure
on the impedance property and dielectric loss of our HDPE sample. HDPE samples were
subjected to aging in the autoclave chamber at 60, 75, and 90 ◦ C for three weeks. With
aging in the presence of saturated seawater and acidic gas (CO2 ) in the chamber, HDPE
aged by showing the following symptoms in terms of color, crystallinity, chemical structure,
morphology, impedance, and dielectric loss. Thermal aging leads to slow and irreversible
changes in terms of material properties.
The appearance of a methyl group, hydroxyl, and alcohol explains the molecular chain
scission in HDPE at 1262, 3400–3500, and 1462 cm−1 . Water absorption into the polymer
matrix around 1647 cm−1 also explains the polymer aging within the chamber after the
exposure. The magnitude of dielectric loss rises by increasing the concentration of the
polar molecule, which is proved by the presence of the O-H absorption band and hydroxyl
group in our FTIR spectra around 1647 cm−1 and within 3400-3500.
DSC thermograms validate the decrease in % crystallinity with a change in Tg . The
reduction in crystallinity occurred due to the breakage of chains inside the polymer struc-
ture at 60 and 75 ◦ C. Moreover, it was enhanced at 90 ◦ C due to higher chain mobility
which helps in molecular rearrangements. CO2 absorption is favored at temperatures 60
and 75 ◦ C, which is why there is a slight increase in Tg here. Thermoplastics such as HDPE
show less CO2 absorption due to their semi-crystalline feature. New peaks have confirmed
the extent of physical aging in the FTIR spectrum and FESEM images. Surface cracks and
roughness were observed in the FESEM images. At 75 ◦ C, the C-X, (X-halide) band appears,
which indicates the roughness on the surface.
The impedance of the virgin sample decreased after the intensive exposure of CO2
and simulated seawater in the autoclave. The presence of a diffusion tail in the Nyquist
diagram indicates that the material aged. The dielectric loss property is related to interfacial
polarization. These effects are caused by the boundaries between the amorphous and
crystalline regions. The impedance and dielectric properties differ indirectly in relation
to one another, and as crystallinity increases, the dielectric loss decreases. Using these
two crucial properties, we can easily demonstrate the aging mechanism within the HDPE
material, and it will facilitate us to monitor and assess the HDPE material degradation in
oil and gas pipelines.
The outcomes of the dielectric property contribute to a more inclusive and systematic
post-permeation monitoring approach. In this way, we can establish some acceptance
requirements for the remaining polymer life. A comprehensive assessment is provided,
showing the challenges allied with the monitoring of the polymer liner material in the
pipeline as it relates to the lifetime prediction requirement. This can provide a lifeline for
the assets in the oil and gas industries.
Materials 2021, 14, 2823 15 of 19

Author Contributions: Conceptualization, H.U.K., M.C.I. and N.N.; methodology, H.U.K.; software,
H.U.K.; validation, M.C.I. and N.N.; formal analysis, H.U.K.; investigation, H.U.K.; resources, M.C.I.;
data curation, H.U.K.; writing—original draft preparation, H.U.K.; writing—review and editing,
H.U.K., M.C.I. and N.N.; visualization, H.U.K.; supervision, M.C.I. and N.N.; project administration,
M.C.I. and N.N.; funding acquisition, M.C.I. and N.N. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by YUTP-FRG grant (015LC0-163).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data sharing is not applicable to this article.
Acknowledgments: The authors acknowledge the Universiti Teknologi PETRONAS.
Conflicts of Interest: The authors declare no conflict of interest.
Materials 2021, 14, x FOR PEER REVIEW 16 of 19
Materials 2021, 14, x FOR PEER REVIEW 16 of 19
Appendix A

Figure A1. Tg of virgin HDPE.

Figure A1. Tg of virgin HDPE.
Figure A1. Tg of virgin HDPE.

Figure A2. Tg of HDPE after Experiment 1.

FigureA2.
Figure A2.TT g of HDPE after Experiment 1.
g of HDPE after Experiment 1.
Materials 2021, 14, 2823 16 of 19

Figure A2. Tg of HDPE after Experiment 1.

Materials 2021, 14, x FOR PEER REVIEW

Figure A3. Tg of HDPE after Experiment 2. 17 of 19
Figure A3. Tg of HDPE after Experiment 2.

FigureA4.
Figure A4.TTgofofHDPE
HDPEafter
afterExperiment
Experiment3. 3.
g

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