polymers

Article
Investigation on the Durability of E-Glass/Epoxy Composite
Exposed to Seawater at Elevated Temperature
Amir Hussain Idrisi 1 , Abdel-Hamid I. Mourad 1,2,3, * , Beckry M. Abdel-Magid 4 and B. Shivamurty 5

1 Department of Mechanical Engineering, United Arab Emirates University,

Al Ain 15551, United Arab Emirates; [email protected]
2 National Water and Energy Center, United Arab Emirates University, Al Ain 15551, United Arab Emirates
3 Mechanical Design Department, Faculty of Engineering, Helwan University, Cairo 11795, Egypt
4 Department of Composite Materials Engineering, Winona State University, Winona, MN 5598, USA;
[email protected]
5 Department of Mechanical and Manufacturing Engineering, Manipal Institute of Technology,
Manipal 572104, India; [email protected]
* Correspondence: [email protected]

Abstract: In this manuscript, the durability of the E-glass/epoxy composite was determined under
a seawater environment. The effect of harsh environment was investigated in terms of seawater
absorption, microstructure and degradation in mechanical properties. E-glass epoxy composite
specimens were conditioned in gulf seawater at 23 ◦ C, 65 ◦ C and 90 ◦ C for the period of 12 months.
It was observed that the mass of the samples increased after the immersion of 12 months at 23 ◦ C
and 65 ◦ C whereas it reduced at 90 ◦ C. The salt deposition was observed at the surface of specimens



without any crack for the seawater conditioning at 23 ◦ C and 65 ◦ C. The swelling and crack formation


were significantly visible on the surface of the specimen immersed for 12 months at 90 ◦ C. It indicates
Citation: Idrisi, A.H.; Mourad, that the degradation mechanism accelerated at elevated temperature results fiber/matrix debonding.
A.-H.I.; Abdel-Magid, B.M.;
The tensile test indicates slight variation in the elastic modulus and reduction in strength of E-glass
Shivamurty, B. Investigation on the
epoxy composite by 1% and 9% for specimens immersed at 23 ◦ C and 65 ◦ C respectively. However,
Durability of E-Glass/Epoxy
at 90 ◦ C, the tensile strength sharply decreased to 7% and elastic modulus significantly increased in
Composite Exposed to Seawater at
the exposure of 12 months. A prediction approach based on a time-shift factor (TSF) was used. This
Elevated Temperature. Polymers 2021,
13, 2182. https://doi.org/
model predicted that the strength retention of E-glass/Epoxy composite will be reduced to 7% in
10.3390/polym13132182 450 years after immersion in seawater at 23 ◦ C. Lastly, the activation energy for the degradation of
the composite was calculated.
Academic Editor: Youhong Tang
Keywords: glass fiber composite; elevated temperature; mechanical properties; microstructural
Received: 13 June 2021 analysis; durability; modeling
Accepted: 27 June 2021
Published: 30 June 2021

Publisher’s Note: MDPI stays neutral 1. Introduction

with regard to jurisdictional claims in
In the past few years, several researchers have investigated the characteristics of com-
published maps and institutional affil-
posites in the marine environment. Glass Fiber-Reinforced Polymer (GFRP) composites
iations.
are commonly used in automobile, aerospace and marine industries because of their high
strength to weight ratio, stiffness and durability. Furthermore, glass fibers are simple to
manufacture, economical, less fragile and high chemical resistant compared to carbon fiber.
However, GFRPs face challenges in various environmental surroundings such as UV, sea-
Copyright: © 2021 by the authors. water, alkaline and various other corrosive environmental conditions [1–8]. Polymer matrix
Licensee MDPI, Basel, Switzerland.
composites trap water in voids at high temperatures and are often fused into hydroxyl
This article is an open access article
radicals of the epoxy polymers [9–12]. The immersion in water results in deterioration in
distributed under the terms and
the physical properties of composites [13–18] which makes epoxy polymers inflate, breaks
conditions of the Creative Commons
their bonds due to hydrolysis and further plasticizes [19–21]. The hot water environment
Attribution (CC BY) license (https://
contributes to small cracks within the polymer matrix due to water absorption and osmotic
creativecommons.org/licenses/by/
4.0/).
edge rupture [22–24], which increases the degradation of composites with immersion time.

Polymers 2021, 13, 2182. https://doi.org/10.3390/polym13132182 https://www.mdpi.com/journal/polymers

Polymers 2021, 13, 2182 2 of 19

The durability of the structures also affected by the presence of defects on the surface of the
polymer matrix composite before immersion. It can be regulated by determining the effect
of the critical size of the osmotic blister [25]. Furthermore, the strength of the structure can
be improved by repairing the structures with glass fiber-reinforced polymer [26,27]. For ma-
terial effectiveness, it is essential to ensure the durability of FRP composites in the seawater
environment. Nanofillers are one effective solution for closing any gaps and increasing the
compositional intensity [28–40]. Several studies have been performed in different aging
conditions for the performance of epoxy-based composites. It was previously observed
that the flexural properties of FRP samples decreased due to seawater immersion [41,42].
Pavan et al. [43] investigated that tensile strength of glass/epoxy reduced from 200.83 MPa
to 146.42 MPa, and 185.27 MPa for atmospheric and subzero temperatures aging for 3600 h.
Yan et. al. [44] noticed a similar reduction in the mechanical properties of flax-fabric/epoxy
composites. The tensile strength of the specimens reduced by 31.1%, 28.3% and 22.6%
under the immersion of alkaline (5% NaOH) solution, seawater and water respectively.
Silva et al. [45] studied the durability of GFRP laminates with epoxy resin by exposing
the composites to saltwater at 30 ◦ C, 50 ◦ C and 65 ◦ C for 5000 h. For the first 1500 h,
the modulus behavior indicated that the prevailing damage mechanism was swelling.
Then, between 1500 h and 2500 h, the elastic modulus behavior represented that plasti-
cization was the predominant damage mechanism, especially for samples aged at 30 ◦ C.
Chakraverty et al. [46] studied the effect of seawater conditioning for up to 12 months (m)
on the mechanical properties, such as interlaminar shear strength (ILSS), tensile stress and
failure strain, elastic modulus and glass transition temperature (Tg) of GFRP composites.
The tensile stress was reduced to 79% after immersion for 6 months but a slow recovery was
observed, and the tensile strength rebounded to 84% after immersion for 12 months. Strain
at rupture decreased by 12% and 20% after 6 months and 12 months of seawater immersion
respectively. These reductions in values of stress and strain at rupture are due to the plasti-
cization and swelling in the composite material. Chen Y. et al. [47] utilized the Arrhenius
equation-based prediction model for predicting the durability of GFRP-reinforced concrete
structures. The GFRP bars were immersed in a concrete solution at temperatures of 20 ◦ C,
40 ◦ C, and 60 ◦ C. The short-term data were used for the accelerated aging tests. Similarly,
Ali et al. [48] investigated the durability performance of the BFRP bars. The specimens
were conditioned at 60 ◦ C after different immersion periods (1000 h, 3000 h, and 5000 h).
The prediction results show that the shear strength of BFRP bars will reduce by 19.8% and
23.0% after 150 years of immersion in the alkaline solution at 10 ◦ C and 30 ◦ C respectively.
Dejke [49] investigated the durability of GFRP bars in alkaline solutions immersed at 20 ◦ C,
40 ◦ C, 60 ◦ C and 80 ◦ C, for a duration of 568 days. Samples were tested for tensile strength
after removal from the solution. The time shift factor (TSF) approach was used for the
prediction of tensile strength retention. It was observed that samples immersed at 60 ◦ C
for 1.5 years have the same tensile strength retention as for 50 years at 7 ◦ C.
Table 1 summarizes the research related to E-glass/epoxy composite immersion at
different temperatures. It is clear from the above literature review and research relevant to
this topic mentioned in Table 1 that the data for harsh environment conditions (i.e., condi-
tioning at 90 ◦ C) are very lacking. Additionally, the harsh environmental conditioning is
limited to a small exposure time. To the authors’ best knowledge, the durability evaluation
of the fiber-reinforced polymer composites at a high temperature for one year has not been
discussed in the literature.
The main objective of this work is to conduct an experimental investigation to evaluate
the durability of E-glass/epoxy composite in harsh environmental conditions. Specimens
were conditioned at different exposure temperatures (23 ◦ C, 65 ◦ C and 90 ◦ C) in Gulf sea-
water for a period of 12 months. After exposure to the harsh environment, tensile strength,
tensile strain and Young’s modulus of the specimen were determined. Furthermore, water
absorption and scanning electron microscopy (SEM) analysis was conducted to investigate
the damage mechanism of the composite. In addition to determining the degradation of
 Polymers 2021, 13, 2182 3 of 19

the composite experimentally, these data were used to predict the durability of composites
using Arrhenius-based models and the time-shift factor (TSF) approach.

Table 1. FRP composite immersed at different environmental conditions.

Authors Composite Conditioning Duration

Silva et al. [45] E-glass/epoxy Saltwater at 30 ◦ C, 45 ◦C and 55 ◦C 750–5000 h (Approx 7 months)
Chakraverty et al. [46] E-glass/epoxy Seawater at room temperature 2, 4, 6, 8, 10, and12 months (1 year)
Glass/polydicycl-opentadiene Saltwater and deionized water
Hu et al. [50] 1, 3, 6, and 12 months (1 year)
and glass/epoxy at·60 ◦ C
Glass/epoxy, carbon/epoxy and
Guermazi et al. [51] Tap water at 24 ± 3, 70 and 90 ◦ C 3 months
glass/carbon/epoxy
Bobba et al. [52] E-glass and S-glass fiber-epoxy Tap water at 90 ◦ C 600, 1200, and 1800 h (2.5 months)
H2 SO4 , NaOH and NaCl at 60
Feng et al. [53] Glass/epoxy 7, 15, 30, and 90 days (3 months)
and 90 ◦ C
Glass fiber-reinforced epoxy
Merah et al. [54] Seawater at outdoor temperature 6 and 12 months
(GFRE)
Glass/epoxy and
Mourad et al. [18] Seawater at 23 ◦ C and 65 ◦ C 3, 6, 9, and 12 months
glass/polyurethane
EminDeniz et al. [55] Glass/epoxy composite Seawater at 20 ◦ C 3, 6, 9, and 12 months
Artificial seawater in sub-zero and 3600 h
Pavan et al. [43] E-glass/epoxy laminates
ambient temperatures (5 months)
Basalt fiber-reinforced plastic
Wei et al. [56] (BFRP) and Glass fiber-reinforced Artificial seawater at 25 ◦ C 10, 20, 30, 60, and 90 days
plastic (GFRP)
Glass/epoxy filament
Antunes et al. [57] Seawater at 80 ◦ C 7–28 days
wound cylinders
Artificial seawater at room
Ghabezi et al. [58] Carbon/epoxy and glass/epoxy 45 days
temperature and 60 ◦ C

2. Experimentation
In this study, E-glass/epoxy composite reinforced with 52 vol% of glass fiber was
utilized. The E-glass/epoxy was manufactured through a continuous lamination process
13, x FOR PEER REVIEW and obtained from Gordon Composites, Inc. Samples with thickness 4ofof3 21 mm for the
tensile test were prepared as per ASTM Standard D-3039 [59]. Samples were conditioned
at different exposure temperatures (23 ◦ C, 65 ◦ C and 90 ◦ C) in Gulf seawater for the period
of 12 months, as shown in Figure 1. Specimens conditioned at 23 ◦ C and 65 ◦ C were tested
after every three months whereas
after every the testing
three months frequency
whereas was
the testing one month
frequency was for
onethe specimen
month for the specimen
◦
immersed at 90 °C.immersed at 90 C.

(a) (b) (c)

Figure 1. Conditioning
Figure of specimen at of
1. Conditioning (a)specimen
23 °C, (b)
at 65 23 ◦and
(a) °C (c)6590◦ C°C.
C, (b) and (c) 90 ◦ C.

3. Results and Discussion

3.1. Water Absorption Test
The specimens were weighed prior to immersion in seawater at different tempera-
Polymers 2021, 13, 2182 4 of 19

3. Results and Discussion

3.1. Water Absorption Test
The specimens were weighed prior to immersion in seawater at different temperatures.
The specimens were taken out from the seawater tank and dried at room temperature for
24 h to determine the change in the mass. The percentage change in mass of specimen was
calculated after drying as follows:

M2 − M1
M (%) = × 100 (1)
M1

where M (%) = mass change percentage, M2 = mass after drying (g), M1 = mass before
immersion (g).
Figure 2a shows the control specimen which is black in color with a clean surface. The
effect of seawater and temperature was observed based on the crack on the surface of the
specimen for different duration of time. In visual inspection, Figure 2b represents clear
evidence of salt deposition on the surface of the samples immersed at 23 ◦ C and 65 ◦ C
without any crack after 12 months of immersion in seawater. However, significant cracks
were observed on the specimen immersed at 90 ◦ C as shown in Figure 2c. The color of
the specimen changed from black to gray for the specimen exposed at 90 ◦ C whereas no
change in color was observed for the specimen immersed at 23 ◦ C and 65 ◦ C. The change in
the color of the specimen could be due to the micro-cracks which allow high-temperature
Polymers 2021, 13, x FOR PEER REVIEW
seawater to penetrate through the layers of matrix and fiber results the removal of 5black
of 21

pigment of the epoxy.

Figure 2. E-glass/epoxy
Figure E-glass/epoxyspecimen conditioned
specimen at various
conditioned temperatures
at various in seawater
temperatures (a) Control
in seawater (a) Control
sample, (b) 65 °C
◦ and (c) 90 °C.
◦
sample, (b) 65 C and (c) 90 C.

Table 2 and Figure

Table Figure 33show
showthe thepercentage
percentagechange
change ininthethe
mass
massof the specimen
of the specimenat dif-
at
different conditioning
ferent conditioning periods.The
periods. Thespecimen
specimenmass massincreased
increasedwith with immersion
immersion time for the the
specimen ◦ C and 65 ◦ C but it reduced for the specimen immersed at
specimen conditioned at at 23
23 °C and 65 °C but it reduced for the specimen immersed at 90
°C.◦ The
90 C. The seawater
seawater absorption
absorption or increase
or increase in mass
in mass waswas
0.9%, 0.9%, 1.3%,
1.3%, 1.7%1.7%
and and
2.5%2.5%
afterafter
3 m,
36 m, 96 m
m,and
9 m12 and 12 conditioning
m of m of conditioning
at 23 °C 23 ◦ C respectively
at respectively whereas whereas 2.8%,4.1%
2.8%, 2.9%, 2.9%, 4.1%
and 5%
and 5% for seawater immersion at 65 ◦ C. Similarly, Ray [60] observed an increase in water
for seawater immersion at 65 °C. Similarly, Ray [60] observed an increase in water absorp-
absorption with the increase in temperature ◦ to 70 ◦ C. However, at 90 ◦ C, the
tion with the increase in temperature from 60from°C to6070 C
°C. However, at 90 °C, the mass of
mass of the specimen
the specimen dropped dropped
by 1%,by 1%,5.9%
3.6%, 3.6%,and5.9%12%
andafter
12% immersion
after immersion
of 3 m,of 36 m,
m, 69m,
m 9and
m
and
12 m12respectively.
m respectively. This
This may maybe be
dueduetoto
thetheseawater
seawaterthat
thatentered
enteredthrough
through thethe crack
crack and
and
degraded
degraded the the fiber/matrix bonding. Furthermore,
fiber/matrix bonding. Furthermore, at at this
this temperature,
temperature, the the epoxy
epoxy andand fiber
fiber
glass
glass may
may not
not fuse
fuse together
together properly
properly andand composite
composite lost
lost epoxy
epoxy andand seawater
seawater occupied
occupiedthethe
vacant
vacant place in the specimen. Wang et al. [61] noted a similar decrease in the mass
place in the specimen. Wang et al. [61] noted a similar decrease in the mass of
of the
the
composite
composite at at elevated
elevated temperatures.
temperatures.

Table 2. Percentage change in mass of E-glass/epoxy specimens.

Conditioning Duration Variation in Mass (%)

 Polymers 2021, 13, 2182 5 of 19

Table 2. Percentage change in mass of E-glass/epoxy specimens.

Conditioning Variation in Mass (%)

Duration (Months) 23 ◦C 65 ◦ C 90 ◦ C
3 0.9 ± 0.2 2.8 ± 0.3 1.07 ± 0.14
13, x FOR PEER REVIEW 6 1.3 ± 0.4 2.9 ± 0.2 6 of
3.6 21
± 0.9
9 1.7 ± 0.7 4.1 ± 0.6 5.9 ± 0.65
12 2.5 ± 0.5 5.0 ± 0.8 12.05 ± 1.67

Figure 3. Effect of seawater conditioning on the mass of the specimen at various temperature.
Figure 3. Effect of seawater conditioning on the mass of the specimen at various temperature.

3.2. Tensile Properties

3.2. Tensile Properties
The tensile test was performed at room temperature (300 K) using an MTS universal
The tensile test was machine
testing performed (MTSat system
room temperature (300 K)
corporation, Eden usingMN,
Prairie, an MTSUSA).universal
The tests were con-
testing machine (MTS system corporation, Eden Prairie, MN, USA). The tests
ducted at a crosshead speed of 2 mm/min. Table 3 represents the tensile propertieswere con- of the
ducted at a crosshead speed of composite
E-glass/epoxy 2 mm/min. Table 3 at
immersed ◦
represents
23 C and the ◦
65 tensile
C for 12properties
months. Theoftensile
the strength
of controlimmersed
E-glass/epoxy composite samples indicates
at 23 °Ctheandtensile properties
65 °C of the samples
for 12 months. testedstrength
The tensile without immersion.
These results were used as a reference and comparison with
of control samples indicates the tensile properties of the samples tested without immer- conditioned samples to deter-
sion. These results were used as a reference and comparison with conditioned samplesoftothe control
mine the effect of exposure temperature and duration. The tensile strength
specimen was 798 MPa. It was observed that the tensile strength of the specimen reduced
determine the effect of exposure temperature and duration. The tensile strength of the
by 1% from 798 MPa to 790 MPa and 9% from 798 MPa to 726 MPa after an immersion of
control specimen 12 was 798 MPa. It was observed that the tensile strength of the specimen
months in seawater at 23 ◦ C and 65 ◦ C respectively. The tensile properties of specimens
reduced by 1% from 798 MPainto
conditioned 790 MPa
seawater and
at 90 ◦ C9% from
for 12 798 MPa
months to 726
are shown inMPa
Tableafter
4. Thean im-indicates a
table
mersion of 12 months in seawater at 23 °C and 65 °C respectively. The tensile properties
sharp decrease in tensile strength by 92.7% from 798 to 57.3 MPa in 12 months of seawater
of specimens conditioned
conditioning at 90 ◦ C. at 90 °C for 12 months are shown in Table 4. The
in seawater
table indicates a sharp decrease in tensile strength by 92.7% from 798 to 57.3 MPa in 12
Tensile properties of E-glass/epoxy ◦ ◦
Table
months of3.seawater conditioning at 90 °C.composite immersed in seawater at 23 C and 65 C.
Immersion Time Tensile Strength (MPa) Tensile Modulus (GPa) Tensile Strain to Failure (%)
Table 3. Tensile properties of E-glass/epoxy
(Months) ◦ composite ◦immersed in seawater
◦ at 23 °C ◦and 65 °C.
23 C 65 C 23 C 65 C 23 ◦ C 65 ◦ C
Tensile
ion Time 0 (Control Strength (MPa)
Sample) 798 ± 43 Tensile
798 Modulus
± 43 (GPa)
37.1 ± 2.5 Tensile Strain to
37.1 ± 2.5 Failure
2.14 ± 0.02 (%) 2.14 ± 0.02
nths) 3
23 °C 65 °C796 ± 40 783
23 °C ± 51 °C± 1.6
6537.8 35.4 ±
23 °C 1.8 2.1 ±65
0.2°C 2.2 ± 0.0
6 794 ± 49 765 ± 17 35.1 ± 2.5 33.5 ± 0.6 2.26 ± 0.03 2.3 ± 0.2
ol Sample) 7989± 43 798 ± 793
43 ± 39 37.1 ±758
2.5± 28 37.136.3
± 2.5
± 1.9 2.14
33.7 ±±0.02
2.3 2.14
2.22 ± 0.02 2.24 ± 0.15
± 0.2
3 79612± 40 51 ± 38
783 ± 790 1.6± 39 35.438.5
37.8 ±726 ± 4.5
± 1.8 2.1 ±±0.2
32.7 3.4 ± 0.21
2.12 2.2 ± 0.0 2.18 ± 0.1
6 794 ± 49 765 ± 17 35.1 ± 2.5 33.5 ± 0.6 2.26 ± 0.03 2.3 ± 0.2
9 793 ± 39 758 ± 28 36.3 ± 1.9 33.7 ± 2.3 2.22 ± 0.2 2.24 ± 0.15
12 790 ± 38 726 ± 39 38.5 ± 4.5 32.7 ± 3.4 2.12 ± 0.21 2.18 ± 0.1

Table 4. Tensile properties of the specimen immersed in seawater at 90 °C.

Polymers 2021, 13, 2182 6 of 19

Table 4. Tensile properties of the specimen immersed in seawater at 90 ◦ C.

Immersion Time Tensile Strength Tensile Strain to Tensile Modulus

(Months) (MPa) Failure (%) (GPa)
0 (Control sample) 798 ± 43 2.14 ± 0.02 37.1 ± 2.5
Polymers 2021, 13, x FOR PEER REVIEW 7 of 21
1 384 ± 55 1.27 ± 0.02 35.49 ± 2.13
2 368.7 ± 51 1.16 ± 0.023 34.07 ± 1.27
3 328.2 ± 19 0.88 ± 0.08 41.87 ± 2.48
4 279.9 ± 9 0.87 ± 0.07 42.79 ± 4.05
6 5 215 ± 16 248 ± 27 0.51 ± 0.14
0.75 ± 0.1 40.43± ±2.81
41.50 1.23
7 6 165.6 ± 14 215 ± 16 0.31 ± 0.09
0.51 ± 0.14 43.35± ±1.23
40.43 4.33
8 7 151.9 ± 17 165.6 ± 14 0.6 ± 0.09
0.40 ± 0.31 42.1± ±4.33
43.35 3.9
8 151.9 ± 17 0.40 ± 0.6 42.1 ± 3.9
9 96.3 ± 26 0.3 ± 0.1 43.8 ± 2.8
9 96.3 ± 26 0.3 ± 0.1 43.8 ± 2.8
10 10 74.7 ± 9 74.7 ± 9 0.27 ± 0.11
0.27 ± 0.11 47.38 ± ±2.8
47.38 2.8
11 11 60.5 ± 10 60.5 ± 10 0.15 ± 0.07
0.15 ± 0.07 47.18± ±1.13
47.18 1.13
12 12 57.3 ± 3.7 57.3 ± 3.7 0.14 ± 0.09
0.14 ± 0.09 46.9± ±4.7
46.9 4.7

Figure
Figure44shows
showsnearly
nearlya constant lineline
a constant for for
the the
specimen immersed
specimen at 23 ◦atC.23
immersed However, a
°C. However,
small drop was observed in the tensile strength for the specimen immersed at 65 ◦ C. At
a small drop was observed in the tensile strength for the specimen immersed at 65 °C. At
90 ◦ C, the tensile strength dramatically reduced to 384 MPa in 1 month which is 48.12% of
90 °C, the tensile strength dramatically reduced to 384 MPa in 1 month which is 48.12% of
the
thestrength
strengthofofcontrol
controlspecimen.
specimen. Furthermore,
Furthermore, thethe
tensile strength
tensile declined
strength declinedlinearly fromfrom
linearly
384
384toto57.3
57.3MPa
MPaininthe
theremaining
remaining period
periodof 11 months
of 11 monthswhich
whichwaswas
almost 14.9%.
almost 14.9%.

Figure4.4.Effect
Figure Effectofofseawater
seawater immersion
immersion onon tensile
tensile strength.
strength.

Figure
Figure55indicates
indicatesthat
thatseawater
seawaterimmersion
immersion slightly
slightlyaffected the elastic
affected modulus
the elastic of of
modulus
the ◦ ◦
the samples
samplesconditioned
conditionedatat23 23 C°Cand
and6565 C.
°C.The
Theelastic
elasticmodulus
modulusvaried
variedfrom
from37.1 GPa
37.1
◦ C and 65 ◦ C
GPa to
to 38.5 GPa and 32.7 GPa for specimen immersed for 12 months at 23
38.5 GPa and 32.7 GPa for specimen immersed for 12 months at 23 °C and 65 °C respec-
respectively. At an elevated temperature of 90 ◦ C, elastic modus increased by 26.7% from
tively. At an elevated temperature of 90 °C, elastic modus increased by 26.7% from 37.1
37.1 GPa to 46.9 GPa in the period of 12 months. The results indicate that the value of elastic
GPa to 46.9 GPa in the period of 12 months. The results indicate that the value of elastic
modulus varied between 34.07 GPa and 47.38 GPa in the entire conditioning duration. The
modulus varied between 34.07 GPa and 47.38 GPa in the entire conditioning duration. The
elastic modulus of the FRP specimen depends on the modulus of fibers. The immersion in
elastic modulus
seawater of themay
environment FRPnotspecimen depends
have any severe on theon
effect modulus of fibers.
the durability Thefibres,
of the immersion
the in
seawaterofenvironment
modulus GFRP has notmay not have
suffered any severe
any obvious effect
change onimmersion
after the durability
[62]. of the fibres, the
modulus of GFRP has not suffered any obvious change after immersion
The failure strain increased progressively from 2.14% to 2.26% after 6 months [62].and then
◦
decreased to 2.12% after 12 months of immersion at 23 C as shown in Figure 6. However,
immersion at 65 ◦ C results in a slight increase in failure strain from 2.14% to 2.3% after
6 months, then reduced to 2.18% after 12 months. For immersion at 90 ◦ C, the opposite
Polymers 2021, 13, x FOR PEER REVIEW 8 of 21

Polymers 2021, 13, 2182 7 of 19

pattern was observed for failure strain. The failure strain dropped sharply from 2.14 to
Polymers 2021, 13, x FOR PEER REVIEW
1.27% 8 of 21
in 1 month which is 59.2% of the control specimen. Thereafter, it declined gradually
to 0.14% in the remaining 11 months with a comparatively slower rate.

Figure 5. Effect of seawater immersion on modulus of elasticity.

The failure strain increased progressively from 2.14% to 2.26% after 6 months and
then decreased to 2.12% after 12 months of immersion at 23 °C as shown in Figure 6. How-
ever, immersion at 65 °C results in a slight increase in failure strain from 2.14% to 2.3%
after 6 months, then reduced to 2.18% after 12 months. For immersion at 90 °C, the oppo-
site pattern was observed for failure strain. The failure strain dropped sharply from 2.14
to 1.27% in 1 month which is 59.2% of the control specimen. Thereafter, it declined grad-
Figure
Figure 5. Effect
5.
ually to Effect of
0.14% inseawater
of seawater immersion
immersion
the remaining on
onmodulus
modulus
11 months with of
ofaelasticity.
elasticity.
comparatively slower rate.

The failure strain increased progressively from 2.14% to 2.26% after 6 months and
then decreased to 2.12% after 12 months of immersion at 23 °C as shown in Figure 6. How-
ever, immersion at 65 °C results in a slight increase in failure strain from 2.14% to 2.3%
after 6 months, then reduced to 2.18% after 12 months. For immersion at 90 °C, the oppo-
site pattern was observed for failure strain. The failure strain dropped sharply from 2.14
to 1.27% in 1 month which is 59.2% of the control specimen. Thereafter, it declined grad-
ually to 0.14% in the remaining 11 months with a comparatively slower rate.

Figure6.6. Effect
Figure Effectof
ofseawater
seawaterimmersion
immersionon
onfailure
failurestrain
strain(%).
(%).

These
Thesedata datademonstrate
demonstratethat thatwater
waterabsorption
absorptioncontributes
contributestotothe theepoxy
epoxymatrix
matrixplasti-
plas-
cization
ticizationwhich
which affects the the
affects failure strainstrain
failure and tensile modulus.
and tensile Over aOver
modulus. duration of 12 months
a duration of 12
of use, the
months matrix
of use, thebecomes stiff and
matrix becomes fragile,
stiff allowing
and fragile, failurefailure
allowing strainstrain
to decrease and ten-
to decrease and
sile modulus
tensile modulus to increase dramatically.
to increase dramatically. TheThe
tensile properties
tensile properties of the samples
of the samplesimmersed
immersed at
90 ◦ C significantly affected in 12 months of immersion. The failure strain of the samples
at 90 °C significantly affected in 12 months of immersion. The failure strain of the samples
reduced
reduced fromfrom 2.14%
2.14% toto 0.14%
0.14% and and tensile
tensile modulus
modulus increased
increased fromfrom 37.1
37.1 GPa
GPa to to 46.9
46.9 GPa.
GPa.
Figure
Merah 6.
et Effect
al. of
[54] seawater
observed immersion
a decrease oninfailure
brittlestrain (%).
fracture and failure strain
Merah et al. [54] observed a decrease in brittle fracture and failure strain due to prolonged due to prolonged
immersion
immersionin inseawater.
seawater.
These
Further,
Further, datathedemonstrate
the effect
effect of that waterin
of temperature
temperature absorption
seawatercontributes
in seawater conditioning
conditioning to was
the
wasepoxy
examinedmatrix
examined byplas-
by the
the
ticization
analogy of stress–strain behavior of the sample immersed for 3 months, 6 months,129
analogy of which affects
stress–strain the
behaviorfailure
of thestrain
sample and tensile
immersed modulus.
for 3 Over
months, 6 a duration
months, 9 of
months
months of use, the ◦ C, 65becomes
23matrix ◦ C and 90 ◦ as shown
and 12 months
months and 12at months at 23 °C, 65stiff
°CCand
andfragile,
90 °C in allowing
as Figure
shown7. failure
inThe strain
strength
Figure toof
7. The decrease and
specimens
strength of
tensile modulus
conditioned to increase
in seawater ◦
at 23dramatically.
C decreasedThe tensileafter
by 0.25% properties
3 m, 0.5%of the samples
after 6 months,immersed
0.75%
at 90 9°Cmsignificantly
after and by 1%affectedafter 12inm12frommonths the of immersion.
control The failure
specimen, as shownstrain
inofFigure
the samples
7a–d,
reduced fromFigure
respectively. 2.14% 7ato 0.14%
showsand thattensile modulus
the gradient of increased
the specimen fromimmersed
37.1 GPa to 23 ◦GPa.
at 46.9 C is
Merah
more asetcompared
al. [54] observed a decrease
to the gradient in brittle
of the controlfracture
specimen and demonstrating
failure strain due thetoincrease
prolonged in
immersion in seawater.
Further, the effect of temperature in seawater conditioning was examined by the
analogy of stress–strain behavior of the sample immersed for 3 months, 6 months, 9
months and 12 months at 23 °C, 65 °C and 90 °C as shown in Figure 7. The strength of
 specimens conditioned in seawater at 23 °C decreased by 0.25% after 3 m, 0.5% after 6
months, 0.75% after 9 m and by 1% after 12 m from the control specimen, as shown in
Polymers 2021, 13, 2182 Figure 7a–d, respectively. Figure 7a shows that the gradient of the specimen immersed 8 of at
19

23 °C is more as compared to the gradient of the control specimen demonstrating the in-
crease in tensile modulus by 1.9% from 37.1 GPa to 37.8 GPa after three months of condi-
tioning. The slope
tensile modulus byand
1.9%modulus
from 37.1 decreased a little
GPa to 37.8 GPaby 5.3%
after after
three 6 months,
months and 2.15% after
of conditioning. The
9slope
monthsand modulus decreased a little by 5.3% after 6 months, and 2.15% after 97b–d,
whereas increased again by 3.8% in 12 months as indicated in Figure months re-
spectively. The plots also demonstrate the equivalent variation in failure
whereas increased again by 3.8% in 12 months as indicated in Figure 7b–d, respectively. strain, first de-
clining
The plots byalso
1.8% then increasing
demonstrate by 5.7% and
the equivalent 3.7% in
variation and againstrain,
failure decreasing by 0.9%by
first declining after
1.8% 3
months, 6 months,
then increasing 9 months
by 5.7% and 3.7% andand
12 months respectively.
again decreasing At 65
by 0.9% °C,3the
after strength
months, of the
6 months,
specimens
9 months and reduced by 1.9%
12 months after 3 months,
respectively. ◦ C, the
At 65 4.13% after 6 months,
strength of the5% after 9 months,
specimens reducedand by
by
1.9% after 3 months, 4.13% after 6 months, 5% after 9 months, and by 9% after the
9% after 12 months as indicated in Figure 7a–d, respectively. The slopes of graphs
12 months
show the decrease
as indicated in tensile
in Figure 7a–d, modulus by 11.8%
respectively. from 37.1
The slopes of theMPa to 32.7
graphs MPa
show theindecrease
a duration in
of 12 months.
tensile modulus Thebyfailure
11.8% strain
fromof37.1
the specimen
MPa to 32.7 slightly
MPa increased by 1.8%
in a duration of 12after 12 months
months. The
of conditioning
failure at 65
strain of the °C as shown
specimen in Figure
slightly 7d.by
increased Maximum
1.8% afterstain-at-failure observed after
12 months of conditioning at
◦ C as shown
665months by 7.5%inisFigure
shown 7d.inMaximum
Figure 7b. stain-at-failure
At 90 °C, the tensile strength
observed afterof the E-glass/epoxy
6 months by 7.5% is
composite declined
shown in Figure 7b. by 90 ◦ C, after
At 58.9% 3 months,
the tensile 76.2%
strength afterE-glass/epoxy
of the 6 months, 86% after 9 m,declined
composite and by
93.5% after 12 months as shown in Figure 7a–d, respectively. The slopes
by 58.9% after 3 months, 76.2% after 6 months, 86% after 9 m, and by 93.5% after 12 months of the graphs
indicate
as shownthat the modulus
in Figure increased byThe
7a–d, respectively. 26.7% fromof37.1
slopes the MPa
graphs to indicate
47 MPa in thethe
that duration
modulus of
increased
12 months.by 26.7% from 37.1 MPa to 47 MPa in the duration of 12 months.

Polymers 2021, 13, x FOR PEER REVIEW 10 of 21

(a) (b)

(c) (d)

Figure
Figure 7. Stress–strain behavior
7. Stress–strain behaviorof
ofspecimen
specimenimmersed
immersedininseawater
seawaterfor
for(a)(a) 3 months,
3 months, (b)(b) 6 months,
6 months, (c)(c) 9 months
9 months andand
(d)(d)
12
12 months.
months.

3.3. SEM Analysis

The microstructure of samples was analyzed using JEOL-JSM 7610F (JOEL Ltd., To-
kyo, Japan) scanning electron microscope. Figure 8a represents the effect of seawater at 23
°C on the surface of the e-glass epoxy composite. The bonding between fiber and matrix
 (c) (d)
Polymers 2021, 13, 2182 9 of 19
Figure 7. Stress–strain behavior of specimen immersed in seawater for (a) 3 months, (b) 6 months, (c) 9 months and (d) 12
months.

3.3. SEM
SEM Analysis
Analysis
The microstructure
microstructureof ofsamples
sampleswas
wasanalyzed
analyzedusing
using JEOL-JSM
JEOL-JSM 7610F
7610F (JOEL
(JOEL Ltd.,
Ltd., To-
Tokyo,
kyo,
Japan)Japan) scanning
scanning electron
electron microscope.
microscope. Figure
Figure 8a represents
8a represents the effect
the effect of seawater
of seawater at◦23
at 23 C
°C
on on
thethe surface
surface of the
of the e-glass
e-glass epoxy
epoxy composite.
composite. TheThe bonding
bonding between
between fiber
fiber and
and matrix
matrix is
is slightly
slightly affectedwithout
affected withoutthethepresence
presenceofofany
anycrack.
crack.However,
However,minor
minor cracks
cracks and
and broken
◦ C as shown in Figure 8b.
fiber were detected on the surface of the sample immersed at 65 °C as shown in Figure 8b.
The crack size increased with the increase of immersion temperature. At the temperature
◦ C,
of 90 °C, shown in Figure 8c, a significantly larger crack was observed which allows the
penetration may cause the strength
seawater to penetrate the fiber layers. This penetration strength reduced by
93% in 12 months of immersion.

(a) (b) (c)

Polymers 2021,Figure
13, x FOR PEERmicrograph
8. Surface REVIEW of specimen immersed for the duration of one-year at (a) 23 ◦°C, (b) 65 ◦°C and (c) 90 ◦°C.
Figure 8. Surface micrograph of specimen immersed for the duration of one-year at (a) 23 C, (b) 65 C and (c) 90 C.

SEM images for the control sample compared with samples immersed at 23 ◦°C
C and
65 ◦°C mentioned in
C mentioned inFigure
Figure9a,b
9a,bfor
forthe
theduration
durationof of
12 12 months.
months. Rough
Rough fracture
fracture andand chip-
chipping
ping
surfaceThe
surfacemicrograph
of fiber
of fiber in Figure in
9a Figure
in Figure 9bthe
9a indicates
indicates represents
the ductile
ductile the of
failure
failure failure
ofthe surface
thefiber.
fiber. of a matrix
Shattered
Shattered specimen im
for
and 12 months
smooth
smooth at 65surface
fractured
fractured °C. The
surface smooth
indicate
indicate cross-sectional
brittle
brittle failureofofthe
failure surface
thematrix.
matrix. The
The ofmicrostructure
the fibersofindicate
microstructure
of
thethe fractured
fractured surface
surface and and
fiberfiber pullout
pullout represents
represents slightslight
fracture of the fiber. The presence of epoxy resin around fibers and degradation
degradation in in fiber/matrix
fiber/matrix bond- on the
dimples
bonding. The composite indicated
onlyonly
a 1%a decrease
1% decrease in tensile strength, a 3.77% increase
of the matrix indicates ductile failure. The fiber/matrix debonding andinpotholin
ing. The composite indicated in tensile strength, a 3.77% increase
in modulus
modulus duedue to swelling
to swelling of matrix
of the the matrix
and aand a 0.93%
0.93% decrease
decrease in failure
in failure strain
strain due to due to
matrix
observed
matrix at the fractured
plasticization.
plasticization. surface which results in a 9% drop in tensile strength.

(a) (b)
Figure
Figure 9.9.Failure
Failure surface
surface of specimen
of specimen immersed
immersed for theofduration
for the duration ofat12
12 months 23 ◦ C, and
(a)months at (b)
(a) 23 °C,
◦
65 °C.
C.
65
The micrograph in Figure 9b represents the failure surface of a specimen immersed
for 12Figure
months10a–c show
at 65 ◦ C. the SEM
The smooth micrograph
cross-sectional of E-glass/epoxy
surface composite
of the fibers indicates brittleimmers
°C for the
fracture of theduration of 3 months,
fiber. The presence of epoxy6 resin
months,
around9 fibers
months and 12 on
and dimples months respective
the surface
rough and corrugated surface of the fiber and dimpled matrix surface indicates the
failure of both fiber and matrix as shown in Figure 10a. The potholing and fiber
debonding observed on the surface may results in a sharp decrease in the tensile s
 Polymers 2021, 13, 2182 10 of 19

of the matrix indicates ductile failure. The fiber/matrix debonding and potholing were
observed at the fractured surface which results in a 9% drop in tensile strength.
Figure 10a–c show the SEM micrograph of E-glass/epoxy composite immersed at
90 ◦ C for the duration of 3 months, 6 months, 9 months and 12 months respectively. The
rough and corrugated surface of the fiber and dimpled matrix surface indicates the ductile
failure of both fiber and matrix as shown in Figure 10a. The potholing and fiber/matrix
debonding observed on the surface may results in a sharp decrease in the tensile strength
of the composite as shown in Figure 4. With the increase of immersion time, resin flow
and fiber/matrix debonding accelerated as shown in Figure 10b. The chipped-out fiber
surface indicates the ductile fracture of the fiber whereas the smooth and mirror-like surface
with matrix chunks indicates its brittle failure. The reaction between water and epoxy
believed to cause a breakdown of the polymer’s molecular weight, leading to the fragile
nature of the matrix. Water can also function as an anti-plasticizer, preventing polymer
segments from moving and making the matrix more brittle [46]. After an immersion of
9 and 12 months, the fiber matrix bonding degraded to the lowest level and an absence of
the resin was observed at the fractured surfaces of the composite as shown in Figure 10c,d.
These SEM images support the observed decrease in the mass of the composite due to resin
flow discussed in the water absorption test and shown in Figure 3. The degradation at
the fiber/matrix interface involves a complex mechanism as the fiber/matrix interface is a
heterogeneous area between the fiber and matrix [63–67]. Fiber-matrix interface damage
for FRP composites is usually caused by debonding between fiber and resin which occurs
mainly in two stages. The first stage is the chemical debonding due to chemical corrosion
Polymers 2021, 13, x FOR PEER REVIEW
between fiber and resin, and the second stage is the poor interlacing between fibers and12 of 21
matrix owing to resin swelling through water absorption [68].

(a) (b)

(c) (d)
Figure10.
Figure 10.Failure
Failuresurface
surface
ofof specimen
specimen immersed
immersed in sea
in sea water
water at 90at◦ C
90(a)
°C3(a) 3 months,
months, (b) 6 (b) 6 months,
months,
(c) 9 months and (d) 12 months.
(c) 9 months and (d) 12 months.

3.4. Differential Scanning Calorimetry (DSC) Test

The differential scanning calorimetry (DSC) for the E-glass/epoxy composite was
conducted on samples immersed at different temperatures and exposure times. This test
was carried out using a TA-Instruments DSC Q200 device (TA-Instruments, New Castle,
 Polymers 2021, 13, 2182 11 of 19

3.4. Differential Scanning Calorimetry (DSC) Test

The differential scanning calorimetry (DSC) for the E-glass/epoxy composite was
conducted on samples immersed at different temperatures and exposure times. This test
was carried out using a TA-Instruments DSC Q200 device (TA-Instruments, New Castle, DE,
USA). The test was performed in an inert environment using nitrogen gas. The experiment
was run between 25 ◦ C and 250 ◦ C with a heating rate of 10.0 ◦ C/min. Three samples for
each condition were considered to determine the glass transition temperature. Figure 11
represents the DSC curves for the control sample and specimens immersed at 23 ◦ C, 65 ◦ C
and 90 ◦ C for 12 months. The glass transition temperatures (Tg) of the samples immersed
at 23 ◦ C and 65 ◦ C found to be close to the Tg of the control sample. The glass transition
temperature for the control specimen and specimen immersed at 23 ◦ C and 65 ◦ C observed
Polymers 2021, 13, x FOR PEER REVIEW 13 of 21
to be 118 ◦ C, 117 ◦ C and 112 ◦ C, respectively, indicating that as exposure temperature
increases, the Tg decreases.

11.DSC
Figure 11.
Figure DSCcurves
curvesforfor
E-glass/epoxy control
E-glass/epoxy sample
control and conditioned
sample samples.
and conditioned samples.

This is an indication of the associated effect of immersion on the physical and chemical
This is an indication of the associated effect of immersion on the physical and chem-
properties of the composite. It was noted that the tensile strength reduced by 1% and 9%
ical
in oneproperties of the
year for the composite.
exposure It wasof
temperature noted
23 ◦ Cthat
andthe65 ◦tensile strengthFurthermore,
C, respectively. reduced by 1% and
9%
SEM micrographs and FTIR analysis support the observed slight degradation. On theFurthermore
in one year for the exposure temperature of 23 °C and 65 °C, respectively. other
SEM micrographs
side, the and FTIR
Tg of the composite wasanalysis support
significantly reduced 42.11 ◦ C after
thetoobserved slight degradation.
seawater aging at On the
90 ◦ C for
other side,
12 the Tg ofThe
months. thevalue
composite
of Tg was was significantly
observed ◦ C, 51.55 ◦ C, 46.57 ◦ C and
reduced
to be 69.8 to 42.11 °C after seawater
◦
aging at 90 °C for 12 months. The value of Tg was observed to berespectively.
42.11 C for the duration of 3 months, 6 months, 9 months and 12 months, 69.8 °C, 51.55This°C, 46.57
significant shift in Tg is because of the combined effect of high temperature
°C and 42.11 °C for the duration of 3 months, 6 months, 9 months and 12 months, respec- and seawater
aging. The degradation in the epoxy composite owes to the existence of hydrophilic groups
tively. This significant shift in Tg is because of the combined effect of high temperature
which form weak hydrogen bonds by reacting with water molecules during immersion
and seawater aging. The degradation in the epoxy composite owes to the existence of hy-
and swelling of the composite at 90 ◦ C [69]. This demonstrates that the moisture uptake
drophilic groups and
acts as a plasticizer which form weak
decreases Tg. Thehydrogen
reduction inbonds by reacting
Tg represents with
thermal water molecules
degradation
during
and loss in mechanical properties which limits the service temperature of the polymer.that the
immersion and swelling of the composite at 90 °C [69]. This demonstrates
moisture uptakeofacts
The mechanisms as achain
the long plasticizer and decreases
of the polymer may startTg. The reduction
to isolate in Tg represents
at high-temperature
thermal
immersion degradation
and react withandeach
lossother
in mechanical propertiesofwhich
to alter the properties limits[70].
the polymer the service tempera-
ture of the polymer. The mechanisms of the long chain of the polymer may start to isolate
3.5. FTIR Results
at high-temperature immersion and react with each other to alter the properties of the
The Fourier
polymer [70]. transform infrared spectroscopy (FTIR) was performed on Perkin Elmer
Spectrum 100 FTIR spectrometer (PerkinElmer Life and Analytical Sciences, Shelton, CT,
USA) at room temperature in the transmission mode. FTIR spectra were logged in between
3.5. FTIR Results
600 cm−1 and 4000 cm−1 at a resolution of 2 cm−1 with 10 scans. Before testing the
The Fourier transform infrared spectroscopy (FTIR) was performed on Perkin Elmer
Spectrum 100 FTIR spectrometer (PerkinElmer Life and Analytical Sciences, Shelton, CT
USA) at room temperature in the transmission mode. FTIR spectra were logged in be-
tween 600 cm−1 and 4000 cm−1 at a resolution of 2 cm−1 with 10 scans. Before testing the
 Polymers 2021, 13, 2182 12 of 19

samples, Background spectra were taken in the empty chamber to eliminate the influence
of moisture and CO2 in air. Figure 12 presents a comparison of typical spectra for E-
glass/epoxy composite immersed at 23 ◦ C, 65 ◦ C and 90 ◦ C for 12 months and compared
with control sample. The seawater exposure will lead to the presence of equivalent FTIR
bands on the residue spectrum due to the leaching of functional groups from the resin of
the composite. The allocation of the representative absorbent bands is given in Table 5 for
Polymers 2021, 13, x FOR PEER REVIEW 14 of 2
the samples and their allocated functional groups. The O–H stretching band is observed
above 3000 cm−1 wavenumbers.

Figure12.
Figure 12.FTIR
FTIR spectrum
spectrum of E-glass/epoxy
of E-glass/epoxy control
control sample
sample and conditioned
and conditioned samples.samples.

Table5.5.FTIR
Table FTIRbands observed
bands in E-glass/epoxy
observed specimens.
in E-glass/epoxy specimens.

BandsBands ) −1 )
(cm−1(cm Assignment
Assignment
3400 3400 Stretchingvibration
Stretching vibration O=H
O=H
~2930 and ~2900 C–H group stretching band
~2930 and ~1732
~2900 C–H group stretching band
C–O non-conjugate ester stretching
~1732~1610 C–O non-conjugate
stretching band ofester stretching
C=C (alkene)
~1610~1509 C=C band
stretching (aromatic nucleus)
of C=C (alkene)
~1245 Asymmetric C–O– Φ stretch
~15091182 C=C (aromatic nucleus)
C–O aromatic ring stretching
~1245~1040 Asymmetric
Symmetric C–O–
C–O– ΦΦstretch
stretch
1182 ~827 Out
C–O of plane bending
aromatic of C–H
ring (benzene)
stretching
~1040 Symmetric C–O– Φ stretch
The difference in intensity of O–H stretching −1
~827 Out of vibration
plane bendingat 3400ofcmC–His(benzene)
due to the
seawater immersion of the specimen [71,72]. The next band is located between 2930 cm−1
and 2900 cm−1 and is attributed to the stretching band of the C–H group of epoxies [71,72].
The difference in intensity of O–H stretching vibration at 3400 cm−1 is due to the sea
The stretching of C–O non-conjugate ester was detected at 1732 cm−1 [73]. The existence of
wateratimmersion
bands 1509 cm−1 andof the specimen
1610 cm−1 are[71,72].
allotted The nextstretching
for C=C band is inlocated between
aromatics 2930 cm−1 and
and alkenes
2900 cm and
−1
respectively is attributed
[72,74,75]. Symmetricto the
andstretching
asymmetric band of thevibration
stretching C–H group of epoxies
of C–O–Φ [71,72]. Th
observed
stretching − of
1 C–O −
non-conjugate
1 ester was detected at 1732
at 1040 cm and 1245 cm wavenumber respectively [71,73]. The band at 1182 cm iscm −1 [73]. The−existence
1 o
bands
due at 1509
to the cm characteristics
vibration −1 and 1610 cmof are
−1 C–Oallotted for C=C
in an aromatic stretching
ring in aromatics
[76] whereas and alkene
C–H bending
in benzene ring[72,74,75].
was detected −1 [72]. The immersion of specimen in seawater
at 827 cmand
respectively Symmetric asymmetric stretching vibration of C–O–Φ ob
produces −1 which indicates stretching vibration of the ether group
served ata1040
bandcm at−1~840
and cm
1245 cm −1 wavenumber respectively [71,73]. The band at 1182 cm−

is due to the vibration characteristics of C–O in an aromatic ring [76] whereas C–H bend
ing in benzene ring was detected at 827 cm−1 [72]. The immersion of specimen in seawate
produces a band at ~840 cm−1 which indicates stretching vibration of the ether group a
Polymers 2021, 13, 2182 13 of 19

as trapped moisture in specimen includes hydrogen bond with the C-O-C groups [72].
Another band that appeared at ~1125 cm−1 could be ascribed to the alteration in the
vibrational C-OH band leading to the formation of hydrogen bond (C–O–H—-OH2) during
hydration [72]. The presence of these bands confirms the leaching of the E-glass/epoxy
matrix into the seawater during immersion.
In the FTIR spectrum, two peaks at 2296.3 cm−1 and 2353.2 cm−1 appeared for the
control sample. This indicates the existence of unreacted –N=C=O groups [77] in E-
glass/epoxy samples. These two peaks become weak after immersion of 12 months at
23 ◦ C and 65 ◦ C and disappeared at 90 ◦ C. The vanishing of the two peaks at 2296.3 cm−1
and 2353.2 cm−1 after immersion for 12 months at 90 ◦ C is due to the reaction between the
water molecules and unreacted –N=C=O groups, which can be presented shown as

R − N = C = O + H2 O → R − NH2 + CO2 ↑ (2)

Therefore, the mass loss of the E-glass epoxy composite specimens during immersion
at 90 ◦ C can be described as the release of CO2 shown in Equation (2). At this immersion
temperature, the sustained release of CO2 is responsible for the increase of mass loss of
the composite [67,78,79].

4. Prediction
Several researchers utilized the Arrhenius method for the prediction of the long-term
behavior of FRP composites [48,80,81]. A fundamental hypothesis was anticipated that the
single dominant degradation mechanism does not alter irrespective of temperature and
exposure time [33], but the damage resistance reduces with the exposure temperatures.
The equation for the degradation rate is mentioned below [82];
− Ea/RT )
k = A e( (3)

where k is the rate of degradation (1/time), A is the constant of material in the degra-
dation process, Ea is the activation energy (kJ/mol), R is the universal gas constant
(8.314 Jmol−1 K−1 ), T is the temperature (K). Equation (3) can be modified as:

1 1 ( Ea )
= e RT (4)
k A
 
1 Ea 1
ln = − ln( A) (5)
k R T
The inverse of k indicates the time taken to achieve a given value for a material
property. The exponential degradation model [83] was utilized as the fiber-matrix interfacial
delamination took place during the seawater immersion of E-glass/epoxy composite
(Figure 13). This model can be expressed as
−t )
Y = 100e( τ (6)

where Y is the tensile strength retention (%), τ is a constant and t is the immersion time
(month). the value of correlation coefficient (R2 ) and τ of E-glass/epoxy composite are
mentioned in Table 6 by fitting Figure 13 using Equation (6).

Table 6. Coefficients of regression equation.

Temperature τ R2
23 1250 1
65 142.86 0.9544
90 4.95 0.966
 delamination took place during the seawater immersion of E-glass/epoxy composite (Fig-
ure 13). This model can be expressed as

= 100 (6)

Polymers 2021, 13, 2182 where Y is the tensile strength retention (%), τ is a constant and t is the immersion 14 of 19
time (month). the value of correlation coefficient (R2) and τ of E-glass/epoxy composite
are mentioned in Table 6 by fitting Figure 13 using Equation (6).

Figure 13. Tensile strength retention of E-glass epoxy samples exposed to seawater at 23 ◦ C, 65 ◦ C, and 90 ◦ C.

A different approach based on a time-shift factor (TSF) was used by Dejke [49]. The
time-shift is defined as the ratio of times (t1 and t2 ) required to determine a certain level of
decrease in the mechanical property at two different temperatures (T1 and T2 ). According to
Equation (7), the time required to obtain a certain level of decrease in mechanical property
is the inverse proportion of the reaction rate K.
Ea
−
t (1 − Y )/K1 K Ae T2 R Ea 1
( − 1 )
TSF = 1 = = 2 = Ea
= e R T2 T1 (7)
t2 (1 − Y )/K2 K1 −
Ae T1 R
This approach also depends on the Arrhenius equation. The time shift is an effect of
accelerated aging due to the increment in temperature from T2 (lower temperature) to T1
(higher temperature) [84]. The TSF was calculated, using Equation (7), shown in Table 7 for
65 ◦ C and 90 ◦ C.

Table 7. Value of time-shift factor and activation energy.

Temperature TSF Ea /R
65 8.7 5155.713
90 456 9731.482

The value of Ea/R can also be calculated using the time-shift approach by plotting the
TSF versus the temperature (in ◦ C) graph as shown in Figure 14 and fitted by regression
analysis so that the fit is given by Equation (7). The values of Ea/R are presented in Table 7.
The durability of composite with a reference temperature of 23 ◦ C calculated by time-
shift from 23 ◦ C to 65 ◦ C and 23 ◦ C to 90 ◦ C. The TSF values calculated from Equation (7)
using temperatures 23 ◦ C and 90 ◦ C is 456 and the time t2 to reach 57% of the strength at
90 ◦ C is 12 months, then the time t1 to reach 7.2% strength at 23 ◦ C is 456 × 12 = 5472 months.
The extrapolations to predict the long-term tensile strength retention at 23 ◦ C from the
strength retention at 65 ◦ C and 90 ◦ C based on the time-shift approach for E-glass/epoxy
are shown in Figure 15. The discussed method can be utilized to predict the durability of
any structure under seawater at any temperature. In contrast, E-glass/epoxy possesses a
long-term performance in tensile strength under seawater immersion at 23 ◦ C. However, at
an accelerated temperature of 90 ◦ C, the tensile and chemical properties of the composite
degraded significantly in a short period of immersion which restricts the application of the
composite at high-temperature immersion.
 65 8.7 5155.713
90 456 9731.482

The value of Ea/R can also be calculated using the time-shift approach by plotting the
Polymers 2021, 13, 2182 TSF versus the temperature (in °C) graph as shown in Figure 14 and fitted by regression 15 of 19
analysis so that the fit is given by Equation (7). The values of Ea/R are presented in Table
7.

Polymers 2021, 13, x FOR PEER REVIEW 17 of 21

The durability of composite with a reference temperature of 23 °C calculated by time-

shift from 23 °C to 65 °C and 23 °C to 90 °C. The TSF values calculated from Equation (7)
using temperatures 23 °C and 90 °C is 456 and the time t2 to reach 57% of the strength at
90 °C is 12 months, then the time t1 to reach 7.2% strength at 23 °C is 456 × 12 = 5472
months. The extrapolations to predict the long-term tensile strength retention at 23 °C
from the strength retention at 65 °C and 90 °C based on the time-shift approach for E-
glass/epoxy are shown in Figure 15. The discussed method can be utilized to predict the
durability of any structure under seawater at any temperature. In contrast, E-glass/epoxy
possesses a long-term performance in tensile strength under seawater immersion at 23 °C.
However, at an accelerated temperature of 90 °C, the tensile and chemical properties of
the composite degraded significantly in a short period of immersion which restricts the
Figure14.
application
Figure The
14.The TSF
ofTSF values
thevalues versusat
composite
versus temperature
forfor
high-temperature
temperature E-glass
E-glass epoxy composite.
immersion.
epoxy composite.

Figure
Figure 15.
15. Durability
Durability prediction
prediction of
of E-glass ◦ C.
E-glass epoxy composite immersed in seawater at 23 °C.

5. Conclusions
5. Conclusions
In this
In this study,
study, E-glass/epoxy
E-glass/epoxycomposites
compositeswere
wereconditioned
conditionedat atdifferent
different exposure
exposure tem-
tem-
peratures (23 ◦ C, 65 ◦ C and 90 ◦ C) in Gulf seawater for a period of 12 months. The water
peratures (23 °C, 65 °C and 90 °C) in Gulf seawater for a period of 12 months. The water
absorption, tensile properties and failure analysis were conducted and the durability of
absorption, tensile properties and failure analysis were conducted and the durability of
the composite predicted using the TSF approach. The outcomes of the investigation are
the composite predicted using the TSF approach. The outcomes of the investigation are
summarized below:
summarized below:
(1) The mass of the specimen increased by 2.5% and 5% after the immersion of 12 months
(1) The mass of the specimen increased by 2.5% and 5% after the immersion of 12 months
at 23 ◦ C and 65 ◦ C respectively. An opposite tendency was observed for the specimen
at 23 °C and 65 °C◦ respectively. An opposite tendency was observed for the specimen
immersed at 90 C in which the mass of the sample reduced by 12.7% for the same
immersed at 90 °C in which the mass of the sample reduced by 12.7% for the same
immersion period.
immersion period.
(2) The tensile strength reduced by 1% and 9% after immersion of 12 months at 23 ◦ C
(2) The tensile strength reduced by 1% and 9% after immersion of 12 months at 23 °C
and 65 ◦ C respectively. The durability of the composite was significantly affected at
and 65◦ °C respectively. The durability of the composite was significantly affected at
at 90 C and tensile strength was reduced to 48.4% in 1 month.
at 90 °C and tensile strength was reduced to 48.4% in 1 month.
(3) Slight variation in the tensile modulus observed for specimen immersed at 23 ◦ C
(3) Slight
and 65 variation
◦ C where in the tensile modulus
it increased observed
significantly at for
90 specimen immersed
◦ C. However, at 23 °C
the failure and
strain
65 °C where it increased significantly at 90 °C. However, the failure strain slightly
slightly increased for specimens at 23 ◦ C and 65 ◦ C but it decreased drastically for the
increased
immersion foratspecimens
90 ◦ C. at 23 °C and 65 °C but it decreased drastically for the immer-
sion at 90 °C.
(4) SEM micrographs indicate fiber/matrix debonding, potholing, fiber pull-out and ma-
trix cracking which indicates deterioration in the tensile properties of the composite.
The deterioration mainly owes to breakage of chemical bonding between fiber and
resin due to chemical corrosion, and poor interlocking between fibers and resin due
to resin swelling through water absorption especially at 90 °C immersion, mainly
Polymers 2021, 13, 2182 16 of 19

(4) SEM micrographs indicate fiber/matrix debonding, potholing, fiber pull-out and
matrix cracking which indicates deterioration in the tensile properties of the composite.
The deterioration mainly owes to breakage of chemical bonding between fiber and
resin due to chemical corrosion, and poor interlocking between fibers and resin due
to resin swelling through water absorption especially at 90 ◦ C immersion, mainly
from the hydrolysis of resin, which was also evidenced by the DSC and FTIR results.
(5) A prediction approach based on a time-shift factor (TSF) was used which utilizes the
accelerated temperature testing results to build a model for the long-term prediction
at room temperature. This model predicted that the tensile strength retention of E-
glass/Epoxy composite will be reduced to 7% 450 years after immersion in seawater at
23 ◦ C. Lastly, the activation energy for the degradation of the composite was calculated.
It was 5155.713 and 9731.482 for composite immersed at 65 ◦ C and 90 ◦ C respectively.
It can also be concluded that the E-glass/epoxy composite showed outstanding per-
formance in seawater immersion up to 65 ◦ C. However, the rate of degradation was
significantly high for immersion at 90 ◦ C and the material almost lost its durability. This
is an indicative measure that the durability of the E-glass/epoxy composite is uncertain
above 65 ◦ C which may limit its utilization for high-temperature applications.

Author Contributions: Conceptualization, A.H.I. and A.-H.I.M.; methodology, A.H.I. and A.-H.I.M.;
formal analysis, A.H.I.; investigation, A.H.I. and A.-H.I.M.; resources, A.-H.I.M. and B.M.A.-M.; data
curation, A.H.I.; writing—original draft preparation, A.H.I.; writing—review and editing, A.-H.I.M.,
B.M.A.-M. and B.S.; visualization, A.H.I. and A.-H.I.M.; supervision, A.-H.I.M. and B.M.A.-M.;
project administration, A.-H.I.M., B.M.A.-M., and B.S.; funding acquisition, A.-H.I.M. All authors
have read and agreed to the published version of the manuscript.
Funding: This research was funded by the UPAR research program at the United Arab Emirates
University, UAE [grant number 31N225].
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: All data and models used during the study appear in the submitted
article.
Acknowledgments: The authors would also like to acknowledge the UAEU and WSU for providing
the research facilities.
Conflicts of Interest: The authors declare no conflict of interest.

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