materials

Article
The Curing Kinetics of E-Glass Fiber/Epoxy Resin Prepreg and
the Bending Properties of Its Products
Lvtao Zhu 1,2, *, Zhenxing Wang 1 , Mahfuz Bin Rahman 1 , Wei Shen 2 and Chengyan Zhu 1

1 College of Textile Science and Engineering (International Institute of Silk), Zhejiang Sci-Tech University,
Hangzhou 310018, China; [email protected] (Z.W.); [email protected] (M.B.R.);
[email protected] (C.Z.)
2 Shaoxing Baojing Composite Materials Co., Ltd., Shaoxing 312000, China; [email protected]
* Correspondence: [email protected]; Tel.: +86-151-5888-8425

Abstract: The curing kinetics can influence the final macroscopic properties, particularly the three-
point bending of the fiber-reinforced composite materials. In this research, the curing kinetics of
commercially available glass fiber/epoxy resin prepregs were studied by non-isothermal differential
scanning calorimetry (DSC). The curing kinetic parameters were obtained by fitting and the apparent
activation energy Ea of the prepreg, the pre-exponent factor, and the reaction order value obtained. A
phenomenological nth-order curing reaction kinetic model was established according to Kissinger
equation and Crane equation. Furthermore, the optimal curing temperature of the prepregs was
obtained by the T-β extrapolation method. A vacuum hot pressing technique was applied to prepare
composite laminates. The pre-curing, curing, and post-curing temperatures were 116, 130, and 153 ◦ C
respectively. In addition, three-point bending was used to test the specimens’ fracture behavior,
and the surface morphology was analyzed. The results show that the differences in the mechanical
Citation: Zhu, L.; Wang, Z.; properties of the samples are relatively small, indicating that the process settings are reasonable.
Rahman, M.B.; Shen, W.; Zhu, C.
The Curing Kinetics of E-Glass Keywords: prepreg; glass fiber/epoxy resin; curing kinetics; bending properties
Fiber/Epoxy Resin Prepreg and the
Bending Properties of Its Products.
Materials 2021, 14, 4673.
https://doi.org/10.3390/ma14164673 1. Introduction
Glass fiber reinforced composites have remained interesting for academia as well as
Academic Editor: Angelo
industry due to their outstanding properties, i.e., lightweight, fatigue resistance, corrosion
Marcello Tarantino
resistance, high specific strength, and easy manufacturing techniques, as well as reasonable
cost compared to other fiber-reinforced composites [1,2]. They have been widely used in
Received: 22 July 2021
Accepted: 9 August 2021
many areas such as aerospace, marine, automotive, medical, sports, machine tools, and
Published: 19 August 2021
for several other structures [3]. E-glass fiber/epoxy resin prepreg is an intermediate for
the manufacture of composite materials [4]. It is a composition obtained by impregnating
Publisher’s Note: MDPI stays neutral
E-glass fiber or fabric with epoxy resin. The epoxy resin in a B-level semi-cured state
with regard to jurisdictional claims in
can be cured under a specific temperature and pressure to obtain composite products.
published maps and institutional affil- This manufacturing method can significantly improve production efficiency but has high
iations. requirements for the rationality of the curing process design [5]. This is mainly reflected
in the setting of process parameters. Setting reasonable process parameters is the key to
obtaining high-quality products.
The study of curing kinetics is an important basis for designing curing conditions [6,7].
Copyright: © 2021 by the authors.
At present, the curing kinetics of resin matrix composites are mainly based on the mecha-
Licensee MDPI, Basel, Switzerland.
nism method and phenomenological method [8,9]. The mechanism method regards the
This article is an open access article
overall reaction as the sum of each elementary reaction and studies each elementary re-
distributed under the terms and action and the related effects. This can accurately describe the curing kinetics, but it is
conditions of the Creative Commons difficult to calculate and model [10]. The phenomenological method is semi-empirical
Attribution (CC BY) license (https:// curing, i.e., the kinetic model. It mainly studies the overall reaction and obtains the kinetic
creativecommons.org/licenses/by/ parameters through a mathematical simulation from the empirical equation. It has the
4.0/). advantage of being simple and intuitive, so it is widely used. Cai et al. used differential

Materials 2021, 14, 4673. https://doi.org/10.3390/ma14164673 https://www.mdpi.com/journal/materials

Materials 2021, 14, 4673 2 of 12

scanning calorimetry under dynamic as well as isothermal conditions to study the curing
kinetics of two epoxy resin/flexible amine systems and established a phenomenological
curing kinetic model. The experimental results have consistency with the predicted results
of the model; thus, these models can be used to describe the curing phenomenon of the
resin well [11]. Liu et al. investigated the phenomenological curing model of epoxy resin
for prediction of the degree of the cure based on an autocatalytic cure kinetic model and a
new modified phenomenological curing model based on Olivier’s model, and they showed
that the modified Olivier’s model is simple, easy to use and more accurate [12]. The curing
kinetics has a significant influence on the macroscopic mechanical properties of composite
materials [13].
The three-point bending experiment is considered as one of the important and most
extensively used tests in measuring the mechanical properties of composite material [14].
Mouzakis et al. used a three-point bending test to study the changes in the bending
strength of polyester/glass fiber reinforced composite materials (GFRPC) under the com-
bined effects of temperature, humidity, and ultraviolet radiation [15]. Ren et al. prepared
a modified fiber-reinforced phthalonitrile-based resin composite laminate and tested its
bending strength through a three-point bending test [16]. Jariwala et al. studied the influ-
ence of fiber structure on the mechanical properties of E glass fiber reinforced composites,
and the bending strength was tested by a three-point bending experiment [17]. Shin et al.
studied the optimal conditions of glass fiber/epoxy resin composites based on the mixing
ratio of the two epoxy resin matrices. Three-point bending was used to test the bending
performance and finally obtained when the epoxy resin mixing ratio is 1:1, the mechanical
performance of the composite material is the best [18]. Therefore, we choose a three-point
bending experiment to test the sample’s mechanical properties in our research.
As the curing process parameters have a crucial influence on the quality of composite
products, we focused on the curing kinetics of epoxy resin. The curing kinetic parameters
were obtained by non-isothermal differential scanning calorimetry, the curing kinetic model
of the resin was established, and the optimal curing temperature parameters of the resin
were obtained by the T-β extrapolation method. Further, the composite laminates were
prepared by the vacuum hot pressing process, and three-point bending was used to test
the difference in mechanical properties between different samples. This method is of
great significance to guide the actual production; it can quickly obtain the best curing
temperature range of the resin and quickly check its quality.

2. Materials and Methods

2.1. Materials
The sample used was a prepreg (composed of ER468-2400 E-glass fiber and 7901 DNK
toughened epoxy resin) purchased from Weihai Guangwei Composite Material Co., Ltd.,
Weihai, China. The 7901 DNK is a resin with good curing and process properties obtained
after modification by a variety of epoxy resins, mainly including DGEBA and BDGE. IPDA
is the main curing agent for this resin. Their structure are shown in the Figure 1. The main
properties of prepreg are shown in Table 1.

Table 1. Main properties of prepreg.

Physical Properties Unit Value

The weight of prepreg per unit area g/m2 2352 ± 5%
Fiber weight per unit area g/m2 1600 ± 5%
Single-layer thickness mm 1.2 ± 0.1
Resin content % 32.0 ± 3.0
Volatile content % ≤1.0
2.1. Materials
The sample used was a prepreg (composed of ER468-2400 E-glass fiber and 7901
DNK toughened epoxy resin) purchased from Weihai Guangwei Composite Material Co.,
Ltd., Weihai, China. The 7901 DNK is a resin with good curing and process properties
Materials 2021, 14, 4673
obtained after modification by a variety of epoxy resins, mainly including DGEBA and 3 of 12
Materials 2021, 14, x FOR PEER BDGE.
REVIEWIPDA is the main curing agent for this resin. Their structure are shown in the Fig-
3 of 12
ure 1. The main properties of prepreg are shown in Table 1.

R PEER REVIEW 3 of
Figure 1. Chemical structure formula of (a) DGEBA, (b) BDGE and (c)12
IPDA.

Table 1. Main properties of prepreg.

Physical Properties Unit Value

The weight of prepreg per unit area g/m2 2352 ± 5%
Fiber weight per unit area g/m2 1600 ± 5%
Single-layer thickness mm 1.2 ± 0.1
Resin content % 32.0 ± 3.0
Figure 1. Chemical structure formula of (a) DGEBA, (b) BDGE and (c) IPDA.
Figure 1. Chemical structure formula of (a) DGEBA, (b) BDGE and (c) IPDA. ≤1.0
Volatile content %

Table 1. Main properties of prepreg.

2.2.2.2.
Manufacturing
Manufacturingof Composite
of CompositeLaminates
Laminates
Physical Properties TheThe
prepregs were
prepregs were Unit
cut cut
to 250 × 300
to 250 mmmm
× 300 andValue
laidlaid
and up to
up15tomm
15 mm on the mold
on the by hand,
mold by hand,
The weight of prepreglaying
perlaying
unit area
5 groups
5 groupsof of
thethe g/mthickness
same
same 2
thicknesstotodetect 2352
detect the±difference
5%
difference inmechanical
in mechanicalproperties
properties after
Fiber weight per after curing.After
unitcuring.
area Afterbeing
beinglaidlaid up,
up,
g/m vacuumtreatment
2 vacuum treatment
1600 was
was
± 5% usedtotoeliminate
used eliminateminute
minutebubbles
bubblesthat
thatmay
Single-layer thicknessmayoccur
occur during
during thethe layup
layup
mm process
process so that
so that the the
1.2good good
± 0.1 mechanical
mechanical properties
properties of theof the
laminate
could could
laminate
Resin content be obtained. Finally,
be obtained. the laminates
%Finally, were
the laminates put
± 3.0into
32.0were a vacuum
put into autoclave
a vacuum for curing
autoclave for
Volatile contentusing
curing 1.33
using MPa
1.33 pressure.
MPa The
pressure.
% curing
The temperature
curing temperature
≤1.0curve of
curve the
of prepreg
the was
prepreg set
was according
set ac-
to thetoDSC
cording test results.
the DSC test results.
2.2. Manufacturing of Composite Laminates
2.3.2.3. Three-Point
Three-Point Bending
Bending TestTest
The prepregs were cut to 250 ×sample
300 mm and×laid up15tomm15 mm on the
outmold by hand,
A sample of 270 × 13 × 13
A of 270 15 ×mm was cut wasoutcutfrom from the
the middlemiddle of each
of each groupgroup of laminates,
of laminates,
laying 5 groups of the sameand thickness
a total to detect
of five the
samples difference
were in
obtained.mechanical properties
and a total of five samples were obtained. TheThe samples
samples were
were placed
placed on aonuniversal
a universal testing
testing
after curing. After being laidmachine
up, vacuum treatment
(M.T.S. landmarkwas370.10,
used to eliminate
Eden minute
Prairie, MN, bubbles
USA) to test the three-point bending
machine (M.T.S. landmark 370.10, Eden Prairie, Minnesota, USA) to test the three-point
that may occur during the layup process The
performance. so that
spanthewas
goodset mechanical
toset
240tomm properties of the 2), and the upper indenter
bending performance. The span was 240(shown in Figure
mm (shown in Figure 2), and the upper
laminate could be obtained.remained
Finally, the laminates
stationary. were
The lower put into a vacuum autoclave forat a speed of 10 mm/min so
indenter remained stationary. The indenter is loaded
lower indenter is upwards
loaded upwards at a speed of 10
curing using 1.33 MPa pressure. The
that the curing temperature curve of the prepreg was set ac-
mm/min so sample
that the is stressed
sample at three at
is stressed points,
three and finally,
points, and afinally,
fracture occurs in
a fracture the middle
occurs in the of
cording to the DSC test results.
the sample. The test was carried out under the conditions of a temperature of 25 ◦ C and a
middle of the sample. The test was carried out under the conditions of a temperature of
humidity of 50%.
25 °C and a humidity of 50%.
2.3. Three-Point Bending Test
A sample of 270 × 13 × 15 mm was cut out from the middle of each group of laminates,
（a）
and a total （b）
of five samples were obtained. The samples were placed on a universal testing
machine (M.T.S. landmark 370.10, Eden Prairie, Minnesota, USA) to test the three-point
bending performance. The span was set to 240 mm (shown in Figure 2), and the upper
indenter remained stationary. The lower indenter is loaded upwards at a speed of 10
mm/min so that the sample is stressed at three points, and finally, a fracture occurs in the
middle of the sample. The test was carried out under the conditions of a temperature of
25 °C and a humidity of 50%.
（c）
10 mm/min
） （b）

240 mm

Figure 2. Three-point
Figure bending
2. Three-point test diagrams:
bending (a) specimen
test diagrams: under bending
(a) specimen load; (b) specimen
under bending fracture closer
load; (b) specimen view;closer
fracture (c) sche-
view;
matic diagram.
(c) schematic diagram.
（c）
10 mm/min

240 mm
Materials 2021, 14, x FOR PEER REVIEW 4 of 12
Materials 2021, 14, 4673 4 of 12

2.4. Characterization
2.4. Characterization
DSC 25 (T.A. Instruments, New Castle, DE, USA) was used for calorimetric measure-
mentsDSCfor25 (T.A. Instruments,
dynamic DSC scans. New
ThreeCastle,
samplesDE,were
USA)heated
was used
fromfor
25calorimetric
to 250◦°C atmeasure-
different
ments for dynamic DSC scans. Three samples were heated from 25
heating rates, i.e., 5, 10, and 15◦°C/min, with approximate sample weightsto 250of 3.50
C at mg
different
under
heating rates,at
an N2 purge i.e.,
505,mL/min.
10, and 15
TheC/min,
DSC waswith
usedapproximate sample
to determine weights
the heat of 3.50
released mg under
while curing
an
theNspecimen
2 purge atunder
50 mL/min. The DSCconditions.
non-isothermal was used toThe
determine
thermalthe heat loss
weight released
of thewhile curing
sample was
the specimen under non-isothermal conditions. The thermal weight loss of the sample was
determined using PerkinElmer PYRIS 1 thermogravimetric analysis (TGA). Then, 5–8 mg
determined using PerkinElmer PYRIS 1 thermogravimetric analysis (TGA). Then, 5–8 mg
of the sample was heated from 25 to 1000 °C at a rate of 10 °C/min under a nitrogen purge
of the sample was heated from 25 to 1000 ◦ C at a rate of 10 ◦ C/min under a nitrogen purge
of 30 mL/min. A scanning electron microscope (SEM, COXEM, Daejeon, Korea) operating
of 30 mL/min. A scanning electron microscope (SEM, COXEM, Daejeon, Korea) operating
at 10 kV was used to observe the SEM images surface morphology of the fractured surface
at 10 kV was used to observe the SEM images surface morphology of the fractured surface
of the composite laminates.
of the composite laminates.
3. Results
3. Results and
and Discussion
Discussion
3.1. Thermogravimetric
3.1. Thermogravimetric Analysis
Analysis
The TGA curve of
The of the
theepoxy
epoxyresin
resinsample
sampleis isshown
shown in in
Figure
Figure 3. The
3. Theweight loss loss
weight pro-
cess of the
process sample
of the sample is roughly divided
is roughly into three
divided processes:
into three the first
processes: thestage
first isstage
before
is 350 °C,
before
350 ◦ C, the loss
the weight rateloss
weight is about
rate 5%; the second
is about 5%; the stage (350–550
second stage°C) has the◦fastest
(350–550 C) hasweight loss,
the fastest
which is
weight about
loss, 85%islower;
which about 85%in the third in
lower; stage (550–1000
the third stage°C), the mass
(550–1000 ◦ C),
loss
theofmass
the sample
loss of
tends
the to be tends
sample stable,towith a loss of
be stable, about
with 2.88%.
a loss The initial
of about 2.88%. weight loss (≤5%)
The initial weight wasloss (≤5%)
attributed
to the
was removal of
attributed to water molecules
the removal and some
of water small organic
molecules and some compounds
small organicfrom the resin [19].
compounds
from the resin [19].
The temperature at 5% Theweight
temperature
loss (Td5at 5% weight
) was 350 °C. loss (Td5 ) was
The thermal 350 ◦ C. The thermal
decomposition temper-
decomposition temperature ◦ C, far more significant
ature at 30% weight loss (Td30at 30%405
) was weight
°C, farloss
more(Td30 ) was 405than
significant any service tempera-
than
ture any service
proposed fortemperature
this resin. The proposed for this resin.
peak degradation The peak degradation
temperature temperature
(Tdeg) was determined by
(T ) was determined
differentiating
deg the by differentiating
degradation curve, the
as degradation
shown in curve,
Figure 3. Tas
deg shown
exhibitedin Figure
a 3. T
single-step
deg
exhibited
degradation a single-step
profile which degradation
suggestsprofile
that thewhich
sharp suggests that the sharp
decomposition of thedecomposition
crosslinked poly- of
the crosslinked polymer network. The heating program was designed
mer network. The heating program was designed to obtain the thermal degradation tem- to obtain the thermal
degradation
perature of the temperature
epoxy resin of the epoxy
sample toresin
ensuresample to ensure
that the samplethat will the
notsample will not de-
be thermally be
thermally degraded
graded during the DSCduring thesoDSC
test, the test, so the maximum
maximum temperature temperature
of the DSCoftest thewas
DSCsettesttowas
250
set ◦
°C.to 250 C.

100

Td5==50℃ TGA
WTighT loss by TGA T%T

80 DTG
DTTivaTivT of TGA

Td=0=405℃

60

40

20 TdTg=4=4℃T54=4%=TT

0
200 400 600 800 1000
TTmTTTaTTTT T℃T

Figure3.
Figure 3. TGA
TGA graph
graph of
of 7901
7901 DNK
DNKtoughened
toughenedepoxy
epoxyresin.
resin.

3.2.
3.2. DSC
DSC Curve
Curve Analysis
Analysis
The
The DSC test results
DSC test results of
of the
the prepreg
prepregunderunder different
differentheating
heatingrates
rates(β)
(β) are
are shown
shown in in
Figure
Figure4.4. The
The DSC
DSC curves
curves of
of the
the prepreg
prepreg underunderdifferent
differentheating
heatingrates
ratesall
allshowed
showedaasingle
single
exothermic
exothermicpeak,
peak,which
whichindicated
indicatedthatthatthe
thecuring
curingreaction
reactionwas
wascompleted
completedininone onestep.
step.This
This
is because the heat flow rate is directly proportional to the heating rate. As the
is because the heat flow rate is directly proportional to the heating rate. As the heating heating rate
increases, the start
rate increases, temperature
the start temperature(Ti ), (T
peak temperature (Tp ),(T
i), peak temperature
and end temperature (Tf )(T
p), and end temperature
off)
unit time increases, and the thermal inertia and temperature difference become larger [20].
The curing process of thermosetting resin is complex, involves a series of chemical
reactions, and finally transforms the low molecular weight monomer into the macromo-
lecular crosslinked network [13]. Under normal circumstances, this process is accompa-
Materials 2021, 14, 4673
nied by a change in heat. The rate of heat generated was plotted against time, and5 of their
12
integration provided the amount of heat released. According to the curve shown in Figure
4, total enthalpy was calculated by the area under the exothermic curve of the DSC. This
is an essential physical quantity representing the total heat released during the curing
the curingas
reaction, reaction
shownalso increase.
in Table As the
2—the heating
amount of rate
heatincreases,
released the heating
by the effect
curing per unit
reaction in-
time increases,
creases and the rate
as the heating thermal inertia and temperature difference become larger [20].
increases.

4
160℃ 5℃/min
10℃/min
= 15℃/min
HTaT Flo= TW/gT

154℃
EXO
2

1
1=1℃

-1
50 100 150 200 250
Temperature (°C)

Figure4.4.DSC
Figure DSCcurve
curvefor
forthe
the7901
7901DNK
DNKtoughened
toughenedepoxy
epoxyresin
resinatatdifferent
different heating
heating rates
rates of of
5 ◦5C/min,
°C/min,
◦ 10 °C/min,
◦ 15 °C/min in N
10 C/min, 15 C/min in N2 atmosphere.2 atmosphere.

Table 2. Thermodynamic
The curing processparameters of prepreg
of thermosetting at different
resin heating
is complex, rates. a series of chemical
involves
reactions, and finally transforms the CurelowTemperature
molecular weight (°C) monomer into the macromolec-
ularβ/(°C·min
crosslinked −1)
network [13]. Under normal circumstances, this process is accompanied Htot/(J·g−1) by
Ti/°C Tp/°C Tf/°C
a change in heat. The rate of heat generated was plotted against time, and their integration
5 122 139 169 257
provided the amount of heat released. According to the curve shown in Figure 4, total
10 128 154
enthalpy was calculated by the area under the exothermic curve of the DSC. This 192 499 is an
essential15 physical quantity135 representing the 160total heat released205 during the curing780 reaction,
as shown in Table 2—the amount of heat released by the curing reaction increases as the
heating The curing
rate of the epoxy resin is a staged process; there are usually three stages of
increases.
curing, commonly referred to as pre-cure, cure, and post-cure, and their respective tem-
peratures
Table obtained on the
2. Thermodynamic DSC curves
parameters are termed
of prepreg as initial
at different heating temperature
rates. (Ti), peak temper-
ature (Tp), and final temperature (Tf) [21], as shown in Figure 5; the temperature at which
theβ/(curing
◦ C·minreaction Cure Temperature
occurs is linearly related to the (◦ C)
heating rate. So, the H curing
tot /(J·gprocess
−1 ) −1 )
◦C ◦C ◦C
temperature is usually Tdetermined
i / by T
extrapolation.
p / T
According
f / to the T-β extrapolated
curve, when5 β is zero, the122 theoretical gel temperature
139 ( ∗ ), theoretical
169 curing temperature
257
( ∗ ), and theoretical post-treatment temperature ( ∗ ) of the prepreg is 116, 130, and 153
10 128 154 192 499
°C, respectively. That is to say; the theoretically reasonable curing process is to heat the
15 135 160 205 780
prepreg to 116 °C. The viscosity of the resin will gradually decrease during this heating
process, which is conducive to the resin infiltration of the reinforcing fibers; then the tem-
The curing
perature of thetoepoxy
is increased 130 °C,resin is a is
the resin staged process;and
crosslinking, there are occurs
curing usuallyatthree stages
this temper-
of curing,
ature; commonly
finally, keep it atreferred
153 °C toforas pre-cure,
a period cure,toand
of time post-cure,
completely cureandthetheir
resin.respective
temperatures obtained on the DSC curves are termed as initial temperature (Ti ), peak
temperature (Tp ), and final temperature (Tf ) [21], as shown in Figure 5; the temperature at
which the curing reaction occurs is linearly related to the heating rate. So, the curing process
temperature is usually determined by extrapolation. According to the T-β extrapolated
curve, when β is zero, the theoretical gel temperature (Ti∗ ), theoretical curing temperature
(Tp∗ ), and theoretical post-treatment temperature (T f∗ ) of the prepreg is 116, 130, and 153 ◦ C,
respectively. That is to say; the theoretically reasonable curing process is to heat the prepreg
to 116 ◦ C. The viscosity of the resin will gradually decrease during this heating process,
which is conducive to the resin infiltration of the reinforcing fibers; then the temperature is
increased to 130 ◦ C, the resin is crosslinking, and curing occurs at this temperature; finally,
keep it at 153 ◦ C for a period of time to completely cure the resin.
Materials 2021, 14, x FOR PEER REVIEW 6 of 12

Materials 2021, 14, 4673 6 of 12

Materials 2021, 14, x FOR PEER REVIEW 6 of 12

200 Ti
TT
Tf
180 200 Ti

TTmTTTaTTTT T℃T
TT
Tf
160 180

TTmTTTaTTTT T℃T
140 160

120 140

5 10 15
120 HTaTing TaTT T℃/minT

Figure 5. Extrapolation
5
curves of10the curing temperature.
15
HTaTing TaTT T℃/minT
3.3. Curing Kinetics
Figure5.
Figure 5. Extrapolation
Extrapolation curves
curvesof
ofthe
thecuring
curingtemperature.
temperature.
The epoxy cure kinetics are well represented by the phenomenological models. It is
3.3.
3.3. Curing
intuitive Kinetics
and straightforward,
Curing Kinetics does not require a large amount of experimental data. The
“degreeThe of cure”
The epoxy is the
epoxy cure measure
kinetics of
cure kinetics arethe
are well
wellchemical reactions
represented
represented by the
by (bond
the exchanges) that models.
phenomenological
phenomenological occurred
models.It Itis
during
is the
intuitive curing
intuitiveandand process of the
straightforward,
straightforward, resin,
does and
does often
notnot it
require
require is the
a large true
a large representative
amount
amount of crosslinking
of experimental
of experimental data.data.
The
density
The or molecular
“degree of weight
cure” is [22,23].
the The
measure degree
of the of cure,
chemical α, is determined
reactions
“degree of cure” is the measure of the chemical reactions (bond exchanges) that occurred (bond by Equation
exchanges) (1)
that
[24]:
occurred
during the during
curingthe curing
process ofprocess
the resin, ofand
the often
resin,itand is the often
trueitrepresentative
is the true representative
of crosslinking of
crosslinking density or molecular weight [22,23]. The degree of cure, α, is determined by
density or molecular weight [22,23]. The degree H (t ) of cure, α, is determined by Equation (1)
Equation
[24]: (1) [24]: α= (1)
HHtot(t)
α= (1)
HH tot (t )
where H(t) is the heat of reaction at time t,αand = H tot is the total heat of the reaction. The (1)
where H(t)between
relationship is the heattheofdegree
reaction of at time of
curing theHH
t, and tottot is sample
resin the totalandheatthe
of temperature
the reaction. is The
relationship
shown in Figure between the degree of curing of the resin sample and the temperature is shown
where
in Figure H(t) is 6.
6. As theAs the heating
theheat of reaction
heating rate
rateatincreases,
timethe
increases, t, andthe H temperature required for the resin to
tot is the total heat of the reaction. The
temperature required for thetheresin to reach
reach the same
relationship degree
between of curing continues
the continues
degree of to to
curing increase.
of the This
resin is mainly because
samplebecause
and the reaction
temperature
the
rateshownsame
increases degree
with 6.of curing
theAsincrease of the increase.
heating rate,theThis is
resulting mainly
in a faster the reaction
increase rateis
inresin
the
in Figure the heating rate increases, temperature
increases with the increase of the heating rate, resulting in a faster increase in the system’s required for the to
system’s viscosity.
reach the Part Part
sameofdegree of the monomers
of curingiscontinues is too late to react or cannot diffuse into the gel
viscosity. the monomers too late totoreactincrease.
or cannot This is mainly
diffuse because
into the gelthe reaction
system in
system
rate in time, and
increases withthethe
resulting
increase temperature
ofgradient
the heating gradientrate, increases,
resulting resulting
in fasterinincrease
a decrease
time, and the resulting temperature increases, resulting in aadecrease in the
in the curing
in the curingviscosity.
system’s of the system during the diffusion phaselateat the same temperature [20].
of the system duringParttheof the monomers
diffusion phase atisthe too same to react
temperatureor cannot
[20]. diffuse into the gel
system in time, and the resulting temperature gradient increases, resulting in a decrease
in the curing of the system during the diffusion phase at the same temperature [20].

Figure 6. Curves of the curing degree temperature.

Figure 6. Curves of the curing degree temperature.
The rate of the kinetics process in kinetic analysis can be described by Equation (2) [25]:
Figure 6. Curves of the curing degree temperature.
dα
= K ( T ) f (α) (2)
dt
Materials 2021, 14, 4673 7 of 12

where K(T) is the reaction rate constant (temperature-dependent), and f (α) describes the
phenomenological reaction model. K(T) can be mathematically presented according to the
Arrhenius relationship.
Ea
K ( T ) = A exp(− ) (3)
RT
where A is the pre-exponential factor, Ea is the activation energy, and R is the universal gas
constant.
Comment model for f (α) is the nth-order model, provided in Equation (4) [26]:

f ( α ) = (1 − α ) n (4)

Combination of Equations (2)–(4) results in the final kinetic expression provided in

Equation (5):
dα − Ea
= A exp( )·(1 − α)n (5)
dt RT
During the dynamic heating process of prepreg, the curing rate is a function of
temperature and curing degree. A common technique for evaluating these data is the
Kissinger method, which can be used to determine the activation energy of the curing
reaction [27,28], as presented in Equation (6):

β AR Ea
ln( 2
) = ln( )− (6)
Tp Ea RTp

β 1
The fitting the linear relationship between ln Tp2
versus Tp can provide value of
apparent activation energy Ea , the pre-exponential factor A through the intercept. The
reaction order n can be calculated according to the Crane Equation [29,30].

d(ln β) Ea
1
=− (7)
d( Tp ) nR

β 1
According to the data in Table 3, using ln Tp2
and Tp to plot, and then perform linear
fitting, the obtained epoxy resin curing reaction activation energy and pre-finger factor
fitting curve is shown in Figure 7a. The slope of the fitted curve is −8.41, and the intercept
is 9.95. The Adj. R-square is 0.9933, indicating a good linear correlation. Substituting
the obtained slope and intercept into Equation 6 can be calculated: Ea = 69.95 kJ/mol,
A = 1.76 × 105 min−1 .
Use lnβ and T1p to the plot, and then perform the linear fitting. The reaction order
fitting curve of the epoxy resin curing reaction is shown in Figure 7b. The slope of the fitted
curve is −9.26, the intercept is 24.04, and the Adj. R-square is 0.9944, indicating a good
linear correlation. Substituting Ea and the slope and intercept of this curve into Equation
(7) can find n = 0.91.
Substituting the obtained curing kinetic parameters Ea , A, n into the nth-order curing
kinetic Equation (5) and integrating them, the following Equation (8) can be obtained,
reflecting the relationship between the curing degree and the reaction temperature and
time.
11.11
8.41 × 103

4
α(t) = 1 − 1 − 1.58 × 10 exp − t (8)
T
Materials 2021, 14, x FOR PEER REVIEW 8 of 12

11.11
Materials 2021, 14, 4673
  8.41×103   8 of 12
α (t ) = 1 − 1 − 1.58 ×104 exp  − t (8)
  T  
Table 3. DSC exotherm peak temperatures of resin at different heating rates.
Table 3. DSC exotherm peak temperatures of resin at different heating rates.
β/(◦ C·min−1 ) Tp /K 1/Tp (1000/K) lnβ ln(β/T2P )
β/(°C·min
5
) −1 Tp412
/K 1/Tp(1000/K)
2.42
lnβ
1.61
⁄ )
(−10.43
5 412 2.42 1.61 −10.43
10 427 2.34 2.30 −9.81
10 427 2.34 2.30 −9.81
15 433 2.31 2.71 −9.43
15 433 2.31 2.71 −9.43

(a) TbT
-1=4 2=8

-1=6 2=6
y = -8=41x+1=15 y = -1=26x+24=04
-1=8 R2 = 0=11== 2=4 R2 = 0=1144
lnTβ/T2TT

lnβ
2=2
-10=0

2=0
-10=2

1=8
-10=4
1=6
-10=6
2==0 2==2 2==4 2==6 2==8 2=40 2=42 2=44 2==0 2==2 2==4 2==6 2==8 2=40 2=42 2=44
1/TT T1000/KT 1/TT T1000/KT

Figure
Figure 7.
7. The
The fitting
fitting curve
curve of
of (a)
(a) activation
activation energy
energy and
and pre-exponential
pre-exponential factor;
factor; (b)
(b) reaction
reaction order.
order.

Compared
Compared with with other
other binders,
binders, this
this article
article uses a modified hybrid epoxy resin whose
main components include
main components includealiphatic
aliphaticandandcycloaliphatic
cycloaliphatic resins.
resins. Similar
Similar research
research compari-
comparisons
with with
sons otherother
systems are are
systems shown in Table
shown 4. 4.
in Table It It
is isfound
foundthat
thatboth
boththe
the apparent
apparent activation
energy EEaa and
energy and the
the reaction order nn are
reaction order are relatively
relatively small.
small. In
In the
the resin
resin system
system of of this
this article,
article,
the apparent
the apparent activation
activation energy
energy is
is relatively
relatively low. This This may
may be be because
because as as the degree of
curing increases,
curing increases, the
thefree
freemovement
movementbetween
betweenmolecular
molecular segments
segments is less restricted,
is less andand
restricted, the
degree of freedom is higher, so more energy is not needed to overcome
the degree of freedom is higher, so more energy is not needed to overcome the energy the energy barrier.
The concentration
barrier. of the resin
The concentration system
of the resinhas a small
system haseffect oneffect
a small the reaction rate, so the
on the reaction reaction
rate, so the
order is small.
reaction order is small.

Table 4.
Table Comparison with
4. Comparison with similar
similar studies
studies of
of other
other systems.
systems.
Type of Bender
Type of Bender Ea (kJ/mol)
Ea (kJ/mol) Reaction OrderOrder
Reaction Ref
RefNumber
Number
Bisphenol-A
Bisphenol-A 71.42 71.42 1.34351.3435 [31]
[31]
TDE-85/BMAPF
TDE-85/BMAPF 73.99 73.99 0.908 0.908 [32]
[32]
Multifunctional P-containing
Multifunctional 72.96 3.21 [33]
72.96 3.21 [33]
Phenolic
P-containing 96.03 - [34]
VTM264
Phenolic 96.03 96.4 - - [35]
[34]
VTM264E51 96.4 102.55 - 1.3064 [36]
[35]
Epoxy 88.549 1.323 [37]
E51 102.55 1.3064 [36]
7901 DNK 69.95 0.91 This work
Epoxy 88.549 1.323 [37]
7901 DNK
3.4. Bending Performance 69.95 0.91 This work

The load-displacement curves and three-point bending test data of the five samples
3.4.shown
are Bending inPerformance
Figure 8 and Table 5. The stress–strain curves of the samples increase linearly
at theThe load-displacement
initial curves
stage; after reaching theand three-point
maximum bending
strain, test data
the bending of suddenly
stress the five samples
drops,
are shown
showing in Figurebrittle
prominent 8 and fracture
Table 5. characteristics.
The stress–strain
It iscurves
worthofnoting
the samples increase
that before the
linearly at the initial stage; after reaching the maximum strain, the bending stress suddenly
drops, showing prominent brittle fracture characteristics. It is worth noting that before the
maximum stress is reached, there is no obvious inflection point in the curve, indicating that
the sample has not been significantly damaged before the final failure.
Materials 2021, 14, x FOR PEER REVIEW 9 of 12

als 2021, 14, x FOR PEER

Materials 2021, REVIEW
14, 4673 9 of 12 9 of 12
maximum stress is reached, there is no obvious inflection point in the curve, indicating
that the sample has not been significantly damaged before the final failure.
maximum stress7000
is reached, there is no obvious inflection point in the curve, indicating
that the sample has not been significantly damaged before the final failure.
SamTlT 1
6000 SamTlT 2
7000
SamTlT =
SamTlT
5000 1 SamTlT 4
6000 SamTlT 2 SamTlT 5
SamTlT =
Load TNT
4000
5000 SamTlT 4
SamTlT 5
=000
Load TNT

4000

2000
=000

1000
2000

0
1000 0 2 4 6 8 10 12 14 16 18
DisTlacTmTnT TmmT
0
0
Figure
Figure 2
4 8.8.6Load–displacement
8 10 12
Load–displacement 14
curve
curve 16
of 18 fiber/epoxy
of E-glass
E-glass fiber/epoxy composite samples.
DisTlacTmTnT TmmT
Table5.5.Three-point
Table Three-pointbending
bendingtest
testdata.
data.
Figure 8. Load–displacement curve of E-glass fiber/epoxy composite samples.
Sample Load Time (s) Displacement (mm)
Displacement Load (N) Flexural Modulus (MPa)
Flexural
Table 5. Three-point1Sample
bending test96.93Load Time (s) 16.82
data. (mm) 6112 Load (N) 411
Modulus (MPa)
2 75.72 13.22 6106 408
Sample Load Time1(s) Displacement (mm)
96.93 Load (N)
16.82 Flexural Modulus
6112 (MPa) 411
3 72.95 12.76 6356 438
1 96.93 2 16.8275.72 611213.22 411
6106
4 79.21 13.79 6315 421 408
2 75.72 13.22 6106 408
5 3 74.34 72.95 12.99 12.76 6231 6356 423 438
3 72.95 12.76 6356 438
4 79.21 4 13.7979.21 631513.79 6315
421 421
5
Figure 9 shows12.99
74.34 5
the74.34
surface morphology
623112.99
of the sample6231
after being destroyed.
423 423
The
damage of the specimen mainly occurs at the compressed place, as shown in Figure 9a,
Figure 9 because
shows Figure
thesurface
the compressed
9 shows the
place has
morphology
surface of the
the most
morphology sample significant
of after
the being
sample
displacement.
destroyed.
after thebeing
When
The the load is
destroyed. The
generated,
damage of thedamage
specimen the
mainlyepoxy resin
occursmainlyis first subjected
at the occurs
compressed to the
place, force, and
as shown then
in Figure force is transmitted
9a, in Figure 9a,
of the
to the glass place specimen
fiber that at the compressed place, as shown
because the compressed
because the compressed has plays
theplace the main
most has the
force-bearing
significant most displacement.role. AsWhen
significant
the load
displacement.theincreases,
loadWhenis the downward
strain
generated, thegenerated, occurs
epoxy resin at the
isepoxy compressed
first subjected area,
to the resulting
force, and in mutual
then extrusion.
the force Epoxy
is transmitted resin hasload is
a poor
ability to the
withstand resin
force. is first subjected
It is first damaged to the
andloadforce, and
thenincreases, then
crushed, leaving the force is transmitted
only a small part
to the glass fiber
to that
the plays
glass fiberthethat
main force-bearing
plays the role. As the
main force-bearing role. As the downward
load increases, downward
on
strain occurs at the glass
the compressed fiber, as
area,shown in Figure
resultingarea, in mutual10a. When
extrusion.the stress
Epoxy reaches
resin has the maximum
a poor that the
strain
glass occurs
fiber can at the compressed
withstand, the glass resulting
fiber breaks;in mutual
one end extrusion.
of the Epoxy
broken resin
fiber has a poor
continues to
ability to withstand
ability toforce. It is first
withstand damaged
force. and
It is first then crushed,
damaged and then leaving
crushed,only a small
leaving part
only a small part on
move
on the glass fiber, downward
as shown under
in shown
Figure in the
10a. squeeze
When of
theWhenthe upper
stressthe reaches indenter, pulling the fiber along the di-
the glass fiber, as Figure 10a. stressthe maximum
reaches the maximumthat the that the glass
rection
glass fiber canfiber
withstand,of the yarn,
the glassthe causing
fiber cracks
breaks; to occur
one endone and
of the expand. The cracks propagate to form
can withstand, glass fiber breaks; endbroken fiber continues
of the broken to
fiber continues to move
move downward different
underfiber
the bundles,
squeeze asthe
of shown upper in indenter,
Figure 10b. The failure
pulling the fibermode of the the sample is mainly
downward under the squeeze of the upper indenter, pulling the along
fiber along di-
the direction of
manifested
rection of thethe
yarn, causingas the slippage
cracks and mutual extrusion of the fiber bundles, which is easier to
yarn, causing crackstotooccuroccurand andexpand.
expand. The The cracks propagate to
cracks propagate toform
formdifferent fiber
be observed
different fiberbundles,
bundles,asasshown in the macroscopic
shownininFigure Figure10b. view,
10b.The as
Thefailure shown
failuremode in Figure
modeofofthe 9b.
thesample This is
sampleisismainly because the
mainlymanifested resin is
as
tightly
manifested asthe combined
theslippage
slippage with
andmutual
mutual the extrusion
fiber and is not easily split into which
individual fibers.
and extrusion ofofthe thefiber
fiberbundles,
bundles, which is is easier
easier totobe observed in
be observed in thethe macroscopic
macroscopic view,
view, as shown
as shown in Figure
in Figure 9b. 9b.
ThisThis is because
is because the resin
the resin is
is tightly combined
tightly combined
withwith the fiber
the fiber and is andnotiseasily
not easily
split split
into into individual
individual fibers.fibers.
(a) (b)
ComTTTssTd

(a) aTTa (b)

ComTTTssTd CTack TToTagaTion
aTTa
CTack TToTagaTion
Figure 9. SEM images of fracture surface with (a) 500× magnification and (b) 80× magnification.

Figure 9. SEM images of fracture surface with (a) 500× magnification and (b) 80× magnification.
Figure 9. SEM images of fracture surface with (a) 500× magnification and (b) 80× magnification.
Materials 2021, 14, 4673 10 of 12
Materials 2021, 14, x FOR PEER REVIEW 10 of 12

TaT TbT

RTsidTal TTsin FibTT bTndlT

Figure 10.
Figure 10. SEM
SEM photos
photos of
of the
the fracture
fracturesurface
surfacewith
with(a)
(a)500
500×
× magnification
magnification and
and (b)
(b) 80×
80×magnification.
magnification.

4. Conclusions
4. Conclusions
Herein, the cure kinetics of an E-glass/epoxy resin prepreg was investigated by DSC.
Herein, the cure kinetics of an E-glass/epoxy resin prepreg was investigated by DSC.
The
The fracture behavior
fracture behavior of of the
the composite
composite waswas studied
studied byby aa three-point
three-point bending
bending test,
test, and
and
surface morphology was assessed. The TGA analysis showed a stable
surface morphology was assessed. The TGA analysis showed a stable thermal structure; the thermal structure;
the resin
resin decomposes
decomposes rapidly
rapidly at about
at about 350 ◦350 °C. DSC
C. DSC studies
studies showed showed
that thethat the optimal
optimal pre-
pre-curing
curing
temperature, gel temperature, and post-treatment temperature of prepreg are 116, 130, 116,
temperature, gel temperature, and post-treatment temperature of prepreg are and
130, ◦and 153 °C, respectively. Based on the Kissinger and Crane Equations,
153 C, respectively. Based on the Kissinger and Crane Equations, the apparent activation the apparent
activation
energy Ea energy Ea of theisprepreg
of the prepreg is 69.95the
69.95 kJ/mol, kJ/mol, the pre-exponent
pre-exponent factor A factor
is 1.76A×is101.76
5 min× 10
−15,
min −1
and the , and the reaction
reaction orderorder n is 0.91.
n is 0.91. Finally,
Finally, the nth-order
the nth-order curingcuring reaction
reaction kinetic
kinetic equa-
equation
tion of the prepreg is established. A three-point bending test was performed
of the prepreg is established. A three-point bending test was performed on the laminate on the lami-
nate sample. The results show that the difference in mechanical properties
sample. The results show that the difference in mechanical properties is relatively small, is relatively
small,
indicatingindicating
that thethat the laminate
laminate has fewerhasinternal
fewer internal
defects, defects, stable and
stable quality, quality, and reasona-
reasonable curing
ble curing temperature
temperature process
process design. Thedesign. The SEM
SEM photos alsophotos
prove also
that prove thatand
the resin thefiber
resinare
and fiber
tightly
are tightly
bonded. bonded.

Author
Author Contributions:
Contributions: Conceptualization, L.Z. and
Conceptualization, L.Z. and Z.W.;
Z.W.;methodology,
methodology,L.Z.;
L.Z.;software,
software,Z.W.;
Z.W.; vali-
valida-
dation, Z.W.;
tion, Z.W.; formal
formal analysis,
analysis, Z.W.Z.W.
andand M.B.R.;
M.B.R.; investigation,
investigation, Z.W.;
Z.W.; resources,
resources, W.S.;W.S.; data curation,
data curation, Z.W.;
Z.W.; writing—original
writing—original draft preparation,
draft preparation, Z.W.; writing—review
Z.W.; writing—review and editing,
and editing, L.Z. andL.Z. andsupervision,
M.B.R.; M.B.R.; su-
pervision, C.Z.;
C.Z.; project project administration,
administration, L.Z.;
L.Z.; funding funding acquisition,
acquisition, L.Z. have
L.Z. All authors All authors
read and have readtoand
agreed the
agreed to the
published published
version of theversion of the manuscript.
manuscript.
Funding:
Funding: This
This research
research was
was funded
funded byby Zhejiang
Zhejiang Provincial
Provincial Natural
Natural Science
Science Foundation
Foundation of China
of China
(LGG21E050025),
(LGG21E050025), Opening Project of Zhejiang Key Laboratory of Clean Dyeing and FinishingTech-
Opening Project of Zhejiang Key Laboratory of Clean Dyeing and Finishing Tech-
nology, (QJRZ1907) and
nology, (QJRZ1907) and Fundamental
FundamentalResearch
ResearchFunds
FundsofofZhejiang
ZhejiangSci-Tech
Sci-TechUniversity,
University, (20202113-
(20202113-Y).
Y).
Institutional Review Board Statement: Not applicable.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data can be provided by the corresponding author on request.
Data Availability Statement: The data can be provided by the corresponding author on request.
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
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