polymers
Article
Experimental Study of Curing Temperature Effect on
Mechanical Performance of Carbon Fiber Composites with
Application to Filament Winding Pressure Vessel Design
Jianguo Liang 1, *, Lihua Liu 1 , Zelin Qin 1 , Xiaodong Zhao 1 , Zhi Li 2 , Uwayezu Emmanuel 1
Citation: Liang, J.; Liu, L.; Qin, Z.;
Zhao, X.; Li, Z.; Emmanuel, U.;
Feng, J. Experimental Study of
Curing Temperature Effect on
Mechanical Performance of Carbon
Fiber Composites with Application to
Filament Winding Pressure Vessel
Design. Polymers 2023, 15, 982.
https://doi.org/10.3390/
polym15040982
Academic Editor: Yang Li
Received: 18 January 2023
Revised: 13 February 2023
Accepted: 14 February 2023
Published: 16 February 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Polymers 2023, 15, 982. https://doi.org/10.3390/polym15040982
and Jun Feng 3, *
1 College of Mechanical and Vehicle Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2 International Cooperation Division, Taiyuan University of Technology, Taiyuan 030024, China
3 National Key Laboratory of Transit Physics, Nanjing University of Science and Technology,
Nanjing 210094, China
* Correspondence: liangjianguo20@tyut.edu.cn (J.L.); jun.feng@njust.edu.cn (J.F.)
Abstract: During the forming process of carbon fiber composite pressure vessels, the parameters of
the curing and forming processes become one of the critical factors affecting the production cost and
forming quality. The curing temperature of 4251 A4/B2 epoxy resin is measured in this research, and
the effect of curing temperature on the mechanical properties of composite materials for winding is
studied, which is finally verified in the test of pressure vessels. First, the actual curing temperature of
the epoxy resin is tested and analyzed using differential scanning calorimetry (DSC). Second, under
two different curing regimes, the tensile and flexural properties are tested by making pure epoxy resin
matrix test pieces, Naval Ordnance Laboratory (NOL) rings, and carbon fiber composite unidirectional
plates that affect the overall performance of composite pressure vessels. At the same time, the test
results provide reliable process parameters for numerical simulation and manufacturing of pressure
vessels. Finally, the filament-wound 35 MPa type III pressure vessel is cured and carried out using
a hydraulic burst test. The results show the resin matrix has good fluidity and excellent interface
bonding with carbon fiber when the curing temperature is 112 ◦ C. Compared with the results in
curing temperature of 100 ◦ C, the tensile strength of the NOL ring reaches 2260.8 MPa, up by 22%.
In the 90◦ direction, the tensile and flexural strengths of the unidirectional plates increase by 68.86%
and 37.42%, respectively. In the 0◦ direction, the tensile and flexural strengths of the unidirectional
plates increase by 5.82% and 1.16%, respectively. The pressure vessel bursting form is reasonable and
meets the CGH2R standard. The bursting pressure of the vessel is up to 104.4 MPa, which verifies the
rationality of the curing regime used in the curing process of the pressure vessel. Based on the results
of this paper, the curing temperature affects the fluidity of the epoxy resin, which in turn affects the
interfacial bonding properties of the composite, and the forming quality of the wound components
and the pressure vessel, ultimately. When using 4251A4/B2 epoxy resin for wet winding pressure
vessels, the choice of a 112 ◦ C curing temperature will help improve the vessel’s overall performance.
This work could provide reliable experience and insight into the curing process analysis of pressure
vessel manufacturing.
Keywords: CFRP; curing temperature; DSC; composite pressure vessel; epoxy resin
1. Introduction
Carbon fiber composites have been widely used in aerospace, transportation, military
products, and biomedical systems [1–5] because of their light weight, high strength, and
high stiffness. In practical engineering applications, it has excellent durability, fatigue
resistance, and corrosion resistance compared to traditional steel materials [6–8]. Car-
bon fiber composite pressure vessels, as the main storage method for gas and energy in
transportation, highlight the importance of composite material development. However, the
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Polymers 2023, 15, 982 2 of 16

performance of carbon fiber composite pressure vessels depends not only on the perfor-
mance of the component materials and the design of the product winding structure but
also on the curing regime of the composite material. With the improvement in carbon fiber
properties and the development of various high-performance resin matrices, the study of
the factors influencing its curing and forming has become an important direction in the
field of carbon fiber composite research based on improving production efficiency and
overall performance.
As a hot spot in the research field of carbon fiber composites, many scholars mainly
consider the influence of winding process parameters in their design and manufacture.
Many studies have focused on winding trajectory, winding sequence, winding angle, liner
optimization, nondestructive testing [9–11], and the evaluation of winding layer forming
quality, fatigue life, and burst pressure [12,13]. However, the curing and molding process
parameters are lacking in-depth studies, and the degree of cure (DOC) is often improved
by changing the curing and forming method, which improves the composite material
performance [14–16].
The DOC depends on the physical properties of the resin matrix (viscosity, specific
heat, melting point, and thermal conductivity) [17–19], which ultimately determine the
mechanical properties of the composite. Curing kinetics can reflect the relationship of the
curing rate to the DOC, curing temperature, and curing time. Therefore, when studying
issues of pressure vessel curing and forming, the curing kinetics of the specific epoxy resin
matrix need to be determined first.
The curing kinetics of epoxy resin systems have been widely investigated, with studies
focusing on the kinetics of epoxy resins with different curing agents [20–22], the proper-
ties of modified versus unmodified epoxy resins [23–25], and the effects of fillers, curing
temperature and curing pressure on the kinetics of different epoxy resin-reinforced com-
posites [26–32]. There are various methods to study curing kinetics, among which DSC
is the most commonly used method [33,34]. The relationship of the curing rate to DOC,
curing temperature, and curing time can be obtained using DSC analysis of the epoxy resin
system by isothermal or non-isothermal methods. The experimental results are analyzed
and fitted with several classical kinetic models to obtain the kinetic parameters [35–37] and
thus accurately predict the kinetic behavior of the reaction system.
Curing temperature has a significant effect on the curing process, and a large number
of researchers have investigated the effect of curing temperature on the properties of
composite materials. Ma et al. [38] investigated the effect of the no-pressure curing
temperature on the flexural properties of 2D-T700/E44 composites, which were prepared
at six different no-pressure curing temperatures. The results showed that either too high or
too low unpressurized curing temperatures were not favorable for the preparation of the
composites. Li et al. [39] investigated the interfacial shear strength and fracture toughness
of the carbon fiber–TiO2 system at different curing temperatures, and the results showed
that the interfacial shear strength and fracture toughness of the carbon fiber–TiO2 system
was significantly improved after high-temperature curing, which could reach 8.34 MPa and
1.68 J/M2 . Man et al. [40] investigated the effect of three groups of curing temperatures,
“without post-curing,” “post-cured at 80 ◦ C for 6 h,” and “post-cured at 120 ◦ C for 3 h,”
on the performance of carbon fiber reinforced polymers (CFRP) and glass fiber reinforced
polymer (GFRP). The results showed that the hardness and flexural strength of both CFRP
and GFRP were improved, but the mechanical strength of CFRP was not significantly
improved, and that of GFRP was slightly improved. Ismail et al. [41] investigated the effect
of curing temperature on the mechanical properties of bio-phenolic/epoxy polymer blends.
The results showed that the tensile strength of the blends was proportional to the curing
temperature, and the tensile modulus was inversely proportional to the curing temperature.
Koushyar et al. [42,43] investigated the effects of autoclave temperature and pressure on
the porosity, compressive strength, and short beam shear strength (SBS strength) of carbon
fiber/epoxy composites. The results showed that the curing degree and glass transition
temperature were closely related to the hot press tank temperature. The SBS strength of
Polymers 2023, 15, 982 3 of 16

the composites was inversely proportional to the autoclave temperature, and their SBS
strength was about 10% lower for specimens cured at 149 ◦ C than for those cured at 160 ◦ C
to 182 ◦ C.
These works mainly focus on composite laminates reinforced by different resin sys-
tems; however, there are few reports on the curing process parameters of pressure vessels.
The purpose of this study is to investigate the effect of the curing temperature of 4251A4/B2
epoxy resin on the mechanical properties of composites for winding and to select a suitable
curing regime for pressure vessel curing and molding. The curing temperature of the
epoxy resin (112 ◦ C) is solved using DSC, and the curing kinetic equations of the epoxy
resin are derived. Based on this, the tensile, flexural, and shear properties of the pure
epoxy resin matrix, NOL rings and composite unidirectional plates are compared for two
different curing regimes. The accurate derivation of the curing kinetic parameters provides
a theoretical basis for modeling pressure vessel curing and molding, and the test results
provide process parameters for numerical simulation and actual winding of pressure ves-
sels. Finally, a hydraulic burst test is conducted on the wound 35 MPa pressure vessel to
verify the rationality of the curing regime. The evaluation of the overall performance of the
pressure vessel and the microstructure state after rupture demonstrate the applicability of
the curing regime.

2. Experimental Program
2.1. Material
The 4251A4/B2 epoxy resin is provided by Guangdong Bohui New Material Technol-
ogy Co., Ltd., Zhaoqing, Guangdong, China and the T700SC-12K carbon fiber is provided
by GuangWei Composite Co., Ltd., Weihai, Shandong, China. The material’s main parame-
ters are shown in Tables 1 and 2.

Table 1. Physicochemical properties of epoxy resin.

Density (g/mL) Viscosity (mPa·s) Gel Time (h) Gel Time (s)
1.47 1400–1500 >12 80–120

Table 2. The main parameters of carbon fiber.

Tensile Strength Linear Density Volume Density

Elongation (%) Diameter (µm)
(MPa) (g/km) (g/cm3 )
4900 800 1.8 2.1 7

2.2. Pure Epoxy Resin Matrix Preparation

First, the 4251A4/B2 epoxy resin was weighed a certain amount of epoxy resin A4
and curing agent B2, respectively, and material A4 and B2 were mixed according to the
mass ratio of 100:90, stirred for 10 min at the same time, and left to stand for 20 min to
eliminate the air bubbles after mixing well. Second, the mixed epoxy resin was cast in the
polytetrafluoroethylene (PTFE) mold. The casting was put into the vacuum drying oven to
finish curing according to two different curing regimes, as shown in Figure 1.
Polymers 2023, 15, 982 4 of 16

Figure 1. Curing regimes.

2.3. Preparation of Composite NOL Rings and Unidirectional Plates

The wet winding method is adopted. First, the mixed epoxy resin was left to defoam
and poured into the dipping tank of the winding machine. Second, the same winding
process parameters (such as winding tension, winding rate, and resin temperature) were
set so as to ensure the same fiber volume fraction of the wound parts. The NOL ring and
unidirectional plate preparation process are shown in Figure 2.

Figure 2. NOL ring and unidirectional plate preparation process.

To ensure the reliability of the experimental test data results, the same batches of
carbon fiber and epoxy resin were used for the test materials. The winding pressure
vessel was designed to verify the reasonableness and excellent characteristics of the curing
temperature and curing regime. With reference to the standard CGH2R [44], the main
design indexes of the pressure vessel are as follows: working pressure of 35 MPa, minimum
design burst pressure of 82.25 (2.35 times the working pressure), and the number of fatigue
life ≥ 11,000. The pressure vessel was wound by spiral and circumferential winding, and
the design of the winding angle and thickness refers to the grid theory [45]. The lay-up
sequence was selected as [902◦ / ± 114◦ /904◦ / ± 112◦ /904◦ / ± 112◦ /904◦ / ± 152◦ /904◦ / ± 152◦ ],
and the pressure vessel aluminum lining was wound according to the winding sequence.
To ensure the validity and comparability of the experimental results, the winding tension
of the NOL ring, unidirectional plate, and composite pressure vessel was designed to be
Polymers 2023, 15, 982 5 of 16

21 N, the winding rate was 10–20 rad/min, and the temperature of the dipping tank was
35–40 ◦ C.

2.4. Thermal Analysis

A DSC provided by Beijing Hengjiu Experimental Equipment Co., Ltd., Beijing, China
was used for the dynamic heating test, which was performed on the epoxy resin in a flowing
argon gas (flow rate of 50 mL/min) environment. An amount of 10 mg of well-mixed epoxy
resin was weighed and put into an aluminum crucible with a sealed lid. The heating range
was from room temperature to 350 ◦ C, and the heating rates were 5 ◦ C/min, 10 ◦ C/min,
15 ◦ C/min, and 20 ◦ C/min.

2.5. Mechanical Performance Test

According to Figure 2, the NOL ring and the unidirectional plate were produced. The
test standard of pure epoxy resin matrix was GB/T 2567-2021 [46]. The composite NOL
ring needed to be polished to a flat surface before testing, and its test is fixed in a unique
NOL ring stretching fixture and refers to standard GB/T 1458-2008 [47]. The standard
sample of composite unidirectional plate test is cut at different angles regarding 0◦ fiber
direction by waterjet cutting equipment to ensure the high-quality shape and size of the
test specimens. Referring to the test standard ASTM D3039 [48], ASTM D3518 [49], glass
fiber reinforcement sheets were pasted on both ends of the tensile and shear specimen,
and the size of the tensile specimen was 250 mm × 15 mm × 2 mm, and the size of the
shear specimen was 250 mm × 25 mm × 2 mm. The flexural specimen needs to ensure
that the span was 32 times the thickness, the test standard was ASTM D790 [50], and the
specimen size was 80 mm × 12.5 mm × 2 mm. The above standard specimens were tested
using an electronic universal material testing machine (INSTRON5969, ITW Group Instron,
Shanghai, China).

2.6. Material Scanning Electron Microscopy (SEM) Testing

In this paper, ZEISS Gemini SEM 300 was used to observe the specimens of hydrogen
storage vessels after hydraulic burst tests, specifically the composite layers of the dome
section, transition section, and cylinder section. The test started by cutting the composite
layers from the selected parts to a size close to 40 mm × 10 mm × 30 mm and then cleaning
the fracture of the composite layer damage using anhydrous ethanol without damaging the
observed end surfaces. Test observation specimens need to be spray-gold treated for 60 s,
and multiples of the dome section, transition section, and cylinder section taken 300 times,
1000 times, and 500 times in turn.

3. Results and Discussion

3.1. Curing Kinetics Analysis
3.1.1. Differential Scanning Calorimetry Curve Analysis
The curing kinetics of epoxy resin 4251A4/B2 were investigated using the dynamic
heating method using DSC instrumental tests. The onset temperature (Ti ), peak temperature
(Tp ), and termination temperature (T f ) of the curing exothermic peak of the epoxy resin at
different heating rates were obtained based on DSC diagrams.
As seen in Figure 3, the following conclusions can be drawn from the DSC diagrams
of the epoxy resin systems.
(1) The onset temperature, peak temperature, and termination temperature of the resin
system increase as the heating rate rises;
(2) The appearance of the exothermic peak of the resin system increases with the rate of
temperature rise and moves to the right, that is, in the direction of high temperature;
(3) With the increase in the heating rate, the curing temperature rises, the curing rate
increases, and the curing time is shortened.
Polymers 2023, 15, 982 6 of 16

Figure 3. Dynamic DSC thermal analysis curves of epoxy resin at different temperature rise rates.

As seen from Figure 4, according to the least square method, three temperature values
(Ti ,Tp ,T f ) can be obtained when the heating rate is zero. The extrapolated temperatures
are the theoretical start, peak, and end temperatures of the epoxy resin system, which
will be used as a reference for resetting the temperature values of the curing conditions.
Table 3 shows the specific values of Ti , Tp , and T f at different heating rates and their
extrapolation results.

Figure 4. Temperature extrapolation curves at different heating rates.

Table 3. Specific values and extrapolation results of Ti , Tp , andT f at different heating rates.

Heating Rate (◦ C/min) Ti (◦ C) Tp (◦ C) T f (◦ C)

5 104.5 121.1 137.2
10 114.0 133.2 152.3
15 121.0 143.1 164.0
20 125.0 151.5 176.4
0 99.0 112.0 125.0

3.1.2. Curing Kinetics Parameters Analysis

The curing kinetic model mainly includes the phenomenological model [51] and the
mechanism model [52]. The mechanism model is more accurate than the phenomenological
Polymers 2023, 15, 982 7 of 16

model, but it is difficult to model because it considers the kinetic mechanism in the whole
reaction process. Therefore, the phenomenological model is widely used in the curing
process of composite materials.
The phenomenological model expression is

dα/dt = K ( T ) f (α) (1)

where dα/dt is the curing reaction rate, T is the absolute temperature, f (α) is the curing
mechanism function, and K ( T ) is the reaction rate constant, following the Arrhenius
equation, as shown in Equation (2).

K ( T ) = Aexp(− Ea /RT ) (2)

where A is the pre-exponential factor, Ea is the activation energy, and R is the universal
gas constant.
There are two kinds of curing mechanism functions: the n-order reaction model and
the autocatalytic reaction model. The n-order reaction model is the simplest model to
describe the curing reaction.
f ( α ) = (1 − α ) n (3)
f ( α ) = α m (1 − α ) n (4)
where n and m are the reaction orders, the epoxy resin model in this paper can be described
by Equation (5).

dα/dt = Aexp(− Ea /RT ) f (α) (5)

The kinetic reaction parameters (activation energy Ea , pre-exponential factor A, and re-
action model f (α)) are determined using a model-free estimation method designed by
Kissinger [53] and Ozawa [54,55] based on the following equations.
Kissinger equation:

d ln( β/Tp2 ) Ea
=− (6)
dTp−1 R
Transforming the two sides of the above equation to Equation (7).

β AR Ea
ln( ) = ln( )− (7)
Tp2 Ea RTp
Ozawa equation:

d ln β Ea
= −1.052 (8)
d1/Tp R
Transforming the two sides of the above equation to Equation (9).

ln β 1.052
=− Ea (9)
1/Tp R
where β is the heating rate, Ea is the activation energy obtained with the Kissinger and
Ozawa equations, and Tp is the peak temperature.
The apparent activation energy can be obtained by fitting the linear relationship
between Kissinger’s ln( β/Tp2 ) versus 1/Tp and Ozawa’s ln β versus 1/Tp according to the
transformed Kissinger and Ozawa equations, as shown in Figure 5. The apparent activation
energy obtained using Kissinger’s method and Ozawa’s method is higher than that of the
epoxy resin 4251A4/B2, but the difference between the two is small, only 3.657 kg/mol.
The average value of 58.564 kg/mol is obtained as the apparent activation energy of the
epoxy resin 4251A4/B2.
Polymers 2023, 15, 982 8 of 16

3.4 Ozawa plot

8.8 Kissinger plot b
a Linear (Ozawa plot)
Linear (Kissinger plot) 3.2

9.0
3.0

9.2
2.8

9.4
ln( /TP)

2.6
2

ln
9.6 2.4

9.8 2.2

y= -6824.036x+7.012 y= -7641.671x+21.039
2
2.0 2
10.0 R =0.9881 R =0.9907

1.8
10.2

1.6
10.4

1.4
0.00235 0.00240 0.00245 0.00250 0.00255 0.00235 0.00240 0.00245 0.00250 0.00255

1/T 1/T
P P

Figure 5. (a) The curve of activation energy of the curing reaction was determined by the
Kissinger method; (b) The curve of activation energy of the curing reaction was determined by
the Ozawa method.

Crane [56] further derives the model proposed by Kissinger to obtain the equation.

d ln β Ea
= −( + 2Tp ) (10)
d1/Tp nR
Ea
when nR is much larger than 2Tp , 2Tp can be neglected.
According to the literature, a linear fit to ln( β/Tp2 ) versus 1/Tp is performed to obtain
the intercept, which is substituted into Ea1 to obtain A as 7.57 * 106 min−1 . The slope is
obtained by linearly fitting ln β versus 1/Tp using the Crane equation and substituting Ea1
so as to get n as 0.89. The specific parameters are shown in Table 4.
Thus, the n-order curing kinetic model equation of 4251A4/B2 is established.

dα
= 7.57 ∗ 106 exp(−6824.04/T )(1 − α)0.89 (11)
dt
Table 4. Kinetic parameters of the 4251A4/B2 epoxy resin system.

E a1 E a2
Model E a (kg/mol) A (min−1 ) n
(kg/mol) (kg/mol)
4251A4/B2 56.735 60.392 58.564 7.57 × 106 0.89

3.1.3. Determination of Curing Temperature

The curing regime is generally divided into two-step and three-step temperature
gradients. The curing step temperature is divided into pre-curing temperature, curing
temperature, and post-curing temperature. According to the Ti , Tp , and T f measured by
dynamic heating experiments, the pre-curing temperature is set as the starting temperature,
the theoretical curing temperature is set as the peak temperature, and the post-curing
temperature is set as the termination temperature. However, due to the small differences
among the three values, the curing temperature setting process chooses Tp as the actual
curing temperature, that is, 112 ◦ C as the actual curing temperature. It is recommended that
the 4251A4/B2 epoxy resin curing temperature is 100 ◦ C × 5 h. The two curing systems
selected for the epoxy resin are shown in Figure 1.

3.2. Effect of Curing Temperature on the Mechanical Properties of Pure Epoxy Resin Matrix
The pure epoxy resin matrix is cured at 100 ◦ C for 5 h and 112 ◦ C for 4 h. As seen in
Figure 6, the tensile strength of the pure epoxy resin matrix is improved by 6.30%, and
Polymers 2023, 15, 982 9 of 16

the flexural performance is improved by 1.60% under two different curing temperatures.
The results show that the change in curing temperature from 100 ◦ C to 112 ◦ C resulted
in a slight increase in the fracture resistance of the pure epoxy resin matrix, and the
flexural resistance remained the same. At the theoretical curing temperature, although the
mechanical properties of the pure epoxy resin matrix are lower, this has a positive effect on
the overall performance of the composite material when combined with fibers.

Tensile strength

100 Flexural strength

1.60%

80 6.30%
Strength (MPa)

60

40

20

0
100 112

Temperature ( )

Figure 6. Temperature extrapolation curve at different heating rates.

3.3. Effect of Curing Temperature on Mechanical Properties of Composites

For the structural design and fabrication of pressure vessels using laminate theory, it
is necessary to obtain the tensile strength and modulus of carbon fiber composites in the 0◦ ,
90◦ , and shear directions of the material. However, NOL rings and unidirectional plates are
two types of unidirectional fiber winding specimens commonly used to test the strength
and modulus of carbon fiber composites, and the strength and modulus of NOL rings
in the 0◦ direction can provide more realistic process strength data for pressure vessels
because of their similar winding and load-bearing conditions. According to the test results
of standard specimens of NOL ring and unidirectional plate in each direction, it can reflect
the interfacial wettability between fiber and resin matrix, bond strength, and its ability to
transfer stress under stress conditions to a certain extent.
In the process of combining epoxy resin with carbon fiber, the epoxy resin itself is
mixed with the curing agent and reaches a uniformly distributed state through a mutual
contact and winding of molecules. The epoxy group with the active hydrogen in the amino
group of the curing agent undergoes a condensation polymerization reaction to form a
high molecular weight epoxy compound. The change of epoxy resin from a liquid to a
solid state under the influence of temperature is caused by chemical changes between
molecules, and the degree of reaction of gradual polymerization directly affects the end-use
properties of the cured product. The crosslinking density is an indicator of the degree of
the polymerization reaction, which is crucial to the final performance of the epoxy resin.
The mechanical properties of the composite NOL rings are listed in Table 5, where
“4251-100” indicates that the curing temperature of the epoxy resin in the carbon fiber
composite is 100 ◦ C. The tensile strength of the composite NOL rings increased by 22%
when the curing temperature was changed from 100 ◦ C to 112 ◦ C. Figure 7 shows the form
of tensile fracture of the unidirectional plate. According to Figure 7, the failure form of
NOL shows the fracture form is reasonable. The gradual delamination of the NOL rings
occurred with an increasing tensile load. Compared with the specimen when the curing
temperature was 100 ◦ C, the delamination of NOL occurred later at 112 ◦ C. Therefore, it can
be concluded to a certain extent that the interfacial bonding ability of epoxy resin and fiber
in the composites at 112 ◦ C is better enhanced, thus improving the overall load-carrying
capacity. After delamination, under the maximum tensile load, the fibers at both ends of
the NOL exerted ultimate strength while producing fracture.
Polymers 2023, 15, 982 10 of 16

Table 5. Tensile properties of NOL rings at different curing temperatures.

Curing Temperature 4251-100 4251-112

Tensile strength (MPa) 1852.37 2260.80

Figure 7. (a) NOL ring tensile test; (b) Unidirectional plate tensile test.

Figure 8 shows the mechanical properties of the composite unidirectional panels at

different curing temperatures. Figure 9 shows the tensile stress-strain curves of the com-
posite unidirectional panels in different directions. The tensile strength, flexural strength,
and tensile modulus of the composite unidirectional plate are significantly improved in the
90◦ direction, and the tensile strength increased by 68.86% and flexural strength increased
by 37.42%, but the flexural modulus changed less. In the 0◦ direction, the tensile strength
increased by 5.82%, but the tensile modulus decreased by 12.54%. However, the flexural
strength, flexural modulus, and shear strength in the 45◦ direction showed little change,
and the test results are in good agreement with Ismail’s [41] results.
The improvement of mechanical properties of NOL rings and composite unidirectional
plates is due to the fact that the epoxy resin is the first to reach the exothermic state at
112 ◦ C, and the molecules reach the temperature at which crosslinking reaction occurs.
The accelerated movement between molecules and the intensification of the crosslinking
reaction increases the crosslinking bonds, resulting in a higher crosslinking density and
more molecular chains, which eventually lead to the improvement of tensile strength. In the
0◦ direction, the polymer is formed during the movement of epoxy resin molecules. Due to
the large size of the polymer, the molecular movement space is blocked, and the free volume
fraction within the epoxy resin system decreases, which eventually leads to a decreasing
trend of the elastic modulus. The results show that the mechanical properties of the carbon
fiber composites are substantially improved, so it is proved that the curing temperature
derived from the extrapolation method is reasonable in this paper. In addition, the obtained
curing regime is also more reasonable to be applied to manufacturing pressure vessels.

3.4. Burst Pressure Results of Composite Pressure Vessel

Based on the fixed epoxy resin model, the new curing temperature (112 ◦ C) is obtained
using the extrapolation method in the curing kinetics analysis section of this paper. Com-
pared with the curing temperature of 100 ◦ C, the mechanical properties of the NOL ring
and unidirectional plate in all directions are better developed at 112 ◦ C. Therefore, it is
applied to the pressure vessel curing process to verify the rationality and advantages of the
curing regime derived with extrapolation.
Polymers 2023, 15, 982 11 of 16

a Tensile modulus b
Tensile strength
100
10 Flexural modulus 35.00%
Flexural strength 37.42%

1.95%
80
8

Modulus (GPa)
Strength (MPa)
60
6

68.86%

40 4

20 2

0 0
100 112 100 112

Temperature ( ) Temperature ( )

200

Tensile strength c Tensile modulus d

180
3000 Flexural modulus
Flexural strength 5.82%
160
12.54%
2500
140 0.02%

Modulus (GPa)
Strength (MPa)

2000 120

1.16%
100

1500
80

1000 60

40
500

20

0
0
100 112
100 112
Temperature ( ) Temperature ( )

40
Shear strength e

3.41%
35

30
Strength (MPa)

25

20

15

10

0
100 112

Temperature ( )

Figure 8. (a) Tensile and Flexural strength in 90◦ direction; (b) Tensile and Flexural modulus in 90◦
direction; (c) Tensile and Flexural strength in 0◦ direction; (d) Tensile and Flexural modulus in 0◦
direction; (e) Shear strength in 45◦ direction.
50

100
a 3000
100
b 70
100
c
112 112 112
60
40
2500

50
Stress (MPa)

Stress (MPa)

Stress (MPa)

30 2000
40

1500
30
20

1000 20

10
10
500

0 0
0.000 0.001 0.002 0.003 0.004 0.005 0.006 0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.000 0.001 0.002 0.003 0.004 0.005 0.006 0.007

Strain Strain Strain

Figure 9. (a) Tensile stress-strain in 90◦ direction; (b) Tensile stress-strain in 0◦ direction; (c) Tensile
stress-strain in 45◦ direction.

The pressure vessel is designed according to the 35 Mpa standard CGH2R and alterna-
tively wound in spiral and circumferential winding methods. A total of 14 layers of spiral
and circumferential winding (28 layers for a single layer) are cured using a 112 ◦ C × 4 h
rotational curing regime, as shown in Figure 10a. The cured pressure vessel is put under a
hydraulic burst test according to standard ISO19881 [57], with a pressure loading rate of
0.35 MPa/s. The experimental process fully complied with the standard.
Polymers 2023, 15, 982 12 of 16

The pressure vessel bursting results are shown in Figure 10b. The burst pressure
reaches 104.4 MPa, 26.93% higher than the minimum design burst pressure. From the
burst test results, it can be shown that the burst location is located in the cylinder part
and meets the standard design. The pressure vessel liner is deformed and bulged on the
side near the transition section, and the fiber layer is fractured from the main load-bearing
circumferential fiber layer. At the place of the liner rupture in the middle of the cylinder
part, the circumferential (90◦ ) fibers first reach the maximum tensile strength in the fiber
direction, so a large area of fiber fracture occurs. As the load gradually increases, the first
failure before the fiber-bearing fracture is the fracture of the resin matrix and the fiber
delamination phenomenon. Due to the high bursting pressure, the first fiber winding layer,
which is the first to start delamination, may be completely separated from the lining surface
as the fibers fracture.

Figure 10. (a) Pressure vessel curing; (b) Hydraulic burst test.

To investigate the overall properties and failure state of the epoxy resin matrix in the
curing regime derived from the extrapolation method, this paper uses the SEM observation
and analysis of a section of composite layer after the hydraulic burst test performed using
the ZEISS Gemini SEM 300. Considering the integrity of the test, three fiber layers of the
dome part, transition part, and cylinder part are observed, respectively, and the observation
results are shown in Figure 11a below.

Figure 11. (a) SEM observation position after burst test; (b) SEM observation of dome part; (c) SEM ob-
servation of transition part; (d) SEM observation of cylinder part.
Polymers 2023, 15, 982 13 of 16

The pressure vessel dome part generally consists of spiral wound fiber layers at
different angles to bear the internal pressure load, as shown in Figure 11b. With the increase
of load up to the bursting pressure, delamination, and fiber fracture occurs in the fiber
layers at different angles. From the figure, it can be seen that although there are many
delaminations, there is no significant debonding of carbon fibers from the resin matrix.
After delamination, the fibers still appear to be bundled under the action of the resin
matrix. Therefore, the fibers and the resin matrix can play a more powerful connecting role
with excellent interface bonding performance under the 112 ◦ C curing regime. From the
micro perspective, it is verified that good bonding performance is essential to the overall
performance of the dome part of the pressure vessel.
As a complex part of the pressure vessel geometry, the structural state of the transition
part is crucial in the bearing process. Excessive matrix fracture and delamination can lead
to a sudden drop in partial load-bearing performance, which may result in early rupture
failure of the pressure vessel at the transition part; a similar analysis and discussion were
presented in the research work of Nebes [9]. As shown in Figure 11c, a small amount
of fracture of the fiber bundle occurs, and there are residual bonded resin matrices on
the fractured fibers, while most of the fibers remain connected to the resin matrix and
continue to bear the load. Such a damage mechanism in the carbon fiber composite layers
of the transition part is more favorable to the load-bearing of the vessel. Therefore, this is
an indirect indication of the excellent curing regime, which maximizes the load-bearing
performance of the fiber composite and avoids early failure of the pressure vessel in the
transition part.
The cylinder part of pressure vessels has both circumferential and spiral fiber winding
layer bearings, but the circumferential fiber winding layer bears more load. As shown in
Figure 11d, this paper focuses on observing the circumferential fibers of the composite
material in the cylinder part. As the most critical load-bearing part of the pressure vessel,
the fractured circumferential fiber bundles still maintain good bonding, while the resin
attached to the fiber surface is uniform and dense, which has a positive effect on the quality
state of the fiber composite layer with low porosity and few defects in the cylinder section.
Thus, this fully reflects the excellent fluidity of the resin at 112 ◦ C curing temperature,
which results in better performance of the bonding interface between the fibers and the
resin matrix. The results of the burst pressure of the pressure vessel show the importance of
the influence of curing temperature on the mechanical properties of carbon fiber composites.
In addition, the microstructure states of different parts after the burst can show that the
curing regime derived in this paper is reasonable and can improve the overall performance
of the pressure vessel.

4. Conclusions
In this study, the curing temperature of 4251A4/B2 epoxy resin and its kinetic param-
eters are derived based on DSC experiments. By comparing the mechanical properties of
the pure epoxy resin matrix, NOL ring, and composite unidirectional plate in two curing
regimes, the curing temperature obtained based on the extrapolation method is proved to
be reasonable, and this corresponding curing regime is applied to a 35 MPa pressure vessel.
The following conclusions are drawn:
(1) Compared to 100 ◦ C, the tensile strength of 4251A4/B2 pure epoxy resin matrix at
a 112 ◦ C curing temperature is improved by 6.30%, and the flexural strength can still
maintain the original level. It shows that the curing temperature of 112 ◦ C positively
affects the improvement of the overall properties of epoxy resin used in composites.
(2) The tensile and flexural strength of the composites for winding were improved using
a curing regime of 112 ◦ C. The tensile strength of NOL rings was enhanced by 22%.
The tensile strength and flexural strength of the unidirectional plates increased by
68.86% and 37.42%, respectively, in the 90◦ direction, and the tensile strength in the 0◦
direction increased by 5.82%. The application of this curing regime provides a strong
Polymers 2023, 15, 982 14 of 16

guarantee for the improvement of composite materials and overall performance in

hydrogen storage vessels.
(3) The 35 MPa pressure vessel is cured and molded at 112◦ C, and its actual burst pressure
reaches 104.4 MPa, 26.93% higher than the minimum design burst pressure. At 112 ◦ C,
the resin fluidity in the pressure vessel is improved, and the interfacial bonding
between the resin matrix and the fibers is enhanced, which ultimately leads to the
good overall performance of the pressure vessel. It shows that the selection of the
curing regime in the molding process of the pressure vessel is an essential factor in
the overall mechanical properties.
(4) The non-isothermal kinetic method is used to analyze the curing kinetics of 4251A4/B2
epoxy resin, and the activation energy values calculated using the Kissinger method
and Ozawa method are 56.735 kJ/mol and 60.392 kJ/mol, respectively. Its n-order
reaction model will be used in pressure vessel curing molding simulation.
(5) The curing temperature is a crucial factor affecting the curing process. In applying
4251A4/B2 epoxy resin wet-forming composite materials and pressure vessels, the
curing temperature of 112 ◦ C is a curing parameter that cannot be ignored to improve
the overall performance of the structure.
In the future, the influence of heating and cooling rates and rotation rates on the
overall performance of pressure vessels will be further studied on the basis of this paper.
The effect of curing temperature will be considered in the pressure vessel curing simulation
to obtain more accurate prediction results.

Author Contributions: Conceptualization, J.L.; Investigation, L.L. and Z.Q.; Methodology, J.L.;
Resources, J.L.; Software, X.Z.; Supervision, U.E.; Data curation, Z.L.; Writing—original draft, L.L.;
Writing—review & editing, J.F.; Funding acquisition, J.L. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was supported by the National Natural Science Foundation of China (No.
52075361). This research was supported by the Major Science and Technology Project of Shanxi
Province (No. 20201102003), and the APC was funded by the Key Research and Development Projects
in Shanxi province (No. 201903D421030).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: Special thanks are given to Yuqin Xue, Zhaotun Jia, and Chunxiang Miao for
their timely help in conducting experiments.
Conflicts of Interest: The authors declare no conflict of interest.

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