polymers

Article
Three-Dimensional Thermo–Chemo–Mechanical Coupled
Curing Analysis for the Filament Wound Composite Shell
Linjiao Lu, Shengsheng Huan, Mengkai Lu *, Tao Shen , Yanhui Tian, Jianying Hu, Jianke Du
and Minghua Zhang *

Zhejiang-Italy Joint Lab for Smart Materials and Advanced Structures, School of Mechanical Engineering and Mechanics,
Ningbo University, Ningbo 315211, China; 2111081018@nbu.edu.cn (L.L.); 2111081104@nbu.edu.cn (S.H.);
shentao@nbu.edu.cn (T.S.); 2311090032@nbu.edu.cn (Y.T.); hujianying@nbu.edu.cn (J.H.); dujianke@nbu.edu.cn (J.D.)
* Correspondence: lumengkai@nbu.edu.cn (M.L.); zhangminghua@nbu.edu.cn (M.Z.)

Abstract: Carbon fiber resin-based composite materials are widely employed in the manufacturing of
composite shells. During the curing process, the temperature gradients and cure degree gradients
make it easy to generate thermal strains in both carbon fibers and resin, with the resin experiencing
cure shrinkage strain due to the curing reaction, ultimately leading to residual stresses and strains. In
this paper, a three-dimensional thermo–chemo–mechanical coupled curing model of the composite
shell was established based on a resin test, and the changes of temperature, curing degree, residual
stress, and strain during the solidification of the composite shell were investigated. First, the curing
property parameters and elastic modulus of HCM-2184 resin were obtained through a curing dynamic
test and a tensile test. Then, considering the heat release and shrinkage reaction of solidification, a
coupled thermo–chemo–mechanical curing model was developed with the CHILE (α) elastic model,
and the curing process of the composite shell was simulated numerically. The results show that
the resin used in the test belongs to the autocatalytic reaction. For thin composite shells, the heat
accumulation inside the shell during curing is not obvious. During the curing process, the curing
shrinkage behavior of the resin is an important factor for the generation of residual stress and
residual strain.
Citation: Lu, L.; Huan, S.; Lu, M.;
Shen, T.; Tian, Y.; Hu, J.; Du, J.; Zhang, Keywords: curing kinetics; thermo–chemo–mechanical coupled; composite shells; curing deformation;
M. Three-Dimensional residual deformation
Thermo–Chemo–Mechanical Coupled
Curing Analysis for the Filament
Wound Composite Shell. Polymers
2024, 16, 1643. https://doi.org/ 1. Introduction
10.3390/polym16121643 Composite materials, which have been widely applied in recent years, typically com-
Academic Editor: Stefano Vecchio
prise two or more materials with distinct physical or chemical properties at the macroscopic
Ciprioti scale. These materials not only retain the advantages of their constituent components,
but also exhibit superior comprehensive performance compared to single materials at the
Received: 27 April 2024 macro level. Compared to traditional metallic materials and alloys, carbon fiber resin-based
Revised: 1 June 2024 composites possess advantages such as low density, high-temperature resistance, corrosion
Accepted: 6 June 2024
resistance, high strength, high modulus, fatigue resistance, and a low thermal expansion co-
Published: 10 June 2024
efficient [1–4], making them extensively used in aerospace and other fields [5]. For instance,
at the same volume, ensuring strength and safety while reducing mass can effectively
decrease the load. Additionally, in high-temperature and high-humidity environments, the
Copyright: © 2024 by the authors.
material properties remain substantially unchanged, aligning with the lightweight manu-
Licensee MDPI, Basel, Switzerland. facturing requirements of modern solid rocket engines, hence justifying their use in engine
This article is an open access article shell fabrication. The resin, serving as the matrix of composite materials, exhibits curing
distributed under the terms and behavior, a chemical change where under external heating, internal groups within the resin
conditions of the Creative Commons undergo cross-linking reactions, releasing heat and transitioning from a viscous flow state
Attribution (CC BY) license (https:// to a glassy state [6], with an increase in viscosity and volume shrinkage. During the curing
creativecommons.org/licenses/by/ process of composite material shells, the presence of thermal expansion and contraction
4.0/). between carbon fibers and resin, resin cure shrinkage [7–9], and mismatches in the thermal

Polymers 2024, 16, 1643. https://doi.org/10.3390/polym16121643 https://www.mdpi.com/journal/polymers

Polymers 2024, 16, 1643 2 of 18

expansion coefficients between different parts of the shell and mold materials [10] lead to
thermo–chemo–mechanical coupled residual stresses and strains during the curing and
molding process. After curing, some residual stresses remain within the shell, causing
deformation that deviates from the designed dimensions, affecting the molding quality of
shell components and their performance indicators. For example, in the strength prediction
of the shell, the residual stresses and strains formed during curing can be considered to
be prestress and prestrain. Therefore, the analysis of shell curing, as a factor affecting the
performance of molded shells, necessitates the study of the evolution and distribution
patterns of residual stresses and strains generated during curing.
The analysis of the structural quality of composite material components during curing
molding essentially involves the study of changes in internal stresses and strains within the
components caused by the combined effects of carbon fiber and resin thermal expansion,
as well as resin curing, under the segmented processes of heating, holding, and cooling
during the curing process. Currently, numerous researchers have employed experimental
and numerical simulation approaches to research the curing process of composite materials
based on thermosetting resins [11–15]. The study of resin cure kinetics forms a crucial
foundation for investigating the curing deformation of composite materials. Differential
Scanning Calorimetry (DSC) is commonly used to study resin curing behavior. Lee et al. [16]
obtained the kinetic parameters of 3501-6 resin by DSC. Zanjanijam [17] studied the curing
kinetics of phenolic resin/coal coke composites.
The curing process significantly impacts the quality of curing molding of composite
materials. On the one hand, temperature affects the curing progression of the resin, leading
to phenomena of uneven curing. On the other hand, the properties of resin [18,19] also
change with temperature variations, such as thermal conductivity, density, and specific
heat capacity. Pedersen et al. [20] investigated the thermal diffusivity of epoxy resin during
the curing process, and discovered that thermal conductivity and specific heat capacity
have functional relationships with the degree of cure. Johnston [21] studied the density
and various thermophysical parameters of AS4/8552 composite materials.
The simulation of composite materials’ curing has undergone a developmental pro-
cess [22–24]. Cheung [25] integrated thermal conduction with resin cure kinetics to study
the temperature field distribution of composite laminate boards during the curing process.
Abdelal [26] utilized thermodynamic parameters that change with temperature to construct
a thermo–chemical coupled model, calculating the temperature and cure degree distribu-
tion of composite material components. To accurately simulate and predict the evolution of
stress and strain during the curing process of composite material components, it is essential
to establish their constitutive model throughout the entire process, and a substantial num-
ber of scholars have researched the constitutive models of composite materials. Among
them, the main categories are linear elastic and viscoelastic constitutive models. Bogetti and
Gillespie [27] proposed a curing-hardened instantaneous linear elastic model, assuming
that the resin behaves linearly elastically at each incremental step during the curing process,
and considering that the elastic modulus has a functional relationship with the degree
of cure, hence referred to as the CHILE (α) model. However, the above methods did not
account for the viscoelasticity of composite materials and the stress relaxation it causes. In
order to more accurately characterize the stress relaxation behavior of composite materials,
researchers introduced viscoelasticity into the calculations for the curing of composite
materials [28–30], with Ding et al. [31,32] establishing a thermo–viscoelastic constitutive
model considering stress relaxation based on a generalized Maxwell model with n Maxwell
elements. The thermo–chemo–mechanical coupled curing process of laminates was numeri-
cally simulated. Nonetheless, due to the significant difficulties in measuring the viscoelastic
parameters of composite materials and the increased complexity of numerical calculations
involving viscoelastic constitutive equations, the CHILE (α) model, by comparison, is
relatively simple and can more accurately predict the stress evolution during the curing of
composite materials, and is thus widely adopted by scholars.
Polymers 2024, 16, 1643 3 of 18

As aforementioned, the fully coupled analysis for thermo–chemo–mechanical curing

is very important. While at present, there are few numerical simulation studies on the
application of specific types of resins in the curing of filament wound composite shells, this
article addresses the issue of residual stresses and strains leading to structural deformation
during the curing process of composite material shells. The test was conducted using
HCM-2184 resin. Differential scanning calorimetry (DSC) was used to test the curing
kinetics of the resin, and the curing properties of the resin were obtained. A tensile test was
carried out to study the tensile properties of resin-casting parts. Based on the consideration
of resin-curing heat release, curing shrinkage, and anisotropy of composite materials, a
thermo–chemo–mechanical coupled curing model of the filament wound composite shell
was established with the CHILE (α) constitutive model. The evolutionary distribution of
temperature, curing degree, and residual strain during curing molding was studied, which
provided a reference for the quality evaluation of curing molding.

2. Resin Test
2.1. Preparation of Resin Matrix
Material: HCM-2184 epoxy resin and curing agent, XTEND832 semi-permanent release
agent. First, the HCM-2184 epoxy resin was mixed with the curing agent at the mass ratio
100:31. Then, through the high speed stirring and mixing evenly, the resin was vacuumed
in the vacuum oven at room temperature for an hour. Finally, when no bubbles appeared,
the resin was removed, and subsequent tests were carried out.

2.2. Non-Isothermal DSC Test

In order to study the curing reaction kinetics of HCM-2184 epoxy resin, according to
the curing characteristics of HCM-2184 epoxy resin, Netzsch DSC-200F3 non-isothermal
DSC tests were carried out. The 5 mg mass sample was placed in an aluminum pot,
heated to 300 ◦ C at the heating rate of 5.0, 10.0, 15.0, and 20.0 ◦ C/min, and tested under
nitrogen atmosphere.

2.3. Tensile Test

When calculating the curing process of composite materials, it is necessary to input the
elastic modulus parameters of the resin. Therefore, tensile tests on the resin are required.
The tensile test specimens of the resin are prepared according to the current national
standard in China [33], with specific dimensions, as shown in Figure 1.

Figure 1. Tensile sample size (unit: mm).

2.4. Experimental Results and Discussions

The DSC heat flow diagram of epoxy resin at different heating rates (5–20 ◦ C/min) is
shown in Figure 2. It can be seen that there is a single heat release peak at different heating
rates, and the peak heat flow and peak temperature increases with the increase in heating
rate, and the heat release peak moves towards the higher temperature direction with the
increase in heating rate, indicating that the resin has a heat transfer lag phenomenon.
Polymers 2024, 16, 1643 4 of 18

Figure 2. Results of non-isothermal DSC testing of HCM-2184 resin.

According to the results of Figure 1, the characteristic parameters such as maximum

heat release temperature (peak temperature), peak heat flow, and total heat release of curing
reaction (∆Hcure , calculated by the area under the peak heat release) are summarized in
Table 1, and the figures in brackets are standard deviations. The results of each heating
rate were averaged by repeated tests (at least three times), and the total curing heat release
calculated at different heating rates was averaged to obtain the final reaction heat of
the resin.

Table 1. Characteristic parameters of resin non-isothermal DSC test.

Heating Rate Peak Temperature Maximum Heat Total Heat Release

(◦ C/min) (◦ C) (W/g) (J/g)
5 164.85 (0.212) 2.891 (0.214) 1962.50 (60.104)
10 184.70 (0.566) 5.604 (0.173) 1965.00 (74.953)
15 199.40 (0.849) 8.191 (0.714) 1938.00 (82.024)
20 204.75 (0.424) 9.263 (0.651) 1763.00 (67.882)

To solve the cure kinetics equation of the resin, it is necessary to determine the resin’s
activation energy through mathematical fitting. Activation energy is defined as the mini-
mum energy required for a chemical reaction to occur: the smaller the activation energy, the
more readily the reaction takes place. Commonly used equations for calculating activation
energy include the Kissinger equation and the Ozawa equation [34]. This article employs
both equations to calculate the activation energy of the resin, and the average of the two
results is taken as the final activation energy.
The Kissinger equation is expressed as follows:

τ AR Ea 1
ln( 2
) = ln( )− , (1)
TP Ea R TP

In the equation, R represents the ideal gas constant, generally taken as 8.314 J/(mol·K);
A denotes the frequency factor, with the unit S−1 . Ea is the activation energy of the cure
reaction being determined, τ is the heating rate, and Tp is the peak temperature obtained
from tests under different heating rates.
The Ozawa equation is expressed as follows:

d(ln τ ) E
  = −1.052 a , (2)
d Tp1 R

In Equation (2), the physical significance of each parameter is the same as that in the
Kissinger equation.
Polymers 2024, 16, 1643 5 of 18

Firstly, the activation energy is determined based on the Kissinger equation.

 Using
 the
2
data from Table 1, a plot is constructed with 1000/T p as the x-axis and − ln τ/Tp as the
y-axis. After linear fitting, the result is presented in Figure 3a. Using the Ozawa equation
to determine the activation energy, a plot is created with 1000/T p as the x-axis and − ln(τ )
as the y-axis. After linear fitting, the result is shown in Figure 4.

Figure 3. Fitting of activation energy: (a) the Kissinger equation; (b) the Ozawa equation.

Figure 4. Changes in curing degree of the HCM-2184 resin at different heating rates.

In Figure 3a, after linear fitting of the HCM-2184 resin, the slope of the line is 5.554,
with R2 = 0.998 indicating a good fit. The reaction activation energy is calculated according
to Equation (1), resulting in Ea = 46.18 kJ/mol. In Figure 3b, the slope of the line is 6.472,
with R2 = 0.998. The reaction activation energy is calculated according to Equation (2),
Ea = 51.15 kJ/mol.
Taking the average of the results calculated from the two equations, the activation
energy for HCM-2184 resin is determined to be 48.67 kJ/mol.
When calculating the degree of cure (α) during the curing process of thermosetting
resin, it can be represented by the ratio of the heat of reaction at the current time to the
total heat of reaction, as shown in Equation (3). Among them, the reaction heat at the
current moment (∆HT ) is obtained by integrating the heat flow curve measured using DSC
in Figure 1 over time, and the total heat released during the curing process is shown in
Table 1:
∆HT
α= , (3)
∆Hcure
The variation trend of the curing degree of HCM-2184 resin with the increase in
temperature under different heating rates is obtained, as shown in Figure 4.
Polymers 2024, 16, 1643 6 of 18

By further deriving the degree of cure with respect to time, the relationship between
the cure reaction rate of the resin and time at different heating rates is obtained. Curves
depicting the degree of cure and cure rate as functions of time under four different heating
rates are plotted, as shown in Figure 5. In the figure, the times at which the cure rate
reaches its peak are marked vertically, and the corresponding degree of cure intervals are
marked horizontally. It can be observed that, at different heating rates, the resin reaches its
maximum cure reaction rate within a degree of cure range of 0.4–0.6, indicating that the
cure reaction is most intense within this interval.

Figure 5. Comparison of curing degree and curing rate at different heating rates: (a) 5 ◦ C/min;
(b) 10 ◦ C/min; (c) 15 ◦ C/min; (d) 20 ◦ C/min.

The N-order reaction model [35] is applicable to the resin system without autocatalytic
behavior in the curing reaction, and its expression is shown in Equation (4):

dα
= K ( T )(1 − α)n , (4)
dt
where n is the order of reaction associated with the material, K is a function of temperature,
and α is the degree of cure.
The curing kinetic model expression of epoxy resin system with autocatalytic charac-
teristics is shown in Equation (5):

dα
= K ( T ) α m (1 − α ) n , (5)
dt
The relationship between the cure reaction rate and the degree of cure for epoxy resin
at different heating rates is shown in Figure 6.

Figure 6. Relationship between the curing reaction rate and curing degree of the HCM-2184 resin at
different heating rates.
Polymers 2024, 16, 1643 7 of 18

As shown in Figure 6, the cure reaction rate is related to the heating rate, with the cure
rate significantly accelerating as the heating rate increases. At four different heating rates,
the cure reaction rate exhibits a parabolic trend of first increasing and then decreasing,
rather than reaching the maximum value at the outset. The interval at which the cure
reaction rate peaks is within the range of 0.4–0.6, largely unaffected by the heating rate.
This indicates that the basic model of the resin’s cure reaction is independent of the heating
rate, thereby suggesting that the cure kinetics model for the HCM-2184 resin system belongs
to an autocatalytic reaction [35].
The cure rate curves obtained from the experiments were subjected to nonlinear fitting
based on the autocatalytic reaction model. Studies indicate that the extremum of the resin’s
autocatalytic reaction generally occurs at a degree of cure around 0.4. Therefore, to fit
the curves more accurately, a degree of cure of 0.4 was used as a demarcation point for
segmental fitting. Figure 7 presents a comparison between the experimental and fitting
results of the cure rate of HCM-2184 resin at different heating rates. It is observable that, at
all four heating rates, the experimental and fitted curves are in basic agreement, indicating
that fitting each curve individually yields good results. Subsequently, by averaging the
characteristic parameters of the cure kinetics equations fitted at different heating rates, a
universal formula is obtained as follows:
 
dα  3802 ∗ exp( − 48670 α0.539 1 − α)1.002 , α ≤ 0.4
8.314∗ T 
= , (6)
dt  3891 ∗ exp( − 48670 α0.404 1 − α)1.264 , α > 0.4
8.314∗ T

Figure 7. Curve fitting results of the curing rate with different heating rate: (a) 5 ◦ C/min;
(b) 10 ◦ C/min; (c) 15 ◦ C/min; (d) 20 ◦ C/min.

Figure 8 presents the comparison results of the curves, revealing that, although there
is a certain discrepancy between the averaged curves and the experimental curves, they
still essentially coincide. At the relatively lower heating rates of 5 ◦ C/min and 10 ◦ C/min,
the fitted curves and experimental curves almost overlap. At the higher heating rates
of 15 ◦ C/min and 20 ◦ C/min, there is a noticeable difference in the maximum values
of the cure rates of the fitted curves, and yet the general trend of the cure rate remains
fundamentally the same.
Polymers 2024, 16, 1643 8 of 18

Figure 8. Average result of the curing rate fitting curve.

For the tensile test, the force-displacement curve measured using the test is shown
in Figure 9a, and the stress–strain curve is drawn with the linear section. The result after
linear fitting is shown in Figure 9b. The slope—that is, the elastic modulus of the resin
after curing—is 1.97 GPa, which is used as the material parameter for the subsequent
curing simulation.

Figure 9. (a) Force-displacement curve; (b) stress–strain curve and fitting results.

3. Construction of the Composite Curing Coupled Model

3.1. The Thermo–Chemo–Mechanical Coupled Model
The curing process of resin-based carbon fiber composite material is essentially the result
of the joint action of the temperature applied externally and the internal heat source generated
from the resin releasing heat. The external applied temperature belongs to the heat conduction,
and the curing of the resin belongs to the chemical reaction. The heat conduction and curing
reaction in composites lead to the generation of residual stress and strain, resulting in curing
deformation. Therefore, the curing process is a thermo–chemo–mechanical coupled process.
The three-dimensional Fourier heat conduction equation of the anisotropic composite and the
internal heat source of the resin are shown as follows:

∂T ∂2 T ∂2 T ∂2 T .
ρc C p = k11 2 + k22 2 + k33 2 + q0 , (7)
∂t ∂x ∂y ∂z

. dα
q0 = ρr Vr Hr , (8)
dt
Polymers 2024, 16, 1643 9 of 18

where ρc is the density of the composite material, k ii denotes the heat conduction coefficient
.
of the composite material, C p is the specific heat capacity, q0 is the internal heat source
generated during the curing process of the resin, ρr is the density of the resin, Vr is the
volume fraction of the resin, Hr is the total heat released after the resin is completely cured
by the test, and dα/dt is the curing rate.
For the resin used in this paper, a semi-empirical phenomenological kinetic model
based on macro-scale was adopted. According to the test, HCM-2184 was determined to be
an autocatalytic resin, and the curing rate equation is shown as Equation (6).
The mechanical behavior during the curing process of thermo–chemo–mechanical
coupled, that is, the constitutive relationship of the composite material, is described in
Section 3.2.

3.2. Constitutive Relationships of the Composite Material

In carbon fiber-reinforced resin composite materials, the carbon fibers acting as the
reinforcement material only undergo thermo–mechanical changes during the curing pro-
cess, and their constitutive behavior is linear elastic. In contrast, the resin, serving as the
matrix, is a polymer material that undergoes chemical changes [36] during curing, and
generally exhibits viscoelastic behavior. Scholars have proposed computational models for
the evolution of modulus during the resin’s curing process, such as the CHILE model, the
path-dependent model, and the viscoelastic generalized Maxwell model, among which the
CHILE model is widely adopted. It assumes that the resin can be approximately considered
to be a linear elastic material within a single time step, with the model linearly varying
with the degree of cure, as shown in Equation (9).
 0
 Er α < αc1
Er = (1 − α ) E0 + αmod Er∞ αc1 ≤ α < αc2 , (9)
 ∞ mod r
Er α ≥ αc2
   
where αmod = α − α gel / 1 − α gel , α gel is the gel point when the resin starts crosslink-
ing. Er0 and Er∞ are the elastic moduli of the resin in the uncured state and when cur-
ing is completed, respectively. Er∞ /Er0 is usually set to be one thousand. In this case,
Er∞ = 1.97 GPa, Er0 = 1.97 MPa. αc1 , and αc2 are the curing degrees corresponding to the
starting and ending points of curing shrinkage, respectively.
The composite shell is composed of fiber winding, which is mainly divided into a
barrel body, a pole hole, and a head. Fiber winding is divided into two types: spiral
winding, and circumferential winding. The circular winding is only distributed in the body,
and the angle is about 90◦ . In the composite shell model with spiral fiber winding, the
winding angle from the barrel to the pole hole is calculated for the fiber winding layer
as follows:
r0
α(r ) = sin−1 ( ), (10)
r
where r0 is the radius at the polar hole of the shell, and r is the radius of the fiber winding
layer at any position of the head section. When r = r0 , the winding angle is 90◦ , that is, the
fiber winding layer is tangent to it at the polar hole. The initial winding angle of the spiral
winding layer in the barrel body is 19.5◦ . When approaching the pole hole, the winding
angle increases to 90◦ . The circumferential winding layer is only distributed in the barrel
body, and the angle is 90◦ , as shown in Figure 10a. Figure 10b shows the change of the
winding angle of the spiral winding layer along the axial direction of the shell.
Polymers 2024, 16, 1643 10 of 18

Figure 10. (a) Winding angle distribution of the spiral layer; (b) the winding angle of the spiral layer
changes along the shell axial direction.

In the actual winding process, the direction of the fibers continuously changes with
the winding angle. Therefore, it is unreasonable to place the direction of the fiber material
in the global coordinate system, which requires two coordinate rotations.
During the first rotation, the entire shell is placed in a cylindrical coordinate system,
with the 1, 2, and 3 axes representing the radial, circumferential, and axial directions,
respectively. For the end-cap section shown in Figure 11, take the 2-axis as the rotation
axis, rotate the 1–3 plane by an angle α, and the rotated plane is a 1′ –3′ plane. α is the
angle between the original radial axis 1 and the axis 1′ along the generatrix direction of the
frustum of a cone.

Figure 11. Schematic of the first rotation.

The second rotation is a plane rotation, taking the 3′ axis as the rotation axis, rotating
from the 1′ –2 plane to the 1′′ –2′′ plane, and the rotation angle θ is the fiber winding angle
α(r ) calculated by Equation (10). The rotation process is shown in Figure 12.

Figure 12. Schematic of the second rotation.

The winding shell is composed of composite materials, which are considered trans-
versely isotropic materials. The material stiffness matrix is denoted as [C], where each
parameter represents the composite material properties calculated using micromechanical
equations for composite materials, incorporating both carbon fibers and resin.
Polymers 2024, 16, 1643 11 of 18

After the rotation, the constitutive equation incorporating angular variables is formed,
with the stress–strain relationship as given in Equation (11). [C′] represents the stiffness
matrix of the composite material after coordinate transformation.
     

 σx  
 εx  
 εx  
σ    εy   εy 


 y












      
σz −1 εz ′ ε z
= [ Tσ ] [C ][ Tε ] = C , (11)

 τxy 
 
 γxy 
 
 γxy 
     
τ  γ  γ 
 xz   xz   xz 

  
  
 
     
τyz γyz γyz

The stress and strain transfer matrices are given as follows:

sin2 θ
 
cos2 θ 2sinθcosθ 0 0 0
 sin2 θ cos 2θ 0 − 2sinθcosθ 0 0 
 
0 0 1 0 0 0 
 
[ Tσ ] =  , (12)

−sinθcosθ sinθcosθ 2 2
0 cos θ − sin θ 0 0 

−sinθ 

 0 0 0 0 cosθ
0 0 0 0 sinθ cosθ

sin2 θ
 
cos2 θ 0 sinθcosθ 0 0
 sin2 θ cos2 θ 0 −sinθcosθ 0 0 
 
0 0 1 0 0 0 
 
[ Tε ] =  , (13)

−2sinθcosθ 2sinθcosθ 0 cos2 θ − sin2 θ 0 0 

−sinθ 

 0 0 0 0 cosθ
0 0 0 0 sinθ cosθ
On the other hand, the equation of the linear elastic constitutive equation is as follows:

σij = Cijkl ε kl , (14)

1−ν23 ν32
 
ν12 +ν13 ν32 ν13 +ν12 ν23
3∆ E2 E3 ∆ E2 E3 ∆ 0 0 0
 ν12E+2 Eν13 ν32 1−ν13 ν31 ν23 +ν21 ν13 
 E2 E3 ∆

E1 E3 ∆ E1 E3 ∆ 0 0 0 
 ν13 +ν12 ν23 ν23 +ν21 ν13 1−ν12 ν21
[C ] =   E2 E3 ∆ E1 E3 ∆ E1 E2 ∆ 0 0 0 , (15)
0 0 0 G12 0 0 


 
 0 0 0 0 G13 0 
0 0 0 0 0 G23
where
1 − ν12 ν21 − ν23 ν32 − ν13 ν31 + 2ν21 ν32 ν13
∆= , (16)
E1 E2 E3
After coordinate conversion, the constitutive equation including temperature and cure
variables can be written as:
Z t
∂
ε kl (τ ) − εtc

σij (t) = Cijkl (α, T, t − τ ) kl (τ ) dτ (i, j, k, l = 1, 2, 3), (17)
−∞ ∂t

3.3. Flowchart of the Curing Coupled Model

The curing analysis flow chart of thermo–chemo–mechanical coupled composite
materials is shown in Figure 13, which is divided into curing dynamics module, heat
conduction module and curing deformation module. Among them, the curing dynamics
module and heat conduction module are coupled with each other, and the two modules
are sequentially coupled with the curing deformation module. The curing calculation of
thermo–chemo–mechanical coupling requires the writing of ABAQUS user subroutines.
Different modules require different subroutines. The curing kinetics module uses UMAT
Polymers 2024, 16, 1643 12 of 18

definitions, the heat transfer module uses DISP, UEXPAN, and UMATHT definitions, and
the curing deformation module uses UMAT definitions.

Figure 13. Thermo–chemo–mechanical coupled curing flow chart.

3.4. FE Model of the Composite Shell

A thermo–chemo–mechanical coupled analysis is performed on the whole structure of
the carbon fiber composite material shell. The shell consists of carbon fiber winding layers,
metal fittings, rubber insulation layers and a sand core mold, as illustrated in Figure 14.
In the figure, the blue part represents the metal fittings, the cyan part denotes the rubber
insulation layer, the gray part is the sand core mold, and the yellow part is the composite
material layer.

Figure 14. The model diagram of the filament wound composite shell.

The specific size of the filament wound composite shell is shown in Figure 15. The
two ends of the shell have symmetrical polar holes, and the size is the same, the thickness
of the rubber insulation layer is 2 mm, the barrel body is 146.5 mm, the length is 400 mm,
the distance from the head to the polar hole is 98 mm, the radius of the metal polar hole
is 50 mm, and the thickness of the single layer of the fiber winding layer is 0.2 mm. The
model was established in the finite element software ABAQUS 2017, and the fiber winding
method was [±19.5◦ /90◦ ± 19.5◦ ]. The coordinate conversion of material parameters
and the calculation of the curing process were carried out by the user subroutine written
by ABAQUS.
Polymers 2024, 16, 1643 13 of 18

Figure 15. Specific dimensions of composite gas cylinders.

Apart from resin and carbon fibers, the model incorporates three other materials:
metal fittings, the sand core mold, and the rubber insulation layer. The insulation layer is
made of ethylene propylene diene monomer (EPDM) rubber, and the front and rear metal
fittings are made of 30CrMnSiA material. The mechanical properties of each material are
presented in Table 2, while the elastic mechanical parameters of T800 carbon fibers are
shown in Table 3.

Table 2. Mechanical property parameters of shell material.

Parameter 30CrMnSiA Steel Core Mold EPDM Rubber Unit

E 2 × 105 1 × 106 7.8 MPa
ν 0.33 0.1 0.47 -
k 29.3 0.16 0.26 w ·m−1 ·K−1
α 1.172 × 10−5 1 × 10−7 1 × 10−5 K−1
CP 520 1000 2200 J·kg−1 ·K−1

Table 3. Mechanics property of T800 carbon fiber.

Parameter Unit Value

E1 MPa 294,000
E2 , E3 MPa 14,000
G12 , G13 MPa 15,000
G23 MPa 5500
ν12 = ν13 - 0.23
ν23 - 0.23

The curing process of the composite shell is shown in Figure 16, which is applied to
the outer surface of the shell model. The contact type between the fiber winding layer and
the insulation layer is the Tie constraint. Considering the symmetry properties of the shell
model [37], the 1/36 model is adopted for calculation. The symmetric boundary conditions
along the column coordinates are set on both sides of the cross-section to prevent rigid
body displacement.
Polymers 2024, 16, 1643 14 of 18

Figure 16. Curing process curve.

4. Results and Discussions

4.1. Temperature and Curing Degree Analysis
A, B, and C are selected as the observation points, which are distributed from the
outside to the inside near the polar hole, as shown in Figure 17.

Figure 17. The position of three points A, B, and C of the shell head segment.

Figure 18a presents the temperature comparison, and Figure 18b compares the degree
of cure and cure rate. In the first heating stage, the outer surface is heated, and temperature
conducts from the outside inwards, resulting in internal temperatures being lower than
external ones. The increase in temperature initiates resin curing, with different temperatures
leading to a gradient distribution in the degree of cure, and external curing reactions
occurring faster than internal ones. When the heating of the first stage is nearly complete
and enters the subsequent heat preservation stage, the temperature is conducted to the
interior. The resin begins to undergo intense curing reactions, with the internal degree of
cure increasing. During this process, a significant amount of heat is released. In Figure 18a,
it can be seen that points B and C have significantly higher temperatures than point A, which
is similar to the results in the literature [38]. In addition, it is evident that the concentration
of heat causes the fastest cure rate at point C, as observed in Figure 18b. However, due to the
thin fiber winding layer of the shell, the phenomenon of heat concentration is not obvious.
In the later stages of heating and holding—that is, after about 650 min—no significant
accumulation of heat occurs as the resin cure reaction weakens. Hence, the temperature
lags behind the curing process. During the cooling stage, internal temperatures are higher
than external, conducting heat from the inside outwards, with temperatures gradually
approaching the cure temperature.
Polymers 2024, 16, 1643 15 of 18

Figure 18. (a) Curve of temperature change; (b) curve of curing degree and curing rate.

4.2. Residual Stress and Residual Strain Analysis

During the curing process, points A, B, and C distributed from the outside to the
inside of the cylindrical section of the shell, as shown in Figure 19, are selected to plot the
trends of axial residual stress and strain, as illustrated in Figure 20a,b. It can be found that,
in the first heating stage, the strain primarily increases due to thermal expansion. At the
holding stage, as the resin curing progresses, the strain decreases due to the cure shrinkage
effect. When the resin curing is near completion, the strain change is positively correlated
with the temperature change, which is similar to the strain change in the literature [39].
When comparing the strain at internal and external points, due to the shell being thin, their
strains are essentially the same.

Figure 19. The position of three points A, B, and C of the shell cylinder body.

Figure 20. (a) Axial stress changes during curing. (b) Axial strain changes during curing.
Polymers 2024, 16, 1643 16 of 18

For the stress situation, the overall trend of stress during the curing process increases.
In each heating stage, stress decreases when the temperature rises. In the holding stage
before the end of curing, the cure shrinkage of the resin causes a significant increase in
stress, indicating that cure shrinkage is a significant factor in the occurrence of residual
stress. Comparing the stress at internal and external points, since the strain is similar, and
points A and C are in the helical winding layer with the same winding angle, the stress
changes are essentially the same. However, point B is in the circumferential winding layer,
and after coordinate transformation, the constitutive equation differs from the other two
points, resulting in stress being greater at point B than at points A and C.

5. Conclusions
In this paper, the results of the curing deformation of filament wound composite
shells are studied using experimental and numerical studies. A thermo–chemo–mechanical
coupled model for the curing analysis of the composite shell is proposed, which can be
used to simulate the curing process and evaluate the quality of the composite shell. The
detailed conclusions are listed as follows:
1. The non-isothermal DSC test was carried out on HCM-2184 resin, and the curing
reaction was analyzed to belong to the autocatalytic reaction model. The parameters of
the curing kinetic formula were obtained by mathematical fitting. The elastic modulus
of the resin after curing was obtained using a tensile test. These material parameters
are used in the curing numerical simulation.
2. Combining the heat conduction, the curing behavior of resin, and the curing deforma-
tion of composite materials, a thermo–chemo–mechanical coupled numerical model
was constructed on the basis of considering the coordinate transformation of the
composite shell, and the curing process of the composite shell model was simulated.
3. The curing process of the composite shell is analyzed. The results show that the heat
accumulation caused by curing heat release can be observed in the thicker parts of
the shell, such as the head section. However, due to the thin shell, the curing heat
generation is not obvious. During the curing process, the strain changes inside and
outside the shell barrel body are close, and the stress is different due to the change in
fiber winding angle. During the intensive curing stage of the resin, the strain decreases
rapidly and the stress increases, indicating that the curing shrinkage behavior of the
resin is an important factor in the generation of residual stress and residual strain.

Author Contributions: Conceptualization: M.Z.; methodology, M.L. and T.S.; software, L.L.; val-
idation, M.L. and L.L.; formal analysis, L.L.; investigation, M.L. and L.L.; resources, J.D.; data
curation, L.L., S.H. and Y.T.; writing—original draft preparation, L.L.; writing—review and editing,
M.L. and M.Z.; visualization, L.L.; supervision, M.Z.; project administration, M.L., J.H. and M.Z.;
funding acquisition, J.D. and M.Z. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China (Grant
No. 11972199), the Key Program of the Natural Science Foundation of Zhejiang Province (Grant No.
LZ22A020001), and the Ningbo Major Research and Development Plan Project (Grant No. 2022Z210).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also form part of an ongoing study.
Conflicts of Interest: The authors declare no conflict of interest.

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