applied

sciences
Article
The Influence of Copper Oxide Particle Size on the Properties of
Epoxy Resin
Patrycja Bazan 1 , Michał Gajda 1 , Przemysław Nosal 2 , Agnieszka Bak
˛ 1 , Kinga Setlak 1 and Michał Łach 1, *

1 Chair of Material Engineering and Physics, Cracow University of Technology, 31-155 Kraków, Poland;
[email protected] (P.B.); [email protected] (M.G.); [email protected] (A.B.);
[email protected] (K.S.)
2 Department of Machine Design and Maintenance, AGH University of Krakow, 30-059 Kraków, Poland;
[email protected]
* Correspondence: [email protected]

Abstract: This study examines the relationship between the size of copper particles and the properties
of epoxy resin. Epoxy resin is a type of thermosetting resin commonly used as a matrix in polymer
matrix composite materials reinforced with glass or carbon fibers. As part of this study, three
microscale and two nanoscale composite samples modified with copper oxide particles of varying
sizes were produced. This study included mechanical property tests such as static tensile tests,
static bending tests, and impact tests. The results of the strength tests were compared to modeling
results. Additionally, an accelerated thermal aging process was conducted to determine the impact
of external conditions on the behavior of the produced composites. This study concluded with
an analysis of thermal conductivity. The test results revealed that the size of the copper particles
significantly impacted the tested properties. The composites with copper oxide particles on the
nanoscale demonstrated the best results. These composites have promising applications in the
automotive and aviation industries due to their strength, resistance to external factors, and increased
thermal conductivity, suggesting their potential for producing materials that effectively dissipate heat.

Keywords: epoxy resin; copper particle size; polymer matrix composite materials; mechanical
properties; ageing

Citation: Bazan, P.; Gajda, M.; Nosal,

P.; Bak,
˛ A.; Setlak, K.; Łach, M. The
Influence of Copper Oxide Particle
Size on the Properties of Epoxy Resin.
1. Introduction
Appl. Sci. 2024, 14, 2534. https:// Polymer matrix composite materials have been used in construction since the 1990s.
doi.org/10.3390/app14062534 They have achieved popularity owing to the large number of combinations of materials
used for reinforcement, such as glass, fibrous polyamides, and carbon reinforcements.
Academic Editors: Dong Guo and
Sheng Zhao
Their weight is four times lower than that of commonly used construction materials
while maintaining similar mechanical properties. The greatest advantage of polymer
Received: 1 February 2024 composites is their corrosion resistance, which translates to their wide use in economic
Revised: 14 March 2024 sectors dealing with the processing of chemically active materials. Examples of interesting
Accepted: 15 March 2024 applications include polymer composites, which can be found as elements supporting
Published: 17 March 2024
the vaults of drilled mining tunnels. Their main advantages include their low weight
and electrical insulation. Materials of this type do not produce sparks during grinding
and cutting, which is a highly desirable feature [1]. The storage of liquefied petroleum
Copyright: © 2024 by the authors.
gas (LPG) typically involves the use of transportation and steel tanks, which have been
Licensee MDPI, Basel, Switzerland. increasingly replaced by composite tanks in recent years. The reason for this is the winding
This article is an open access article method used to produce tanks made of carbon prepreg. These composite tanks offer a
distributed under the terms and volume-to-weight ratio that is four times higher than conventional tanks, resulting in a
conditions of the Creative Commons significant reduction in vehicle weight, increased fuel efficiency, and decreased pollution.
Attribution (CC BY) license (https:// Therefore, these tanks are widely utilized in industries that manufacture land and air
creativecommons.org/licenses/by/ vehicles, as well as in rescue operations, for water transport for firefighting helicopters,
4.0/). and as pressure tanks for filling rescue pontoons [2]. The utilization of polymer composites

Appl. Sci. 2024, 14, 2534. https://doi.org/10.3390/app14062534 https://www.mdpi.com/journal/applsci

Appl. Sci. 2024, 14, 2534 2 of 19

in the Airbus A380 aircraft accounts for approximately 22% of its overall weight. These
composites are typically layered, or laminate, structures that incorporate various materials.
Examples of such composites include GFRP (“glass-fiber-reinforced polymer”), CFRP
(“carbon-fiber-reinforced polymer”), and GLARE aluminum matrix composites (“glass-
reinforced laminate”). These materials are favored due to their high stiffness relative to
their low weight and are commonly employed in the construction of fuselage plating,
wings, and tails. The anticipated demand for new materials for military vehicles in the near
future will likely drive the innovation and development of materials utilized in civilian
transportation [3,4]. Thermoplastics, including chemo- and thermosetting resins, are
widely utilized as materials for polymer composite matrices, commonly serving as fibrous
reinforcements. Notable representatives of these materials include unsaturated polyester
and vinyl ester resins, polyamides, bismaleimides, phenyl-formaldehyde resins, and epoxy
resins. Among these, epoxy resins are available in various molecular weights. The most
commonly utilized epoxy resins are bisphenol resins, which are employed as matrices for
glass or carbon reinforcements. These resins are produced through the polyaddition of
bisphenol and glycerine epichlorohydrin [5].
Epoxy resins can be described using two key measures: the epoxy number and the
hydroxyl number. These figures indicate the quantity of hydroxyl and epoxy groups present
in every 100 g of the substance. A greater hydroxyl number signifies a higher viscosity
or softening point, as well as a lower proportion of epoxy groups, which can affect the
form of the substance. This may take the form of a viscous liquid or semi-solid [6]. The
resin hardness is increased and retains its shape during the cross-linking process. The
resulting oligomer chains are subjected to various cross-linking processes, most often at high
temperatures. The cross-linking of the resin involves a copolymerization reaction involving
the double bonds of both components. The main strength properties, including hardness,
HDT deflection temperature, elastic modulus, tensile strength, and elongation at break,
depend on the cross-linking process [7]. The use of epoxy resins is preferred over polyester
resins due to their superior adhesion to fibers. Epoxy resins exhibit better wettability,
leading to increased strength parameters and enhanced resistance to water. Additionally,
after curing, epoxy resins do not contain ester groups, which significantly improves their
corrosion resistance. An analysis of various studies provides pertinent information on
the comparison of wettability between epoxy and polyester resins. Mohan [8] found that
difunctional epoxy displays superior wettability among thermoset resins, regardless of the
surface structure of the carbon nanotube material. Additionally, Nodehi [9] highlighted the
improved wettability achieved by curing epoxy resin with specific surface sizing, indicating
its effectiveness in fostering adhesion with carbon fibers. Furthermore, Bing et al. [10]
characterized the wettability between carbon fibers and an epoxy resin matrix, emphasizing
the significance of dynamic contact angle measurements in evaluating their interface. In
contrast, Landowski et al. [11] and Cui et al. [12] discussed the challenges arising from poor
wettability between polyester resins and materials such as thiolenic resins and natural fibers,
respectively. These studies emphasized the importance of addressing wettability issues to
enhance the performance of composite materials. Overall, the literature suggests that epoxy
resin generally exhibits superior wettability characteristics compared to polyester resin,
attributable to factors such as resin structure, curing processes, and surface treatments. It is
essential to understand and optimize wettability to achieve robust interfacial bonding and
enhance the overall performance of composite materials. These advantages make epoxy
resins suitable for replacing polyester resins in the production of prepregs, which are used
in the aviation industry. Table 1 provides a comparison of the mechanical properties of the
most commonly utilized thermosetting resins.
Epoxy resins offer several advantages when used with a hardener. They have a longer
working time, which facilitates application, and exhibit low shrinkage during the hardening
process. Additionally, they can be hardened at temperatures as low as 7 ◦ C, which makes
them suitable for use in colder environments. However, they come with some drawbacks,
including their higher price, which is typically double that of polyester resin. Moreover,
Appl. Sci. 2024, 14, 2534 3 of 19

the amine hardeners used with epoxy resins can be toxic, and the need to use thinners and
plasticizers increases the overall cost [9].

Table 1. List of selected properties of thermosetting resins. Adapted with permission from Ref. [8].
2013, Taylor & Francis Online and from Ref [9]. 2022. Springer.

Type of Resin
Properties
Polyester Vinylester Epoxy
Density, g/cm3 1.23 1.04 1.14
Tensile strength, MPa 70 85 75
Modulus of elasticity, GPa 3.8 3.3 3
Elongation at break, % 2.3 5 5
Thermal expansion coefficient, 6–10/◦ C 80–160 65 80–120

Epoxy composites also incorporate reinforcement in the form of particles, such as

silica particles. These particles may be used individually or in conjunction with a fibrous
reinforcement to enhance the strength and durability of the material [10–13].
Singh et al. examined the influence of the size and volume fraction of spherical silica
particles on the fracture toughness of epoxy composites. The researchers incorporated
fractions ranging from 1.56 µm to 240 nm and volume fractions from 0 to 0.35 into the
epoxy resin. The study revealed that the fracture toughness significantly improved with an
increase in volume fraction and a decrease in diameter. It was observed that as the volume
fraction of small particles increased, so too did the fracture toughness. Furthermore, the
researchers noted that the size of the particles played a role in the enhancement of strength
when smaller particles were utilized [14]. Ahmad et al. conducted a study comparing the
properties of mineral silica-based composites to conventional fused silica composites, which
are commonly used as filler materials. The study examined the effect of three different
particle shapes—angular, cubic, and elongated—on tensile strength, modulus, flexural
strength, modulus, thermal stability, and Tg at filler contents ranging from 15 to 45 wt%.
The results showed that the addition of particulate filler increased the mechanical properties
of the composites while also reducing the coefficient of thermal expansion. The elongated
silica mineral particles demonstrated higher flexural strength and tensile properties, as
well as a comparable coefficient of thermal expansion, compared to composites with fused
silica-based fillers, features attributed to the higher aspect ratio of the elongated particles
and thus a stronger bond between the resin and the filler [15].
In their work, Sanya et al. examined the influence of the particle size and content of
silicon carbide particles in an epoxy matrix on the mechanical properties of epoxy com-
posites. The study investigated the effects of particle sizes of <45 µm and 90–45 µm and
tested densities of 2, 4, 6, and 8 wt%. SiC. The results revealed a strong negative corre-
lation between hardness and flexural strength, as well as a positive correlation between
hardness and the flexural modulus and between compressive stress and the compressive
modulus. The test results also indicated that the addition of smaller silicon carbide particles
(<45 µm) resulted in excellent mechanical properties in terms of bending and compression
and hardness test results. Furthermore, it was observed that an increase in SiC particle
content led to a decrease in flexural strength, while compressive strength and hardness
increased with increasing particle loading [16]. Abenojar et al. investigated the influence of
extremely small SiC particles on the nano- and microscales, using particle contents of 6%
and 12%. The results showed that the incorporation of silicon carbide decreased the glass
transition temperature Tg due to a reduction in cross-linking points. This effect was less
pronounced when using nanoscale particles. The mechanical test results revealed hetero-
geneity attributed to the non-uniform distribution and agglomeration of nanoparticles in
the composite, as well as problems with wettability leading to material porosity. However,
it was clearly demonstrated that nanoparticles increased the material’s plasticity when
Appl. Sci. 2024, 14, 2534 4 of 19

bending. Additionally, 6% nano-SiC significantly reduced die wear. Microparticles were

found to be an effective additive for increasing the strength of the composite, but they
decreased wear resistance [17].
Jayaseelan et al. investigated the influence of fiber reinforcement and macro- and
microparticles of banana on the characteristics of epoxy resin, focusing on the properties
of tensile strength, bending strength, impact strength, and hardness. The study involved
testing composite materials with different additive contents ranging from 25 to 35% by
weight. The outcomes of the tests revealed that while fibers contributed to the highest tensile
strength, the particles led to the greatest increase in the bending modulus. Additionally,
both banana fibers and macroparticles were found to enhance impact strength compared
to unmodified resin. Furthermore, the mechanical properties of the composites were
observed to improve as the additive content of both fibers and particles increased [18]. In
his study, Asi analyzed the impact of Al2 O3 particles on the characteristics of epoxy–glass
composites. The Al2 O3 content in the composites was between 2% and 15% by weight. The
findings revealed that the tensile strength and shear strength of the composites significantly
decreased as the Al2 O3 content increased. However, the addition of aluminum oxide
particles resulted in an increase in Young’s modulus and bending strength with a rise in
particle content, up to 10% by weight, and then a decrease [19]. Li et al. conducted a study
to examine the influence of aluminum oxide particle size on the dielectric and mechanical
properties of epoxy composites. The study’s findings demonstrated that incorporating
nanofillers can enhance the breakdown strength and discharge resistance of the dielectric.
Conversely, microfillers can result in a decrease in short-term puncture strength with an
increase in content, a phenomenon attributed to the emergence of more defects. However,
it was observed that the short-term puncture strength of the nanocomposite increased with
an increase in the level of nanofiller dispersion [20]. Zhou and Yu conducted research to
investigate the impact of aluminum oxide on the thermal and dielectric properties of epoxy
composites. Specifically, they examined the effect of varying the microparticle content at
4%, 9%, 14%, 21%, 28%, 37%, and 48% volume. The study revealed that the incorporation of
aluminum particles had no effect on the thermal stability of the epoxy composites. However,
it did reduce the glass transition temperature (Tg). The size, concentration, and surface area
of the aluminum particles were found to influence the thermal conductivity and dielectric
properties of the composites. The dielectric permittivity increased with an increase in the
aluminum particle content. Furthermore, the dielectric permittivity and losses increased
with temperature due to the segmental mobility of the polymer molecule [21].
Copper oxide, also known as copper(II) oxide, is a semiconductor compound with a
monoclinic structure that has attracted considerable interest due to its status as the simplest
member of the copper family and its potential for various physical properties. These
properties include high-temperature superconductivity, electron correlation effects, and
spin dynamics. CuO is an essential p-type semiconductor with a wide range of applications
such as in gas sensors, catalysis, batteries, high-temperature superconductors, solar energy
conversion, and field emission emitters. In the realm of energy saving, energy transfer
fluids enriched with CuO nanoparticles can improve fluid viscosity and increase thermal
conductivity. The narrow band gap of CuO crystal structures endows them with useful pho-
tocatalytic, photovoltaic, and photoconductive properties. CuO is also a more economical
alternative to silver, miscible with polymers, and relatively stable in terms of chemical and
physical properties. Additionally, metal oxide nanoparticles with a high degree of ioniza-
tion, such as CuO, can be useful as antimicrobial agents due to the possibility of producing
them with an extremely large surface area and unusual crystal morphology [22]. Copper ox-
ide nanoparticles are typically available in the form of a brown-black powder. They can be
reduced to metallic copper under the influence of hydrogen or carbon monoxide at elevated
temperatures. These nanoparticles have diverse applications in fields such as catalysis, gas
sensors, magnetic storage media, batteries, solar energy transformers, semiconductors, and
field emission. Copper oxide nanoparticles, with their P-type semiconductor properties
and narrow band gap, have garnered significant interest for their potential use in elec-
Appl. Sci. 2024, 14, 2534 5 of 19

tronic, optoelectronic, and sensing nanostructures. They are commonly utilized as effective
heterogeneous catalysts, characterized by their high activity and selectivity in oxidation
and reduction reactions [23]. Copper oxide also exhibits bactericidal properties, making it
suitable for use in food-processing equipment as a means of self-sterilizing the environment
and preventing the spread of microorganisms. The increasing cost of silver particles has
led to a shift toward using copper as a more cost-effective alternative. Copper’s ability to
generate toxic hydroxyl radicals, which can disrupt bacterial cell membranes, contributes
to its effectiveness in combating microbial growth [24].
The primary objective of this investigation was to explore the viability of manufac-
turing and employing epoxy-resin-based composites that are modified with copper oxide
particles. The variable component in the examined materials was the size of the rein-
forcement particles, ranging from 10 nm to 10 µm. As part of the evaluation process,
basic physical and mechanical properties were determined using assessments such as
impact tests, and strength properties were assessed through static tensile tests and static
bending tests. Accelerated aging tests were conducted to determine the influence of envi-
ronmental conditions on the properties of the composites. Additionally, scanning electron
microscopy was used to capture microscopic images of the materials produced, and the
thermal conductivity of the composites was measured.

2. Materials and Methods

2.1. Materials
The test samples were made using LG206 epoxy resin and HG359 hardener (GRM
Systems, Bielsko-Biała, Poland), and copper oxide particles of various sizes were used as
reinforcements, that is, in the ranges of 1–10 µm, 40–60 nm, and 10–30 nm, (Suzhou Canfuo
Nanotechnology Co., Ltd., Suzhou, China). The resin-to-hardener weight ratio was 100:34.
The reinforcement content corresponded to 10% of the weight. The sample production
process included accurately weighing the proportions of resin and hardener on a Radwag
22 W laboratory scale (Radom, Poland), the ingredients were then mixed using a SH-II-7C
series mechanical digital mixer up to 40 L, with a power of 80 watts (Chemland, Stargard,
Poland). Mixing was carried out at a speed of 500 rpm by gradually introducing copper
oxide powder. In order to obtain a homogeneous suspension, a dispersion disk stirrer
with a diameter of 5 cm was used. The mixing time lasted approximately 5 min after the
introduction of the reinforcement. After mixing the ingredients, the mixture was placed in
a vacuum chamber. During the production of the samples, a VC3028AG vacuum chamber
(VacuumChambers, Białystok, Poland) was used to minimize porosity resulting from,
among other factors, mixing the ingredients. The mixture was de-aerated at a pressure of
10 mbar (abs). The hardening process was carried out at room temperature. The setting time
was 24 h, and the test samples were demolded 7 days after their production. Samples for
strength tests were made in accordance with the standard for plastics PN-EN ISO 3167 [25],
and type A shapes were selected at dimensions of 120 mm × 10 mm × 4 mm, whereas
samples for the thermal conductivity tests had the shape of a plate with the following
dimensions: 150 mm × 24 mm.

2.2. Methods
Sample density tests were performed using the hydrostatic weighing method on a
Radwags 22 W hydrostatic scale (Radom, Poland). As part of the mechanical property
tests, static tensile, static bending, and impact tests were conducted. The static tensile test
was performed on a Shimadzu AGS-X testing machine in accordance with the PN-EN
ISO 527-1:2019 standard [26]. The test speed was set to 10 mm/min. The static bending
test was performed on an MTS Criterion Model 43 testing machine (MTS System Corp.,
Eden Prairie, MN, USA), according to the PN-EN ISO 178:2011 standard [27], at a test
speed of 10 mm/min. Impact strength tests were performed using a Charpy hammer
(Zwick/Roell HIT 5.5P.) with a hammer energy of 5 J.
Appl. Sci. 2024, 14, 2534 6 of 19

The impact of the aging factors on the mechanical properties of the composites was
determined. Accelerated aging tests were performed in a QUV ACCELERATED WEATH-
ERING TESTER aging chamber (Q-LAB Corporation, Westlake, OH, USA), using a research
method in which the aging processes of materials are simulated depending on temperature
and humidity. The samples were exposed to elevated temperatures, light radiation, and
moisture to determine their rate of degradation. In this study, the test lasted 336 h (14 d)
and 850 h (35 d), and the thermal cycle included the parameters presented in Table 2. The
samples were then subjected to static tensile tests.

Table 2. Parameters of one thermal cycle.

Function Intensity, W/mw/nm Temperature, ◦ C Time, min

UV radiation 1.55 60 08:00
Cycle
Shower - - 00:15
Condensation - 50 03:45

A thermal conductivity test was performed using an HFM 446 Lambda Eco-Line
(NETZSC, Sleb, Germany) plate apparatus. The test consisted of placing the sample
between two heat sources and examining the sample temperature in several places. Owing
to this test, it is possible to determine the amount of heat absorbed by the sample and the
heat conduction ability of the material.

3. Results and Discussion

3.1. Mechanical Properties
Table 3 shows a comparison of density and flexural properties for all tested materials.
The highest density value was achieved by a composite reinforced with copper particles
with a size of 40–60 nm. A general increase in density can be seen for all materials compared
to the unreinforced material. The density values of the composites with the addition of
copper oxide ranged from 1.26 to 1.30 g/cm3 . The additive content for each was 10%
by weight; therefore, the composites have similar density values, and the differences
that appear in the results were most likely caused by the different shapes of the particles
because particles with a size of 40–60 nm showed a dendritic character, which could result
in a greater ability to create clusters in sample areas. Impact strength tests focus on the
amount of energy needed to dynamically fracture a sample. The higher the impact strength
value, the more energy the material absorbs, and the more plastic cracking occurs. The
highest value was obtained for particles in the range of 10–30 nm. This effect was caused
by the even dispersion of copper in the matrix, thus reducing the possibility of particle
agglomeration, which directly reduces the mechanical properties of the material. For
materials with reinforcements in the range of 40–60 nm, we notice a decrease in impact
strength which may be caused by microcracks in the matrix structure. The decrease
in impact strength is most often associated with the poor adhesion of particles to the
polymer matrix, irregularity in the composite structure, the formation of microcracks, for
example, during the manufacturing process related to matrix shrinkage, and the presence
of inclusions or defects in the form of voids and air bubbles [28,29].
Table 3 also lists the results from the static bending test. An analysis of the results
showed increases in bending strength and the bending modulus for each of the tested
materials. The best bending properties were obtained when copper oxide with a particle
size in the range of 40–60 nm was used. Both bending strength and the bending modulus
increased by over 30% compared to the unmodified material. The remaining composite
materials were also characterized by increased strength properties, but the increases were
slightly smaller. The addition of copper oxide with the smallest grain size resulted in
an increase in bending strength of approximately 25%; however, this material was char-
acterized by the lowest modulus of elasticity compared to the other composites, which
is most likely related to the increased plasticity of the material. Al-Turaif examined the
Appl. Sci. 2024, 14, 2534 7 of 19

influence of TiO2 nanoparticles on the mechanical properties of epoxy resin. The particle
sizes were 17 nm, 50 nm, and 220 nm. The modification of the epoxy resin with a small
percentage of 1% TiO2 particles resulted in a marked increase in bending stresses. As the
particle size decreases, the bending strength increases, and these changes are explained
by the fact that smaller particles have better mechanical properties than larger particles
and adhere better to the matrix [30]. In a study conducted by Ozsoy et al., the impact of
Al2 O3 , TiO2 , and fly ash on the properties of epoxy resin was examined. The researchers
observed a decline in the flexural strength of the composites as the age of the particles at
the nanoscale decreased. This reduction in strength was attributed to the agglomeration of
nanofillers at higher concentrations and the presence of weak adhesion between the filler
and matrix materials at high microfiller contents. The increase in the elastic modulus as
the filler content increased is attributed to the stiffening effect of the fillers on the polymer
composite [31].

Table 3. Results for basic physical and mechanical properties.

Impact Strength, Flexural Strength, Flexural Modulus, Deflection at

Material Density, g/cm3
kJ/m2 MPa MPa Failure, mm
EP 1.157 ± 0.001 8.66 ± 1.32 63.9 ± 0.9 3747 ± 277 2.6 ± 0.1
10% micro Cu 1.265 ± 0.005 14.93 ± 2.11 72.4 ± 4.0 4391 ± 222 2.6 ± 0.1
10% 40–60nmCu 1.301 ± 0.005 12.10 ± 1.51 83.4 ± 9.3 4993 ± 658 2.6 ± 0.7
10% 10–30nmCu 1.267 ± 0.002 16.86 ± 3.82 79.8 ± 3.9 4245 ± 265 3.0 ± 0.1

Research by Nur and others focused on analyzing the impact of recycled copper
particles. Their goal was to investigate how different particle sizes affect mechanical
properties. The particle sizes were 10 µm and 300–400 µm, and the effects of mixing
different particle sizes were studied. The results of the study showed that epoxy composites
with a blend of recycled copper particles had higher flexural modulus values compared
to composites whose filler consisted of recycled copper with a particle size of 10 µm.
Smaller filler particles contributed to the creation of a more compact structure, which
in turn provided the composites with better strength. The presence of particles caused
local changes in the stress field which could partially reduce the effects of cavitation
deformation and instead initiate plastic deformation in the surrounding matrix during
shear. Smaller particles have been shown to be more desirable due to their ability to provide
better bonding; however, particles that are too small may require more polymers, resulting
in reduced flexural strength. On the other hand, particles that are too large can act as
discontinuities, which also reduces flexural strength. Differences between particle size
groups are likely due to differences in packing density. A denser fill leads to less porosity
of the composite, which in turn increases flexural strength. The results suggest that the fine
filler in the mixture filled the gaps between the larger particle sizes, which contributed to
the increased stiffness of the composites. The use of two different particle sizes allowed
for a more even distribution of particle sizes, which in turn reduced agglomeration and
increased the composite’s resistance to cracking [32].
The presented test results and examples of other results available in the literature
confirm the influence of particle size on bending properties while also showing that this
influence is not clear and depends on many factors. The research results confirm the need to
conduct this type of research due to gaps in the science related to the influence of particles
on the properties being tested.
A study conducted by Sharma et al. focused on the impact of food waste particle
size on epoxy resin properties. The filler content was fixed at 15% by weight, and the
particle size was varied, namely, (i) 100–250 mm, (ii) 350–500 mm, and (iii) 650–800 mm.
The researchers investigated the effect of particle size on the impact strength of epoxy resin.
It was observed that as the particle size decreased, the impact strength increased, indicating
Appl. Sci. 2024, 14, 2534 8 of 19

better energy absorption during dynamic impact. Three potential reasons were proposed to
explain this outcome: improved compatibility of the fine fillers with epoxy resin, reduced
void content, and the finding that smaller particles do not readily detach from the matrix
compared to larger particles [33].
The test results from the static tensile test are presented in Figures 1 and 2. Strength
tests have shown that the introduction of copper particles has a beneficial effect on strength
properties. As the particle size of the introduced additive decreased, an increasing tendency
in strength properties was noticed. The best parameters were obtained for the material
modified with copper oxide particles with sizes ranging from 10–30 nm. An increase in
tensile strength by approximately 30% compared to the base material, a several percent
increase in the elastic modulus, and an almost 40% increase in strain at break were observed.
The use of larger copper oxide particles (40–60 nm) causes slight changes in tensile strength
while increasing the elastic modulus. Adhesion forces between components are largely
responsible for the strengthening effect in polymer composites. Adhesion is caused by
forces occurring at the reinforcement/matrix interface. These forces result from the chem-
ical structure of the matrix and the composite reinforcement in the form of Cu particles.
Chemical actions can also occur due to the similarity of functional groups. Adhesion
additionally depends on the degree of wetting, the magnitude of friction forces at the phase
boundary, the direction of shrinkage stress, the compactness and geometry of the filler,
as well as defects in the form of voids and air bubbles [34,35]. The results show that the
composite with the smallest particle size has the best properties, which is probably related
to the greater number of contact points at the particle–matrix interface. However, the
introduction of larger particles with a dendritic structure resulted in decreases in strength
Appl. Sci. 2024, 14, 2534 9 of 21
and plastic properties, which may be related to the formation of agglomerations and defects
in the form of voids, which weakened the composite material.

70.0 6000

60.0 5000
50.0
4000
σM, MPa

E, Mpa
40.0
3000
30.0
2000
20.0

10.0 1000

0.0 0

Figure1.
Figure 1. Comparison
Comparison of
of tensile
tensile strength
strengthand
andYoung’s
Young’smodulus.
modulus.

Nourbakhsh et al. studied the effect of the particle size of 30% wood flour in a
3.5
polypropylene-based composite. The test results showed that in the case of smaller particles
3.0 0.25 mm), there was a moderate increase in strength, and the particle size had
(0.30 and
a moderate
2.5 impact on the elastic modulus of the composites. In this work, the authors
also cite the results of other studies that confirm the positive effect of wood flour on the
2.0
properties of polymer composites with decreasing particle size, giving possible reasons for
ε, %

this type
1.5 of behavior. The increase in strength is attributed to better interfacial adhesion
between the matrix and the particles, along with other factors influencing properties such
1.0
as the particle size and size distribution of the wood, the aspect ratio and abrasion during
0.5 the adhesion of fibers to the matrix, the transfer of stresses at the interface, and
processing,
0.0
EP 10%microCu 10%40–60nmCu 10%10–30nmCu

Figure 2. Comparison of strain at break values.

 Appl. Sci. 2024, 14, 2534 9 of 21
Appl. Sci. 2024, 14, 2534 9 of 19

70.0 6000
temperatures mixing [36]. Sharma et al. reached similar conclusions. They investigated
the influence
60.0 of the size of food waste particles on the properties of epoxy resin. The filler
5000
content was 15% by weight. The particle size was (i) (100–250) mm, (ii) (350–500) mm,
50.0
and (iii) (650–800) mm. The tests showed a decrease in mechanical properties 4000 with an

σM, MPa

E, Mpa
increase40.0
in particle size. These results were explained by the fact that larger particles detach
more easily than small particles. This debonding results in more voids,3000 which ultimately
30.0
reduces the stiffness of the composites [33]. In turn, Ozsoy and others pointed out other
2000
potential20.0problems related to the introduction of micro- and nanoscale additives. They
examined the influence of Al2 O3 , TiO2 , and fly ash on the properties of1000 epoxy resin. The
10.0
filler content ranged from 10 to 30 wt%, and the particle sizes were 10 nm and 40 nm and
45 and 50 0
0.0µm. The results clearly show that the tensile strength of microfiller composites
decreases with increasing filler content. This can be explained by the fact that increasing
the filler content caused poor adhesion between the matrix and the fillers and led to a
decrease in the strength of the epoxy composite. In the case of the nanofiller, the decrease
in strength was due to the uneven distribution of fillers at high filler proportions, which
led to agglomeration and caused areas of stress concentration, which led to some decrease
in strength
Figure [31].
1. Comparison of tensile strength and Young’s modulus.

3.5
3.0
2.5
2.0
ε, %

1.5
1.0
0.5
0.0
EP 10%microCu 10%40–60nmCu 10%10–30nmCu

Figure2.2.Comparison
Figure Comparisonof
ofstrain
strainat
atbreak
breakvalues.
values.

Fu and others presented

Nourbakhsh in their
et al. studied thework
effecta summary of various
of the particle sizestudies
of 30%onwood polymerflourmatrix
in a
composites modified with
polypropylene-based particles The
composite. of different sizes. showed
test results Conclusions thatcan
in bethedrawn from
case of their
smaller
work.
particles In (0.30
summary,
and 0.25 there
mm),appears
theretowasbe aamoderate
certain critical particle
increase size beyond
in strength, and thewhich no
particle
significant
size had a effect on the
moderate modulus
impact on theof the composite
elastic modulus is ofobserved. When the
the composites. In particle
this work,sizethe
is
smaller than this critical value, the particles’ effect on the modulus of the
authors also cite the results of other studies that confirm the positive effect of wood flour composite becomes
more
on the significant.
properties However, the precise
of polymer value of
composites this decreasing
with critical particle size cannot
particle be predicted
size, giving in
possible
advance because it depends on various factors such as the properties of the
reasons for this type of behavior. The increase in strength is attributed to better interfacial particle, the matrix,
and their mutual
adhesion between adhesion.
the matrix Thisand
work thepresents a comprehensive
particles, along with other review of experimental
factors influencing
results and theories
properties such as regarding
the particlethesize
mechanical
and sizeproperties,
distribution including the modulus,
of the wood, the aspectstrength,
ratio and
and
fracture toughness, of micro- and nanocomposites containing polymer-based
abrasion during processing, the adhesion of fibers to the matrix, the transfer of stresses at particles. The
influence
the interface,of particle size, particle adhesion
and temperatures to the
mixing [36]. matrix,etand
Sharma al. particle
reachedloading
similaron composite
conclusions.
stiffness, strength, and crack resistance was analyzed in detail, examining
They investigated the influence of the size of food waste particles on the properties a wide range of of
composites that contain both micro- and nanofillers of various shapes.
epoxy resin. The filler content was 15% by weight. The particle size was (i) (100–250) It has been shown
mm,
that all three factors
(ii) (350–500) mm, and mentioned have a significant
(iii) (650–800) mm. The impact on the strength
tests showed a decrease andinresistance
mechanical of
the composite, especially the adhesion of particles to the matrix. This is expected because the
properties with an increase in particle size. These results were explained by the fact that
effective stress transfer between the filler and matrix and strength/brittleness are strongly
larger particles detach more easily than small particles. This debonding results in more
related to adhesion. Various trends in the influence of particle loading on the strength and
voids, which ultimately reduces the stiffness of the composites [33]. In turn, Ozsoy and
resistance of the composite were observed which result from complex interactions between
others pointed out other potential problems related to the introduction of micro- and
the factors studied. However, the stiffness of the composite depends largely on particle
nanoscale additives. They examined the influence of Al2O3, TiO2, and fly ash on the
loading and not only on particle–matrix adhesion because fillers usually have a much higher
properties of epoxy resin. The filler content ranged from 10 to 30 wt%, and the particle
modulus of elasticity than the matrix. There is also a critical particle size value, usually on the
sizes were 10 nm and 40 nm and 45 and 50 µm. The results clearly show that the tensile
Appl. Sci. 2024, 14, 2534 10 of 19

nanometer scale, below which the stiffness of the composite increases significantly, probably
due to the increased surface influence of “nano” effects [37].

3.2. Mechanical Modeling

Particle size, particle–matrix adhesion, and particle loading stand out as important
determinants in understanding the behavior of a composite material. Several parameters are
intricately linked to determine strength and mechanical characteristics such that the quality
of particle adhesion to the matrix has a major effect on a composite’s strength and toughness.
It is observable that when particle sizes are in the micron or greater range, the Young’s
modulus values of composites are insensitive to their size. On the other hand, as particle
sizes approach the nanoscale, a notable increase in stiffness is shown [38]. It was shown
that micro-fibrils with sizes between 10 and 30 nm have been seen to influence interphase
boundaries more significantly than those in bulk. The composite modulus is expected
to increase with decreasing particle size, with a critical particle size of 30 nm [37]. It is
generally known that the smaller the dispersed phase, the greater its specific surface area,
resulting in shorter distances within the vicinity of the dispersed phase when the volume
fraction of the dispersed phase remains the same. This also means that the mechanical
responses of a thin layer placed between the stiff dispersed phase and the matrix would
differ from those of the dispersed phase.
In this study, the effect of particle size on the Young’s modulus of polymer composites
is shown. To describe this effect, a three-phase Takayanagi model [39] was used which
provides better insight into the intricate interaction of various components. The averaged
Young modulus of composite Ec was calculated by following formula:
√
q q
3
1 1 − [(r + τ )/r ] ϕ [(r + τ )/r ]3 ϕ − ϕ
= + 
Ec Em
q q
1 − [(r + τ )/r ]3 ϕ Em + [(r + τ )/r ]3 ϕ(κ − 1) Em / ln κ
√ (1)
ϕ
+
√ √
q  q 
1 − [(r + τ )/r ]3 ϕ Em + [(r + τ )/r ]3 ϕ − ϕ (κ + 1) Em /2 + ϕEr

where Em , Er are, respectively, the Young’s modulus values of the matrix and reinforcement,
r is the radius of a spherical particle, τ is the thickness of the interfacial region, and κ
denotes a linear gradient change in the modulus between the matrix and the particle
surface, indicating the modulus ratio of the adjacent interface to the particle surface. In
Equation (1), the term ϕ denotes the volume fraction of the second phase instead of the
mass proportion wt. Thus, this fraction should be calculated using the following equation:

1
ϕ=   (2)
ρf 1
1+ −1
ρm wt

where ρf and ρm represent, respectively, the density of the reinforcing phase and the
matrix density.
Additionally, the Voigt and Reuss models were used as theoretical frameworks for
comparisons with experimental data, aiming to understand the elastic properties of a
composite with different particle sizes. The Voigt model [40], based on an assumption
of uniform strain, provided an upper bound estimate of the stiffness of the material by
averaging the stiffness tensors.
k
V
E = ∑ ϕi Ei (3)
j =0

where ϕi is the volume fraction of i-th phase, labelled i = 0, . . . , k. Conversely, the Reuss
model [41], which assumes uniform stress, provides a lower bound.
 composite with different particle sizes. The Voigt model [40], based on an assumption of
uniform strain, provided an upper bound estimate of the stiffness of the material by
averaging the stiffness tensors.

𝐸 ∑𝜙𝐸 (3)
Appl. Sci. 2024, 14, 2534 11 of 19

where 𝜙 is the volume fraction of 𝑖 -th phase, labelled 𝑖 0, … , 𝑘 . Conversely, the

Reuss model [41], which assumes uniform stress, provides a lower bound.
" # −1
k   −1
𝐸 R∑𝜙 𝐸 (4)
E = ∑ ϕ Ei i
(4)
j =0
The calculations were based on the properties described in this paper with an
The
exception in calculations
which 70.5 GPa were based
was takenonasthe
theproperties
copper oxidedescribed
stiffnessinbased
this paper
on thewith
workan ofexception in
which 70.5
Lehmann et al.GPa
[42].was
Thetaken as of
density theCuO
copper wasoxide stiffness
6.31 g/cm 3. Thebased
valueon
of the work
volume offraction
Lehmann et al. [42].
obtained for theofadopted
The density CuO was data
6.31was
g/cm 3 . The
0.02. Thevalue
valuesofof
thestiffness
volumefor nanoscale
fraction particles
obtained for the adopted
inside
datathe
wasarea
0.02.were described
The values by theoretical
of stiffness models particles
for nanoscale (Figure 3a).
insideHowever,
the areafor
werethedescribed by
composite in which larger particles were used, a lower Young’s modulus value
theoretical models (Figure 3a). However, for the composite in which larger particles were used,was
characterized than inmodulus
a lower Young’s the presented
valueestimations.
was characterized than in the presented estimations.

(a) (b)

Figure 3. Comparison of experimental results for different particle sizes with theoretical evaluations
using the Voigt and Reuss models (a) and estimations of the composite Young’s modulus based on
Equation (1), where κ = 4 (b).

It is important to note that the Voigt and Reuss models are generally used to estimate
the bounds of the elastic properties of bulk materials. They do not take into account the
influence of particle size or other microstructural characteristics that can significantly affect
the mechanical properties of materials. Their role was to provide theoretical boundaries
for the elastic moduli of the materials. The deviations observed in the experimental data,
related to changes in particle size, highlight the limitations of these models in capturing the
effects of microstructural variations.
Analytical estimations using the Takayanagi model exhibited higher stiffness values
than the experimental data (Figure 3b). The increase in the thickness of the interfacial
region results in stiffer behavior of the material. However, in the micro-size range, this
effect is negligible. The level of the approximated Young modulus is close to results of the
Voigt model but, as previously mentioned, this simple model does not consider the size of
the reinforcement particles. This is the reason why the Voigt and Reuss models cannot be
directly compared with the Takayanagi model. Nevertheless, the three-phase model does
not accurately describe the empirical data, which leads to the conclusion that it requires
further development.

3.3. Microscopic Observations

As part of this work, an analysis of the microstructure of the base material and the
produced composites was carried out. Figure 4a,b show the structure of epoxy resin.
This material is characterized by typical brittle fractures. Figure 4c–h present microscopic
photographs of both the copper oxides used and the composites modified with them. The
copper oxides with particle sizes of 1–10 µm and 10–30 nm show similar types of fine-
grained particles which are characterized by a whisker-like structure, while the copper
oxide particles with a size of 40–60 nm are characterized by a more developed, dendritic
structure. An analysis of the photographs of the microstructures of the produced composites
showed that composites with copper with particle sizes of both 1–10 µm and 40–60 nm
are brittle, while the use of copper oxide with a particle size of 10–30 nm changes the
 material is characterized by typical brittle fractures. Figure 4c–h present microscopic
photographs of both the copper oxides used and the composites modified with them. The
copper oxides with particle sizes of 1–10 µm and 10–30 nm show similar types of fine-
grained particles which are characterized by a whisker-like structure, while the copper
oxide particles with a size of 40–60 nm are characterized by a more developed, dendritic
Appl. Sci. 2024, 14, 2534 structure. An analysis of the photographs of the microstructures of the12produced of 19
composites showed that composites with copper with particle sizes of both 1–10 µm and
40–60 nm are brittle, while the use of copper oxide with a particle size of 10–30 nm changes
the nature of the matrix to a more developed one, which suggests some plasticization of
nature of the matrix to a more developed one, which suggests some plasticization of the
the material. Additionally, strength tests seem to confirm this effect because the materials
material. Additionally, strength tests seem to confirm this effect because the materials were
were characterized by the highest deformation at break and the highest impact strength
characterized byvalue.
the highest deformation at break and the highest impact strength value.

Appl. Sci. 2024, 14, 2534 13 of 21

(a) (b)

(c) (d)

(e) (f)

(g) (h)

Figure 4. StructureFigure 4. Structure

of copper oxide of powders
copper oxide
andpowders and manufactured
manufactured composites.composites. (a) Structure
(a) Structure of epoxy
of epoxy
resin fracture. (b) Structure of fracture structure of epoxy resin. (c) Structure of copper particles with
resin fracture. (b)aStructure of fracture structure of epoxy resin. (c) Structure of copper particles with
size of 1–10 µm. (d) Fracture structure of resin composite reinforced with copper particles with a
size of 1–10 µm. (e) Structure of copper particles with a size of 40–60 nm. (f) Fracture structure of
resin composite reinforced with copper particles with a size of 40–60 nm. (g) Structure of copper
particles with a size of 10–30 nm. (h) Fracture structure of resin composite reinforced with copper
particles with a size of 10–30 nm.

3.4. Accelerated Aging

Appl. Sci. 2024, 14, 2534 13 of 19

a size of 1–10 µm. (d) Fracture structure of resin composite reinforced with copper particles with a
size of 1–10 µm. (e) Structure of copper particles with a size of 40–60 nm. (f) Fracture structure of
resin composite reinforced with copper particles with a size of 40–60 nm. (g) Structure of copper
particles with a size of 10–30 nm. (h) Fracture structure of resin composite reinforced with copper
particles with a size of 10–30 nm.

3.4. Accelerated Aging

The manufactured materials were also subjected to accelerated aging tests. Aging
is a picture of all the irreversible physical and chemical changes occurring in a material
at a specific time. The tested conditions were temperature, chemical compounds, and
mechanical loads. When all these parameters are known, it is worth increasing one factor
to speed up the test.
We mention two types of aging: internal and external. The internal aging of polymer
materials is the result of thermodynamic instability, which manifests itself through recrys-
tallization, the relaxation of residual stresses, the dispersion of phases in multi-component
systems, and the migration of plasticizers. On the other hand, external aging refers to
processes such as thermo-oxidative degradation, the formation of stress and fatigue cracks,
and swelling, which are directly related to environmental chemical or physical impacts on
plastic. Aging is also divided into physical and chemical aging, but a given environmental
factor can cause both effects at the same time, which significantly complicates the clear
affiliation to a given group, e.g., increased temperature can cause both physical (secondary
crystallization) and chemical (chain breakdown) effects. Changes in structure, secondary
crystallization, and disorientation or the relaxation of residual stresses are physical phe-
nomena typical of aging processes. Physical aging phenomena may occur during the
evaporation or migration of volatile components or with mass increases through water
absorption or swelling. However, the chemical structure is most often changed under
the influence of chemical effects such as the impact of heat in combination with oxygen
or other aggressive substances or radiation, with a strong emphasis on solar UV radia-
tion. Increased temperature and, consequently, heat absorbed by the material, can initiate
cross-linking, which changes the properties of the material while improving its thermal,
mechanical, and physical properties. In the medium term, however, this may contribute
to the degradation of the chains and the formation of cross-linking, which has a negative
impact on the material. Oxygen has the ability to attach to other polymer chains, resulting
in the formation of thermally unstable hydroxides, causing chain breakage. Ozone and
radiation support oxidation, which accelerates the breakdown of chains. UV radiation
causes the material to crumble, and in the case of condensation polymers, water combined
with heat leads to the hydrolysis of the material; an example is polyamide. Four types of
chemical degradation can be distinguished: (1) depolymerization, (2) chain breakdown,
(3) thermo-oxidation, and (4) radiation. The first one involves the formation of monomers,
while the second one can occur at any point in the chain. The last two types are related to
cross-linking reactions and the detachment of substituents and their elimination. The type
of degradation and the degree of changes during aging depend on the chemical structure
of the material, the environmental conditions, wall thickness, and the test sample. The
sample’s electrical, mechanical, and thermal properties are changed under the influence
of the test. In addition, surface changes are noticeable, such as a change in the color of
crystallinity or structure [43,44]. Figures 5–7 show test results from before and after the ag-
ing process. The applied aging conditions resulted in a significant decrease in the strength
properties of the unmodified material. The introduction of copper oxide particles resulted
in an increase in the stability of the tested materials, both in tensile strength and Young’s
modulus. The strain at break decreased with an increase in the accelerated thermal aging
time for all materials, but in this case, copper particles also limited the negative impact
of the external environment on the tested materials. The best results were achieved by
materials modified with copper nanoparticles. In their research, Abenojar and colleagues
 Appl. Sci. 2024, 14, 2534 14 of 19

investigated the impact of temperature, humidity, and their combined effect on the ther-
mal and mechanical properties of epoxy micro- and nanocomposites containing SiC. The
study results indicated that under the aging conditions analyzed, water absorption and
desorption exhibited a close correlation with the mechanical properties and the softening
transition temperature (Tg) of the material. Specifically, water absorption led to the plas-
ticization of the material, which in turn reduced its strength and Tg. Conversely, water
Appl. Sci. 2024, 14, 2534 desorption resulted in increased brittleness and cross-linking in the material, leading 15 to of 21
Appl. Sci. 2024, 14, 2534 15 of 21
increased strength and Tg. Moreover, an increase in temperature favored the cross-linking
process of the material, contributing to improvements in the mechanical properties of the
polymer composite and an increase in Tg. Interestingly, the size of SiC particle showed
significant
no significant
significant effect on
effecton
effect property
onproperty trends, although
property trends, althoughallall
although allmajor
major
major changes
changes
changes werewere observed
observed
were observed for
for for
nanocomposites
nanocomposites compared
nanocompositescompared
compared to microcomposites
to microcomposites
to microcomposites [45].
[45]. It [45]. It
seemsItthatseems that
in thethat
seems in
presented the
in the presented
research
presented
research
results, results,
changing changing
cycles of cycles
moisture of
and moisture
temperature and temperature
caused an caused
increase
research results, changing cycles of moisture and temperature caused an increase in an
strengthincrease
after in in
strength
the
strength after
accelerated the
after the accelerated
thermal
accelerated thermal
aging process,
thermal aging
but process,
the influence
aging process,of but the
other
but influence
the factors
influencesuchof
ofasother factors
particle
other such
sizesuch
factors
as
and particle
shape size
shouldand
alsoshape
be should
taken into also be
account.taken
Aging into account.
changes can Aging
be
as particle size and shape should also be taken into account. Aging changes can be seenchanges
with thecan be seen
naked seen
with
eye; the naked
Figure eye;
8 shows Figure 8
macroscopicshows macroscopic
surface surface
changes observed changes
with anobserved with an
optical microscope.
with the naked eye; Figure 8 shows macroscopic surface changes observed with an optical optical
The samples were
microscope. The additionally
samples were
werecharacterized
additionallyby characterized
a change in color by and a cracked surface
microscope. The samples additionally characterized by aa change
change in color
in color and aa
and
through which copper oxide particles were visible.
cracked surface through which copper oxide particles were visible.
cracked surface through which copper oxide particles were visible.

70.0
70.0
60.0
60.0
50.0
MPa

50.0
σM,MPa

40.0
40.0
30.0
30.0
σM,

20.0
20.0
10.0
10.0
0.0
0.0
conditioned

conditioned

conditioned

conditioned
days

days

days

days

days

days

days

days
conditioned

conditioned

conditioned

conditioned
aged1515days

aged3535days

aged1515days

aged3535days

aged1515days

aged3535days

aged1515days

aged3535days
aged

aged

aged

aged

aged

aged

aged

aged
EP 10%microCu 10%40–60nmCu 10%10–30nmCu
EP 10%microCu 10%40–60nmCu 10%10–30nmCu

Figure5.5. Comparison
Figure Comparisonofoftensile
tensilestrength
strength values
values before
before andand
afterafter
the the accelerated
accelerated thermal
thermal agingaging
Figure 5. Comparison of tensile strength values before and after the accelerated thermal aging
process.
process.
process.

7000
7000
6000
6000
5000
5000
MPa
E,E,MPa

4000
4000
3000
3000
2000
2000
1000
1000
0
0
conditioned

conditioned

conditioned

conditioned
days

days

days

days

days

days

days

days
conditioned

conditioned

conditioned

conditioned
aged1515days

aged3535days

aged1515days

aged3535days

aged1515days

aged3535days

aged1515days

aged3535days
aged

aged

aged

aged

aged

aged

aged

aged

EP 10%microCu 10%40–60nmCu 10%10–30nmCu

EP 10%microCu 10%40–60nmCu 10%10–30nmCu

Figure 6. Comparison of Young’s modulus values before and after the accelerated thermal aging
Figure6.6.Comparison
Figure ComparisonofofYoung’s
Young’s modulus
modulus values
values before
before andand
afterafter the accelerated
the accelerated thermal
thermal agingaging
process.
process.
process.
Appl. Sci.
Appl.Sci.
Appl. 2024,
Sci.2024, 14, 2534
14,2534
2024,14, 16
19 of 21
1615ofof21

3.53.5
3.03.0
2.52.5
2.02.0

ε, %
ε, %
1.51.5
1.01.0
0.50.5
0.00.0

conditioned

conditioned

conditioned

conditioned
aged 15 days

aged 35 days

aged 15 days

aged 35 days

aged 15 days

aged 35 days

aged 15 days

days
conditioned

conditioned

conditioned

conditioned
aged 15 days

aged 35 days

aged 15 days

aged 35 days

aged 15 days

aged 35 days

aged1535days

aged 35 days
aged
EP 10%microCu 10%40–60nmCu 10%10–30nmCu
EP 10%microCu 10%40–60nmCu 10%10–30nmCu
Figure 7. Comparison of strain at break values before and after the accelerated thermal aging
Figure7.7.Comparison
Figure
process. Comparison of strain
of strain at break
at break values values before
before and afterand after the accelerated
the accelerated thermal
thermal aging process.aging
process.

(a) EP (epoxy resin). (b) 10%microCu.

(a) EP (epoxy resin). (b) 10%microCu.

(c) 10%40–60nmCu. (d) 10%10–30nmCu.

Figure
Figure8.8.Macroscopic
Macroscopicphotos
photosofofsample
samplesurfaces
surfacesafter
afterthe
theaccelerated
acceleratedthermal
thermalaging
agingprocess.
process.
(c) 10%40–60nmCu. (d) 10%10–30nmCu.
3.5.Thermal
3.5. ThermalConductivity
Conductivity
Figure 8. Macroscopic photos of sample surfaces after the accelerated thermal aging process.
Analyzing Table 4 and
Analyzing Table 4 andFigure
Figure9, 9,
it can be seen
it can that that
be seen the addition of copper
the addition in the amount
of copper in the
of 10%
3.5.
amount by
of weight
Thermal 10% byhas
Conductivitya positive
weight has aeffect on thermal
positive conductivity.
effect on The greatest increase
thermal conductivity. is no-
The greatest
ticeable
increase for particles
is noticeable with a size of
for 4particles 40–60 nm.
with a9,size Taking into
of 40–60 account
nm.that
Taking the given graphs, it can be
Analyzing Table and Figure it can be seen theinto account
addition of the given
copper in the
concluded that the increase is caused by the natural conductive properties of copper which,
graphs,
amount it ofcan10%be by concluded
weight that athe
has increase
positive is caused
effect on by the
thermal natural conductive
conductivity. The greatest
after reaching a given value, creates percolation paths, enabling thermal flow. The smaller
properties
increase isofnoticeable
copper which, after reaching a given value, creates
Takingpercolation paths,
the particles, the higherfor theparticles with a size
thermal conductivity of 40–60
value nm.
until it reaches ainto account
critical value;the
forgiven
enabling
graphs, thermal
it can flow. The smaller
beinconcluded the particles, the higher the thermal conductivity value
Cu particles, this is the range ofthat10–30thenm.increase is caused
The decrease in thermalby conductivity
the natural may conductive
be
until it reaches
properties acopper
critical which,
value; for Cureaching
particles, athis is invalue,
the range of 10–30 nm. Thepaths,
caused by anof insufficient after
distribution given
of copper particles creates
and, consequently, percolation
the creation of
decrease in thermal conductivity may be caused by an insufficient distribution of copper
enabling thermal
significant flow. The
spaces, which smaller
prevent the particles,
the creation the higher the
of uninterrupted thermal conductivity
conductive paths. value
until it reaches a critical value; for Cu particles, this is in the range of 10–30 nm. The
decrease in thermal conductivity may be caused by an insufficient distribution of copper
 particles and, consequently, the creation of significant spaces, which prevent the creation
Appl. Sci. 2024, 14, 2534 of uninterrupted conductive paths. 16 of 19

Table 4. Thermal conductivity results.

Table 4. Thermal conductivity results.
10%40– 10%10–
Parameter EP 10%MikroCu
Parameter EP 10% MikroCu 10% 40–60nmCu 60nmCu
10% 10–30nmCu 30nmCu
Thermal conductivity, 0.24741 ± 0.25824 ± ± 0.0080.25238 ±
Thermal conductivity, W/(m·K) 0.21717 ± 0.007 0.24741
0.21717 ± 0.007 0.25824 ± 0.008
± 0.007 0.25238
W/(m·K) 0.007 0.008 0.008
Average temperature, K 10.5 ± 0.03 10.6 ± 0.03 10.7 ± 0.03 10.7 ± 0.03
Average temperature, K 10.5 ± 0.03 10.6 ± 0.03 10.7 ± 0.03 10.7 ± 0.03
Percentage change, % 13.92 ± 0.42 18.91 ± 0.57 16.21 ± 0.49
Percentage change, % 13.92 ± 0.42 18.91 ± 0.57 16.21 ± 0.49

25.00
Percentage change, %

20.00

15.00

10.00

5.00

0.00
10%mikroCu 10%40–60nmCu 10%10–30nmCu

Figure9.9. Percentage
Figure Percentageincrease
increase in in thermal
thermal conductivity
conductivity compared
compared to thetoinitial
the initial
value value of thermal
of thermal
conductivityofofthe
conductivity the epoxy
epoxy resin.
resin.

Composites
Compositesreinforced
reinforced with copper
with copperparticles are good
particles conductors
are good conductorsof electricity and and
of electricity
heat; this is possible thanks to a phenomenon called percolation. In order for
heat; this is possible thanks to a phenomenon called percolation. In order for a composite a composite
to become a conductor throughout the entire material, it is necessary to form continuous
to become a conductor throughout the entire material, it is necessary to form continuous
conductive paths. Thanks to the formation of a conductive network, it is possible to observe
conductive paths. Thanks to the formation of a conductive network, it is possible to
the free flow of electrons through the connected paths, which guarantees an increase in
observe the free flow of electrons through the connected paths, which guarantees an
thermal and electrical conductivity. A percolation barrier describes the minimum concen-
increase
tration in thermal and
of reinforcement electrical
particles neededconductivity.
to form conductiveA percolation barrier
beams. If a given valuedescribes
is not the
minimum concentration of reinforcement particles needed to form conductive
achieved, the particles are randomly distributed in the material, which causes disturbances beams. If a
given
in value is reducing
the network, not achieved, theofparticles
the flow areThis
electrons. randomly distributed
phenomenon in when
is crucial the material,
forming which
causes disturbances
composites reinforced in thecopper
with network, reducing
particles the thanks
because, flow oftoelectrons. This phenomenon
the appropriate selection is
crucial when forming composites reinforced with copper particles because, thanks to the
of concentration, we can achieve the desired conductivity. Moreover, the phenomenon
of network formation
appropriate selectioncanofbe concentration,
improved using we surface
cantreatment
achieve techniques
the desired to improve
conductivity.
dispersion
Moreover,and thereduce particle agglomeration
phenomenon of network in the composite
formation can matrix [39]. Misiura
be improved using andsurface
colleagues investigated the mechanical properties as well as the electrical
treatment techniques to improve dispersion and reduce particle agglomeration in the and thermal
conductivity of epoxy composites modified with copper and nickel. It was found that the
composite matrix [39]. Misiura and colleagues investigated the mechanical properties as
electrical conductivity of the composites exhibited percolation behavior at specific threshold
well as the electrical and thermal conductivity of epoxy composites modified with copper
values of 9.9% and 4.0% vol% for EP-Cu and EP-Ni composites, respectively. Using the
and nickel. It was found that the electrical conductivity of the composites exhibited
Lichtenecker model, the theoretical thermal conductivity of the dispersed metallic phase
percolation
in the compositesbehavior at specifictothreshold
was estimated be 35 W/mK values
for of
Cu9.9%
powderandand 4.0% 13vol%
W/mK forforEP-Cu
Ni and
EP-Ni composites,
powder. The findings respectively. Usingand
of the theoretical theexperimental
Lichteneckerstudies
model,overlapped.
the theoretical Unlikethermal
electrical conductivity, thermal conductivity did not exhibit percolation properties. These be 35
conductivity of the dispersed metallic phase in the composites was estimated to
W/mKare
values fornearly
Cu powder
an orderand of13 W/mK for
magnitude Ni powder.
lower than the The findings
thermal of the theoretical
conductivity of solid and
metals. This phenomenon
experimental can be attributed
studies overlapped. Unlike to the presence
electrical of high thermal
conductivity, thermal resistances at did
conductivity
the particle-to-particle and particle–polymer interfaces which impede heat
not exhibit percolation properties. These values are nearly an order of magnitude lower transfer in the
metal-filled polymer
than the thermal matrix [46]. of solid metals. This phenomenon can be attributed to the
conductivity
presence of high thermal resistances at the particle-to-particle and particle–polymer
interfaces which impede heat transfer in the metal-filled polymer matrix [46].
Appl. Sci. 2024, 14, 2534 17 of 19

4. Conclusions
Summing up the obtained test results, a positive effect of using copper particles
as reinforcements in the context of strength parameters was noticed. An increase in
mechanical properties was observed in relation to the control sample of a pure polymer
for all tested composites. In addition, an upward trend in parameters was observed with
reductions in individual particle sizes. The best strength parameters were achieved for
composites reinforced with particles in the size range of 10–30 nm. For these materials,
the best results in the static tensile test were recorded, which is consistent with the
theory in the literature on the dependence of strength on adhesion forces and a larger
contact surface between the matrix and the reinforcement. In addition, it was noted
that larger particles cause agglomeration, which adversely affects strength properties.
In the flexural strength tests, the composite modified with particles in the 40–60 nm
range had the best strength. This is related to the examined structure of copper particles
which, due to their developed dendritic surfaces, showed greater plastic properties.
Thus, it can be concluded that the strength parameters depend not only on the size of
the particles but also on their structural nature. Composites reinforced with copper
oxide do not degrade under the influence of environmental conditions in the short term.
Ultimately, the copper particles improve the thermal conductivity of the composite
relative to the reference material. An increase of more than 18% was obtained for the
material modified with particles in the 40–60 nm range, and a 16% increase was obtained
for the material reinforced with particles in the 10–30 nm range, which means that
reducing the particle diameter has a positive effect on thermal conductivity; however,
it occurs at a certain critical value, blocking the formation of a continuous percolating
network. The novelty of the field of copper–epoxy composites has been addressed
in various studies. Xu et al. [47] introduced a foamed copper–epoxy composite that
showed improved wear resistance, making it a unique material for abrasion-resistance
applications. Nur and colleagues [32] also observed flexural strength and modulus im-
provements by incorporating mixed copper particles into epoxy composites, highlighting
the potential for innovative material improvements. Mykhalichko and Lavrenyuk inves-
tigated using copper(II) hexafluorosilicate-modified epoxy–amine composites for flame
protection, which showed progress in increasing thermal stability through chemical
interactions [48]. Biswas et al.’s study on adding copper slag filler to bamboo–epoxy
composites showed improved physical and mechanical properties, suggesting the inno-
vative development of composite materials [49]. Lavrenyuk and colleagues developed
self-extinguishing copper(II)-coordinated epoxy–amine composites for pouring poly-
mer floors, demonstrating progress in creating materials with improved properties [50].
Honda et al. demonstrated a strengthening of the epoxy–copper heterojunction by
incorporating sulfur-containing polymers, suggesting new approaches to improving
material interfaces [51].
In summary, the research results presented, the discussion in this article, and the
examples illustrated above highlight the need for the further development of epoxy
composites modified with copper and copper oxides. These comparisons indicate the
continuing need for research in this field and the need to create new copper–epoxy
composites that can be used in various areas, ranging from wear-resistant materials and
flame protection to composites with improved mechanical and thermal properties. The
research studies mentioned above jointly contribute to the development of materials
engineering by introducing innovative recipes and applications of copper–epoxy com-
posites. Epoxy composites reinforced with copper particles can be widely used in the
electronics industry and in control and conductive devices manufactured for transport
and maneuvering machines; however, in to further develop work on a given material, its
compatibility with other types of reinforcements should be checked.
Appl. Sci. 2024, 14, 2534 18 of 19

Author Contributions: Conceptualization, P.B.; methodology, P.B. and P.N.; validation, P.B., P.N.
and M.Ł.; formal analysis, P.B. and M.G.; investigation, P.B., A.B., K.S. and P.N.; data curation, P.B.;
writing—original draft preparation, P.B.; writing—review and editing, P.B. and P.N.; visualization,
P.B.; supervision, M.Ł.; All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author. The data are not publicly available due to privacy.
Conflicts of Interest: The authors declare no conflicts of interest.

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