materials

Article
Optimization of Tensile Strength and Young’s Modulus of
CNT–CF/Epoxy Composites Using Response Surface
Methodology (RSM)
Md. Rezaur Rahman 1, *, Nur-Azzah Afifah Binti Taib 1 , Mohammed Mahbubul Matin 2 ,
Mohammed Muzibur Rahman 3 , Muhammad Khusairy Bin Bakri 1,4 , Taranenko Pavel Alexanrovich 5 ,
Sinitsin Vladimir Vladimirovich 6 , Khairuddin Sanaullah 1 , Diana Tazeddinova 7 and Afrasyab Khan 5, *

1 Faculty of Engineering, Universiti Malaysia Sarawak, Jalan Datuk Mohammad Musa,

Kota Samarahan 94300, Sarawak, Malaysia
2 Department of Chemistry, University of Chittagong, Chittagong 4331, Bangladesh
3 Department of Chemistry, Center of Excellence for Advanced Materials Research (CEAMR),
Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia
4 Composite Materials and Engineering Center, Washington State University, 2001 East Grimes Way,
Pullman, WA 99143, USA
5 Research Institute of Mechanical Engineering, South Ural State University, 454080 Chelyabinsk, Russia
6 Research Laboratory of Technical Self-Diagnostics and Self-Control of Devices and Systems,
South Ural State University, 454080 Chelyabinsk, Russia
7 Department of Food Technology and Organization of Public Catering, South Ural State University,
454080 Chelyabinsk, Russia
* Correspondence: rmrezaur@unimas.my (M.R.R.); khana@susu.ru (A.K.)
Citation: Rahman, M.R.; Taib,
N.-A.A.B.; Matin, M.M.; Rahman, Abstract: Composites such as carbon fiber are used extensively by automotive, aerospace, marine,
M.M.; Bakri, M.K.B.; Alexanrovich, and energy industries due to their strong mechanical properties. However, there are still many
T.P.; Vladimirovich, S.V.; Sanaullah, areas it is lacking in testing, especially related to its electrophoretic deposition. In this research
K.; Tazeddinova, D.; Khan, A.
work, the tensile strength and Young’s modulus of CNT–CF/epoxy composites were measured
Optimization of Tensile Strength and
using the tensile test by varying the electrophoretic deposition (EPD) process parameters. Response
Young’s Modulus of CNT–CF/Epoxy
surface methodology (RSM) was used to optimize the three main parameters in this EPD process:
Composites Using Response Surface
the volume ratio (water as the basis), deposition voltage, and time to obtain the maximum tensile
Methodology (RSM). Materials 2022,
15, 6746. https://doi.org/10.3390/
properties of the composites. There were four volume ratios (0%, 20%, 80% and 100%) used in this
ma15196746 design of experiment (DoE) with ratios’ pairs of 0%, 100%, and 20%, 80%. For this study, water
and methanol were used as the suspension medium. This design’s deposition voltage and time
Academic Editor: Ricardo J.
were 10 to 20 V and 5 to 15 min. ANOVA further verified the responses’ adequacy. The optimum
C. Carbas
conditions for the first Design of Experiment (DoE) (0% and 100%) were identified as a volume
Received: 11 September 2022 ratio of 99.99% water, deposition voltage of 10 V, and 12.14 min. These conditions provided the
Accepted: 24 September 2022 maximum strength of these composites with a tensile strength of 7.41 N/mm2 and Young’s modulus
Published: 28 September 2022 of 279.9 N/mm2 . Subsequently, for the second DoE (20% and 80%), tensile strength of 7.28 N/mm2
Publisher’s Note: MDPI stays neutral and Young’s modulus of 274.1 N/mm2 were achieved with the ideal conditions: volume ratio of
with regard to jurisdictional claims in 44.80% water, deposition voltage of 10.04 V, and time of 6.89 min. It can be concluded that the ideal
published maps and institutional affil- interaction between these three EPD parameters was necessary to achieve composites with good
iations. tensile properties.

Keywords: electrophoretic deposition (EPD); volume ratio; deposition voltage; deposition time;
CNT–CF/epoxy composite; response surface methodology; ANOVA; tensile strength; Young’s modulus
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
1. Introduction
conditions of the Creative Commons
Attribution (CC BY) license (https:// Carbon fiber (CF)/epoxy composites, also known as carbon fiber-reinforced polymer
creativecommons.org/licenses/by/ composites (CFRPs), are used extensively in various automotive, aerospace, marine, and
4.0/). energy replacements of conventional metal materials. High strength and stiffness combined

Materials 2022, 15, 6746. https://doi.org/10.3390/ma15196746 https://www.mdpi.com/journal/materials

Materials 2022, 15, 6746 2 of 20

with moderately low density have increased the industry demand for CFRPs [1]. CFS are
used extensively in lightweight polymer composite materials as reinforcement materials
owing to their excellent properties, such as electrically conductivity and low coefficient of
thermal expansion, while still being chemically inert [2]. Moreover, epoxy has long-term
dimensional stability, good adhesiveness, and excellent chemical, thermal, and mechanical
resistance. These excellent properties made this thermoset polymer widely used as a matrix
in fiber-reinforced polymer (FRP) composites [3]. The interfacial interactions of the CFs
and epoxy matrix greatly influence the performance of CFRPs, especially their mechanical
properties [4]. The load transfer from the “weak” matrix to “strong” fiber and from fiber
to thread through the matrix is guaranteed by the interphase, known as the third phase.
The interphase has noticeable physicochemical properties. The fiber/matrix adhesion
influences the interphase’s load transfer capability [5]. However, interactions between
the fiber and matrix for the CF and resin epoxy are not favored, as the CF surface is non-
polar, while the epoxy resins are polar [6]. Additionally, CF surfaces that are chemically
inert, hydrophobic, and intrinsically smooth have caused low interfacial bonding strength
between the CF and the polymer matrix [7].
Hence, to overcome the inertness of the CF and obtain strong fiber/matrix interfacial
adhesion, modifications should be done at the fiber surface [8]. The composite properties
would be better when the fiber/matrix interfacial interaction is stronger. Hence, many
studies have been done to enhance the bond strength, including integrating different
types of nanoparticles onto the fiber’s surface [9]. Studies have shown that the CFRPs’
interfacial properties could be improved by introducing carbon nanotubes (CNTs) onto
the reinforcing CF [10]. Owing to their outstanding mechanical properties, the addition of
CNTs may effectively enhance the CF–matrix interaction [11]. In addition, the CFs’ surface
roughness is improved with the presence of CNT and subsequently increases the CF–matrix
interfacial adhesion [12]. Not only taking advantage of the excellent properties of CNTs,
but the reinforced FRP material also maintained the superiority of the conventional fiber
reinforcements. Strength, crackles, wear resistance, and rigidity is the properties in the
original materials which could be enhanced with CNTs as reinforcement [13].
CNT–CF hybrids can be fabricated using several methods such as chemical vapor
deposition (CVD), spray coating, dip coating, electrophoretic deposition (EPD), etc. Then,
the nanoparticles are successfully deposited or attached to the CF surface. EPD has several
advantages among these methods and is thus used for CF surface modification. Good
surface homogeneity, control over film deposition, high deposition rate, and ease in process
up-scaling make EPD the more favorable method [7]. Thus, EPD was chosen as the
deposition method for the CNT onto the CF surface in this study.
Electrophoretic deposition (EPD) is a colloidal process in which electric fields are
introduced in a suspension medium. The particles compactly packed in the medium
are impelled onto the substrate [14,15]. Therefore, it is essential to use stable suspension
media throughout the EPD process to ensure that the particles are dispersed stably [16].
Water is commonly used in the EPD process for several reasons: cost-effectiveness, low
requirement of an electric field, ease of temperature regulation throughout the process,
and environmentally compatible [17]. However, water electrolysis may occur when high
voltage is applied, compromising the quality of the depositions. Organic solvents such as
alcohols are used to overcome this issue. However, a high applied voltage is needed for
pure organic solvents. Their particle mobility is also low due to the small electric charge on
the particles. This can be overcome by combining organic solvent and water as the solvent
for the EPD process [18]. For this study, methanol (CH3 OH) was the chosen organic solvent.
There are two groups of parameters that characterize the EPD process, i.e., parameters
related to the suspension stability, and those related to the deposition process. Six parame-
ters are associated with the strength of the suspension, namely, particle size, the dielectric
constant of liquid, the conductivity of suspension, suspension viscosity, the zeta potential,
and suspension stability. Moreover, the deposition process is influenced by four param-
Materials 2022, 15, 6746 3 of 20

eters: deposition time, solid concentration in suspension, applied voltage, and substrate
conductivity [19].
For this study, the effect of the parameters, suspension medium, deposition time, and
voltage was investigated during the EPD process on the tensile properties of the composites.
The interaction of those parameters was observed and optimized using response surface
methodology (RSM). RSM combines the mathematical and statistical techniques to construct
models by evaluating the effect of multiple independent variables to achieve the variables’
optimum values, obtaining desirable outcomes [20]. The EPD process was used to develop
the experimental model using RSM to obtain the optimum input and output factor values.
The effect of the CNTs on the fiber composites was ascertained by evaluating the composites’
tensile properties, scanning electron microscopy (SEM), and Fourier transform infrared
(FTIR) spectroscopy. Furthermore, optimization was carried out to determine the ideal
value of parameters from the design data, which exhibited maximum mechanical properties
of the composites by RSM using Design Expert (StatEast Minneapolis, MN, USA) software
(version 11).

2. Materials and Methods

2.1. Materials
The solution used for the EPD process consisted of two solvents, namely, methanol,
and water. The methanol (CH3 OH) was supplied by Merck kGaA (Darmstadt, Germany),
whereas water was obtained using an Arium Pro UV Ultrapure water system (Sartorius,
Göttingen, Germany). The MWCNTs (Product No. 0552CA) were from SkySpring Nano-
materials, Inc. (Houston, TX, USA). These MWCNTs were 95% purity, <8 nm in size, and in
black powder form.
The carbon fibers used in the experiment were black plain weave CF supplied from
PiCarbon (Kuala Lumpur, Malaysia). In addition, Epocast PT100 (clear type epoxy resin)
and Epoharden PT100S (amine-based epoxy hardener) were obtained from Portal Trading
(P.T.) (Pulau Pinang, Malaysia) and were used as matrix and curing agents, respectively.

2.2. Methods
2.2.1. Design of Experiments
The effects of various combinations of input factors, i.e., volume (% w/w), voltage (V),
and time (min), on the tensile properties of the hybrid CNT–CF/epoxy composites were
investigated using a central composite design (CCD) response surface study. The values of
the input factors are indicated in Tables 1 and 2, where 2 pairs of different volume ratios
were used in the experiment. The design generated 18 runs of varying factor conditions for
each volume ratio. The tabulated experimental designs are shown in Tables 3 and 4.

Table 1. Input factors used in the experiment for a volume ratio of 0 and 100% water.

Coded Coded
Factor Name Units Type Minimum Maximum Mean Std. Dev.
Low (–) High (+)
A Volume % (w/w) Numeric 0.0000 100.00 0.00 100.00 50.00 38.35
B Voltage V Numeric 10.00 20.00 10.00 20.00 15.00 3.83
C Time min Numeric 5.00 15.00 5.00 15.00 10.00 3.83

2.2.2. Fabrication of the Hybrid MWCNT–CF Strips

Before the EPD process, the suspension mediums were prepared by placing 80 mL of
methanol (MeOH), water (W), and the mixtures of MeOH/W (as per experimental design)
in laboratory glass sample bottles. The MWCNTs were dispersed in each suspension
medium with the MWCNTs suspension of 0.05 mg/mL (0.004 g of MWCNTs were dispersed
in 80 mL of solvent). The suspension was then ultrasonicated using an ultrasonic cleaner
(sonicator) (KUDOS SK2200HP, Shanghai, China) for 15 min to ensure uniform dispersion
Materials 2022, 15, 6746 4 of 20

of the MWCNTs before pouring it into the glass deposition bath. The EPD was performed
following the above obtained experimental design. The experimental set-up of the EPD
process consisted of a direct current (DC) power supply (Model 1672, B&K Precision, CA,
USA), 2 multimeters (Fluke 115, Fluke, USA, and UNI-T UT61C, Batronix, Germany),
copperplate electrode, mini-LED, and glass deposition bath, as illustrated in Figure 1.
Alligator clips attached the CF and copper plate to the non-insulator electrode holder. The
gap between the two electrodes was fixed at 1.5 cm using a retort stand, and the electrodes
were then immersed in the MWCNTs suspension. This study used the CF as the cathode,
while the copper plate was positioned as the anode (counter electrode). The EPD process
was then carried out as per the design of the experiment, as shown in Tables 3 and 4.

Table 2. Input factors used in the experiment for 20 and 80% water volume ratio.

Coded Coded
Factor Name Units Type Minimum Maximum Mean Std. Dev.
Low (–) High (+)
A Volume % (w/w) Numeric 20.00 80.00 20.00 80.00 50.00 23.01
B Voltage V Numeric 10.00 20.00 10.00 20.00 15.00 3.83
C Time min Numeric 5.00 15.00 5.00 15.00 10.00 3.83

Table 3. Experimental design for a volume ratio of 0%, 100% water.

Factor 1 Factor 2 Factor 3

Run A: Volume B: Voltage C: Time
%(w/w) V min
1 100 20 15
2 50 15 15
3 50 15 10
4 0 10 15
5 100 10 5
6 100 15 10
7 100 10 15
8 50 15 5
9 50 15 10
10 100 20 5
11 50 10 10
12 50 15 10
13 50 20 10
14 0 15 10
15 0 10 5
16 0 20 5
17 0 20 15
18 50 15 10
Materials 2022, 15, 6746 5 of 20

Table 4. Experimental design for a 20% and 80% water volume ratio.
Materials 2022, 15, 6746 5 of 20
Factor 1 Factor 2 Factor 3
Run A: Volume B: Voltage C: Time
%(w/w) V min
16 80 20 5
1 50 10 10
17 50 15 15
2 20 20 5
18 50 15 10
3 50 15 10
4 2.2.2. Fabrication
20 of the Hybrid MWCNT–CF
15 Strips 10
5 Before the20 EPD process, the suspension 10mediums were prepared by 15 placing 80 mL of
6 methanol (MeOH),
80 water (W), and the mixtures
10 of MeOH/W (as per experimental
5 design)
in laboratory glass sample bottles. The MWCNTs were dispersed in each suspension me-
7 20 20 15
dium with the MWCNTs suspension of 0.05 mg/mL (0.004 g of MWCNTs were dispersed
8 50
in 80 mL of solvent). 15 ultrasonicated using an ultrasonic
The suspension was then 5 cleaner
9 (sonicator) (KUDOS
50 SK2200HP, Shanghai, China)
15 for 15 min to ensure uniform
10 dispersion
10 of the MWCNTs 50 before pouring it into the glass
20 deposition bath. The EPD10was performed
following the above obtained experimental design. The experimental set-up of the EPD
11 80 10 15
process consisted of a direct current (DC) power supply (Model 1672, B&K Precision, CA,
12 20
USA), 2 multimeters (Fluke 115, Fluke, USA,10and UNI-T UT61C, Batronix,5Germany), cop-
13 50
perplate electrode, 15
mini-LED, and glass deposition bath, as illustrated in10
Figure 1. Alliga-
14 tor clips attached
80 the CF and copper plate to
20 the non-insulator electrode holder. The gap
15
15
between the 80 two electrodes was fixed at 1.515
cm using a retort stand, and 10
the electrodes
were then immersed in the MWCNTs suspension. This study used the CF as the cathode,
16 80 20 5
while the copper plate was positioned as the anode (counter electrode). The EPD process
17 50 out as per the design of the
was then carried 15 experiment, as shown in Tables15 3 and 4.
18 The average
50 size of the deposited MWCF–CNT
15 strip via the EPD process
10 was 7.7 cm
× 1.8 cm. After the EPD process, the deposited CF strip was dried at 70 °C for 12 h [21].

Figure1.1.Schematic
Figure Schematicdiagram
diagramofofthe
theEPD
EPDprocess
processfor
forthe
the fabrication
fabrication ofof hybrid
hybrid MWCNT–CF
MWCNT–CF materi-
materials.
als.
The average size of the deposited MWCF–CNT strip via the EPD process was
2.2.3.
7.7 cm Composite the EPD process, the deposited CF strip was dried at 70 ◦ C for
Preparation
× 1.8 cm. After
12 h [21].
The matrix resin was prepared by mixing the Epocast PT100 (matrix) and Epoharden
PT100S (curing agent) in a ratio of 2:1 by weight as per supplied guidelines by the manu-
facturer. Next, the composites were fabricated using a silicon mold, and alternate layers
of matrix resin and CF strips were placed in that mold. After the last layer of the CF strip,
the remaining resin was poured until it filled up the top of the mold. Figure 2 shows the
schematic illustration of the composites with their dimensions. Finally, the samples were
left at room temperature for 24 h to solidify and cure. Table 5 describes the composites
produced in this process.
Materials 2022, 15, 6746 6 of 20

Materials 2022, 15, 6746 2.2.3. Composite Preparation 6 of 20

The matrix resin was prepared by mixing the Epocast PT100 (matrix) and Epoharden
PT100S (curing agent) in a ratio of 2:1 by weight as per supplied guidelines by the manu-
facturer. Next, the composites
Table 5. Description were fabricated using a silicon mold, and alternate layers
of the samples.
of matrix resin and CF strips were placed in that mold. After the last layer of the CF strip,
Samplethe remaining resin was poured until it filled Composite
up the topDescription
of the mold. Figure 2 shows the
Pure CF/epoxy composite
schematic illustration of the Epoxy laminated
composites composite
with their with 3 Finally,
dimensions. layers ofthe
woven CF were
samples
left at room temperature for 24 h to solidify and cure. Table 5 describes the composites
Epoxy laminated composite with 3 layers of woven CF reinforced
MWCNT–CF/epoxy composite
produced in this process. with CNT

Figure2.2.Schematic
Figure Schematicillustration
illustrationof
ofcomposites
compositesand
andtheir
theirdimension.
dimension.

2.2.4.5.Evaluation
Table Descriptionof
ofTensile Properties of Composites
the samples.
Tensile strength and Young’s modulus of the composites were conducted using uni-
Sample Composite
versal testing instruments (Shimadzu Autograph Description Shidmadzu, Kyoto, Japan)
AGS–50kNX,
Pure CF/epoxy composite
following ASTM D638-14 [22] Epoxy laminatedthe
to evaluate composite with 3 layersThe
tensile properties. of woven CF speed was
cross-head
0.5
MWCNT–CF/epoxy compositemm/min; the sample’s test length was 40 mm (the measurement for test grip CNT
Epoxy laminated composite with 3 layers of woven CF reinforced with was ex-
cluded), while the width and thickness of the samples were 27 mm and 2 mm, respec-
tively. Tensile strength, TS (N/mm2), was calculated using the following equation:
2.2.4. Evaluation of Tensile Properties of Composites
Tensile strength and N maximum force to rupture F
TSYoung’s modulus of the composites were conducted using uni- (1)
mm
versal testing instruments (Shimadzu cross section
Autograph A
AGS–50kNX, Shidmadzu, Kyoto, Japan)
following
Fmax (N)ASTM D638-14
is the [22] to
maximum evaluate
force the tensile
required properties.
to rupture The cross-head
the sample during the speed
test, andwasA
0.5
(mmmm/min;
2 ) is the the sample’s
sample’s test length was
cross-section 40 mm with
calculated (the measurement
the formula for A test
length
grip was width
ex-.
cluded),
Moreover, while
thethe width andgraph
stress–strain thickness
was of the samples
plotted were
using the 27 obtained,
data mm and 2andmm, respectively.
from the slope
Tensile strength, 2 ), was calculated using the following equation:
of the chart, the TS (N/mm
Young’s modulus (E) of the composite was determined.
 
2.2.5. Fourier Transform N
Infrared maximum force to rupture Fmax
TS 2
= (FTIR) Spectroscopy = (1)
mm cross sec tion A
In order to study the difference in the functional groups of the carbon fibers’ surfaces
when Fmaxthe(N)EPD is factors were varied,
the maximum force FTIR analysis
required was done
to rupture on a Shimadzu
the sample IRAffinity-1.
during the test, and
AEach
(mm 2 ) is the
sample was analyzed
sample’s in the 4000–400
cross-section cm−1 regions
calculated with thewith a resolution
formula of 1 cm×
A = length −1 [23,24].
width.
Moreover, the stress—strain graph was plotted using the data obtained, and from the slope
2.2.6.
of Scanning
the chart, the Electron Microscopy
Young’s modulus (E) (SEM)
of the composite was determined.
The surface morphology of the MWCNT–CF/epoxy composites was performed via
2.2.5. Fourier
scanning Transform
electron Infrared(SEM;
microscopy (FTIR)Hitachi
Spectroscopy
TM4000Plus Tabletop Microscope, Tokyo,
In
Japan). order to study the difference in the functional groups of the carbon fibers’ surfaces
when the EPD factors were varied, FTIR analysis was done on a Shimadzu IRAffinity-1.
Each −1 regions with a resolution of 1 cm−1 [23,24].
2.2.7.sample wasand
Statistical analyzed in theAnalysis
Graphical 4000–400ofcm Composite’s Tensile Properties
From the RSM in the Design Expert software, the fit statistics and mathematical
model in terms of coded factors were used for the statistical analysis of the composites.
Moreover, the three-dimensional (3D) response surface plot analysis (3D surface) and pre-
dicted versus actual graphs were obtained using graphical analysis. The chosen model
was the cubic model, since there were three input factors in the experiment.
Materials 2022, 15, 6746 7 of 20

2.2.6. Scanning Electron Microscopy (SEM)

The surface morphology of the MWCNT–CF/epoxy composites was performed via
scanning electron microscopy (SEM; Hitachi TM4000Plus Tabletop Microscope, Tokyo, Japan).

2.2.7. Statistical and Graphical Analysis of Composite’s Tensile Properties

From the RSM in the Design Expert software, the fit statistics and mathematical model
in terms of coded factors were used for the statistical analysis of the composites. Moreover,
the three-dimensional (3D) response surface plot analysis (3D surface) and predicted versus
actual graphs were obtained using graphical analysis. The chosen model was the cubic
model, since there were three input factors in the experiment.

2.2.8. Optimization of the Composite’s Tensile Properties

After the analysis, the data were optimized to obtain the optimal condition for the EPD
process, maximizing the tensile strength and Young’s modulus of the composites. Both
numerical and graphical optimization options were chosen in the Design Expert software
for identifying the optimum values.

3. Results and Discussion

3.1. Characterization
3.1.1. Functional Group Analysis
Figure 3 shows that the peaks obtained covered all regions from the fingerprint until
the single bond region for the pure CF/epoxy composite. As for the composites reinforced
with CNT, the identifiable peaks started from the triple bond region. For the pure CF/epoxy
composite, the peaks from 900–670 cm−1 were ascribed to an aromatic C–H out-of-plane
bend [25]. This was further verified by a study by Cecen et al. [26], where they ascribed an
828 cm−1 band to an aromatic ring bend out of the plane. In addition, apart from the pure
CF/epoxy composite, the other samples exhibited peaks at around 2800 and continued
till 2999 cm−1 . It corresponded to C–H stretching, indicating the presence of methanol
impurity [27]. Methanol was used in the study as the organic solvent for the EPD process,
hence explaining the presence of methanol.
The presence of a peak around 2312 cm−1 in all the composites showed that carbon
fiber and epoxy resin reacted strongly with one another. Thus, bonding occurred between
the OH (hydroxyl) groups and carbon fiber and developed two reaction groups, namely, the
epoxide and the hydroxyl group [26]. When MWCNTs were introduced in the CF/epoxy
composite, a shift in peaks was observed from 3288 to 3313 cm−1 , indicating strong O–H
stretching. Therefore, the matrix and reinforcement had formed good interaction and
dispersion [28].

3.1.2. Surface Morphological Analysis

Figure 4 shows the surface of pure CF/epoxy composite, while Figures 5 and 6
show the surface of MWCNT–CF/epoxy composites in different conditions. The figures
show that the CFs remained attached to the epoxy matrix, indicating interfacial adhesion
between the CF and epoxy. Though some voids can be seen in the images since no CFs were
pulled out from the composites, the adhesion was deemed sufficient [29]. Additionally,
the FTIR peak showed an interaction between CF and epoxy resin. The EPD process
successfully deposited the MWCNTs, as the CFs were seen to be closely packed in the
composite, shown in Figures 5 and 6. However, the orientation of deposited MWCNTs
was randomly distributed along the CF strips. The highest direct electric field of 20 V
in this EPD process for all the composites is shown in Figure 5. It can be observed that
the MWCNTs accumulation in the composites shown in Figure 5 was more than those in
Figure 6. Excessive collection of similar charged electrons occurred when a high direct
electric field was applied to the MWCNT–CF hybrid. As a result, the MWCNTs strongly
repelled one another due to the exact electrical charges (high repulsion forces), forcing them
to relocate into the most stable position at the CF strips [11]. In addition, incrementing the
 continued till 2999 cm−1. It corresponded to C–H stretching, indicating the presence of
methanol impurity [27]. Methanol was used in the study as the organic solvent for the
EPD process, hence explaining the presence of methanol.
The presence of a peak around 2312 cm−1 in all the composites showed that carbon
Materials 2022, 15, 6746 fiber and epoxy resin reacted strongly with one another. Thus, bonding occurred between 8 of 20
the OH (hydroxyl) groups and carbon fiber and developed two reaction groups, namely,
the epoxide and the hydroxyl group [26]. When MWCNTs were introduced in the
CF/epoxy composite,
deposition time in this aEPD
shift in peaks
process was observed
enhanced from in
the MWCNTs 3288
theto 3313 cm
vertical
−1, indicating
fiber, making it
strong to
harder O–H
pullstretching.
out MWCNTs Therefore,
from thethe matrix
epoxy andThus,
resin. reinforcement had interfacial
the CF/epoxy formed good inter-
adhesion
action and dispersion
was increased [30]. [28].

Materials 2022, 15, 6746 8 of 20

3.1.2. Surface Morphological Analysis

Figure 4 shows the surface of pure CF/epoxy composite, while Figures 5 and 6 show
the surface of MWCNT–CF/epoxy composites in different conditions. The figures show
that the CFs remained attached to the epoxy matrix, indicating interfacial adhesion be-
tween the CF and epoxy. Though some voids can be seen in the images since no CFs were
pulled out from the composites, the adhesion was deemed sufficient [29]. Additionally,
the FTIR peak showed an interaction between CF and epoxy resin. The EPD process suc-
cessfully deposited the MWCNTs, as the CFs were seen to be closely packed in the com-
posite, shown in Figures 5 and 6. However, the orientation of deposited MWCNTs was
randomly distributed along the CF strips. The highest direct electric field of 20 V in this
EPD process for all the composites is shown in Figure 5. It can be observed that the
MWCNTs accumulation in the composites shown in Figure 5 was more than those in Fig-
ure 6. Excessive collection of similar charged electrons occurred when a high direct electric
field was applied to the MWCNT–CF hybrid. As a result, the MWCNTs strongly repelled
one another due to the exact electrical charges (high repulsion forces), forcing them to
relocate into the most stable position at the CF strips [11]. In addition, incrementing the
deposition time in this EPD process enhanced the MWCNTs in the vertical fiber, making
it harder to pull out MWCNTs from the epoxy resin. Thus, the CF/epoxy interfacial adhe-
Figure
Figure 3. The
3.
sion was The FTIR analysis
FTIR analysis
increased of the
[30]. of the composites.
composites.

Figure4.4.Surface
Figure Surfacemorphology
morphologyof
ofpure
pureCF/epoxy
CF/epoxy composite.
composite.

3.2. Tensile and Statistical Analysis of Composites’ Properties

3.2.1. Tensile Properties of MWCNT–CF/Epoxy Composites
The evaluation of the hybrids’ applicability as polymeric matrix reinforcements was
done by studying the mechanical properties of the composites. For example, the reinforcing
effect of CF could be significantly improved when there were high compatibility and
interaction between CF and matrix. Furthermore, with the addition of active nanomaterials
such as MWCNTs, the interaction could be further enhanced [11]. The tensile properties
of the pure CF/epoxy were individually tested, and the obtained values are listed in
Table 6. Additionally, 36 specimens of the CNT–CF hybrid were prepared according to
Materials 2022, 15, 6746 9 of 20

the experimental design. Tables 7 and 8 show the trial conditions and results of the tensile
testing of the fiber composites under various process factors.
Figure 4. Surface morphology of pure CF/epoxy composite.

Materials 2022, 15, 6746 9 of 20

Figure
Figure5.5. SEM
SEM images
images ofof CNT–CF/epoxy composites when
CNT–CF/epoxy composites when deposition
deposition voltage
voltageis
is 20
20 V
V and
and deposition
deposition
time
timeisis15
15min:
min: (a)
(a) 0%
0% water,
water,(b)
(b)20%
20%water,
water,(c)
(c)80%
80%water,
water,(d)
(d)100%
100%water.
water.

Figure6.
Figure 6. SEM
SEM images
images of
of CNT–CF/epoxy
CNT–CF/epoxy composites when deposition
composites when deposition voltage
voltageis
is 10
10 V
V and
and deposition
deposition
time is 5 min: (a) 0% water, (b) 20% water, (c) 80% water, (d) 100% water.
time is 5 min: (a) 0% water, (b) 20% water, (c) 80% water, (d) 100% water.

3.2. Tensile and Statistical Analysis of Composites’ Properties

3.2.1. Tensile Properties of MWCNT–CF/Epoxy Composites
The evaluation of the hybrids’ applicability as polymeric matrix reinforcements was
done by studying the mechanical properties of the composites. For example, the reinforc-
ing effect of CF could be significantly improved when there were high compatibility and
interaction between CF and matrix. Furthermore, with the addition of active nanomateri-
als such as MWCNTs, the interaction could be further enhanced [11]. The tensile proper-
ties of the pure CF/epoxy were individually tested, and the obtained values are listed in
Materials 2022, 15, 6746 10 of 20

Table 6. Tensile strength and Young’s modulus of pure CF/epoxy composite.

Tensile Strength Young Modulus

Sample
N/mm2 N/mm2
Pure CF/epoxy composite 5.062215 255.52

Table 7. Tensile strength and Young’s modulus of CNT–CF/epoxy composites with different factor
values for 0% and 100% water.

Factor 1 Factor 2 Factor 3 Response 1 Response 2

Run A: Volume B: Voltage C: Time Tensile Strength Young Modulus
%(w/w) V min N/mm2 N/mm2
1 100 20 15 7.61305 243.22
2 50 15 15 2.79761 225.49
3 50 15 10 6.70479 243.25
4 0 10 15 5.19014 229.48
5 100 10 5 4.91122 226.02
6 100 15 10 6.99095 250.91
7 100 10 15 6.62504 279.9
8 50 15 5 4.63372 223.49
9 50 15 10 4.48362 230.14
10 100 20 5 7.72467 260.16
11 50 10 10 7.05371 277.86
12 50 15 10 5.40961 277.92
13 50 20 10 3.96249 252.71
14 0 15 10 7.41783 241.61
15 0 10 5 4.07182 265.58
16 0 20 5 4.47299 249.36
17 0 20 15 6.59651 252.66
18 50 15 10 4.90024 243.5

Composites from design run 7, 10, 11, and 12 showed enhancement in the tensile
strength compared to the pure CF/epoxy composite, with an increment of 30.87%, 52.59%,
39.34%, and 6.86%, correspondingly, as can be seen in Table 7 (0% and 100% water). As for
the Young’s modulus, in comparison to the pure CF/epoxy, increments of 9.54%, 1.82%,
8.74%, and 8.77% was observed, respectively. From these composites, the composite from
design run 10 (100% water, 20 V, 5 min) showed the highest improvement in terms of
the tensile strength (52.59%) but relatively low improvement in Young’s modulus (1.82%).
Moreover, as seen in Table 8 (20% and 80% water), compared to pure CF/epoxy, composites
from design runs 6, 8, 9, 13, 16, and 18 showed improvements in their tensile strength with
1.39%, 2.59%, 24.49%, 38.26%, 37.14%, and 20.68%, accordingly. In addition, their Young’s
modulus was enhanced by 6.44%, 4.41%, 4.99%, 0.36%, 4.33%, and 6.99%, respectively.
From these composites, the composite from design run 13 (50% water, 15 V, 10 min) showed
the highest improvement in terms of the tensile strength (38.26%) but little improvement in
Young’s modulus (0.36%).
Materials 2022, 15, 6746 11 of 20

Table 8. Tensile strength and Young’s Modulus of CNT–CF/epoxy composites with different factor
values for 20% and 80% water.

Factor 1 Factor 2 Factor 3 Response 1 Response 2

Run A: Volume B: Voltage C: Time Tensile Strength Young Modulus
%(w/w) V min N/mm2 N/mm2
1 50 10 10 7.27661 251.96
2 20 20 5 6.10913 240.39
3 50 15 10 6.91568 211.87
4 20 15 10 4.04905 273.44
5 20 10 15 4.72418 223.92
6 80 10 5 5.13248 271.98
7 20 20 15 3.96751 216.1
8 50 15 5 5.19331 266.78
9 50 15 10 6.30199 268.28
10 50 20 10 7.22907 229.04
11 80 10 15 2.15553 218.42
12 20 10 5 4.19924 263.34
13 50 15 10 6.99927 256.43
14 80 20 15 7.1577 229.22
15 80 15 10 7.00801 251.08
16 80 20 5 6.94222 266.59
17 50 15 15 2.77799 187.59
18 50 15 10 6.1089 273.39

Generally, the matrix elongates as the tensile load increases, but the nanofillers (MWC-
NTs) resist the deformation. As a result, lower deformation occurs in the composite than
in the neat polymer. Thus, higher tensile modulus and strength were obtained compared
to the composite without any nanofiller, as the composites could sustain more loads [31].
The presence of MWCNTs helped the interface between layers to have good bonding with
one another, as illustrated in the SEM presented in Figures 5 and 6 [32]. The interfacial
behavior of CF/epoxy was changed by introducing MWCNTs in the composite. The CF’s
non-polar and inert surface properties caused weak interfacial adhesion between the woven
CF and the epoxy matrix. Thus, the total CF/matrix interfacial area was decreased with the
deposition of the MWCNTs on the woven CF surface, and the CNT/matrix interfacial area
was increased instead. In addition, the stress transfer between CF and epoxy was improved
due to the load-carrying capacity of CF with increased surface roughness. The twists and
kinks created mechanical interlocks between MWCNTs and the epoxy matrix in the CNTs
structure. As a result, the tensile strength of the MWCNT–CF/epoxy was improved, as
MWCNTs had excellent mechanical properties [12]. However, since the improvement of
the Young’s modulus was insufficient, this indicated that the agglomeration and orien-
tation of MWCNTs formed on the CF surface were not sufficient to raise the interfacial
interaction [11]. Therefore, it was implied that the overall composite’s Young’s modulus
was not affected by adding nanostructure onto the epoxy system, though it increased the
tensile strength of composites [33].
In addition, the composite from the design run 10 of 0% and 100% water (Table 7)
showed that the applied voltage had a significant influence on increasing the tensile
properties of the composite where the composite’s EPD was done at the highest voltage of
20 V but the lowest deposition time (5 min). Moreover, the composite from the design run
13 of 20% and 80% water (Table 8) demonstrated that for these reinforced composites, the
Materials 2022, 15, 6746 12 of 20

applied time of the electric field during the deposition process had a direct influence on the
tensile properties (10 min of the EPD process in 15 V applied voltage).

3.2.2. Fit Statistics

Table 9 lists the fit statistics of both experimental designs, and the coefficient of
variation, C.V., and prediction error sum of squares (PRESS) are shown in Table 10. From
Table 9, it can be seen that the determination coefficients, R2 , were relatively high, between
0.7 and 0.9. Generally, a good model fit has an R2 value of at least 0.8 [34]. When the R2
value is closer to unity (1), the model’s agreement with the experimental data is better,
with a lesser difference between the calculated and measured values [35]. The obtained
R2 values obtained were considered sufficient. Other than R2 , adjusted R2 , predicted
R2 , and prediction error sum of squares (PRESS) were also used to evaluate the model
adequacy. A large R2 and low PRESS imply an excellent model [35]. A small value of PRESS
is desired because it is used to determine the ability of the model to be used for future
prediction [20]. However, only two PRESS values (30.25 and 1.455 × 105 ) were considered
fitting in this study.

Table 9. The fit statistics of the experimental responses.

Design of Experiment Response R2 Adjusted R2 Predicted R2 Adequate Precision

Tensile strength 0.9234 0.6743 0.1744 6.5963
0% and 100% water
Young’s modulus 0.7687 0.0170 −13.3109 3.4278
Tensile strength 0.9688 0.8676 −24.2311 10.5406
20% and 80% water
Young’s modulus 0.7825 0.0756 −11.9025 3.9312

Table 10. The C.V. and PRESS values of the responses.

Design of experiment Response C.V. % PRESS

Tensile strength 14.85 30.25
0% and 100% water
Young’s modulus 7.29 81,140.52
Tensile strength 10.56 1119.50
20% and 80% water
Young’s modulus 10.13 1.455× 105

Additionally, the difference between R2 and R2 adjusted must be evaluated to demon-

strate the number of independent variables in the experiment. This study showed a
significant difference between those two values, indicating that nominal terms had been
included in the model [20]. The R2 adjusted was used to represent a rectified value for R2 after
excluding unnecessary model terms. When the R2 adjusted was outstandingly smaller than
R2 , this implied a massive influx of non-significant terms present in the model [36]. Apart
from that, the R2 predicted obtained in this study was primarily negative, which suggested
that the overall mean should be a better response predictor [35].
Moreover, the coefficient of variation C.V. refers to the standard deviation to mean
ratios. Therefore, the model is reproducible when the C.V. value is less than 10 [37]. For
this study, only one of the C.V. values was less than 10, while the other three were slightly
higher than 10. In addition, the signal-to-noise ratio (S/N ratio) was measured by adequate
precision (AP). Therefore, when the AP value is greater than four, the model discrimination
is considered satisfactory [38]. Moreover, the predicted values’ ranges at the design point
to the average prediction error are compared using AP [34]. Therefore, the AP obtained
from the experimental values could be considered adequate, as most values were around
four, which is a good sign and implies that the model can be used to navigate the design
space [37].
Materials 2022, 15, 6746 13 of 20

3.2.3. Mathematical Model for Tensile Strength and Young’s Modulus (in Terms of
Coded Factors)
Using the experimental results, the mathematical models for tensile strength and
Young’s modulus for each experimental design were obtained (in terms of coded factors).
The mathematical models were derived from the relationship between the input and output
parameters, where the factors volume %, voltage, and time are represented as A, B, and
C, respectively.
The following equations are the final mathematical models (in term of coded factors)
for the experimental design 0% and 100% water:
Tensile strength, TS:

TS = 5.33 − 0.2134A − 1.55B − 0.9281C + 0.2492AB − 0.2050AC − 0.1025BC + 1.91A2 + 0.2180B2 − 1.57C2
− 0.3538ABC + 2.25A2 B + 1.52A2 C + 1.03AB2

Young Modulus, E:

E = 454.96 − 0.9508A − 32.800B + 8.112C + 0.075AB + 0.204AC + 0.394BC − 0.014A2 + 0.974B2 − 0.783C2
− 0.011ABC + 0.001A2 B − 0.000039A2 C − 0.0025AB2

Similarly, the following equations are the final mathematical models for tensile strength
and Young’s modulus (in term of coded factors) for 20% and 80% water:
Tensile strength, TS:

TS = 6.31 + 1.48A − 0.0238B − 1.21C + 0.7073AB − 0.1431AC + 0.0657BC − 0.5027A2 + 1.22B2 − 2.05C2 +
0.7324ABC + 1.02A2 B + 0.6604A2 C − 1.18AB2

Young Modulus, E:

E = 249.39 − 11.18A − 11.46B − 39.59C + 4.52AB − 3.40AC + 3.92BC + 15.97A2 − 5.79B2 − 19.10C2 +
0.1325ABC + 8.29A2 B + 20.26A2 C + 16.49AB2

Additionally, the positive coefficient indicated a synergistic effect, while the negative
coefficient demonstrated an antagonistic influence [39–41].

3.3. Graphical Analysis of Composites’ Mechanical Properties

3.3.1. Response Surface Plots Analysis of Tensile Properties
The effects of the interaction between the volume ratio of the suspension medium and
the deposition voltage on the composites’ tensile strength and Young’s modulus under
the conditions of 10 min of the EPD process are shown in Figures 7 and 8. The response
surface plot in Figure 7a shows that when the volume ratio of the suspension medium
was increasing (approaching 100% water), the tensile strength also increased. Additionally,
Figure 7b shows that when the voltages of the deposition process were at the maximum
and minimum values, and the volume ratio increased, the Young’s modulus obtained was
higher than the others.
Moreover, Figure 8a demonstrates that tensile strength increased as the volume ratio
and voltage increased but slightly decreased when the volume ratio was approaching
80% water. In addition, Figure 8b illustrates that the Young’s modulus of the composites
was comparatively high at lower voltage and higher volume ratios. Despite that, the
obtained graphs were plotted with the deposition time being fixed as the actual factor at
10 min. As shown in Tables 7 and 8, even when the volume ratios and deposition voltage
were similar, the values of responses obtained differed depending on the deposition time.
Materials 2022,
Materials 2022, 15,
15, 6746
6746 1414of
of 20
20
Materials 2022, 15, 6746 14 of 20

10 290
10 290
280
8 280
270
8

(N/mm2)
(N/mm2)

270
260

(N/mm2)
(N/mm2)

6 260
6 250

modulus
250
strength

240

modulus
4
strength

240
4 230

Young's
230
Tensile

2 220

Young's
Tensile

2 220

20 100 20 100
20 18 80 100 20 18 80 100
18 16 60 80 18 16 60 80
16 14 40 60 16 14 40 60
B: Voltage (V) 14 12 20 40 A: Volume (%(w/w)) B: Voltage (V) 14 12 20 40 A: Volume (%(w/w))
B: Voltage (V) 12 10 0 20 A: Volume (%(w/w)) B: Voltage (V) 12 10 0 20 A: Volume (%(w/w))
10 0 10 0
(a) (b)
(a) (b)
Figure 7. Three-dimensional response surface plots for experimental designs of 0% and 100% water:
Figure 7.
Figure Three-dimensional response
7. Three-dimensional response surface
surface plots
plots for
forexperimental
experimental designs
designs of
of0%
0%and
and100%
100%water:
water:
(a) Tensile strength, (b) Young’s modulus.
(a) Tensile strength, (b) Young’s modulus.
(a) Tensile strength, (b) Young’s modulus.

10 280
10 280
260
8
260
8
(N/mm2)
(N/mm2)

240
(N/mm2)
(N/mm2)

6 240
6 220
modulus
strength

220
modulus

4
strength

200
4
200
Young's
Tensile

2 180
Young's
Tensile

2 180

20 80 20 80
20 18 70 80 20 18 70 80
18 16 60 70 18 16 60 70
50 60 50 60
16 14 40 16 14 40
50 50
B: Voltage (V) 14 12 30 A: Volume (%(w/w)) B: Voltage (V) 14 12 30 A: Volume (%(w/w))
40 40
B: Voltage (V) 12 10 20 30 A: Volume (%(w/w)) B: Voltage (V) 12 10 20 30 A: Volume (%(w/w))
10 20 10 20
(a) (b)
(a) (b)
Figure 8. Three-dimensional response surface plots for experimental designs of 20% and 80% water:
Figure
(a) 8. Three-dimensional
Tensile response
strength, (b) Young’s surface plots for experimental designs of 20% and 80% water:
modulus.
Figure 8. Three-dimensional response surface plots for experimental designs of 20% and 80% water:
(a) Tensile strength, (b) Young’s modulus.
(a) Tensile strength, (b) Young’s modulus.
3.3.2. Prediction versus Actual
3.3.2. Prediction
3.3.2.The
Prediction versus
Versus Actual
Actual
other response was the prediction versus actual. The responses of prediction ver-
The
The other
sus actual other response
response
graphs was
wasthe
are demonstrated prediction
the prediction versus
in Figures versusactual.
9 and 10.The
actual. responses
The responses
Furthermore, of prediction
Tables ver-
of prediction
11 and 12
sus actual
versus graphs
actual graphsare demonstrated
are demonstrated in Figures
in Figures 9 and
9 and 10.
10. Furthermore,
Furthermore,
show the experimental and predicted results of the output response, i.e., tensile strength Tables
Tables 11
11 and
and 12
12
show
show the
the experimental
experimental and
and predicted
predicted results
results of
of the
the output
output response,
response,
and Young’s modulus. The residual values indicate the deviation between the actual and i.e.,
i.e., tensile
tensile strength
strength
and
and Young’s
Young’s
predicted modulus.
If the The
modulus.
values. The residual
residual values
experimental errors indicate
values indicate
are random, the
the deviation
deviation between
between
the residuals the
the actual
are expected actualtoand
and
fol-
predicted
predicted values.
values. If the
If experimental
the experimental errors
errorsare random,
are random, the residuals
the are
residuals
low a normal distribution [42]. As seen in Figure 9, the residuals formed a straight line, expected
are expectedto fol-
to
low
followa normal
a normaldistribution
distribution [42]. As
[42]. seen
As in
seen Figure
in 9,
Figure the9,residuals
the formed
residuals
indicating a normal distribution of residuals of both tensile strength and Young’s modu- a
formed straight
a line,
straight
indicating
line,for
lus the adesign
normal
indicating ofdistribution
a normal
0% and of water,
residuals
distribution
100% of bothin
of residuals
whereas oftensile strength
both tensile
Figure and
strength
10a, even Young’s
though and modu-
theYoung’s
tensile
lus for
modulus the design
for the of
design0% and
of 0%100%
and water,
100% whereas
water, in
whereasFigure in 10a, even
Figure
strength’s residuals formed slightly S-shaped curves, they could still be accepted. 10a,though
even the
thoughtensile
the
The
strength’s residuals
tensile strength’s formedformed
residuals slightlyslightly
S-shaped curves,curves,
S-shaped they could still be
they could accepted.
still The
be accepted.
Materials 2022, 15, 6746 16 of 20
Materials 2022, 15, 6746 16 of 20

14
Materials 8015, 6746
2022, 20 15 7.16 7.09 0.07 0.96 229.22 228.44 0.78 0.3415 of 20
1514 8080 1520 1015 7.16
7.01 7.09
7.28 0.07
–0.28 0.96
−3.92 229.22 228.44
251.08 254.18 0.78
−3.10 0.34
−1.23
1615 8080 2015 510 7.01
6.94 7.28
6.87 –0.28
0.07 −3.92
0.99 251.08 254.18
266.59 265.81 −3.10
0.78 −1.23
0.29
1716 5080 1520 The
5
15 curves 6.94
2.78were not6.87
3.05 0.07 0.99
–0.28enough−9.90
significant to hold
266.59 265.81
187.59 190.69
additional response
0.78
−3.10 0.29
−1.65
transformation
1817 5050 1515 1015 2.78
6.11 3.05 –0.28 −9.90 273.39187.59 249.39
190.69 24.00−3.10 −1.65[42].
Additionally, most 6.31 –0.20
residual points −3.23
were still close to the straight line. As for Figure8.78
10b, the
18 50 15 10 6.11 6.31 –0.20 −3.23 273.39 249.39 24.00 8.78
residuals were considered to follow the normal distribution except for a few points.

Predicted vs. Actual Predicted vs. Actual

Predicted vs. Actual Predicted vs. Actual
8 290
8 290

280
7
280
7
270
6 270
6
260

Predicted
Predicted

260

Predicted
Predicted

5
5
250
250
4
4 240
240
3
230
3
230

2 220
2 220
2 3 4 5 6 7 8 220 230 240 250 260 270 280 290
2 3 4 5 6 7 8 220 230 240 250 260 270 280 290
Actual Actual
Actual Actual
(a) (b)
(a) (b)
Figure 9. Prediction versus actual graphs for experimental designs of 0% and 100% water: (a) Tensile
Figure 9.
Figure Prediction versus actual
9.Prediction actualgraphs
graphs for
forexperimental
experimental designs
designs of
of 0%
0% and
and 100%
100% water:
water: (a)
(a)Tensile
Tensile
strength, (b) Young’s versus
modulus.
strength, (b)
strength, (b) Young’s
Young’s modulus.
modulus.
Predicted vs. Actual Predicted vs. Actual
8
Predicted vs. Actual 280
Predicted vs. Actual
8 280

7
260
7
260

6
6 240
Predicted

Predicted

240
Predicted

Predicted

5
5
220
4 220
4

200
3
200
3

2 180
2 180

2 3 4 5 6 7 8 180 200 220 240 260 280

2 3 4 5 6 7 8 180 200 220 240 260 280
Actual Actual
Actual Actual
(a) (b)
(a) (b)
Figure 10. Prediction versus actual graphs for experimental designs of 20% and 80% water: (a) Ten-
Figure
sile 10. Prediction
strength, versus
(b) Young’s actual graphs for experimental designs of 20% and 80% water: (a) Ten-
modulus.
Figure 10. Prediction versus actual graphs for experimental designs of 20% and 80% water: (a) Tensile
sile strength, (b) Young’s modulus.
strength, (b) Young’s modulus.

The percentage error was also calculated in Tables 11 and 12. In Table 11, between
the actual and predicted value for TS and E, the percentage error range of TS was approx.
−18.94 to 20.45% and for E was approx. −7.06 to 11.35%. Additionally, for Table 12, the
percentage error ranges of TS and E were as follows: TS approx. −9.9 to 9.9%, and E approx.
−17.71 to 8.78%. Therefore, it can be deduced that experimental values were analogous to
Materials 2022, 15, 6746 16 of 20

the predicted values as they were in close agreement [38]. Additionally, as the residuals
matched the diagonal line, the created model was adequate [43].

Table 11. Experimental and predicted results of the output response for experimental design of 0%
and 100% water.

Volume Tensile Strength (TS) Young’s Modulus (E)

Run Voltage Time
Ratio Actual Pred Residual Error (%) Actual Pred Residual Error (%)
1 100 20 15 7.61 7.6 0.01 0.14 243.22 242.64 0.58 0.24
2 50 15 15 2.8 2.84 −0.04 −1.51 225.49 227.81 −2.32 −1.03
3 50 15 10 6.7 5.33 1.37 20.45 243.25 246.38 −3.13 −1.29
4 0 10 15 5.19 5.18 0.01 0.20 229.48 228.9 0.58 0.25
5 100 10 5 4.91 4.9 0.01 0.22 226.02 225.44 0.58 0.26
6 100 15 10 6.99 7.03 −0.04 −0.60 250.91 253.23 −2.32 –0.92
7 100 10 15 6.63 6.61 0.01 0.16 279.9 279.32 0.58 0.21
8 50 15 5 4.63 4.68 −0.04 −0.91 223.49 225.81 −2.32 −1.04
9 50 15 10 4.48 5.33 −0.85 −18.94 230.14 246.38 −16.24 −7.06
10 100 20 5 7.72 7.71 0.01 0.14 260.16 259.58 0.58 0.22
11 50 10 10 7.05 7.1 −0.04 −0.60 277.86 280.18 −2.32 −0.83
12 50 15 10 5.41 5.33 0.08 1.43 277.92 246.38 31.54 11.35
13 50 20 10 3.96 4 −0.04 −1.07 252.71 255.03 −2.32 −0.92
14 0 15 10 7.42 7.46 −0.04 −0.57 241.61 243.93 −2.32 −0.96
15 0 10 5 4.07 4.06 0.01 0.26 265.58 265 0.58 0.22
16 0 20 5 4.47 4.46 0.01 0.24 249.36 248.78 0.58 0.23
17 0 20 15 6.6 6.59 0.01 0.16 252.66 252.08 0.58 0.23
18 50 15 10 4.9 5.33 −0.43 −8.82 243.5 246.38 −2.88 −1.18

Table 12. Experimental and predicted results of the output response for 20% and 80% experimental
water design.

Volume Tensile Strength (TS) Young’s Modulus (E)

Run Voltage Time
Ratio Actual Pred Residual Error (%) Actual Pred Residual Error (%)
1 50 10 10 7.28 7.55 −0.28 −3.78 251.96 255.06 −3.10 −1.23
2 20 20 5 6.11 6.04 0.07 1.13 240.39 239.61 0.78 0.32
3 50 15 10 6.92 6.31 0.61 8.80 211.87 249.39 −37.52 −17.71
4 20 15 10 4.05 4.32 −0.28 −6.79 273.44 276.54 −3.10 −1.13
5 20 10 15 4.72 4.66 0.07 1.46 223.92 223.14 0.78 0.35
6 80 10 5 5.13 5.06 0.07 1.34 271.98 271.2 0.78 0.29
7 20 20 15 3.97 3.9 0.07 1.73 216.1 215.32 0.78 0.36
8 50 15 5 5.19 5.47 −0.28 −5.30 266.78 269.88 −3.10 −1.16
9 50 15 10 6.3 6.31 0.00 −0.07 268.28 249.39 18.89 7.04
10 50 20 10 7.23 7.5 −0.28 −3.80 229.04 232.14 −3.10 −1.35
11 80 10 15 2.16 2.09 0.07 3.19 218.42 217.64 0.78 0.36
12 20 10 5 4.2 4.13 0.07 1.64 263.34 262.56 0.78 0.29
13 50 15 10 7 6.31 0.69 9.90 256.43 249.39 7.04 2.75
14 80 20 15 7.16 7.09 0.07 0.96 229.22 228.44 0.78 0.34
15 80 15 10 7.01 7.28 –0.28 −3.92 251.08 254.18 −3.10 −1.23
16 80 20 5 6.94 6.87 0.07 0.99 266.59 265.81 0.78 0.29
17 50 15 15 2.78 3.05 –0.28 −9.90 187.59 190.69 −3.10 −1.65
18 50 15 10 6.11 6.31 –0.20 −3.23 273.39 249.39 24.00 8.78

3.4. Optimization of the EPD Process

Figures 11 and 12 illustrate the numerical optimization results in terms of ramp graphs,
while Tables 13 and 14 list the constraints for the EPD process optimization. Numerical
optimization uses a ramp graph to clarify the results. Generally, depending on the aim of
the research, the design factors and responses are set to achieve the study’s objective [20].
For this study, the responses, namely, tensile strength and Young’s modulus, were set
 Table 13. Constraints for optimization for experimental design of 0% and 100% water.

Constraints Conditions Lower Limit Upper Limit Solution

Volume ratio, % (w/w) In range 0 100 99.99
Materials 2022, 15, 6746 Voltage (V) In range 10 20 1017 of 20
Time (min) In range 5 15 12.14
Tensile strength Maximize - - 7.41
to theYoung’s
maximum option, and factors
modulus Maximize including volume
- ratio, voltage,
- and time279.9were set
in the range option. Based on Figure 11 (experimental design of 0% and 100% water),
the optimum
Table conditions
14. Constraints for maximum
for optimization responses
for 20% and 80%were volumewater
experimental ratiodesign.
(water as the basis)
of 99.99%; deposition voltage of 10 V; and deposition time of 12.14 min. In addition,
Constraints
the desirability value was 0.968 Conditions Lower
for this response, limitto 1.Upper
close On the Limit Solution
other hand, for the
Volume ratio,
experimental % (w/w)
design In range
of 20% and 80% water, shown in 20Figure 12, the 80 44.80
ideal conditions for the
Voltage (V) In range 10 20
maximum responses were volume ratio (water as the basis) of 44.80%; deposition voltage 10.04
of 10.04 V;Time
and(min)
deposition time In of range 5
6.89 min. The desirability 15for the experimental
value 6.89
designTensile
was 1. Overall,
strengthboth desirability
Maximize values indicated
- that the formulation
- was desirable
7.28
to fulfill the responses’
Young’s modulusobjectives, as the desirability- value was close- to one [44]. 274.1
Maximize

0 100 10 20

A:Volume = 99.9994 B:Voltage = 10

5 15 2.79761 7.72467

C:Time = 12.1391 Tensile strength = 7.41045

Desirability = 0.968
223.49 279.9 Solution 1 out of 59

Young's modulus = 279.9

Materials 2022, 15, 6746

Figure11.
Figure 11.Ramp
Rampchart
chartfor
forstatistically
statisticallyoptimized
optimized factors
factors and
and response
response for for experimental
experimental design
design of
18ofof0%
20
0% and 100% water.
and 100% water.

20 80 10 20

A:Volume = 44.8023 B:Voltage = 10.0438

5 15 2.15553 7.27661

C:Time = 6.89485 Tensile strength = 7.44669

Desirability = 1.000
187.59 273.44 Solution 1 out of 82

Young's modulus = 274.076

Figure12.
Figure 12.Ramp
Rampchart
chartfor
for statistically
statistically optimized
optimized factors
factors andand response
response for experimental
for experimental design
design of
of 20%
20% and 80% water.
and 80% water.

4. Conclusions
An EPD process to fabricate a CNT–CF hybrid was conducted using two DoE ob-
tained from CCD and three parameters, i.e., volume ratios (water as the basis), deposition
voltage, and deposition time. The laminated composites were manufactured using epoxy
as the matrix and were varied with these design parameters. The effects of these three
design parameters were studied on the tensile properties of the composites (tensile
strength and Young’s modulus). The optimum conditions for the first DoE (0% and 100%)
Materials 2022, 15, 6746 18 of 20

Table 13. Constraints for optimization for experimental design of 0% and 100% water.

Constraints Conditions Lower Limit Upper Limit Solution

Volume ratio, % (w/w) In range 0 100 99.99
Voltage (V) In range 10 20 10
Time (min) In range 5 15 12.14
Tensile strength Maximize - - 7.41
Young’s modulus Maximize - - 279.9

Table 14. Constraints for optimization for 20% and 80% experimental water design.

Constraints Conditions Lower limit Upper Limit Solution

Volume ratio, % (w/w) In range 20 80 44.80
Voltage (V) In range 10 20 10.04
Time (min) In range 5 15 6.89
Tensile strength Maximize - - 7.28
Young’s modulus Maximize - - 274.1

4. Conclusions
An EPD process to fabricate a CNT–CF hybrid was conducted using two DoE obtained
from CCD and three parameters, i.e., volume ratios (water as the basis), deposition voltage,
and deposition time. The laminated composites were manufactured using epoxy as the
matrix and were varied with these design parameters. The effects of these three design
parameters were studied on the tensile properties of the composites (tensile strength and
Young’s modulus). The optimum conditions for the first DoE (0% and 100%) were achieved
as a volume ratio of 99.99% water, deposition voltage of 10 V, and time of 12.14 min to obtain
maximum tensile strength of 7.41 N/mm2 and Young’s modulus of 279.9 N/mm2 . As for
the second DoE (20% and 80%), tensile strength and Young’s modulus of 7.28 N/mm2
and 274.1 N/mm2 , respectively, were achieved when the ideal conditions were volume
ratio of 44.80% water, deposition voltage of 10.04 V, and 6.89 min. In conclusion, an ideal
interaction between these three EPD parameters was necessary to achieve composites with
good tensile properties.

5. Future Work
According to this study, various limitations might be seen throughout the research
work. One of them is to alter the thickness of the sample specimen and learn how thickness
affects it. Another kind of study that may be done is switching from water to deionized
water to investigate the influence of altered medium on deposition. Other than that,
increasing the test range below and beyond the designation range could be conducted to
understand the behavior after the limitations, i.e., below 20% and after 80%.

Author Contributions: Conceptualization, M.M.R. and M.K.B.B.; Data curation, M.R.R. and N.-A.A.B.T.;
Formal analysis, N.-A.A.B.T., M.M.R., M.K.B.B., S.V.V., K.S., D.T. and A.K.; Investigation, M.R.R.,
N.-A.A.B.T. and M.M.M.; Methodology, N.-A.A.B.T., D.T. and A.K.; Project administration, M.R.R.
and K.S.; Resources, M.M.M.; Software, M.K.B.B., T.P.A., S.V.V., K.S. and A.K.; Validation, M.M.M.;
Writing–original draft, N.-A.A.B.T., D.T. and A.K. All authors have read and agreed to the published
version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: The authors wish to acknowledge the Faculty of Engineering, Universiti Malaysia
Sarawak (UNIMAS), for their lab facilities support.
Conflicts of Interest: The authors declare no conflict of interest.
Materials 2022, 15, 6746 19 of 20

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