Composites Science and Technology 228 (2022) 109646

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Composites Science and Technology

journal homepage: www.elsevier.com/locate/compscitech

Designing BN@CF hybrid to enhance the epoxy resin towards outstanding

anti-corrosion and anti-wear performances
Kui Wang a, b, *, Lu Shen a, b, Nengbo Wen a, b, Qiong Jiang a, b
a
School of Materials Science and Engineering, Yancheng Institute of Technology, Yancheng, 224051, PR China
b
Key Laboratory for Ecological-Environment Materials of Jiangsu Province, Yancheng Institute of Technology, Yancheng, 224051, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Carbon fiber-reinforced composites (CCs) have been widely used in many advanced applications due to their high
BN@CF hybrid specific strength, good corrosion resistance, and wear resistance. Despite recent progresses, obtaining high-
Interfacial reinforcement performance and durable CCs remains difficult because of low fiber/matrix interfacial adhesion. Here, we
anti-Corrosion
designed and fabricated hexagonal boron nitride modified carbon fiber (BN@CF) by chemically grafting func­
Tribological properties
tional hexagonal boron nitride (F-BN) nanosheets on polydopamine modified carbon fiber (PDA-CF) surface and
used it in increasing the strength of interfacial adhesion between the fibers and epoxy resin (EP). Tensile strength
and interfacial shear strength (IFSS) of EP/BN@CF composite increased by 13.8% and 87.2%, respectively,
compared with those of pure EP. BN@CF hybrid with unique structure endowed the epoxy composite coating
with excellent corrosion resistance property, which greatly enhanced the impedance by two orders of magnitude
relative to those of other coatings. Comparing with pure EP, EP/BN@CF composite had a 37.8% reduction in
coefficient of friction and 83.0% reduction in wear rate. Such distinguished anti-corrosion performance and
wear-resistance were ascribed to the increased fiber/matrix interfacial adhesion strength of EP/BN@CF com­
posite. We believe that the fabricated BN@CF hybrid will open up avenues for various applications.

1. Introduction
Corrosion of metals in industrial applications must be taken seriously
because it can cause huge economic losses [1]. The application of
polymeric coatings is a cost-effective and efficient method for protecting
metals from corrosion due to the formation of an isolate layer between
metals and corrosive species [2]. Among the polymeric coatings, epoxy
resin (EP) has characteristics of outstanding chemical inertness, notable
mechanical properties, superior adhesion under different aggressive
solutions, which is widely used in anticorrosion field [3]. Unfortunately,
evaporation of solvent during coating formation leads to the appearance
of pores in a coating. Hence, the resulting coating cannot provide
satisfactory barrier protection during long-term exposure. Besides, the
wear resistance of pure EP is poor due to its 3D network structure, which
could form during curing. One of the most beneficial solutions to over­
come the malfunctions of pure EP is the introduction of mirco- or nano-
fillers. Two-dimensional materials, including graphene [4,5], layered
hydrotalcite [6,7], hexa-boron nitride (h-BN) [8,9], metal-organic
frameworks (MOFs) [8], and MXenes [10] have been applied to anti­
corrosion coatings. However, 2D nanosheets easily agglomerate due to
their strong van der Waals forces and large specific surface area.
Carbon fibers (CFs) have distinctive structures that endow them with
high tensile strength and elastic modulus and excellent chemical resis­
tance. They are widely used to improve the mechanical properties of
matrices [11–14]. Xu et al. reported an increase of 70.5% in the inter­
facial shear strength of poly (cyclotriphosphazene-co-4,4′ -oxy­
dianiline)-coated CF/epoxy composites. In addition, a polyphpsphazene
sheath can heal surface defects in fibers effectively, increasing fiber
tensile strength by more than 10.0% [15]. Unfortunately, the low sur­
face energy and inert surface of CFs inhibit interactions with the poly­
mer resins, leading to poor adhesion between fiber and matrix [16].
To improve the filler/matrix interphase properties of composites,
surface treatment of CFs with functional groups is a common means
[17]. The surface of fibers could be chemically modified with the
functional groups such as carbonyl and hydroxyl groups which could
enhance the interfacial interaction with the epoxy resin [17]. Never­
theless, Jones et al. demonstrated that the adhesion between the fiber
and matrix was not obviously enhanced after the introduction of surface
functional groups [18]. Kim et al. found that electrochemical oxidation
of CFs led to an increment in interfacial shear stress between CFs and

* Corresponding author. School of Materials Science and Engineering, Yancheng Institute of Technology, Yancheng, 224051, PR China.
E-mail address: wangkuiwork@outlook.com (K. Wang).

https://doi.org/10.1016/j.compscitech.2022.109646
Received 14 April 2022; Received in revised form 4 June 2022; Accepted 13 July 2022
Available online 19 July 2022
0266-3538/© 2022 Elsevier Ltd. All rights reserved.
K. Wang et al.
epoxy and decrease in tensile strength of CFs [16]. The bio-inspired
surface modification method reported by Lee et al. was inspired by the
adhesion mechanism of mussels [19]. Mussels were able to attach to
almost any kind of material and this universal adhesive property origi­
nated from 3,4-dihydroxy-L-phenylalanine-lysine (DOPA-K) motif in
mussel foot proteins [20]. Researchers were inspired and used small
molecules with catecholamine moiety like dopamine as an adhesive
agent to mimic the mussel’s adhesion [20]. The oxidative
self-polymerization of dopamine formed thin layers on the substrate.
Additionally, polydopamine (PDA) layer acted as a platform for sec­
ondary reactions, facilitating the tailoring the layers for extensive ap­
plications [21].
Decorating nanoparticles on fibers is another approach for
improving the interphase properties of fiber/matrix. Yao et al. reported
that the composite reinforced with carbon nanotube (CNT)-coated CFs
exhibited higher shear strength, whereas the composite reinforced with
graphene oxide (GO)-coated CFs exhibited good humidity resistance
[22]. But we should consider that CNT with high conductivity may lead
to galvanic corrosion of the coating during the immersion process in
NaCl solution. Moreover, the thermal conductivity of GO is undesirable.
Fortunately, hexagonal boron nitride (h-BN) nanosheets with
outstanding thermal conductivity can spread heat during the friction
process, which may weaken adhesive wear [23]. Given that h-BN
nanosheets are electronically insulators, the galvanic corrosion was
considerably inhibited, resulting in the desirable corrosion protection of
composite coatings.
In the current work, BN@CF hybrid was designed and successfully
fabricated, which greatly improved the interfacial compatibility be­
tween fibers and epoxy matrix. The surface morphology and chemical
structure of BN@CF hybrid were systematically investigated. Anticor­
rosion mechanism and tribological mechanism were discussed. The re­
sults showed that the unique structure of BN@CF and the synergistic
effect derived from PDA-CF and F-BN endowed the epoxy composite
with outstanding mechanical properties, advanced corrosion resistance,
and enhanced wear resistance.
2. Experimental section
2.1. Chemicals
The chemicals used in this work were shown in supplementary
information.
2.2. Modification of carbon fibers
A dopamine solution with a centration of 2 g/L was produced by
adding the dopamine-HCl to DI water. A Tris base was used in adjusting
the pH value to 8.5. Exactly 0.4 g of CFs was added to the above solution,
and the mixture was continuously stirred for 24 h. Then, the fibers were
rinsed in DI water for the removal of unreacted dopamine. Finally, the
product was freeze-dried and denoted as PDA-CF.
2.3. Preparation of F-BN
First, h-BN was treated in a 5 mol/L NaOH solution at 120 ◦ C for 24
h, washed with DI water, and filtered several times to neutral. The hy­
droxylated BN was modified with KH560 for chemical grafting of –NH2
groups. A mixture containing 4 g of DI water, 10 g of 3-Glycidyloxypro­
pyltrimethoxysilane (KH560), and 36 g of alcohol were prepared and
stirred for 10 min. Then, 0.5 g of hydroxylated BN was added to the
above solution. The resulting solution was subjected to ultrasonic
dispersion for 1 h and stirred for another 8 h at 70 ◦ C. After that, the
product was centrifuged and washed for the removal of unreacted silane
coupling agent. Finally, the product (F-BN) was freeze dried for 24 h.
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Composites Science and Technology 228 (2022) 109646
2.4. Preparation of BN@CF hybrid
F-BN (0.4 g) was mixed with 0.1 g of PDA-CF in alcohol, and the
obtained solution was ultrasonically dispersed for 60 min. The bond
formation reaction between F-BN and PDA-CF was conducted by mixing
the previous solution for 8 h at 70 ◦ C. Finally, the product was washed
with ethanol and DI water and freeze dried for 24 h. The product was
denoted as BN@CF, and the schematic illustration of the synthesis
process was shown in Fig. 1.
2.5. Preparation of the composite coatings
Epoxy coatings containing F-BN, PDA-CF, and BN@CF were denoted
as EP/F-BN, EP/PDA-CF, and EP/BN@CF, respectively. Preparation
method was depicted in supplementary information.
2.6. Characterization techniques
The characterization techniques were employed to characterize the
morphology, and chemical structure of the prepared samples. In addi­
tion, electrochemical impedance spectroscopy (EIS) measurement and
localized electrochemical impedance spectrum were applied to evaluate
the anticorrosion performance of the coatings. UMT-3 ball-on-disk
tribometer was used in examining the tribological properties of the
coatings. Specific description of characterization techniques was shown
in supplementary information.
3. Results and discussions
3.1. Characterization of the additives
The morphology of CFs, PDA-CF, BN@CF and F-BN was shown in
Fig. 2(a–d). By comparing scanning electron microscope (SEM) images
of CFs, PDA-CF and BN@CF, there was an obvious difference in
roughness for them. Untreated CF had a smooth surface, whereas PDA-
CF had a rough surface after modification with PDA. Increase in the
roughness of the surface of BN@CF indicated that F-BN nanoparticles
were successfully attached to the fiber surface (Fig. 2c). Fig. 2d pre­
sented the SEM image of F-BN nanoparticles, which was in granular
form and loosely packed together. As shown in Fig. 2e, the pristine h-BN
without introduction of a silane coupling agent displayed a multilayered
structure with agglomeration. After grafting of a silane coupling agent,
ultrathin flakes appeared in F-BN because the agent effectively dispersed
BN nanoparticles, as shown in the transmission electron microscope
(TEM) image. The scanning probe microscope (SPM) image of F-BN
presented the thickness was about 3.5 nm suggesting that it was almost
exfoliated with few layers (Fig. 2g). Elements of F-BN included B, N, O,
and Si, which were evenly distributed on the entire surface and
demonstrated the successful grafting of the silane coupling agent (Fig. 2
(h–k)).
In order to clarify the chemical composition and element state of the
samples, X-ray photoelectronic spectroscopy (XPS) elemental analysis
was performed on h-BN, F-BN, CFs, PDA-CF and BN@CF (Fig. 3). Fig. 3a
depicted the full spectrum of the samples. With regard to F-BN and
BN@CF, O element content of them was higher than that of h-BN, which
indicated that silane coupling agent was grafted on the surface of F-BN.
Fig. 3b shows that the N 1s spectrum can be curve fitted with two peaks.
The peak located at a low binding energy of 398.6 eV was associated
with imino species (=N-), and the peak at a high binding energy of
401.0 eV was associated with the (C)2–NH species. These peaks indi­
cated that the in situ spontaneous oxidative polymerization of dopamine
on CFs was successfully carried out [20,24]. We estimated that during
the preparation of BN@CF, R2-NH of PDA-CF reacted with the C–O–C of
F-BN, finally forming (C)3–N. In Fig.3c, N 1s of BN@CF was composed of
two subpeaks centered at 398.6 eV (=N-) and 399.8 eV ((C)3–N.),
respectively. The results were in agreement with the predicted chemical
K. Wang et al. Composites Science and Technology 228 (2022) 109646

Fig. 1. Schematic illustration of the synthesis process of PDA-CF, F-BN, and BN@CF

Fig. 2. SEM images of (a) CFs, (b) PDA-CF, (c) BN@CF, and (d) F-BN. TEM images of (e) h-BN and (f) F-BN. (g) SPM image of F-BN and corresponding height profiles.
(h–k) TEM mapping images of F-BN.

reaction mechanism. The single peak at 102.3 eV in Fig. 3d indicated the
presence of Si–O–C which barely existed in F-BN and BN@CF. All the
above results proved F-BN was successfully grafted on PDA-CF.
Raman spectroscopy is usually employed to examine the structure of
carbon materials. Raman spectrum of CFs included a G-band located at
approximately 1599 cm− 1 and a D band located at 1323 cm− 1. Ac­
cording to Raman peak positions of PDA as reported earlier [25], we
considered the peaks located at 1397 and 1485 cm− 1 of as-prepared
PDA-CF corresponded to the aromatic C–N stretching mode of the
indole structure of PDA and C–– C vibration, respectively. As for BN@CF,
except the characteristic peaks of CFs and PDA, a strong peak located at
1362 cm− 1 was observed, which was related to the characteristic peak of
h-BN (Fig. 3e) [26]. Accordingly, Raman results also confirmed F-BN
was successfully grafted on PDA-CF, which was in agreement with XPS
results.

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K. Wang et al. Composites Science and Technology 228 (2022) 109646

Fig. 3. Full spectrum of (a) h-BN, F-BN, CF, PDA-CF and BN@CF. High-resolution XPS N 1s profiles of (b) PDA-CF and (c) BN@CF. High-resolution XPS Si 2p of (d) h-
BN, F-BN and BN@CF. Raman spectra of (e) CF, PDA-CF and BN@CF. Typical tensile stress-strain curves (f) and elongation at break (g) of the specimens. SEM
fracture morphologies of (h) EP/PDA-CF and (i) EP/BN@CF

3.2. Mechanical properties reinforced after F-BN was grafted on the fiber surface.

The tensile stress and elongation at break of epoxy composites

3.3. Interfacial shear strength (IFSS)
reinforced by F-BN, PDA-CF, and BN@CF were presented in Fig. 3(f and
g). In the curves of the composite coatings, tensile strength and elon­
The strength of interfacial bonding between CFs and the epoxy ma­
gation of the coatings displayed improvements compared with those of
trix was evaluated by examining the IFSS. The debond regions of various
the pure EP coating. The contribution of toughening epoxy matrix
fibers-matrix through micro-bond test are presented in Fig. 4(a–c). The
mainly due to the resistance of stress concentration and crack formation
final data were the average of 20 values. The schematic diagram of the
brought by the uniformly dispersed nano-/micro fillers. In the fraction
micro-bond test was shown in Fig. 4d. The IFSS values as a function of
process, additional fracture energy was required to initiate and propa­
time are depicted in Fig. 4e. EP/BN@CF showed 70.8 MPa with 87.2%
gate cracks in the interphase regions in the composite coatings. The
and 40.7% increment relative to the values of pure EP and EP/PDA-CF,
average values of tensile strength and modulus and elongation at break
respectively. In terms of BN@CF, the change in IFSS directly correlated
were listed in Table S1. Notably, EP/BN@CF showed the highest tensile
with F-BN grafted on the fiber surface. First, F-BN significantly further
strength, increased up to 44.8 MPa with 13.8% increment relative to the
improved the roughness of BN@CF compared with PDA-CF. Surface
value of pure EP. EP/BN@CF showed 25.8% improvement in elongation
roughening increased the contact area between fiber and matrix. Sec­
at break compared with the pure EP. In addition, tensile modulus of EP/
ond, F-BN was a two-dimensional layered material, and the resin easily
BN@CF increased from 1.32 to 1.58 GPa in comparison to pure EP. The
attached to F-BN surface, which built the interfacial mechanical inter­
results demonstrated that the optimal interfacial compatibility between
locking [22]. Besides, the increase in the IFSS for EP/PDA-CF was
BN@CF and epoxy matrix resulted in a strong interaction, which
obvious because the interfacial compatibility between PDA-CF and
effectively enhanced the mechanical interlock and compactness of the
epoxy matrix improved to some extent [28]. To further support the IFSS
composite [27]. Accordingly, the adhesion between filler and matrix
results, we examined the fractured morphology of the IFSS samples
was crucial to toughen the mechanical properties of the composites. To
through SEM. The results are displayed in Fig. 4. As expected, the matrix
directly support the mechanical properties results, we examined the
completely detached from the untreated CF surface of the composites
fracture surface morphology of EP/PDA-CF and EP/BN@CF composites.
(Fig. 4a). The surface of the pulled-out CF was quite smooth suggesting
Fig. 3(h and i) showed that the epoxy matrix was completely detached
the interfacial adhesion was extremely weak. By comparison, apparent
from the CF surface in EP/PDA-CF, whereas the epoxy matrix was tightly
resin fragments adhered to the BN@CF surface. This result showed the
attached to the fiber surface in EP/BN@CF. This finding indicated that
interfacial adhesion between BN@CF and the matrix was considerably
the interfacial adhesion between BN@CF and matrix was greatly
enhanced after F-BN was grafted on the fiber surface, as shown in

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K. Wang et al.
Fig. 4. Debond regions of various fibers-matrix through micro-bond test. (a) untreated CF, (b) PDA-CF, (c) BN@CF, (d) schematic diagram of the micro-bond test, (e)
The IFSS values as a function of time.
Fig. 4c. In addition, a small number of resin fragments were observed on
the PDA-CF surface (Fig. 4b), consistent with the IFSS results.
3.4. Anticorrosion properties of the coatings
The open circuit potential (OCP) results of the coatings were
measured at different periods. The results are shown in Fig. 5. The OCP
data of steel covered by pure EP coating presented a continuous
downward trend during the whole immersion process as a result of the
rapid deterioration of the coating brought by the penetration of large
amount of corrosive medium. The OCP values of EP/F-BN and EP/PDA-
CF coatings were − 0.43 V and − 0.49 V after 40 days of exposure, which
was higher than that of pure EP coated steel (− 0.64 V). In terms of the
steel coated with EP/BN@CF coating, the OCP values fluctuated slightly
during the immersion process, the excellent barrier properties were
originated from the improved interfacial compatibility between BN@CF
and epoxy matrix and lengthened diffusion path of corrosive agents.
EIS plots were further applied to evaluate the anticorrosion perfor­
mance of the coatings. Fig. 6 presents Nyquist and Bode plots of the
steels coated with EP, EP/F-BN, EP/PDA-CF, and EP/BN@CF coatings
during immersion in 3.5 wt% NaCl solution for 40 days. The semicircle
Fig. 5. Evolution of OCP values of the coatings.
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Composites Science and Technology 228 (2022) 109646
diameters of the capacitive loops of the specimens decreased with
increasing immersion time, indicating gradual reduction in anticorro­
sive performance. However, with respect to EP/BN@CF, the semicircle
diameters of the capacitive loops did not present an obvious decreasing
trend, and were much larger than those of the others. The larger semi­
circle diameters of EP/BN@CF coating suggested that it provided
optimal corrosion protection. Impedance modulus at lowest frequency
(Zf = 0.01Hz) is an effective parameter for evaluating the corrosion
resistance of coatings. After immersion for 5 days, Zf = 0.01Hz values of all
the coatings exceeded 109 Ω cm2, except EP coating. At the end of im­
mersion, Zf = 0.01Hz values of EP, EP/F-BN, and EP/PDA-CF coatings
decreased to 4.15 × 106, 6.05 × 106 and 5.60 × 106 Ω cm2, respectively.
Nevertheless, Zf = 0.01Hz value of EP/BN@CF coating slowly fell to 6.25
× 108 Ω cm2, which was approximately two orders of magnitude higher
than those of other coatings. The higher Zf = 0.01Hz value of EP/BN@CF
coating suggested its better corrosion resistance. Bode-phase spectra of
the coatings were shown in Fig. 6 (a3-d3). The coatings gradually showed
two time constants as immersion time increased. The time constant
located between 103 and 105 Hz reflected the coating dielectric char­
acteristics, whereas the time constants located between 103 and 105 Hz
and between 10◦ and 103 Hz indicated defect response and corrosion
response, respectively. In terms of pure EP coating, phase spectra
exhibited obvious defect response and corrosion response after 5 days of
immersion, suggesting that the pure EP coating failed rapidly as the
immersion time increased. Compared with the pure EP coating, EP/F-BN
and EP/PDA-CF coatings exhibited obvious corrosion response after 20
days of immersion. For EP/BN@CF coating, phase spectra did not
exhibit obvious corrosion response until immersion in 3.5 wt% NaCl
solution for 40 days, and the addition of BN@CF effectively filled the
pores of the coating and improved the compactness of the coating.
Moreover, corresponding equivalent electric circuits were used in
fitting the EIS plots (including Modes I and II), as shown in Fig. 6e. In
Modes I and II, Rs is the solution resistance; Rc and Rct correspond to the
coating resistance and charge transfer resistance, respectively, and Qc,
Qdl, and Zw represent coating capacitance, double-layer capacitance,
and Warburg impedance, respectively [29]. Variations in the Rc and Rct
values as function of immersion time were shown in Fig. 6(f and g).
Generally speaking, Rc value always decreased with extending the im­
mersion time which was attributed to the ingress of the aggressive
species. Rc values of the pure EP dropped dramatically from 8.79 × 107
Ω cm2 to 9.70 × 105 Ω cm2 during the immersion for 10–20 days. This
result was attributed to the penetration of the corrosive agents to the
K. Wang et al. Composites Science and Technology 228 (2022) 109646

Fig. 6. Nyquist and Bode plots of the coatings at different time intervals (a1-a3) pure EP, (b1-b3) EP/F-BN, (c1-c3) EP/PDA-CF, (d1-d3) EP/BN@CF. (e) Equivalent
electrical circuits (f) Rc and (g) Rct of the coatings at different time intervals.

coating/substrate interface and the initiation of electrochemical reac­
tion. In contrast, Rc values of EP/F-BN and EP/PDA-CF coatings
decreased from 1.80 × 109 and 1.95 × 109 Ω cm2 to 1.09 × 106 and 2.70
× 106 Ω cm2 during the whole immersion process. For EP/BN@CF
coating, Rc values finally fluctuated to 1.05 × 108 Ω cm2, which was
about two magnitude higher than those of EP/F-BN and EP/PDA-CF
coatings. In addition, Rct values showed a downward trend as a whole
during the immersion stage (Fig. 6g). At the end of immersion, Rct value
of EP/BN@CF coating was 4.10 × 109 Ω cm2, which was four magni­
tudes higher than that of pure EP coating and two magnitudes higher
than those of EP/F-BN and EP/PDA-CF coatings. These findings proved
that the superior interfacial properties of BN@CF effectively reduced
microspores or defects of the coating and reinforced the corrosion
resistance of epoxy coating.
To further investigate the local corrosive phenomena and developing
process of the defects, localized electrochemical impedance spectrum
(LEIS) test was carried out in investigating coatings with artificial de­
fects (approximately 1.0 mm long and 0.2 mm wide) in 3.5 wt % NaCl
solution at different time nodes (Fig. 7). We easily found that the
impedance value increased with increasing distance from the defect. The
lowest impedance modulus at the center of defect on the LEIS map
corresponded to the maximum of admittance values. After 2 h of im­
mersion, the lowest |Z|local values for pure EP, EP/F-BN, EP/PDA-CF,
and EP/BN@CF were 3.00 × 105, 6.43 × 105, 7.84 × 105 and 1.15 × 106
Ω cm2, respectively. The results suggested that the corrosion reaction at
the defect for pure EP was more intense than those of the composite

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K. Wang et al. Composites Science and Technology 228 (2022) 109646

Fig. 7. LEIS mappings for (a) pure EP, (b) EP/F-BN, (c) EP/PDA-CF, (d) EP/BN@CF immersed in 3.5 wt% NaCl at different time intervals.

coatings. In the case of EP/BN@CF, the diffusion of corrosion medium to for 48 h.

the defect was slower than that in the other coatings. This phenomenon
mainly resulted from the superior interfacial adhesion between BN@CF
and epoxy matrix and the uniform dispersion of the BN@CF hybrid in
the epoxy matrix. As the immersion time increased, the “dark blue” area
on the maps gradually increased, indicating the increase in the degree of
electrolyte invasion. However, the lowest impedance modulus with
respect to EP/BN@CF was still greater than 106 Ω cm2 after immersion
3.5. Characterization of morphology and structure of steel after corrosion
After 40 days of immersion, the coatings were mechanically peeled
off from the steel substrates, and the surface morphology under the
coatings was analyzed through SEM. For the steel substrate coated with
pure EP coating, corrosion products began to appear on the surface of

Fig. 8. SEM images and corresponding surface roughness of steels coated by (a) pure EP, (B) EP/F-BN, (c) EP/PDA-CF, (d) EP/BN@CF. EDS results (e) and Raman
results (f) of steel surface coated by the coatings. (g) Corrosion mechanism of EP/BN@CF coating.

7
K. Wang et al.
steel after immersion for 13 days. Therefore, large amounts of corrosion
products were generated on the steel surface coated with pure EP
coating at the end of immersion (Fig. 8a). With regard to the steel pro­
tected by EP/F-BN or EP/PDA-CF coating, corrosion occurred after 25
days of immersion. As immersion time increased, corrosion products
were gradually accumulated on the steel substrates protected by the EP/
F-BN and EP/PDA-CF coatings. By contrast, no obvious corrosion
products were observed on the steel protected by EP/BN@CF coating,
and the surface morphology of the steel was similar to that of ground
steel. Laser confocal microscope (LSM) results showed the surface
roughness (R) of the steel substrates after the coatings were peeling off.
The surface roughness of the steel substrates coated with pure EP, EP/F-
BN, EP/PDA-CF, and EP/BN@CF coatings were 5.03, 2.20, 2.53, and
1.12 μm, suggesting that the steel coated with EP coating suffered from
serious corrosion. Steel coated with EP/BN@CF coating was not
evidently corroded. In Fig. 8e, the corresponding EDS results exhibited
the element composition of the steel surfaces after immersion for 40
days. Due to the corrosion reaction of the steels was caused by the water,
oxygen and NaCl solution, about 51.94 wt% Fe, 40.84 wt% O and 7.23 C
element were detected on the steel surface protected by pure EP, which
indicated the steel was severely corroded. In terms of the steels pro­
tected by EP/F-BN and EP/PDA-CF coatings, about 25.14 wt% and
26.97 wt% O element were observed, respectively. In addition, a small
amount of Cl element was still tested. As far as the steel protected by EP/
BN@CF coating was concerned, element composition was just Fe and C,
which also indicated the substrate was not obviously corroded. Raman
spectra were used in identifying steel corrosive products on the surface
(Fig. 8f). The steel coated with pure EP coating displayed bands at 307,
Fig. 9. (a) Mean COF under 5 N, 2 Hz and 30 min, (b) cross-sectional profiles of the wear tracks and (c) wear rate. (d) 3D profiles and SEM image.
8
Composites Science and Technology 228 (2022) 109646
387, 418, 544, and 719 cm− 1, which corresponded to β-FeOOH and
Fe2O3 corrosion products [30], and implied serious corrosion on the
steel surface. The steel protected by EP/F-BN coating showed typical
corrosion activities at 220, 282, 399, 484, and 599 cm− 1, which corre­
sponded to the Fe3O4 corrosion products [31]. This result was similar to
that obtained in the steel protected by EP/PDA-CF coating. As we ex­
pected, a weak peak at 663 cm− 1 related to Fe3O4 was detected for the
steel protected by the EP/BN@CF coating. The results were in agree­
ment with the SEM and energy dispersive spectrometer (EDS) results.
3.6. Corrosion protection mechanism of the EP/BN@CF composite
coating
As stated in EIS, OCP, and LEIS results and the corrosion morphology
of steel substrates, the introduction of BN@CF significantly enhanced
the corrosion resistance of the composite. F-BN chemically grafted on
the surface of PDA-CF and formed a BN@CF hybrid. The special struc­
ture of BN@CF increased the surface roughness of fibers and greatly
enhanced the interfacial compatibility between BN@CF and epoxy
matrix. Furthermore, BN@CF improved the compactness of the coating
by filling the microdefects of the coating, zigzagged the passages of the
electrolyte, and prolonged the durability of the coating. The corrosion
resistance mechanism of EP/BN@CF coating protected steel is depicted
in Fig. 8g.
K. Wang et al.
3.7. Tribological properties of the pure EP, EP/F-BN, EP/PDA-CF and
EP/BN@CF coatings
To study the effects of additives on the tribological properties of the
composite coatings, we examined the coefficient of friction (COF), cross-
sectional profiles of the wear tracks, and wear rate (Fig. 9). According to
the COF curves of the samples, EP/BN@CF composite coating presented
the best friction property and the lowest COF (0.28), which decreased by
37.8% compared with pure EP. The outstanding friction reduction of the
EP/BN@CF coating might be ascribed to the following reasons. First,
grafting F-BN on PDA-CF improved the surface roughness and improved
the interfacial compatibility between the fibers and matrix. Second, the
BN@CF dispersed uniformly in the coating enhanced the strength and
hardness of epoxy matrix and thereby indirectly reduced friction. Third,
BN@CF was exposed to the abraded surface and formed a thin transfer
film during the friction test [32].
As shown in the histogram, the wear rates of EP/F-BN, EP/PDA-CF,
and EP/BN@CF obviously decreased compared with the wear rate of
pure EP coating. Importantly, BN@CF hybrid had a superior effect than
single PDA-CF or F-BN reinforcement. The wear rate of EP/BN@CF
composite decreased by 83.0% relative to that of pure EP. The 3D pro­
files of the wear scars showed that the widest and deepest wear scar
emerged on pure EP surface and the narrowest and shallowest wear scar
Fig. 10. (a) Schematic diagram of worn surface evolution of EP/BN@CF composite. (b) TEM image of tribo-film formed on wear scar of EP/BN@CF composite and
(c) HRTEM image of tribo-film in Fig. 9b. (d) HAADF image of tribo-film in Fig. 9c. (e) Mapping images of the tri-film in Fig. 9d.
9
Composites Science and Technology 228 (2022) 109646
emerged on the EP/BN@CF surface. To further explore the enhancing
effects of additives on tribological properties, we observed the
morphology of wear traces through SEM. The results were exhibited in
Fig. 9d. The images presented track widths of 777.8, 617.3, 646.6, and
486.1 μm for pure EP, EP/F-BN, EP/PDA-CF, and EP/BN@CF coatings,
respectively. These values were in agreement with the wear rate results.
Numerous cracks and deep furrows existed on the destroyed worn sur­
face of pure EP. In the case of EP/F-BN, it had a relative smooth wore
surface than pure EP. The reason could be attributed to the nano-size
effect of F-BN and the decreasing wear rate. Cracks and furrows could
also be viewed for EP/PDA-CF, it was noteworthy that the cracks did not
completely crack and some small cracks existed on the worn surface. The
findings might result from the high tensile strength and elastic modulus
of carbon fibers strengthened the performance of anti-wear. In terms of
EP/BN@CF, friction surface became rough and several shallow cracks
were observed suggesting it only experienced slight wear and presented
optimal wear resistance among the coatings. The better enhancement
effect of BN@CF on the tribological properties of the epoxy matrix was
mainly ascribed to the special BN@CF structure, which considerably
improved the interfacial compatibility between the fibers and matrices.
The schematic diagram of worn surface of EP/BN@CF composite was
displayed in Fig. 10a. When EP/BN@CF composite started to show wear,
BN@CF was exposed to the abraded surface and formed a thin transfer
K. Wang et al.
film under shear stress. Accordingly, the wear resistance of EP/BN@CF
was greatly improved. Notably, BN@CF has excellent interfacial
compatibility with epoxy matrix, which further enhanced the mechan­
ical properties of the EP/BN@CF composite and boosted the transfer of
applied stress from the epoxy matrix to BN@CF. We adopted a visual
method using focused ion beam (FIB) SEM and transmission electron
microscope (TEM) to observe the morphology of the tribo-film. The
cross-sectional TEM images of the tribo-film on the wear track of EP/
BN@CF were displayed in Fig. 10(b and c). A layer of tribo-film was
observed between Pt and 316 L steel (Fig. 10c). The mapping images of
the tribo-film included B, C, Si, N, Fe and O elements, proving that the
tribo-film contained BN@CF. Therefore, the excellent tribological
properties were mainly due to the fabricated BN@CF with special
microstructure.
4. Conclusions
We designed and successfully developed BN@CF hybrid by chemi­
cally grafting F-BN on PDA-CF surface to increase the interfacial adhe­
sion strength between fibers and epoxy matrix. EP/BN@CF showed
13.8% and 87.2% improvement in tensile strength and IFSS, respec­
tively, compared with pure EP. EP/BN@CF coating exhibited extraor­
dinary anticorrosion performance, which greatly enhanced impedance
by two orders magnitude higher than those of other coatings. Notably,
the COF and wear rate of the EP/BN@CF decreased by approximately
37.8% and 83.0%, respectively, relative to those of pure EP. The
outstanding anticorrosion and wear resistance of BN@CF reinforced
epoxy composite suggested its potential application in corrosion resis­
tance and wear resistance fields.
Author statement
Kui Wang: Investigation, Resources, Data Curation, Writing-Original
Draft.
Lu Shen: Supervision, Project administration, Funding acquisition.
Nengbo Wen: Software, Formal analysis.
Qiong Jiang: Test, Measurement.
Author contributions
The manuscript was written through contributions of all authors. All
authors have given approval to the final version of the manuscript.
Notes
The authors declare no competing financial interest.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
We gratefully appreciate the National Natural Science Foundation of
China (No. 51801172), Natural Science Foundation of Zhejiang Prov­
ince (No. LQ20E020002), School-level Research Projects of Yancheng
Institute of Technology (No.xjr2020002, xjr2021039) for the financial
support of this research work.
Appendix
CCs carbon fiber-reinforced composites
F-BN functional hexagonal boron nitride
EP epoxy resin
10
Composites Science and Technology 228 (2022) 109646
h-BN hexa-boron nitride
CFs carbon fibers
CNT carbon nanotube
DI water deionized water
EIS electrochemical impedance spectroscopy
TEM transmission electron microscope
XPS X-ray photoelectronic spectroscopy
LEIS: localized electrochemical impedance spectrum BN@CF:
hexagonal boron nitride modified carbon fiber
PDA-CF polydopamine modified carbon fiber
IFSS interfacial shear strength
MOFs metal-organic frameworks
PDA polydopamine
GO graphene oxide
KH560 3-Glycidyloxypropyltrimethoxysilane
SEM scanning electron microscope
SPM scanning probe microscope
OCP open circuit potential
EDS energy dispersive spectrometer
COF coefficient of friction
FIB SEM focused ion beam SEM
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.compscitech.2022.109646.
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