Surface & Coatings Technology 390 (2020) 125682

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Surface & Coatings Technology

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

Enhancing the corrosion resistance of Q235 mild steel by incorporating poly T

(dopamine) modified h-BN nanosheets on zinc phosphate-silane coating
⁎
Mustafa Muhammad, Shihao Hu, Ruina Ma, An Du, Mengzhe Wang, Yongzhe Fan , Xue Zhao,
⁎
Huazhen Yang, Chong Chong Li, Xiaoming Cao
School of Materials Science and Engineering, Hebei University of Technology, Key Lab for New Type of Functional Materials in Hebei Province, Tianjin Key Lab Material
Laminating Fabrication and Interface, Tianjin Engineering and Technology Centre for Environmental-friendly Coating on Pipeline Tianjin, 300132, People's Republic of
China

A R T I C LE I N FO A B S T R A C T

Keywords: Phosphate-silane coatings were developed on the Q235 mild steel by incorporating poly(dopamine) modified h-
Zinc phosphating BNs into the zinc phosphating bath to enhance the corrosion resistance. The effects of PDA modified h-BNs with
Corrosion resistance varying concentrations (0.10–0.90 g/L) on the surface modification, and corrosion resistance of the composite
Boron nitride coatings were investigated. Results show that denser and uniform coatings were achieved for samples containing
Mild steel
poly(dopamine) modified h-BN. Sample 0.60 g/L attained outstanding corrosion resistance, which is in one order
Dopamine
of magnitude lower than the pure coatings with a current density of 1.95 × 10−5 A/cm2. Modified h-BN ef-
Silane treatment
fectively accelerates and enhances the corrosion resistance of the phosphate-silane coatings.

1. Introduction hazardous and intoxicated accelerators (nitrites, nitrates, chlorates, and

Steel is an essential and cost-effective engineering material that is
being utilized in the construction and automotive industries. However,
corrosion limits its effectiveness when being subjected to different en-
vironments. Various techniques towards its corrosion protection have
been employed, such as anodic and cathodic protection, protective
metallic coatings, organic coatings, and inhibitor additions [1–4].
Surface pretreatment has been considered as a primary treatment for
zinc coatings to protect and enhance their corrosion resistance com-
monly practiced in industrial processing by developing a protective
layer on the surface of metallic substrates, to create the bonding of the
organic coatings on the surface of metal giving short-term lubrication
and insulation protection towards corrosion [5]. However, a variety of
chemical conversion coatings such as chromate coatings, phosphate
coating, and molybdate coating have been studied, but chrome coating
has a better performance of them all [6,7]. Unfortunately, great harm
has been done to the environment because of chromium salts. There-
fore, phosphate coating is considered environmentally acceptable for
surface pretreatment [8,9].
Phosphating, with the development of the modern industry, a
technique with an environmentally friendly nature and an essential
chemical conversion process, has been practiced for domestic and au-
tomotive purposes. Surface treatment overcame the problem of
hydroxylamine) and additives for ferric and non-ferric materials with
incredible cost-effectiveness, active applicability, more reliable adhe-
sion, and lubricity [10]. However, corrosion resistance of zinc phos-
phate coating is limited and sometimes did not satisfy the required
industrial requirements while affecting the corrosion-resistant perfor-
mance of the whole coating operation [11].
Recently, many researchers put many efforts and employed different
methods to improve the corrosion resistance of phosphate coating. The
phosphate coating thickness was enhanced by changing the reaction
time, temperature or accelerators of various kinds were added into the
phosphating bath [12,13]. Firstly, accelerators were added into the
phosphating bath to improve the phosphate coating thickness. Amini
et al. had improved the phosphate coating thickness formed on the
magnesium AZ31 alloy by employing sodium dodecyl sulfate (SDS) as
an accelerating agent [14]. Secondly, dense phosphate coatings were
developed onto the surface of a metallic substrate by doping metallic
ions as an additive. Rezaee et al. used a metallic ion additive Mn+2 ion
and developed a low-temperature zinc phosphate coating to enhance
corrosion resistance, forming a dense and compact phosphate coating
doped with Mn+2 ions on the surface of mild steel [15]. Furthermore,
the phosphate coating structure was enhanced by co-precipitating na-
noparticles into the coating structure to improve the barrier perfor-
mance. The pure phosphate coating was formed on a galvanised zinc

⁎
Corresponding authors.
E-mail addresses: fyz@hebut.edu.cn (Y. Fan), gd_sam@galvanize.com.cn (X. Cao).

https://doi.org/10.1016/j.surfcoat.2020.125682
Received 20 November 2019; Received in revised form 20 March 2020; Accepted 21 March 2020
Available online 23 March 2020
0257-8972/ © 2020 Elsevier B.V. All rights reserved.
M. Muhammad, et al. Surface & Coatings Technology 390 (2020) 125682

surface by Shibli et al. with higher corrosion resistance performance by Table 1

incorporating TiO2 nanoparticles into the phosphating bath, which has Chemical composition of Q235 mild steel.
enhanced the barrier protection properties [16]. Element C S Si P Mn Fe
Subsequently, a dihydric phosphate solution was used in the phos-
phating bath for the improvement of silane coating to the inter- weight% 0.22 0.05 0.35 0.05 1.40 Balance
molecular interaction between the adhesion of the layer and the
phosphate coating. Y. Yue et al. developed a dihydric phosphate solu-
tion to form a phosphate-silane pretreatment surface on the AZ31 2. Experimental method
magnesium alloy in a hot-humid environment to enhance its corrosion
protection performance, adhesive-bonded ability, and durability [17]. 2.1. Materials
The efficiency of nanoparticles like TiO2 was less effective with the low
specific area showing poor ability in capturing and depositing free ions Phosphoric acid (H3PO4) 85%, Phosphorous acid (H3PO3) 99%,
and phosphate crystals due to spherical shape. Higher concentration epoxy functionalized silane (3-glycodyloxypropyltrimethoxysilane)
was required for the co-precipitation method of such nanoparticles were obtained from Shanghai Macklin Biochemical Co., Ltd. (China). Zn
combined with some chemical accelerators. Graphene oxide (GO) two- (H2PO4)2·2H2O, Zn(NO3)2·6H2O, and NaOH were purchased from
dimensional (2D) material, nanosheets with the high specific area were Tianjin Aladdin Co., Ltd., respectively. Hexagonal Boron Nitride (h-BN)
employed in the phosphating bath to proficiently overcome the dis- nanosheets, dopamine hydrochloride, and Tris (hydroxymethyl ami-
advantage of capturing the metal ions followed by the nucleation of nomethane) were procured from Shanghai Aladdin Biochemical
phosphate crystals. Xie Y et al. used the GO-phosphate coating on steel Technology Co., Ltd. (China). The commercially available Q235 steel
which showed better corrosion resistance and uniform crystal structure specimens were used for the zinc phosphating experiments and were
but required concentrated acid and active oxidant agents, which con- cut into the dimensions of 40 mm × 40 mm × 3 mm having a com-
sumed more energy that makes it non-eco-friendly [18]. Because of position as given in Table 1. In this work, all the chemicals employed
nanomaterial's unique and extraordinary properties, another 2D-mate- were of empirical grade and utilized as obtained without additional
rial, hexagonal boron nitride (h-BN) gained significant attention to- purification.
wards research and has been enormously used in many potential ap-
plications [19,20]. It has been broadly used in industrial applications 2.2. Synthesis of poly(dopamine) modified hexagonal boron nitride (h-
with leading mechanical strength, higher thermal stability, resistivity BN@PDA)
towards corrosion, chemical inertness, and corrosion resistance, making
it an advantageous material for anti-corrosion applications [21,22]. The 2D boron nitride (h-BN) nanosheets of 0.6 g were dispersed into
However, many studies of boron nitride nanosheets have faced specific a solution mixture of 0.16 g Tris (hydroxyethyl aminomethane). The
weaknesses, comprising the bulkier size of the boron nitride particles solution mixture was sonicated for about 30 min, further adding to the
and their insufficient distribution strength. Additionally, hexagonal mix of 30 ml ethanol and dopamine hydrochloride of 0.24 g while
boron nitride tends to agglomerate due to its poor blending properties constantly stirring at 60 °C for 6 h, to improve the dispersibility of BNs
with matrix, limiting the anti-corrosion applications of BN nanosheets nanosheets and slowing down the polymerization rate of poly(dopa-
[23]. Therefore, in this work, poly(dopamine) modified boron nitride mine), which also prevents the BNs aggregation with each other.
nanosheets are employed for the development of phosphate coatings on
the mild steel to improve its anti-corrosion performance. Besides, the 2.3. Mild steel surface pre-treatment
existence of micropores in the phosphate coating leads to the low cor-
rosion resistance of the phosphate coated steel. Therefore, many or- The Q235 steel specimens were first discreetly ground and refined
gano-silane surface pretreatments have been investigated and found to by sandpapers of 600 and 800 grits to remove dust particles or any
be environmentally safe with enhanced corrosion resistance perfor- other contaminants present on the surface. After careful polishing, the
mance as compared to the chromate procedures [17]. Silane coating has de-rusted steel samples were degreased in a solution of 10.0 weight
the superior sealing effect over the defects that arise in the phosphate percentage NaOH at 40 °C for 10 min. The deionized water was used to
coatings and also gives the composite layer resulting in the develop- clean these degreased steel specimens and finally dried at room tem-
ment of more enduring corrosion protection. perature.
In this present work, corrosion resistance of the mild steel speci-
mens is enhanced because of the unique properties of the poly(dopa- 2.4. Formulation of zinc phosphating bath
mine) modified hexagonal boron nitride nanosheets. For improving the
dispersibility and modification of the chemical joining between silane The zinc phosphating bath consists of phosphoric acid (85%),
(KH560) and zinc phosphate composite coating, we acquired a uni- phosphorous acid (99%), Silane (KH560), Zn(H2PO4)2·2H2O, and Zn
versal and straightforward technique for modifying the surface of (NO3)2·6H2O into a 1 litre (L) distilled water (H2O). The parameters,
hexagonal boron nitride (h-BN) by poly(dopamine) (PDA). Variant chemical composition of the bath, and operating conditions are given in
concentrations of poly(dopamine) modified hexagonal boron nitride Table 2. Before the phosphating procedure was carried out, a homo-
{(h-BN@PDA), 0.10–0.90 g/L} were added into the phosphating bath genous dispersion system of the PDA modified h-BN into the zinc
for the preparation of zinc phosphate coatings through co-precipitation phosphating bath was formed by ultra-sonication for 30 min while
on the surface of mild steel. Scanning Electron Microscopy (SEM), X-ray
Diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy Table 2
are used to characterize the poly(dopamine) modified hexagonal boron Chemical composition and working conditions of zinc phosphating bath.
nitride (h-BN@PDA). Scanning Electron Microscopy also investigates
Formulae Concentration Working conditions
the morphology and phase composition of the phosphate-silane coat-
ings (SEM), Energy Dispersive Spectrometer (EDS) mapping, X-ray H3PO4 (85%) 3.0 g/L Temperature: 40 °C
photoemission spectroscopy (XPS) and X-ray Diffraction (XRD). The KH560 (silane) 1.50 g/L Time: 30 min
evaluation of the anti-corrosion performance of the poly(dopamine) H3PO3 (99%) 2.0 g/L
Zn(H2PO4)2·2H2O 50 g/L
modified hexagonal boron nitride (h-BN@PDA) is tested by Copper
Zn(NO3)2·6H2O 80 g/L
Sulfate dropping tests, Potentiodynamic polarization (Tafel), h-BN@PDA 0–0.9 g/L
Electrochemical (EIS) measurements.

2
M. Muhammad, et al.
continuous stirring. Immersing de-rusted steel specimens into the
phosphating bath at 40 °C to prepare zinc phosphate-silane coatings for
30 min. The concentrations of poly(dopamine) modified h-BN na-
nosheets used for the zinc phosphating bath consisted of 0 g/l, 0.10 g/l,
0.30 g/l, 0.60 g/l, and 0.90 g/l and assigned as MBN-0, MBN-0.10,
MBN-0.30, MBN-0.60, MBN-0.90, respectively. Then, the Q235 mild
steel was introduced into the phosphating bath containing poly(dopa-
mine) modified hexagonal boron nitride. After the phosphating process,
the steel substrates were washed with distilled water to eliminate any
absorbed acid and soluble salts followed by drying with compressed air
at nominal temperature for further characterization.
2.5. Phosphate-silane coatings characterization
The surface morphologies and structure of phosphate-silane coated
steel specimens were investigated by employing scanning electron
spectroscopy (SEM; JSM-06510A, JEOL, Japan) at 20.0 kV acceleration
voltage, X-ray photoemission spectroscopy (XPS ESCALAB 250Xi,
Thermo Scientific), and X-ray Diffraction analysis (Bruker D8
ADVANCE), respectively.
Mass per unit area (MPA), the coating weight of phosphate coatings
(M − M )
was calculated according to the equation MPA = 1 S 2 , where M1
and M2 are the discarded mass of steel substrates before and after the
phosphate coating, while S is the surface area of a phosphate steel
specimens [24]. The specially prepared solution was used to calculate
phosphate coating deposited on the steel specimen, by dissolving the
phosphate coating completely while bare steel substrate was left be-
hind, being immersed in the solution at 70 °C for 5 min. Mass mea-
surement of steel specimens for pre dissolving process and post dis-
solving process was carried out and labelled as M1 and M2, respectively
[25].
2.6. Electrochemical measurements
Potentiodynamic polarization (Tafel) and Electrochemical im-
pedance spectroscopy (EIS) measurements, respectively, were utilized
to analyze the anti-corrosion performance of the phosphate-silane
composite coating on mild steel. A conventional three-electrode setup,
containing a saturated Ag/AgCl reference electrode, with the phos-
phate-silane treated steel samples as a working electrode (exposed area
of 1 cm2) including a counter electrode of platinum (Pt) foil was used.
The electrochemical working station CHI660E (chenhua, Shanghai,
China) was used. A 3.5% NaCl aqueous electrolyte was employed to
carry out the electrochemical tests of the phosphate-silane coated steel
specimens, which were performed at room temperature. The samples
for EIS measurements were set to a stabilization time of 400 s at an
open-circuit potential (OCPT) with an amplitude of 5 mV between
10 mHz–100 kHz frequency range. EIS results were observed and
evaluated by using software ZSimp Win (EChem Software, Q5 Ann
Arbor, MI, USA). The polarization curves were obtained by analyzing
the potentiodynamic polarization from the cathodic to an anodic region
(OCP −300 mV − OCP +300 mV) with a scanning rate of 1 mV/s. The
Tafel extrapolation provides the corrosion current density, electro-
chemical parameters, and corrosion potential by operating the program
connected to the electrochemical workstation. The reliability of the
tests was ensured by performing all the measurements three times, and
average values were adopted.
3. Results and discussion
3.1. Characterization of poly(dopamine) modified hexagonal boron nitride
(h-BN@PDA)
Fig. 1(a, b) illustrates the SEM images of the boron nitride and poly
(dopamine) modified hexagonal boron nitride. BNs nanosheets are
3
Surface & Coatings Technology 390 (2020) 125682
commercially round disk-shaped, exhibiting stronger Van der Waals
interactions, stacked and agglomerated together with a diameter of
256 nm and a thickness of 34 nm showing a well-flaked structure and
smooth surface (Fig. 1(a)) [26–28]. After modification, the aggregation
of BNs cannot be observed, while smaller and rough particles become
visible on the surface of BNs nanosheets to form poly(dopamine) par-
ticles during the modification. The XRD patterns of the boron nitride
and poly(dopamine) modified hexagonal boron nitride nanosheets
Fig. 1(c) illustrates the analytical details about the phase patterns. The
notable characteristic peaks at 26.9°, 41.6°, 43.9°, 50.2°, and 55.1°
could be attributed to (002), (100), (101), (102) and (004), respectively
crystallographic planes of boron nitride nanosheets [28–30]. After the
modification, the characteristic peak at (002) plane slightly decreases,
representing a new phenomenon that the diffraction peak intensity
dramatically decreases. Moreover, the strength of other peaks is also
weakened due to a poly(dopamine) layer on boron nitride. Therefore,
the XRD pattern of h-BN@PDA indicates the successful modification of
boron nitride with poly(dopamine) from the intensity of the diffraction
peaks.
FT-IR also confirms the successful modification of boron nitride
through poly(dopamine). Fig. 1(d) shows the comparative spectra for
BNs and h-BN@PDA, respectively. The existence of sharp peaks near
1376 cm−1 and 819 cm−1 belong to the BeN stretching vibrations and
B-N-B bending vibrations, respectively. The stretching vibrations at
3442 cm−1 were associated with –OH groups at the edge planes of BN
or surface moisture. A similar spectrum was obtained for poly(dopa-
mine) modified h-BN. However, new small absorption bands at
2924 cm−1 and 2854 cm−1 corresponded to symmetric and asymmetric
–CH2– stretching vibrations, respectively. The CeC bending vibrations
of phenol rings were located between 1300 cm−1 and 1600 cm−1, re-
spectively [31,32]. The boron nitride particles tend to agglomerate due
to the bulkier size and poor dispersion stability because of their com-
patibility with the phosphating solution, limiting their potential appli-
cation for anti-corrosion performance towards many applications.
The chemical inertness of BNs nanosheets is challenging to modify;
therefore, poly(dopamine) is being utilized for the surface modification
of BNs nanosheets, as shown in Fig. 2 [23]. Digital photos of boron
nitride and poly(dopamine) modified boron nitride nanosheets, dis-
persed in phosphating bath at a concentration of 0.30 g/L after 5 min of
sonication are shown in Fig. 2. The BNs and h-BN@PDA were dispersed
in phosphating bath after 5 min of sonication, exhibiting the color of
white and greyish, respectively. However, BNs nanosheets were pre-
cipitated at the bottom while h-BN@PDA remained well-dispersed in
the phosphating bath after 3 h and 6 h respectively. The h-BN@PDA
reduced its compatibility with the phosphating solution with time due
to the PDA layer over the BNs nanosheets and confirmed the mod-
ification of BNs nanosheets (Fig. 2).
3.2. Presence of boron nitride in h-BN@PDA incorporated phosphate-silane
coatings
Phosphate-silane coated samples incorporated with h-BN@PDA
were examined by high-quality SEM to analyze MBN-0 (pure coating
specimen) and MBN-0.30 g/L (h-BN@PDA incorporated phosphate-si-
lane coating) specimens, to prove the presence of poly(dopamine)
modified boron nitride nanosheets into the composite phosphate-silane
coating. The development of phosphate film is an intricate and complex
electrochemical process. Fig. 3 shows that both the samples have uni-
formity and compactness, but the smooth surface can be seen in MBN-
0.30 g/L samples. During the phosphating process, big phosphate
crystals are deposited on the surface of MBN-0 specimen while some
part is left uncoated with phosphate crystals, as shown in Fig. 3(a).
In contrast, smaller phosphate crystals can be seen in some parts of
the specimen, as shown in Fig. 3(a). High-resolution scanning electron
microscope (FE-SEM) Fig. 3(b) shows the stacking of phosphate parti-
cles with larger area remained uncoated. However, a primary
M. Muhammad, et al.
Fig. 1. SEM image of (a) BNs, (b) h-BN@PDA, and (c) XRD layout of BNs, h-BN@PDA. (d) FT-IR spectra of BNs and h-BN@PDA.
phosphate is converted into an insoluble tertiary phosphate during the
phosphating process and sediments on the surface of a metal, which
leads to the beginning of an intricate chemical and electrochemical
process for the formation of phosphate film. Five steps were considered
to be developed on steels during the composition of conversion coat-
ings, as studied by Ghali et al., that includes an electrochemical en-
counter of steel in an acidic medium, a small incursion of re-liberated
phosphoric acid (H3PO4) on steel, asymmetrical deposition, irregular
crystallization and crystalline reconstruction [33].
At an initial phosphating stage, the asymmetrical shape of phos-
phate salts comprises mostly of smaller phosphate particles. A simple
phosphating bath (MBN-0) lacks efficiency consisting of noncrystalline
phosphate salts, with no additional accelerators, it cannot promote
growth into a crystalline form. While stacked phosphate crystals could
be seen at the significant areas in MBN-0.30 specimens possessing and
displaying more uniformity and denseness than MBN-0 specimen, as
shown in Fig. 3(c). We are hence showing that the compactness of the
final coating was effectively enhanced with the introduction of
Fig. 2. Digital Photos of BNs and h-BN@PDA nanosheets dispersion stability in phosphating bath at 0 h, 3 h, and 6 h.
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Surface & Coatings Technology 390 (2020) 125682
modified h-BN into the phosphating-silane bath. Fig. 3(d) from the FE-
SEM, we can observe that the poly(dopamine) modified hexagonal
boron nitride can be well scattered into the phosphate-silane coating,
exhibiting not entirely on the surface of phosphate crystals but also
below them as a part of crystals. This unusual phenomenon could be
associated with the co-precipitation and adsorption of poly(dopamine)
modified hexagonal boron nitride (h-BN@PDA). It shows that the
phosphate crystals modify a homogeneous dispersion indicating a ro-
bust interfacial adhesion between the hexagonal boron nitride and
phosphate coating.
3.3. Energy-dispersive spectrometer mapping of h-BN@PDA incorporated
phosphate-silane coating
Energy-dispersive spectrometer (EDS) mapping was analyzed at
20.0 kV on the MBN-0.60 specimen surface to characterize the ele-
mental distribution of the phosphate-silane coating. Elemental
Distribution and surface morphology of the phosphate-silane coating is
M. Muhammad, et al.
Fig. 3. The phosphate-silane coating's high-quality SEM image in a phosphating bath of MBN-0 (a, b) and MBN-0.30 (c, d).
shown in Fig. 4. The phosphate salts are represented by O and P ele-
ments in the EDS mapping. The entire region of the substrate shows the
homogenous occurrence of P and O elements, which explains that the
big crystals and the gaps within the phosphate sample together re-
present the phosphate crystals possessing different appearances. The
EDS mapping showed the Fe elements which possibly come from the
(phosphophylite Zn2Fe(PO4)2·4H2O), P-Fe-Zn crystals or steel substrate
altogether. Because phosphate coating is permeable, and the electron
beam can infiltrate through it, showing a more considerable amount of
Fe elements. EDS mapping represented a massive concentration of Zn+2
ions at the phosphate crystals in the phosphating bath than at the gaps
and showed more Zn elements on the phosphate crystals. Likewise, the
mappings of B, Si, and N elements also showed up at small region of
phosphate coated samples, resulting in compactness of the phosphate-
silane coating. It can be seen from the FE-SEM in Fig. 3(d); the structure
of phosphate-silane crystals could easily co-precipitated by the mod-
ified h-BNs.
3.4. Coating weight of h-BN@PDA incorporated phosphate-silane treatment
The mass per unit area (MPA) determined the quality and density of
the phosphate-silane coatings by immersing steel samples into the
phosphating bath with varying concentrations of poly(dopamine)
modified h-BNs (0–0.90 g/L) at 40 °C for 20 min. MPA was calculated
by chemically eradicating the phosphate coating on the phosphate
coated steel to measure the weight loss. Significantly, the mass per unit
area of the coatings is improved by the addition of poly(dopamine)
modified h-BNs into the phosphating bath up to 26.8 g·m−2, as shown
in Fig. 5. The MPA for MBN-0 is 15.2 g·m−2. However, after h-BN@PDA
addition to the zinc phosphating bath, firstly MPA achieves the value of
19.3 g·m−2 for 0.10 g/L content. The values for MBN-0.10 and MBN-
0.90 decreased to be (19.3 g·m−2) and (18.5 g·m−2), respectively. The
increased weight of the coatings is caused by the modified h-BN@PDA
nanosheets that result in the accelerated production of the phosphate
crystals. Therefore, modified hexagonal boron nitride could be acquired
5
Surface & Coatings Technology 390 (2020) 125682
as an environmentally safe catalyst for preparing the phosphate film.
Therefore, MPA of the phosphate coatings would improve with the
addition of modified hexagonal boron nitride to the phosphating bath
following the similar operating conditions. Average values are adopted
for all measurements and repeated three times. It was observed that the
modified h-BN incorporated phosphate-silane coatings had increased
weight due to the accelerated formation of the phosphate crystals,
which is caused by the addition of modified h-BNs. Hence, from the
above point, modified h-BNs are considered the environmentally
friendly non-chemical accelerators at low temperature for the fabrica-
tion of larger-scale phosphate-silane composite coatings. Also, when the
concentration of modified BNs has increased; the weight of the coating
drops, as shown in Fig. 5. In our study, MBN-0.60 is considered to be
the most optimal for preparing phosphate-silane coating, as coating
thickness and coating weight of most of the phosphate-silane coatings
has a relation of 1 μm corresponding to 1.5–2 g−2 [11].
Hence, our study confirms that the heavier and uniform phosphate-
silane coating is produced by the introduction of poly(dopamine)
modified h-BNs into the phosphating bath at a low temperature as
compared to the pure coatings.
3.5. XRD characterization of poly(dopamine) modified h-BN
XRD analysis is employed to characterize the phase composition of
poly(dopamine) modified h-BN coated steel specimens (Fig. 6). XRD
pattern clearly shows that Zn3(PO4)2·4H2O (hopeite, JCPD file #37-
0465), Zn2Fe(PO4)2·4H2O (phosphophylite, JCPD file #29-1427) are
formed on the surface of steel specimen. XRD pattern shows no shift in
peak position representing that the addition of modified h-BN did not
change the nature of phosphate crystals of coatings. However, the peak
intensities of Zn3(PO4)2·4H2O increases with the increasing content of
modified h-BN, showing that the modified h-BN accelerates the for-
mation of Zn3(PO4)2·4H2O which allows the preferential growth of
phosphate crystals and does not change the phase composition of the
coating, while can enhance the preferential growth of the phosphate
M. Muhammad, et al. Surface & Coatings Technology 390 (2020) 125682

Fig. 4. EDS mapping of MBN-0.60 specimen. All images have scale bars of 5 μm.

crystals. Also, with the addition of h-BN@PDA into the phosphating
bath, the growth rate of hopeite increases as compared to the phos-
phophyllite.
3.6. XPS analysis of the coatings
The thickness, as well as smoothness of the surface appearance of
the specimen, increases after the phosphate-silane treatment. The de-
tailed study of the phosphate-silane composite coating is analyzed by X-
ray photoemission spectroscopy (XPS) of specific binding energies for
various elements. To investigate the elemental composition and che-
mical structure of the h-BN@PDA incorporated phosphate-silane com-
posite coating, X-ray photoelectron spectroscopy (XPS) analysis was
carried out. Fig. 7(a) shows the survey spectra of XPS analyses of the

Fig. 5. Phosphate-silane coatings weight versus varying concentrations of h-BN@PDA in the phosphating bath.

6
M. Muhammad, et al.
Fig. 6. XRD spectra of phosphate-silane coatings from phosphating bath at
varying contents of poly(dopamine) modified h-BN (0–0.9 g/L).
treated (MBN-0.60) and untreated (MBN-0) samples. According to the
electron binding energy, reacting products of the phosphate coating
consists of the main elements Fe, O, P, Zn, and C, while phosphate-
silane layer includes a large amount of C, O, and Si elements. Because of
Fig. 7. (a) XPS spectra of modified h-BN incorporated phosphate-silane coating. (b) C1s. (c) B1s. (d) N1s.
7
Surface & Coatings Technology 390 (2020) 125682
the key elements of silane “Y(CH2)3Si(CH3)3” are C, Si, and O elements.
Here, Y stands for “(CH2OCHCH2O)”, high intensity of these elements
shows a silane coating is formed on the surface of phosphate-silane
coated steel substrates (Fig. 8a–o) [34]. Compared with the XPS spec-
trums of MBN-0 and MBN-0.60, the wide-scan spectrum of the phos-
phate coated steel substrates displayed the peak components of C1s,
B1s, and N1s attributed to the existence of C, B, and N elements, as
shown in Fig. 7(a). However, the intensity of the C1s and B1s in MBN-
0.60 is due to the presence of modified h-BN, which mainly comes from
dopamine that suggests its successful introduction on to phosphate
coated steel surface. The detailed XPS analysis of particular electron
binding energies for various elements of the phosphate-silane coatings
was carried-out for attaining the principle of reacting products on the
surface of phosphate-silane coated steel specimens [35–38]. Fig. 7(b)
shows the XPS spectrum of C1s. High-resolution C1s spectra show peaks
at binding energies 283.8 eV, 284.5ev, 285.5 eV, and 286.5 eV corre-
sponding to CeSi species, C=C/C species, CeN species and C–N/C–O
species, respectively. The additional peak of the CeO species represents
the addition of the PDA layer over the BNs nanosheets. Fig. 7(c) shows
the spectrum of B1s; the existence of peaks at binding energies
190.78 eV, 190 eV, and 191.6 confirms the formation of B–O–C species,
BeN species and BeO species, respectively. Fig. 7(d) shows the spec-
trum of N1s with binding energies at 401.9 eV, 399.8 eV, and 403.3 eV
corresponding to CeN species, O=C–N species, and BeN species, re-
spectively. These chemical bonds are associated with the modified h-
BN@PDA and phosphate-silane coating [34]. The silanol bonds may
have increase the adhesive bond between the coated substrates and the
adhesive, which are difficult to distinguish thus improving the effect of
M. Muhammad, et al.
Fig. 8. SEM pictures of phosphate-silane coatings attained from the phosphating bath with varying content of modified h-BN at different times.
the bond strength in phosphate silane coated samples. The elemental
increase is due to the effect of hydrolysis and ring opening reaction of
the silane treatment in the phosphating bath, which could improve the
intermolecular interaction between the adhesive and the phosphate
coating and also the sealing effect of the phosphate-silane coating to the
micro pores.
8
Surface & Coatings Technology 390 (2020) 125682
3.7. SEM characterization
During the phosphating process, the microstructural changes that
occurred during phosphate coating are investigated through SEM. Also,
the phosphating mechanism is proposed and discussed.
Fig. 8(a–o) presents the SEM images of MBN-0, MBN-0.10, MBN-
0.30, MBN-0.60, and MBN-0.90, respectively, phosphate-silane com-
posite coatings during the phosphating process to evaluate the micro-
structure. It is evident from the images that the phosphate-silane
M. Muhammad, et al.
crystals progressively grow, and with the addition of modified h-BN
nanosheets, the increasing rate is accelerated, as shown in Fig. 8. The
crystals of the MBN-0.60 specimen showed the fastest growth rate. In
the early stage, phosphating for 1 min (MBN-0), showed no signs of any
crystal formation. While for the specimens having modified h-BNs@
PDA, there is an apparent crystal formation at the same stage. As the
phosphating time increases, small phosphate crystals are covering the
substrate; however, MBN-0 shows no crystal formation. The modified h-
BN@PDA would facilitate the crystal formation as well as precipitation
of phosphate crystals by propagating crystals smaller in size after
15 min of phosphating, as shown in Fig. 8(e). Fig. 8(h) shows the MBN-
0.30 sample after 15 min of phosphating, where small phosphate
crystals are fully covering the surface while the majority of the MBN-0
sample is uncoated. MBN-0.60 specimens achieved the most substantial
uniform crystal structure of phosphate-silane coatings Fig. 8(j–l). After
the phosphating process is completed, the crystals first decreased and
reached the smallest at the amount of MBN-0.30. As the amount of
modified h-BN@PDA nanosheets increases, the generation of smaller
crystals on the surface of the steel increases, covering the gap among
larger crystals of MBN-0.60. A uniform and well-distributed layer of
silane film is also produced on the phosphate-silane coating because of
the silane and steel substrate reaction, which filled the micropores ex-
isting in the phosphate coating, that could be seen on MBN-0.30 and
MBN-0.60 samples, respectively as shown in Fig. 8(i–l).
Furthermore, it is noted that after carrying out the phosphating
process, MBN-0.30 and 0.90 contains bigger phosphate crystals, which
is very different from MBN-0 and MBN-0.10. From this, it is observed
that the increased amount of modified h-BN@PDAs does not give thick
and more delicate phosphate coating. At the end of the phosphating, the
steel substrate remains uncoated at some parts for MBN-0.10, MBN-
0.30, and MBN-0.90, depicting a less compact structure.
The MBN-0.60 was observed to be deposited with modified h-BN@
PDA nanosheets under high-resolution SEM images, like GO sheets,
where phosphate crystals grow, proposing modified h-BN@PDA na-
nosheets as the active positions for the nucleation of phosphate crystals.
Additionally, MBN-0.30 and MBN-0.60 contained the higher content of
modified h-BN, resulting in phosphate crystals to be wrapped with a
higher content of modified h-BN. Like GO nanosheets, modified h-BN
similarly favored various orientations for phosphate crystal growth and
affecting the trend of phosphate crystals, resulting in the formation of
variant phosphate crystal structure [22]. Due to which growth of
crystals of MBN-0.30 and MBN-0.60 are strip-shaped crystals while
MBN-0 and MBN-0.10 form flat plate-like crystals. From the above
observation, modified h-BNs could be useful and change the kinetics of
crystallization reorganization.
3.8. Mechanism of phosphating process incorporated with modified h-BN
nanosheets
The development of phosphate-silane coating is an intricate che-
mical and electrochemical process with micro anodic and cathodic
terminals [39,40]. Furthermore, depending on the reaction between
silane and metallic substrate and hydrolysis of silane. During the
phosphating process, the immersion of metal in a phosphating bath
undergoes a series of chemical reactions depending on the mutual in-
teractions and oxidation-reduction reactions of the accelerators [41].
Because of the electrochemical attack of steel in the acidic media, when
the steel substrate is being immersed into a phosphating bath, acid
attacks and generates iron(II) ions (Fe2+) while liberating hydrogen gas
(H2) representing an anodic reaction of phosphating process.
Fe + 2H+ → Fe2 + + H2 ↑ (1)
Free phosphoric acid is being rapidly consumed by the H2 released
at the interfaces of a substrate and the phosphating solution due to the
increase of pH.
9
Surface & Coatings Technology 390 (2020) 125682
H3 PO4 → H2 PO−4 + H+ → HPO24− + 2H+ → PO34− + 3H+ (2)
Due to the increase in pH, conversion of primary soluble phosphate
to insoluble tertiary phosphate occurs and phosphate coating deposits
on the mild steel substrate, which are amorphous salts.
2PO34− + 3Fe2 + + 8H2 O → Fe3 (PO4 )2 ·8H2 O↓ (3)
2Zn2 + + Fe2 + + 2PO34− + 4H2 O → Zn2 Fe(PO4 )2 ·4H2 O↓ (4)
3Zn2 + + 2PO34− + 4H2 O → Zn2 Fe(PO4 )2 ·4H2 O↓ (5)
The whole reaction process depends on both the anodic and
cathodic electrodes, and at the speed of the reaction increases si-
multaneously. Modified h-BN nanosheets could be absorbed on the
surface of steel because of the particular leading area and other silanol
functional groups. Therefore, the ring-opening reaction starts between
the silanol functional groups and phosphating solution forming hy-
drogen bonding with –OH groups of the solution, and finally, a covalent
linkage with the substrate is formed, forming at least one bond of si-
licon from each silanol group with the substrate surface. Also, silanol
groups would react with the hydroxyl groups of the poly(dopamine)
residue present in the phosphating solution, which is much more active
groups present in PDA, forming a layer over the surface of the substrate
due to the self-polymerization process [42]. The hydrolysis reactions of
silane KH560 with Fe specimen are schematically represented as
[34,43]:
Y (CH2 )3 Si(CH3 )3 → Y (CH2 )3 Si(CH3 )3 + H2 O (6)
Fe (OH )2 + Y (CH2 )3 Si(CH3 )3 → OHFe − O − Si(OH )2 Y (CH2 )3 + H2 O
(7)
Y (CH2 )3 Si(CH3 )3 + Y(CH2 )3 Si(CH3 )3 → Y(CH2 )3 Si − O − SiY
(CH2 )3 + H2 O (8)
Eq. (6) shows that the silanol groups (Si-OH) are produced within
the silane solution during the hydrolysis reaction of silane KH560.
Therefore, hydroxides of the phosphate coating would react with these
silanol groups, forming a durable Si–metal bond (Eq. (7)), while re-
sidual silanol groups would be condensed into Si–O–Si bonds (Eq. (8)),
creating a vastly cross-linked three-dimensional network of silanol
chains. Similar to graphene oxide, hexagonal boron nitride by poly
(dopamine) nanosheets captures dissociative ions of Fe2+and Zn2+ and
deposits on the specimen serving as the sedimentary bed's [18].
Meanwhile, accelerating the phosphating process and promoting in the
formation of indissoluble phosphate crystals at unimpregnated cir-
cumstances. On the other hand, modified h-BN acts as the nucleation
site, which results in a dense and finer phosphate coating on the surface
of the steel.
3.9. Corrosion resistance of the phosphate-silane coating
3.9.1. Characterization by potentiodynamic polarization
To evaluate the corrosion-resistant properties of the phosphate
coated steel specimens, electrochemical analysis, potentiodynamic po-
larization, including EIS analysis, was performed utilizing a three-
electrode system. Fig. 9 and Table 3 represents the results of polariza-
tion curves of MBN-0, MBN-0.10, MBN-0.30, MBN-0.60, and MBN-0.90,
respectively. It could be evident from Fig. 9 and Table 3 that the in-
troduction of modified h-BN nanosheets to the phosphating bath sig-
nificantly shows a good effect on the corrosion behaviour of phosphate-
silane coated specimens. The excellent stability of thermodynamics in
the corrosive medium suggests that the corrosion potential (Ecorr) shifts
towards a positive direction because of the coating of an anticorrosion
layer. Table 3 represents that the Ecorr of untreated samples is more
negative than the modified h-BN treated phosphate samples. The cor-
rosion current density (iCorr) of the coatings was lowered, especially
after the addition of modified h-BN nanosheets showing excellent anti-
M. Muhammad, et al. Surface & Coatings Technology 390 (2020) 125682

inferior coating weight and compactness than MBN-0.90, thus re-

presenting less effective corrosion protection but better than untreated
sample MBN-0. The compactness and corrosion resistance of MBN-0.10
displayed almost similarity to that of MBN-0.
These results indicate that the modified h-BN incorporated in
phosphate-silane coatings offer better corrosion barrier and restrain the
invasion and transmission of corrosive electrolytes to the surface of the
metal.

3.9.2. Electrochemical impedance spectroscopy measurements

Electrochemical Impedance Spectroscopy (EIS) is assessed as the
most vital technique to examine the electrochemical characterization of
the phosphate-silane coatings incorporated with modified h-BNs by
poly(dopamine). Nyquist, Bode, and Phase Angle plots were used for
analyzing EIS measurements. EIS can be used to analyze the mechanism
of corrosion of the phosphate-silane coated steel specimens. The im-
pedance is a complex quantity with real component Z′ and imaginary
component Z″ generally represented in Nyquist and Bode plots for EIS
data of electrochemical cells. Nyquist plots of varyingly treated samples
represent the values of impedance spectra that are categorized by high-
Fig. 9. Potentiodynamic polarization curves of steel samples received from the
frequency capacitive loop and low-frequency inductive loop, which
phosphating bath.
signifies that the addition of modified h-BN nanosheets into the phos-
phating bath enhances the anti-corrosion performance of final zinc
Table 3 phosphate-silane coatings. To understand the mechanism of corrosion,
Parameters of the potentiodynamic polarization curve. the entire experiments of EIS testing were carried out at ordinary
Sample ECorr (V) iCorr (A/cm2) Corrosion rate (mil/year) η% temperature to establish the linearity measurements, causality, and
durability of the system [46]. Fig. 10 displays the EIS results of phos-
−4
MBN-0 −0.638 1.43 × 10 2.87 × 101
– phate-silane coatings. Fig. 10(a) displays the Nyquist plots of varying
MBN-0.1 −0.636 6.21 × 10−5 2.85 × 101 56%
MBN-0.3 −0.633 3.55 × 10−5 1.62 × 101 75%
concentrations of modified h-BN nanosheets. The semi-circle diameter
MBN-0.6 −0.557 1.95 × 10−5 8.93 × 100 86% increases with the addition of the modified h-BNs until MBN-0.60, as
MBN-0.9 −0.637 8.29 × 10−5 3.80 × 101 42% represented by the coating weight tests, and then decreases with the
increased content of the modified h-BNs. This analysis shows that the
most massive weight of coating gives the thicker coating thickness.
corrosion efficiency of phosphate-silane coated steel. Also, the value of Also, in a 3.5% NaCl solution, thicker phosphate coating possesses
Ecorr with specimens containing modified h-BNs shifts towards positive corrosion inhibition of higher value because of insulating features of
direction, depending largely on the coating intactness and mass of the phosphate-silane coating [47]. Higher the impedance, the broader the
deposited coating. And most positive shift is seen for MBN-0.60 spe- semi-circle size [48]. Fig. 10(b) shows the phase angle plots of phos-
cimen. Compared with that of the untreated sample, the iCorr of the phate-silane coated substrates. At higher frequencies, coating integrity
coated samples reduces by one order of magnitude, with a minimum is determined by phase angle (−θ), stating to be useful because of its
value of 1.95 × 10−5 A/cm2. exposure to the corrosive electrolytes [11]. The corrosion processes
According to Eq. (1), the percentage of protection efficiency (η) for usually act as follows: initially, the water that exists in the electrolyte
each phosphate coated steel sample was calculated. Where, i0Corr and solution penetrates inside to reach the coating and the metal substrate;
iCorr are the corrosion current densities of untreated and treated with finally accumulation of corrosion products onto the metal/coating in-
modified h-BNs for anti-corrosion film, respectively. The protection terface [49]. Modified h-BN@PDA would result in the superior struc-
efficiency (η) of the MBN-0.60 sample increases by almost 10% com- tural integrity of phosphate-silane coatings, and there are minimum
pared to other samples. Also, Eq. (2) was used for calculating the cor- possibilities of phosphate crystals to delaminate from steel specimens
rosion rate of each sample. Where, E, K, and ρ represents the equivalent, cathodically. Superior phase angles were obtained on the high-fre-
equivalent coefficient, and density of the steel [44]. The MBN-0 (un- quency range for all the h-BN@PDA incorporating coatings, compared
treated) has the maximum corrosion rate, which by the addition of the with the untreated coatings, as shown in Fig. 10(b). Fig. 10(c) shows
modified h-BN decreased, but with the increased concentration of Bode impedance plots. At low frequency the impedance value (|Z|0.01
modified h-BN reaches a minimum of 8.93 mills per year for MBN-0.60, Hz) shows the same arranging tendency as Nyquist plots, representing
by the one order of magnitude smaller than the MBN-0. that the anticorrosion performance of final phosphate-silane coatings
0
[(icorr − icorr )] are enhanced by the addition of modified h-BNs into the phosphating
η= 0
× 100 bath. However, MBN-0.60 has the highest impedance value (|Z|0.01 Hz),
icorr (1)
which is almost two orders of magnitude higher than the (MBN-0)
K × icorr untreated sample.
CR = These results reveal that the hexagonal boron nitride modified by
ρ×E (2)
poly(dopamine) incorporated on phosphate-silane coatings have out-
Denser and heavier phosphate coatings possessed the more effective standing inhibiting properties and are consistent with those derived
barrier protection from the corrosive electrolytic attacks, thereby from SEM and polarization curves. The EIS analysis indicates that the
achieving better properties of corrosion resistance [45]. SEM analyses EEC model is required to fit the results. The proposed EEC circuit of two
Fig. 8, and the coating weight tests Fig. 5 in our coating tests, the times constant for further investigations of the EIS measurements are
sample MBN-0.60 has achieved the most effective corrosion resistance fitted, consisting of five components represented in Fig. 10(d) [44]. This
with most substantial coating weight as well as densest coating com- circuit is constituted of solution resistance (Rs), charge transfer re-
pactness with one order of magnitude higher as compared to that of the sistance (Rct) and first constant phase element denoted as coating ca-
untreated substrate. While phosphate coated sample (MBN-0.30) shows pacitance (CPEc) in parallel with the pore resistance (Rc) of the coating

10
M. Muhammad, et al. Surface & Coatings Technology 390 (2020) 125682

Fig. 10. EIS measurements of phosphate-silane coating samples with different concentrations of modified hBN (a) Nyquist plots, (b) Phase angle plots, (c) Bode plots,
(d) equivalent circuit diagram.

Table 4
Electrochemical parameters based on the circuit.
Sample Rs (Ω cm2) Rc (Ω cm2) CPEc (Ω−1 cm−2) n CPEdl (Ω−1 cm−2) n Rct

MBN-0 6.47 229 2.42 × 10−4 0.55 9.5 × 10−4 0.52 378
MBN-0.1 3.71 705 7.57 × 10−4 0.62 4.67 × 10−4 0.61 489
MBN-0.3 5.34 899 1.14 × 10−4 0.66 1.79 × 10−4 0.69 566
MBN-0.6 5.60 1676 4.28 × 10−4 0.79 3.92 × 10−4 0.77 1183
MBN-0.9 4.42 159 3.20 × 10−3 0.59 4.66 × 10−4 0.62 359.5

resolved in the high-frequency region and is attributed to the intrinsic
properties of the coating, such as coating thickness, quantities, and pit-
holes in the coating. The fitting results are represented in Table 4. The
CPE can be defined as the constant phase element of the phosphate
coatings. CPEc and Rc could be representatives of the barrier properties
of the coating. It could be seen from the Table 4 that, because the
phosphate-silane coating has thicker coating thickness and the phos-
phate-silane coating adequately seals the pores in the phosphate coat-
ings, therefore the pore resistance Rc of the phosphate-silane coating is
noticeably higher than that of the untreated sample [17]. While the
final section symbolizes the second constant phase element denoted as
double-layer capacitance (CPEdl) in parallel with the charge transfer
resistance (Rct). The CPE has the impedance of the dispersion according
to the relation Z = [Y(jω)n]−1 Here, Z represents the impedance of
CPE, Y is the proportional factor, j is the imaginary number while ω is
the angle frequency with maximum imaginary impedance and n re-
presents the heterogeneity of the electrochemical reactions [44].
Table 4 presents the electrochemical parameters based on the circuit
that was fitted using ZsimpWin software. Therefore, proving the system
reliability and neglecting the abnormalities in the testing parameters
affected by the solution resistance (Rs), the chi-square values were also
relatively small, confirming the fitting results to be reliable. No no-
ticeable difference exists in Rs values. The calculated results show better
values for MBN samples than the untreated sample. As previously in-
dicated, h-BN modified by PDA enhances the corrosion resistance of the
phosphate-silane coating because of the increase in the homogeneity
and compactness of the phosphate-silane coating. However, MBN-0.90
specimens show a decline in charge transfer resistance because of the
increased content of the hexagonal boron nitride by poly(dopamine) to
the phosphating bath that leads to loss of coating resistance. Results
show that the h-BN@PDA addition leads to the increasing Rct values for
treated samples as compared to untreated samples. Because the silane
coating sealed the pores in the phosphate coating due to the thicker
coating thickness of the phosphate-silane coating, which results in the
increase of the barrier properties of the coating to corrosive solution
due to the decrease of micropores in the phosphate coating [49]. Be-
sides, the most significant increase was obtained for MBN-0.60, which
is three times larger than the MBN-0 specimen, although the further
increase in the content of modified h-BN nanosheets decreases the Rct
value. Hence, the results prove that the addition of Modified h-BN
sheets can also act as the barrier film to restrict the permeation and
transportation of corrosive electrolytes, thus giving larger Rct values.

11
M. Muhammad, et al.
Fig. 11. Different timings of copper sulfate test for color changing of phos-
phate-silane coating containing h-BN@PDA with the average measurements up
to five values.
3.10. Copper sulfate dropping corrosion tests
A spot-test method was employed to determine the corrosion re-
sistance of the phosphate-silane coating, in which CuSO4.6H2O solution
drop was dropped on to the surface of the sample and time to the
coating color change was recorded. The experiment of copper sulfate
dropping works on the principle of displacement reaction in such a way
that the Fe in the steel specimen is displaced by Cu+2 ions [50,51].
After the drop of CuSO4·6H2O solution on to the phosphate steel
sample, Cu+2 ions immediately react with the Fe of sample beneath the
phosphate coating, due to the porosity of phosphate coating. The dis-
placement reaction ends as the color of CuSO4 solution drop fades;
however, the sample corrodes. The coating color changing time is as-
sociated with the compactness of the phosphate coating.
Fig. 11 represents the time recorded for coating color change for
modified h-BNs incorporated on phosphate samples. Untreated samples
MBN-0 has the minimum color changing as compared with the MBN-
0.60 after the modified h-BNs incorporated into the phosphate-silane
coating. The time for MBN-0 is 60 s, while after the modified h-BNs
addition, the time for color change increases to 300 s for MBN-0.60. The
increasing amount of modified h-BNs into the phosphate-silane coatings
decreases to 120 s. The variation in time for the color change is ana-
logous to the findings of coating weight tests, SEM observations, Tafel,
and EIS characterization curves, as discussed above. In our case study,
the above analysis verifies that the MBN-0.60 contains the ideal con-
centration for high anti-corrosive efficiency for fabricating the phos-
phate-silane coatings.
4. Conclusions
This paper investigates the incorporation of hexagonal boron nitride
modified by poly(dopamine) (h-BN@PDA) to the phosphating bath by
phosphate-silane surface treatment to enhance Q235 mild steel corro-
sion-resistant performance. Varying amounts of h-BN@PDA
(0.10–0.90 g/L) were employed to phosphating bath for studying the
effects of polydopamine modified h-BN nanosheets on phosphate-silane
coatings. SEM characterizations, XRD patterns and XPS analysis verifies
that adding h-BN@PDA to phosphating bath effectively forms compact,
most substantial, thicker, and less porous phosphate coating structure
on phosphate-silane coated steel as compared to the untreated one.
Modified h-BN@PDA offers the sites for nucleation to deposit phos-
phate crystals and metal ions at the time of phosphating, hence im-
proving the phosphate coating on a metallic substrate. With a coated
layer of silane coating on the modified h-BN@PDA incorporated
phosphate samples, the coating obtains the denser and more elegant
structure with better anti-corrosive performance in an aqueous solution
12
Surface & Coatings Technology 390 (2020) 125682
of 3.5% NaCl. A significant improvement in the anti-corrosion perfor-
mance is achieved as compared to the pure phosphate-silane coatings.
Besides, the optimized concentration of MBN-0.60 (0.60 g/L of mod-
ified h-BN) sample shows the most substantial coating weight of 26.8 g/
m2 and the most reliable anti-corrosion performance (1.95 × 10–5 A/
cm2 of iCorr and 300 s for copper sulfate spot testing). Hence, hexagonal
boron nitride modified by poly(dopamine) h-BN@PDA could be em-
ployed as an accelerator for the phosphating process at low tempera-
tures with superior corrosion performance.
CRediT authorship contribution statement
Mustafa Muhammad: Writing - original draft, Visualization,
Investigation, Software, Validation. Shihao Hu: Writing - review &
editing. Ruina Ma: Conceptualization, Methodology, Supervision. An
Du: Conceptualization, Methodology, Supervision. Mengzhe Wang:
Conceptualization, Methodology, Supervision. Yongzhe Fan: Writing -
review & editing. Xue Zhao: Writing - review & editing. Huazhen
Yang: Conceptualization, Methodology, Supervision. Li Chong Chong:
Writing - review & editing. Xiaoming Cao: Conceptualization,
Methodology, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
National Natural Science Foundation of China (grant numbers
51501055, 51601056), and Hebei province Science and Technology
Support Program (grant number 19274009D) provided support for this
work.
Data availability statement
The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of an ongoing study.
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