Progress in Organic Coatings 135 (2019) 51–64

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Progress in Organic Coatings

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

Corrosion investigation of new hybrid organic/inorganic coatings for carbon T

steel substrates: Electrochemical and surface characterizations
⁎
P. Salazar-Bravoa, D. Del Ángel-Lópeza,b, A.M. Torres-Huertaa, , M.A. Domínguez-Crespoa,
D. Palma-Ramíreza,c, A.B. López-Oyamad
a
Instituto Politécnico Nacional, CICATA-Altamira, km 14.5 Carretera Tampico-Puerto Industrial Altamira, C.P. 89600, Altamira, Tamaulipas, Mexico
b
Tecnológico de Monterrey, Escuela de Ingeniería y Ciencias, Ave. Eugenio Garza Sada 2501, Monterrey, N.L., 64849, Mexico
c
Instituto Politécnico Nacional, Centro Mexicano para la Producción más Limpia (CMPL), Av. Acueducto s/n, la Laguna Ticomán, C.P. 07340 México City, Mexico
d
CONACYT Research Fellow-CICATA-Altamira, Ave. Insurgentes Sur 1582, Col. Crédito Constructor, Del. Benito Juárez, C.P. 03940, Ciudad de México, Mexico

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

Keywords: This work examines the synthesis of Mn5(PO3(OH))2(PO4)2⋅4H2O particles (MnPhos) by reflux method, it was
Hureaulite particles proposed their addition into waterborne polyurethane and used as hybrid coatings to improve the barrier
Waterborne polyurethane properties of AISI 1018 carbon steel substrates. The effect of different MnPhos amounts (2, 4 and 6 wt.%) and
Hybrid coatings dispersion times (30, 60 and 120 min) on the corrosion properties in chloride medium (3.0 wt.%) were de-
AISI 1018 carbon steel
termined using electrochemical impedance spectroscopy (EIS). Additional characterizations to evaluate changes
Barrier properties
in the structural, morphological, UV absorption and mechanical properties were realized by X-ray diffraction
patterns (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), ultra-
violet visible spectroscopy (UV–vis), nanoindentation and adhesion test were also evaluated. MnPhos particles
correspond with a monoclinic structure and a prismatic morphology of ˜10 μm in length. The addition of MnPhos
particles into the waterborne polyurethane (WPU) matrix helps to reduce the polymer degradation under UV-
light by inducing a microphase separation phenomenon between the hard and soft segments. Mechanical and
corrosion properties also increased by incorporating different amounts of MnPhos particles but, an adequate
modulation in the final properties was observed with an amount of 4 wt.% after 30 min of dispersion.

1. Introduction
Carbon steel (CS) is still one of the most widely used engineering
material that belongs to the most important group of metallic alloys [1].
Due to its microstructure and mechanical properties is suitable for a
wide variety of applications [2]. Unfortunately, CS is highly susceptible
to internal and external corrosion in different aggressive media, leading
to a huge economic loss [3,4]. CS degradation is attributed to micro-
and macro-environmental alterations due to the presence of some ions
such as chloride, sulfur or weather conditions as temperature and hu-
midity. Surface treatments such as chemical conversion coatings in
combination with top coats has emerged as an alternative to improve
the adhesion in the metal-coating interface and prevent the substrate
from corrosion [5,6]. Organic coatings mainly polyurethane coatings
have been extensively applied to retard the corrosion degradation.
Properly applied coatings can effectively prevent steel substrates from
corrosion in different media for long periods. This coating, however,
tends to fail by degradation in presence of electrolyte and subsequent
loss adhesion, letting to aggressive ions electrolyte reach the metallic
surface. Traditional polyurethane (PU) coatings use solvents that con-
tain a large amount of volatile compounds provoking severe environ-
mental pollution. Waterborne polyurethane (WPU) emerges as an al-
ternative to improve corrosion resistance of different metallic substrates
without detriment in the mechanical properties overall when different
nanostructured fillers are added [7]. Incorporation of small amounts of
particles into polymers leads to improve in thermal stability, mechan-
ical, barrier but above all, anticorrosive properties. Specifically, nano-
clays, carbon nanotubes, graphene and its derivatives have been ex-
plored [8–11]. Particles based on ZnO (zinc oxide), TiO2 (titanium
oxide), SiC (silicon carbide), Al2O3 (aluminum oxide), rare earth salts
(phosphates, cinnamates and silicates) have also been incorporated as
reinforcement [12]. Manganese phosphate (hureaulite) coating applied
on steel has recently reported as an excellent mechanical resistance and
lubricant retention properties [13]. As additive, it is widely used to
obtain highly corrosion resistant surfaces and improve the wear re-
sistances of different steels [14]. Mn5(PO3(OH))2(PO4)2⋅4H2O

⁎
Corresponding author.
E-mail address: atohuer@hotmail.com (A.M. Torres-Huerta).

https://doi.org/10.1016/j.porgcoat.2019.05.038
Received 27 March 2019; Received in revised form 8 May 2019; Accepted 24 May 2019
Available online 10 June 2019
0300-9440/ © 2019 Elsevier B.V. All rights reserved.
P. Salazar-Bravo, et al.
Fig. 1. (a) XRD patterns of MnPhos particles and its morphological aspects at different magnifications (b, d) 250x (g) 1200x (h) 2500 × . The histograms of (c) length
and (e) width of MnPhos particles are also shown in the figure.
(Hureaulite), labeled in the manuscript as MnPhos, is formed with an
open three-dimensional lattice structure that can stabilize the metal
ions of different oxidation states due to the relatively high charge in the
phosphate tetrahedral, facilitating anionic frameworks, which in turn
helps to improve mechanical, chemical and thermal stabilities [14–16].
These coatings on metallic substrates are usually applied by the im-
mersion method at temperatures ca. 90 °C. The formation of Mn-Fe
crystalline phase is the main cause of the protection against corrosion
[14,17].
The investigation reported herein, waterborne polyurethane (WPU)
hybrid coatings reinforced with different amounts of MnPhos particles
(2, 4 and 6 wt.%) were applied onto commercial carbon steel (AISI-
1018) in order to avoid its anodic dissolution in chloride media.
MnPhos particles were synthesized by reflux process under atmospheric
52
Progress in Organic Coatings 135 (2019) 51–64
pressure following the method elsewhere reported [14]. Due to the fact
that a proper dispersion of fillers in the polymeric matrix can condition
the transport of water and oxygen molecules through organic coatings
affecting the oxygen reduction reaction and cathodic delamination of
the coatings; during the addition of hureaulite particles to WPU matrix,
it was also analyzed the effect of dispersion time for 30, 60 and 120 min
by magnetic stirring.
2. Experimental method
2.1. Synthesis of MnPhos nanoparticles
Precipitation method was used to obtain the Manganese (II)
Dihydrogen Phosphate (Mn(H2PO4)2͎ ⋅ 2H2O) precursor as follows: 3.3 g
P. Salazar-Bravo, et al. Progress in Organic Coatings 135 (2019) 51–64

Table 1
Estimation of the crystallite size obtained from the average of the three most
intense peaks of MnPhos structural phase using the Scherrer´s equation.
Sample Dispersion time Crystal size
(min) (nm)

MnPhos – 186
MnPhos (2 wt.%)/WPU 30 151
MnPhos (2 wt.%)/WPU 60 130
MnPhos (2 wt.%)/WPU 120 126
MnPhos (4 wt.%)/WPU 30 143
MnPhos (4 wt.%)/WPU 60 134
MnPhos (4 wt.%)/WPU 120 96
MnPhos (6 wt.%)/WPU 30 146
MnPhos (6 wt.%)/WPU 60 139
MnPhos (6 wt.%)/WPU 120 141

The synthesis of hureaulite was realized based on the method de-

scribed in ref [14]; 30 mmol of Mn(H2PO4)2͎ ⋅ 2H2O were dissolved in
100 mL of deionized water. Then, 1.7 mL of a H3PO4 solution were
slowly added and refluxed under magnetic stirring at 100 °C for 12 h.
Thereafter, 2 mL of sodium hypochlorite (NaClO) (> 99.99%, Sigma-
Aldrich) were added and stirred for other 20 min. The resulting sus-
pension was air-dried, filtered and wetted successively with acetone
until obtain a conductivity lower than 10 μS cm −1; and again dried in
an oven at 60 °C during 12 h.

2.2. Synthesis of MnPhos/WPU hybrid coatings

The waterborne polyurethane (WPU) was supply by COMEX® (U-

5510® HDI). This WPU is integrated of “base resin” (polyols) and
“catalyst” (Hexamethylene diisocyanate). The hybrid coatings were
synthesized using 10 g of base resin (Component A) and 1 mL of de-
mineralized water which were mixed and magnetic stirred for 20 min.
Then, different amounts of MnPhos particles to reach 2, 4 or 6 wt.%
with respect to the weight of A component were added. In order to
evaluate the dispersion degree of the MnPhos particles in the polymeric
matrix and its influence in the electrochemical performance, the final
solution was magnetically stirred for 30, 60 and 120 min; thereafter,
3.3 g of catalyst (component B) was added to complete the poly-
merization. Finally, the solution was sprayed onto the substrate to reach
a wet film about 50 μm.
In order to obtain an adequate substrate-coating adhesion, carbon
steel substrates (AISI 1018) were previously sand with silicon carbide
(SiC) papers from #180 to #1500 up to obtain a uniform surface.
Substrates were then rinsed with distillated water and industrial-grade
acetone to remove impurities and moisture.

2.3. Characterization of MnPhos particles and MnPhos/WPU hybrid

coatings

Structural characterization of MnPhos particles and MnPhos/WPU

Fig. 2. XRD patterns of MnPhos/WPU hybrid coatings deposited on carbon
steel substrates using different amounts of MnPhos (2, 4 and 6 wt.%) and dis-
persion times. (a) 30, (b) 60 and (c) 120 min.
of Manganese (II) carbonate (MnCO3) (> 99.99%, Sigma-Aldrich) were
dissolved in 70 wt.% of aqueous phosphoric acid (H3PO4) (85.2 wt.%,
Fermont); this solution was dropwise added into 0.75 g of hydro-
xylamine hydrochloride (NH2OH ⋅ HCl) (99%, sigma-Aldrich), under
stirring for 1 h at 70 °C. Subsequently, the precipitate was filtered,
rinsed with acetone and dried at room temperature.
hybrid coatings on carbon steel was performed by X-ray diffraction
analysis (XRD). XRD analyses were acquired in a Bruker D8 Advance
Diffractometer, using Cu K α (λ = 1.5405 Å ) in the 2 θ range of 5 to 90°
with a step size of 0.05°, 35 kV and 25 mA.
UV-vis analysis was used to determine the optical properties of light
absorption in the ultraviolet and visible regions. The measurements
were performed by using a diffuse reflectance accessory in a UV–vis-
NIR spectrophotometer (Agilent Technologies), model Cary 5000 in a
range of 700 to 200 nm.
Fourier Transform Infrared Analysis (FTIR) was used to identify the
functional groups of the WPU and possible changes in the chemical
bonds after adding MnPhos particles to the polymer. The equipment
used for FTIR analysis was a Spectrum One of Perkin Elmer, in a range
of 500 to 4000 cm−1.
Morphological study of the MnPhos particles was realized by

53
P. Salazar-Bravo, et al.
Fig. 3. Evolutions of EOCP vs SCE in a 3.5 wt.% NaCl solution for uncoated carbon steel, pure WPU and hybrid coatings synthesized with different MnPhos amounts
and dispersion times deposited on CS (AISI 1018) substrates. (a) 30 min, (b) 60 min and (c) 120 min.
Scanning Electron Microscopy (SEM) using a Quanta 3D FEG from FEI
Co. Micrographs were obtained at different magnifications from 230x to
5000x using secondary electrons with an energy of 5 kV. Atomic force
microscopy (AFM) was used for mapping the topography of MnPhos/
WPU hybrid coatings using a Veeco Di Multi mode V AFM/STM, in the
contact mode with RTESP Si cantilever with a nominal force of 20 nN.
The dispersion of MnPhos particles in the polymeric matrix after
30 min of stirring was characterized by CLSM using a Carl ZEISS mi-
croscope, model LSM 700. This tool is equipped with a spectral canal
used to detect autofluorescence signals which comes from sample
components. The measurements of fluorescence intensity were per-
formed using the built software ZEN of the LSM 710. The intensity peak
characteristic of fluorescence emission signal was 470 nm for WPU and
627 nm for MnPhos particles.
Nanoindentation was used to evaluate the mechanical properties of
the MnPhos/WPU hybrid coatings deposited on carbon steel in a NHT3®
Nanoindentator (Anton Paar) fitted with a diamond Berkovich type tip.
A Poisson ratio, vp = 0.48, for polyurethane was considered [18]. Load-
displacement curves were obtained using the Oliver-Pharr method.
F = B (h − hf ) m
Where, B and m are fitting parameters and hf is the final indentation
depth after complete unloading. The unloading slope, i.e., contact
stiffness, S, was estimated by analytical differentiating Eq. (1) con-
sidering the maximum indentation depth.
(dF )
S= = Bm (hmax − hf ) m − 1
dh h = hmax
Contact stiffness from Eq. (2) is used to estimate the contact depth,
hc, under the maximum indentation force,
Progress in Organic Coatings 135 (2019) 51–64
Fmax
hc = hmax − ε
S (3)
Where, ε is a constant which depends on the indenter geometry
(ε = 0.75 for Berkovich tip). The projected contact area, A, under the
maximum indentation force for an indenter is determined by indenter
tip´s included angle, θ, and the estimated contact depth, hc, from Eq.
(3), that is,
A = π (hc tanθ)2 (4)
Then, the elastic modulus, E, can be calculated as follows:
1 π S
E= (1 − vp2)
β 2 A (5)
Where β is a correction factor; 1.05 is recommended by Oliver and
Pharr [19].
An elcometer tester (Elcometer 106 series) was used to measure the
force at which aluminum studs removed MnPhos/WPU hybrid film
from carbon steel surface, according to the ASTMD-4541 standard. 21-
mm diameter aluminum studs were glue onto the treated specimens for
(1) each test with epoxy resin, followed by a de-aeration process at room
temperature over 24 h. The adhesive strength is defined as the ratio
between the failure load and test area. In all the samples reported here,
the area was pre-cut in-situ fitting the sized of the pull head plates. The
pre-cut was realized up to reach the surface substrate. Then, a per-
pendicular force to the sample was applied up to determine the max-
imum adhesion strength.
The electrochemical behavior of the coated samples was in-
(2)
vestigated by means of the open circuit potential (Eocp), electrochemical
impedance spectroscopy (EIS) and Potentiodynamic polarization curves
using a 3 wt.% NaCl solution at room temperature. The analyses were
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P. Salazar-Bravo, et al. Progress in Organic Coatings 135 (2019) 51–64

Fig. 4. Nyquist and Bode spectra of coated electrodes with MnPhos/WPU hybrid coatings using different amounts of MnPhos particles (2, 4 and 6 wt.%) and
dispersion times (30, 60 and 120 min). For comparison are also shown the response of bare CS and coated samples with pure WPU.

Fig. 5. Equivalent circuits (EC) used to fit the EIS data for MnPhos/WPU hybrid coatings after being dispersed for 30 min an applied on CS, its comparison with bare
steel and coated samples with pure WPU. (a) EC of bare CS, (b) EC used to fit WPU and (c) EC proposed to fit hybrid coatings.

carried out at room temperature in a conventional three-electrode-
corrosion cell using a Gill AC (ACM Instruments) potentiostat/galva-
nostat. The counter electrode was a large-area-graphite bar. The re-
ference electrode was a saturated calomel electrode, SCE, (0.2415 V vs.
SHE) and the exposed area of the sample was 0.79 cm2. The tests were
performed after monitoring the open circuit potential (Eocp) for 900 s.
The EIS measurements were obtained logarithmically within the fre-
quency space (ten frequency points per decade) ranging from 100 kHz
to 10 mHz. The width of the sinusoidal voltage signal applied to the
systems was 10 mV (root-mean-square). Potentiodynamic polarization

55
P. Salazar-Bravo, et al. Progress in Organic Coatings 135 (2019) 51–64

Table 2
Value obtained from simulation of uncoated carbon steel, pure WPU and MnPhos/WPU 30 min hybrid coatings deposited on carbon steel.
Sample Rs CPEcoat Rcoat CPEdl Rct RL L CPEpore Rpore χ2 Equivalent
circuit
Yo1coat n1 Yo2dl n2 Yo3 pore n3
(Ω cm2) (Ω−1 cm-2 sn) (Ω c m2) (Ω−1 cm-2 sn) (Ω cm2) (Ω cm2) (H) (Ω−1 cm-2 sn) (Ω cm2) (10−3)

Uncoated CS 16.0 – – – 1.59E-3 0.82 7.39E2 5.42E2 2.35E3 26.0 a

Pure WPU 45.1 3.64E-6 0.65 3.02E2 1.18E-4 0.44 1.32 E4 8.18E3 4.51E4 2.6 b
MnPhos (2 wt. 112 8.60E-8 0.71 3.18E3 3.03E-8 0.91 4.00E5 2.77E5 1.77E5 39.5 b
%)/WPU
MnPhos (4 wt. 150 3.70E-8 0.93 2.19E7 3.59E-7 0.96 2.30E7 2.69E-9 0.87 1.22E7 33.1 c
%)/WPU
MnPhos (6 wt. 180 2.28E-8 0.63 1.63E6 3.34E-7 0.62 3.81E6 1.98E-9 0.94 1.98E5 23.0 c
%)/WPU

Fig. 6. Electrochemical impedance spectra of (a) Nyquist and (b and c) Bode plots of WPU/hybrid. For comparison, the responses of CS and pure WPU were also fitted
and shown in the figure.

curves were realized in the region from −300 mV vs Eocp to +1200 mV
vs Eocp at a scan rate of 1 mV s−1.
3. Results and discussion
3.1. Structural and morphological characterization of MnPhos particles
The formation of MnPhos particles was structurally corroborated by
XRD patterns (Fig. 1a).The peak intensities of MnPhos particles
matched well with the C2/c (15) space group of the monoclinic struc-
ture according to PDF # 01-086-1521 card. The morphology of MnPhos
particles was analyzed from scanning electron microscopy/energy dis-
persive x-ray spectroscopy (SEM/EDS) and the micrographs at different
magnifications are displayed in Figs. 1 b, d, f, g. MnPhos particles were
integrated by a prismatic morphology derived from the early formed
crystals growth and fusion of nucleation sites and also by the formation
of separate, smaller grains. Once a prismatic structure is formed, the
growth in c direction continues up to reach its final length [20,21]. The

56
P. Salazar-Bravo, et al.
Fig. 7. Potentiodynamic polarization curves for pure WPU, MnPhos/WPU
coatings and uncoated substrate in 3 wt.% NaCl solution after being dispersed
for 30 min.
frequency distribution in width and length of the particles is shown in
Figs. 1c, e. The particles present a wide variety of sizes from 10 to
50 μm in length. The mainly size of the particles ranging between
15–30 μm. A width from 2 to 18 μm with very few particles of 25 μm
was obtained; most of these particles were in the range from 5 to 12 μm.
Morphology of MnPhos particles was quite similar to those reported by
Hui Yin [14] and comparable with di-hydrogen phosphate tetrahydrate
manganese crystals [22].
3.2. Structural characterization of MnPhos/WPU hybrid coatings
XRD data were also used to analyze possible changes in the struc-
tural phases and crystallite size of MnPhos particles after being added to
the WPU matrix and coated carbon steel. For comparison, XRD spectra
of MnPhos powders is shown at each experimental setup. The Fig. 2a–c
shows XRD spectra of hybrid coatings using different amounts of
MnPhos particles (2, 4 and 6 wt.%) and dispersion times (30, 60 and
120 min). XRD patterns of coated carbon steel samples displayed typical
signals from the substrate at 44.6° (110), 64.89° (200) and 82.2° (211),
PDF # 001-1262 card. The most intensity peaks of monoclinic MnPhos
are observed at (200), (110), (220), (330) and (350) planes, although
the intensity is dependent of the particles amount. WPU is shown in the
spectra as a wide signal at 13.3° which is characteristic of a semi-
crystalline polymer.
The crystal size of each sample was estimated by analyzing the three
most prominent reflections of MnPhos monoclinic phase using the
Kλ
Scherrer´s equation [23]; D = βcosθ where K is shape factor, λ is the
incident wavelength of CuKα radiation (λ =0.154252 nm), θ is the
Bragg´s angle and β is the full width at half maximum (FWHM). The
Scherrer´s constants linking apparent and true crystallite sizes for the
parallelepiped geometry are well known. For crystals in form of rec-
tangular parallelepipeds such as MnPhos, it is reported a value of K
between 1.000 to 1.1547 [24]. Then, a value of 1.0607 was used in this
analysis [25] and the results are shown in Table 1. Initially, the crystal
size of MnPhos structures was 186 nm; after adding 2 wt.% and 30 min
Table 3
Kinetic parameters obtained from potentiodynamic polarization curves, polarization resistance, coating porosity and corrosion rate.
Sample Ecorr (mVSCE) jcorr (A cm−2) βa (mV dec−1)
Uncoated CS −580 1.62E-2 184
Pure WPU −523 2.17E-4 267
MnPhos (2 wt.%)/WPU −226 4.55E-6 – −134
MnPhos (4 wt.%)/WPU −140 8.06E-6 – −214
MnPhos (6 wt.%)/WPU −209 1.43E-5 – −244
Progress in Organic Coatings 135 (2019) 51–64
of dispersion in WPU, it was observed a reduction until 151 nm, which
decreases gradually up to 126 nm after 120 min of dispersion. This
trend was also observed after adding 4 wt.% of MnPhos particles,
143 nm (30 min), 134 nm (60 min) and 96 nm (120 min). However, by
adding a 6 wt.%, this crystallite size remains between 146 nm and
139 nm. The reduction in crystal size with the dispersion time is asso-
ciated to the agglomerate to be disrupted into smaller fine-particles that
generates smaller crystals [26,27].
3.3. Corrosion measurements of MnPhos/WPU hybrid coatings deposited
on AISI 1018 carbon steel substrates
3.3.1. OCP measurements
As a first step, it was evaluated the corrosion performance of overall
coatings to determinate optimal dispersion time (30, 60, 120 min) and
wt.% of MnPhos (2, 4 or 6 wt.%). It is important to highlight that
overall coated samples present a dry film thickness ca. 20 μm. Open
circuit evolutions of bare and coated samples in chloride medium
(3.0 wt.% of NaCl) are shown in Fig. 3 a–c. The OCP measurements of
bare CS showed typical behavior in chloride media; i.e. a strong de-
crease of the potential below 100 s followed by a gradual reduction in
the potential in the range of 100 s (-0.53 VSCE)-3600 s (-0.66 VSCE). In
comparison with uncoated substrates, coated samples with pure WPU
exhibited a displacement in the EOCP about 180 mVSCE in positive di-
rection with a less noticeable reduction in the time-dependent potential
up to reach a value about -0.48 VSCE. The EOCP response for almost
hybrid/CS systems showed a tendency to move the potential to more
electropositive values in contrast with uncoated substrates and pure
WPU coatings. The shift is dependent of the both MnPhos amount and
mixing time. It is also important to highlight that important variations
in the potential versus time are observed during OCP measurements
after the addition of MnPhos particles. The OCP evolutions displaced
randomly in cathodic and anodic directions (Fig. 3 a–b); however in
general tend to displace in negative direction with the dispersion time.
Taking into account that interpretation of OCP measurements for
metal/coating systems becomes complex [28], the only feature that it is
worth to mention is the observed displacements attributable to the in-
teraction between chloride media and hybrid coatings. Porous, cracks
in the hybrid coating or agglomeration of nanoparticles as well as the
number of interacted carboxyl groups can contribute to the instability
of OCP evolutions [29]. In this context, a quasi-constant OCP and the
displacement in positive direction can be partially correlated with an
enhancement of barrier properties; as it is the case when 2 and 4 wt.%
of MnPhos particles were added (30 min); whereas the opposite beha-
vior may be related with a detriment of the protection against corrosion
(Fig. 3c). Furthermore, the equilibrium potential, condition at which
anodic and cathodic reactions are equal, depends on many variables
such as the rate of the anodic and cathodic reactions or real areas
(frequently unknown); i. e. the solution simultaneously contains both
molecular oxygen and chloride ions, whereas the hybrid coatings have
anodic or even cathodic sites inhibiting the corrosion process [30,31].
Therefore, it is assumed that combining suitably the amount of MnPhos
particles and dispersion time can help to improve the coating stabili-
zation. During OCP measurements, a maximum displacement was ob-
tained with samples containing 4 wt.% of MnPhos and 30 min of dis-
persion (-0.016 VSCE), although with 2 wt.% (30 min), it is seen a steady
βc (mV dec−1) Rp (Ω cm2) Porosity (%) PEF (%) Corrosion rate MPY (E3)
−352 1.3E3 – – 14.7595
−339 2.2E4 2.896 98.66 0.3523
6.85E5 2.26E-3 99.97 0.0041
5.71E7 1.00E-5 99.96 0.0073
5.64E6 2.20E-4 99.91 0.0129
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P. Salazar-Bravo, et al.
Fig. 8. (a) DR spectrum of MnPhos particles (b) UV–vis spectra of pure WPU and MnPhos/WPU hybrid coatings on glass substrates after 30 min of dispersion time.
state after 740 s (-0.061 VSCE); whereas, the minimum was observed
with a dispersion time of 120 min. CS is commonly pseudo-passivated
in aerated solution forming some oxides that are complexing dissolved
in chloride ions. This makes a porous corrosion film favoring the con-
tinuous access of the electrolyte to the metallic surface and so on
[32–34]; then, the positive shift in comparison with CS and pure WPU/
CS is entirely associated with the properties of MnPhos particles, and
the differences between samples pointed out the importance of an
adequate dispersion depending on inherent particle properties.
3.3.2. EIS measurements
Fig. 4 a–c shows the EIS plots of the hybrid coatings on carbon steel
substrates which were carried out after 3600 s of stabilization to com-
pare and investigate the anticorrosion performance in the aggressive
solution (3.0 wt.% NaCl). EIS spectra provided detailed understanding
of the corrosion protection of hybrids coatings on CS substrates. Fig. 4a
showed the Nyquist and Bode plots of the hybrid coatings containing 2,
4 and 6 wt.% and 30 min of magnetic stirring during the polymerization
process followed by a spraying method on CS. In general, even the long
immersion time to obtain a stable open circuit electrode, the impedance
of the hybrid coatings do not reduce drastically, which seems to be
consistent with an increase in the charge transfer resistance. For com-
parison, uncoated and specimens with pure WPU were also evaluated.
Nyquist plots show that the arc of impedance of uncoated samples was
about 900 Ω cm−2 and increase up to 10,590 Ω cm-2 when it was coated
with pure WPU. The size of radius in the Nyquist plots is related with
the charge transfer resistance (Rct), thus, the addition of MnPhos par-
ticles increased the Rct to ˜4.5 × 105 Ω cm−2, 5.11 × 107 Ω cm−2 and
˜4.3 × 106 Ω cm−2 for samples having 2, 4 and 6 wt.% of MnPhos
particles, respectively. Important variations can be observed in the
number of capacitive loops during the corrosion process, which are
dependent of the amount of MnPhos particles. It is well known that the
impedance spectra can be divided into two or three parts: the high
frequency part is related to the porous of the coating or organic-in-
organic coating itself, at low-intermediate frequencies is observed the
hybrid coating, whereas at low frequencies appears the reactions oc-
curring on the metal through defects and pores in the coating. At 30 min
of magnetic stirring, samples with 2 wt.% and 4 wt.% of MnPhos par-
ticles tend to show two time constants that are physically attributable
with the hybrid coating and the charge transfer resistance (Rct), Fig. 4a.
On the other hand, samples with 4 wt.% show clearly three capacitive
loops which recall typical series-parallel time constants involving pore,
coating and charge transfer resistances.
By increasing the dispersion time (60 min), it was seen that with
4 wt.%, it is reduced the frequency range of the loop at high fre-
quencies, but at the same time occurred a decrement in the Rct up to
˜8.7 × 106 Ω cm−2 (Fig. 4b). Other compositions still showed two ca-
pacitive loops and also reduced the polarization resistance about
6.7 × 105 Ω cm−2 (2 wt.%) and 1.1 × 105 Ω cm−2 (6 wt.%). Fig. 4c
58
Progress in Organic Coatings 135 (2019) 51–64
shows coated specimens using a dispersion time of 120 min where are
seen very poor barrier properties with values even lower than pure
WPU (10,590 Ω cm−2); 5951 Ω cm−2 (2 wt.%), 1991 Ω cm−2 (4 wt.%)
and 3, 534 Ω cm−2 (6 wt.%); the shape in the Nyquist plots is quite
similar to that pure WPU. The fact that weakening barrier properties
were obtained after 60 and 120 min of dispersion time, suggested that
during this process, the total energy of the system is increased by local
heating [35], provoking unstable systems, which in turns accelerates
the kinetics during curing process with more agglomerate regions di-
minishing the properties against corrosion. The low quality of these
hybrid coatings (60 and 120 min) let to diffuse different species such as
H2O, Cl-1, O2, into the hybrid matrix catalyzing its degradation up to
reach the surface substrate.
Under these experimental conditions, our results show that only
with the dispersion time of 30 min, a significant increase in the im-
pedance modulus and the dispersive points can be obtained at high and
intermediate frequency regions are attributable to initial electrolyte
diffusion into the polymer. Thus, typical pathway of corrosion process
for samples dispersed for 30 min considers that corrosive ions penetrate
into the hybrid coatings through irregular pores but they did not reach
the surface of the metallic substrate. On the other hand and in-
dependently of MnPhos amount, the electrolyte reached the surface of
CS starting the corrosion process when 60 or 120 min were used to
disperse inorganic particles [36].
The quantitative interpretation of the EIS plots for samples dis-
persed at 30 min was realized with the ZView® software and the
equivalent circuits are shown in Fig. 5 a–c.
The bare CS was fitted using a series parallel circuit Rs(CPEdl(Rct(RL
L))) considering the electrolyte resistance (Rs), the kinetic of the charge
transfer resistance which was fitted with an constant phase element
(CPEdl) in parallel with the charge transfer resistance (Rct). Also, it was
necessary to represent adsorbed ions during the redox reactions with an
inductance (L) and layer resistance (RL), Fig. 5a. Coated samples with
pure WPU were simulated considering, additionally, the coating fea-
tures using an Rs(CPEcoat(Rcoat (CPEdl(Rct(RL L))))) circuit. In this case,
Rcoat and CPEcoat represent the high-frequency time constant related
with the coating features (roughness, porous) whereas the kinetic of the
charge transfer resistance observed in the second semicircle was fitted
with an constant phase element (CPEdl) in parallel with Rct (Fig. 5b).
Finally, for the circuit to fit the response of hybrid MnPhos/WPU
coatings, it was considered that the electrolyte does not reach the me-
tallic substrate; Rs(CPEpore(Rpore (CPEcoat(Rcoat(Rct CPEdl))))). In this
equivalent circuit the Rpore and CPEpore are the pore resistance in par-
allel with their constant phase element of the pores, respectively
(Fig. 5c). In the models, CPE is given ZCPE = 1 Yo (jω) n ; with Yo , n, j and ω
are the parameters related to capacitance, exponential term related to
roughness of the electrode surface, imaginary number and angular
frequency. The fitted electrochemical parameters of coating properties
for CS, WPU/CS and AISI 1018 coated with hybrid coatings are
P. Salazar-Bravo, et al.
Fig. 9. FTIR spectra studies on a) Pure WPU, b) MnPhos (2 wt.%)/WPU, c) MnPhos (4 wt.%)/WPU, d) MnPhos (6 wt.%)/WPU.
presented in the Table 2 and the fitted impedance plots are shown in
Fig. 6a–c.
Considering that polarization resistance (Rp) is the sum of overall
resistances and that is frequently compared with the corrosion prop-
erties [37,38]; the obtained Rp values corroborate that the addition of
MnPhos nanostructures into the WPU matrix increased the coating
hydrophobicity and avoid diffusion of aggressive ions by sealing the
polyurethane porous. As shown in Table 2, the coated electrode with
4 wt.% of MnPhos particles has the highest Rp values (5.71 × 107 Ω
cm2) followed by prepared samples with 6 wt.% of MnPhos particles
(5.64 × 106 Ω cm2). The hybrid coatings containing 2 wt.% displayed a
Rp value of 6.8 × 105 Ω cm2 which is still better than bare CS
59
Progress in Organic Coatings 135 (2019) 51–64
(1.3 × 103 Ω cm2) and coatings with pure WPU (2.2 × 104 Ω cm2).
Hybrid coatings resistance confirms that a combination of appropriate
dispersion time and amount of MnPhos particles added to polymeric
matrix can efficiently inhibit the ingress of corrosive ions. Although,
there are evidences supporting that larger crystallite sizes help to pro-
duce more effective corrosion protection coatings [39]; in this study, it
was observed that the coated samples with larger crystal size (2 wt.%
MnPhos /WPU) did not show an improvement in the barrier properties.
Thus, it was not found a relationship between crystal size and barrier
properties in the coated samples since the best performance, obtained
with 143 nm, was too high in comparison with other samples of similar
crystal size. Electrochemical performance in the interface metal-hybrid
P. Salazar-Bravo, et al.
Fig. 10. 3D AFM images showing changes in the topography and phase separation as a function of the amount of MnPhos particles (a–b) 2 wt.%, (c–d) 4 wt.% and
(e–f) 6 wt.%.
coating depends on several factors such as structures of fillers, particles
morphology, interaction between organic-inorganic phases, final mor-
phology, dispersion of organic/inorganic phases and interaction with
electrolyte to form additional products (oxides) affecting the layer
properties [39,40]. Particularly in this study, the dispersion time is a
key factor to improve properties against corrosion.
3.3.3. Potentiodynamic polarization curves
Potentiodynamic polarization curves is a common method for
characterization of metal corrosion behavior. Fig. 7 shows the anodic
polarization curves recorded for pure WPU and MnPhos/WPU coated
electrodes dispersed 30 min by magnetic stirring and the kinetic para-
meters are shown in Table 3. All the samples were stabilized for 600 s in
the NaCl solution before polarization curves. The curves showed a clear
displacement towards to low corrosion current densities after adding
MnPhos particles. It is recognized that displacements to lower current
densities and noble corrosion potentials indicated an improved in the
barrier properties [41–43]. Among the examined samples, bare CS
displays a continuous dissolution in the anodic branch with an Ecorr of
-580 mVSCE and a corrosion current density of 1.62 × 10−2 A cm-2,
whereas pure WPU showed an active dissolution followed with a region
that tends to passivation between -108- 668 mVSCE. The corrosion po-
tential value in this case is ca. -523 mVSCE with a corrosion current
density of 2.17 × 10-4 A cm-2. Hybrid coatings move the anodic branch
to low corrosion current and reduce the partial dissolution. Also, it is
seen a displacement in the corrosion potential to more positive values.
Among the hybrid coatings, the corrosion current density and as a
consequence corrosion rate was lower with 2 (4.55 × 10-6 A cm-2) and
4 wt.% (8.06 × 10-6 A cm-2) followed by 6 wt.% (1.43 × 10-5 A cm-2).
Due to different researchers coincide that porosity is a key parameter in
the evaluation of organic coatings [41,44], the porosity of the hybrid
coatings was determined by the following equation:
−ΔE
P = Rpbs Rpc × 10 β corr × 100%. In this equation, P is the porosity; Rpbs
a
60
Progress in Organic Coatings 135 (2019) 51–64
and Rpc are the polarization resistances of bare substrates and re-
sistances of coated samples, respectively. ΔEcorr is the difference in the
corrosion potentials of bare and coated samples; βa is the anodic Tafel
slope of the uncoated sample. The results evidence that incorporation of
MnPhos reduces the number of defects and from these the low porosity
values were observed with 4 wt.%. The protection efficiency was also
j (uncoated) − jcorr (coated)
calculated using the equation; PEF % = corr j (uncoated )
× 100%
corr
[44]. It is remarkable that the PEF% after the addition reaches values of
99.97 and 99.96% for samples 2 and 4 wt.%. As it is seen in these
calculations some small discrepancies can be found between potentio-
dynamic polarizations in comparison with EIS measurements; however,
the overall behavior is still better for samples with 4 wt.% in compar-
ison with samples containing 2 or 6 wt.%. To support the electro-
chemical performance of coated samples with MnPhos/WPU hybrid
coatings using 30 min of dispersion time and different particles
amounts, additional characterizations were realized.
3.4. UV–vis spectroscopy of MnPhos particles and MnPhos/WPU hybrid
coatings
Fig. 8a shows diffuse reflectance (DR) analysis of MnPhos particles
where it is seen the light scattering properties. The DR spectrum dis-
plays three strong bands near to 300 nm, 450 nm and 560 nm. It has
been reported that Manganese ions in MnOCeO-P2O5 systems produce
spectrum of absorption with peaks at 541 nm and 500 nm while MnO-
ZnO doped with RE oxides spectra [45] display three characteristic
absorption peaks [46]. The band at 450 nm has been attributed to the
Mn+3 ions [47]. Also, it is well known that the Mn in 2+ oxidation
state appears centered near ultraviolet regions while Mn in 3+ oxida-
tion state appears in the visible region [48]. Therefore, based on the
UV–vis diffuse reflectance spectra of MnPhos where it is seen three
strongest absorption bands at 300 nm, 450 nm and 560 nm is reason-
able to assume that Mn ions mostly exist in both oxidation states in the
P. Salazar-Bravo, et al.
Fig. 11. CLSM of MnPhos/WPU coatings using different load of phosphate particles after 20 min of magnetic stirring, images obtained on the hybrid coatings with
(a–b) 2 wt.%, (c–d) 4 wt.% and (e–f) 6 wt.%.
Mn5(PO3(OH))2(PO4)2(H2O)4 system. Also, the absorption in the UV
range indicates that MnPhos particles could act as an inorganic UV
absorber helping to protect polymer coatings that are commonly sus-
ceptible to degradation from the harmful effects of UV radiation.
The addition of these particles into WPU was assessed under UV–vis
spectroscopy using absorption mode. Absorption spectra in the UV–vis
region for WPU and WPU hybrid samples with 2, 4 and 6 wt.% of
MnPhos at 30 min of dispersion are shown in Fig. 8b. It can be seen that
the UV–vis absorption spectra of the hybrid films increased with the
MnPhos content. Two characteristic absorption bands can be seen at
61
Progress in Organic Coatings 135 (2019) 51–64
313 nm and 333 nm in pure WPU spectrum. After the addition of
MnPhos particles, it is observed a spectrum with an additional band and
a shifting in the peaks; these bands are seen at ˜263 nm, ˜300 nm and
˜345 nm. The optical properties of WPU coatings matched well with
previous reports [49,50] where the first optical band detected at
263 nm is attributed to manganese ions of hureaulite while that at
300 nm is due to the π →π* transitions of the lowest excited state of the
aromatic nucleus in the urethane group [51,52] and at 345 nm it is
found the n→π* transitions of the carbonyl groups. Another feature to
highlight is that the intensity of absorption increases with the content of
P. Salazar-Bravo, et al. Progress in Organic Coatings 135 (2019) 51–64

Fig. 12. Overview of possible interaction mechanism of MnPhos particles into the WPU matrix.

3.5. FT-IR analysis of MnPhos/WPU hybrid coatings

The segmented structure of WPU defines its properties, on the extent

Fig. 13. Comparison of the load-displacement curves for hybrid coatings and its
comparison with pure WBPU after 30 min of dispersion time.
MnPhos particles which can be associate to the improvement in the
optical properties to avoid the degradation of the polymer under UV
light exposure.
of the phase mixing, as well as on hydrogen bonds between NeH and
carbonyl or ether oxygen atoms. FTIR spectroscopy is a powerful tool
for studying any changes in the H-bond interactions. The Fig. 9 a–d
shows the FTIR spectra of pure WPU and MnPhos/WPU hybrid coatings
using different amounts of MnPhos particles (2, 4, and 6 wt.%).
The FTIR spectra of pure WPU displays typical bands corresponding
to NeH stretching between 3645-3145 cm−1. The centered band at
2946 and 1454 cm−1, correspond to the eCH asymmetric stretching
vibration mode of eCH2 and eCH3 groups, respectively. The C]O
carbonyl stretching of urea was observed at wavenumbers of 1683
cm−1 and urethane at 1725 cm−1. Characteristic bands of NeCOeO
stretching was centered at 1243 cm−1. A weak band observed at
1162 cm−1 was associated to the CeOeC linkage. The missing band of
isocyanate groups (eN]C]O) at 2280-2260 cm−1 confirmed that PU
prepolymer have reacted completely [53]. The FTIR for hybrid coatings
showed that the intensity of NeH stretching band (3645-3145 cm−1)
increased in dependence of the MnPhos amount corroborating that the
organic-inorganic interaction, modifies the absorption properties. Al-
though, it was hard to separate signals, the amplification of the signals
suggests that quite small bands at 911 and 939 cm−1 can be assigned to
the PO42- and PO symmetric stretching vibrations; the centered band at
981 cm−1 was attributed to the PO43- symmetric stretching. Also, the
bands at 1027, 1075, 1137 cm−1 are assigned to the HPO42- and PO43-
antisymmetric stretching.

Table 4
Nanoindentation data and pull off tests of the MnPhos/WBPU hybrid coatings on the metallic substrates using 30 min of magnetic stirring. For pull off tests, samples
were bonded to aluminum cylinder (dollies), cross section area 314.1 mm2 with a commercial epoxy adhesive.
Sample HIT (MPa) HVIT (Vickers) EIT (GPa) Bond strength (MPa)

Pure WPU 79.3 ± 4.0 7.3 ± 0.4 3.3 ± 1.0 1.0

MnPhos (2 wt.%)/WPU 194.1 ± 5.0 17.9 ± 0.4 4.1 ± 0.001 1.2
MnPhos (4 wt.%)/WPU 108.3 ± 6.0 10.0 ± 0.5 3.67 ± 0.05 5.2
MnPhos (6 wt.%)/WPU 80.1 ± 9.0 7.4 ± 0.8 5.1 ± 3.0 2.8

62
P. Salazar-Bravo, et al.
3.6. Topographical and morphological studies
The AFM analysis was performed to study the effect of the MnPhos
content on the microphase separation phenomenon into the polymer
matrix during the polymerization process on the metallic substrate. The
roughness and height images were acquired from WSxM software. AFM
images of the hybrid coatings in 3D representation are shown in Fig. 10
a–f. As expected with the amount of MnPhos particles the topographical
features displayed holes and cylinder-like structures; i.e. images display
hard globules in height images and they attributed to hard-segment
nanocylinders dispersed within a soft-segment [54]. It is well re-
cognized that topographical and morphological features of WPU (hard
and soft segments) can be modified in dependence of the polymeriza-
tion parameters, dispersion and kind of particles used as fillers [54–56].
The bright and dark areas confirm a phase separation between the soft
and hard segments; the high spots (majority phase) are correlated with
the harder segment of the WPU which is apparently favored with both
MnPhos addition and content. Such differences are also observed in the
roughness mean average values; 28.1 nm, 33.1 nm and 60.5 nm and an
average height of 301.5 nm, 259.1 nm and 369.1 nm for hybrid coatings
synthesized with 2, 4 and 6 wt.%, respectively. These results suggest
that a high dispersion can be reached when it is added during poly-
merization an amount of 4 wt.%, which matched well with electro-
chemical data. A cross-sectional analysis of AFM images (not shown
here) confirms that MnPhos particles promotes the formation of
roughness coatings with porous from 20 to 50 nm in length and
50–150 nm in height. To confirm AFM measurements confocal laser
scanning microscopy measurements (CLSM) were also realized in the
MnPhos/WPU/AISI 1018 CS systems (Fig. 11 a–f). In this figure, it is
also observed a phase separation between the hard and soft segments
forming the hybrid coatings. From the image, it can be seen that the
dispersion is quite dependent on the amount of the MnPhos particles,
i.e. although they form a uniform dispersion within WPU matrix, tend
to form agglomerates in dependence of the quantity of inorganic par-
ticles. The differences can be correlated with the electrostatic interac-
tions between the fillers and polymeric matrix [57], which also provoke
variations in the surface roughness [58].
At higher MnPhos concentration, the images show a pronounced
layering of the small particles around the large ones with a roughness of
2.1 nm but reduces up to 0.2 nm (4 wt.%) and 1.5 nm (2 wt.%). Then,
uniform electrostatic interaction of organic-inorganic is reached with
4 wt.% whereas with a content of 6 wt.% particles start to agglomerate
and using 2 wt.% particles are not enough to provoke an adequate re-
inforcement of the WPU matrix. Additional to this main interaction
(which was previously confirmed by FT-IR spectra), other possible in-
teractions such as donor-acceptor interactions between the oxygen-free-
electrons (OH terminal and the urethane CeOeC groups) and the ni-
trogen (NH urethane) with the manganese ions and/or HO⋯HN,
NH⋯PO4 or PO3 and the C]O⋯(HO)2 interactions can be possible
(Fig. 12) [59–61]. Thus, the choice of particle fillers, quantity fillers and
dispersion time is fundamental to inhibit the agglomeration process by
breaking soft agglomerates and favoring microphase separation phe-
nomenon [62].
3.7. Mechanical properties
The mechanical properties of MnPhos/WPU coatings were eval-
uated to analyze the effect of the amount of MnPhos particles at 30 min
of dispersion time.
Fig. 13 displays load-displacement curves of hybrid coatings de-
posited onto AISI 1018 CS as a function of the MnPhos amount using a
maximum indentation load of 5 mN. For comparison, the response of
pure WPU on the same substrate is also presented. It is evident that the
incorporation of MnPhos improves the mechanical properties in-
creasing the penetration resistance in comparison with pure WPU. The
displacement of pure WPU was about 1647 nm, followed with 1379 nm
63
Progress in Organic Coatings 135 (2019) 51–64
for samples with 4 wt.%, 1379 nm (6 wt.%) and 1124 nm (2 wt.%). The
data about the instrumented hardness (HIT), Vickers instrumented
hardness (HVIT) and instrumented elastic modulus EIT (GPa) are shown
in Table 4.
An increase in HIT and HVIT is observed conversely with the wt.%
of MnPhos particles, thus the highest hardness was observed in samples
containing 2 wt.% (194.1 ± 5) and reduces with 4 wt.% (108.3 ± 6),
but losses with 6 wt.% (80.180.1 ± 9) in comparison with pure WPU
(79.3 ± 4). Hardness is a useful property where the strength and tri-
bological properties of a material are defined. Factors such as the par-
ticle size, volume percent, distribution of reinforcement phase and the
method of preparation as well as the density can modulate the final
value [63,64]. A combination of MnPhos particles amount and its dis-
persion into the polymeric matrix help to reach a balance between
barrier and mechanical properties [65]. The elastic modulus EIT was
also slightly increased with 2 wt.% and 4 wt.% (from 3 to 4 and 3.6 GPa,
respectively), however, with 6 wt.% the elastic modulus increases to
5 GPa which is characteristic of a more fragile material, most probably
by the agglomeration of MnPhos particles.
Due to Adherence is considered the most important property of a
coating-substrate system, because it determines the durability and
lifetime of the entire system [66]; pull off tests was realized in selected
samples using a dry film thickness of ˜ 20 μm and the results are also
shown in Table 4. The adhesion was quantified in terms of the strength
required to detach the test dollies glued to the film from underlying
metal. From these results it was observed that the addition of MnPhos
particles improve the bond strength in the coating-metal interphase.
When hybrid coatings were synthesized with 4 wt.% of MnPhos parti-
cles it was obtained the high bond strength (5.2 MPa); it is probably due
to the enhance of the chemical interaction of WPU with the surface area
of the MnPhos prismatic structures forming in consequence a more
stable hybrid composite [67,68].
It is well known, that hybrid materials combine the flexibility of the
polymer matrix with the hardness of the ceramic particles. In general,
the evaluated hybrid coatings showed an enhance in the adhesion
strength, hardness and elastic module dependent of the matrix-particle
interface, which in turn is related to the particle size, dispersion into the
polymeric matrix and quantity of the MnPhos particles in the coating.
An adequate modulation of electrochemical and mechanical properties
was reached using 4 wt.% of MnPhos after being magnetic stirred for
30 min during the polymerization of waterborne polyurethane to coat
commercial CS.
4. Conclusions
In this paper, we present as first time the synthesis, characterization
and electrochemical performance of MnPhos structures embedded in
waterborne polyurethane coatings as an alternative to delay corrosion
of AISI 1018 carbon steel substrates. The as-prepared systems were
evaluated in dependence of the amount of MnPhos particles (2, 4 and
6 wt.%) and dispersion time (30, 60 and 120 min).
The MnPhos particles matched well with the C2/c (15) space group
of the monoclinic structure formed from crystals that growth in c di-
rection up to reach a final length. XRD analysis of the hybrid coatings
present a reduction in the crystallite size with the dispersion time which
is associated to the disruption of agglomerates into smaller fine-parti-
cles. Based on the electrochemical measurements, the charge transfer
resistance is significantly increase only at 30 min, highlighting that
under these conditions, MnPhos into the WPU matrix increased the
coating hydrophobicity and diffusion of aggressive ions sealing the
polyurethane porous. UV–vis absorption spectra of hybrid films confirm
that MnPhos acts as UV absorber that helps to delay the WPU de-
gradation under UV light exposure. Additionally, the MnPhos induced
the microphase separation phenomenon between soft-hard segments of
WPU, nanocylinders-shape are dispersed within soft segments. Finally,
from all the evaluations, MnPhos/WPU coatings with 4 wt.% showed
P. Salazar-Bravo, et al.
superior corrosion inhibition on carbon steel followed by 2 and 6 wt.%
demonstrating that MnPhos particles can be used as a filler of WPU for
use as anticorrosion coating materials on different metals.
Acknowledgments
Patricia Salazar Bravo is grateful for postgraduate fellowship
through CONACyT. The authors are also grateful for the financial
support provided by the CONACYT Research Fellowship-IPN-CICATA
Altamira agreement, 2014-1905 and CONACyT CB2015-252181 pro-
jects; Instituto Politécnico Nacional through the SIP2019-6650,
SIP2019-6670, SIP2019-6718 projects; as well as SNI-CONACyT.
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