Industrial Crops & Products 188 (2022) 115719

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Industrial Crops & Products

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

Smart lignin-based polyurethane conjugated with corrosion inhibitor as

bio-based anticorrosive sublayer coating
Jinsong Wang a, Farzad Seidi a, *, Yang Huang a, Huining Xiao b, *
a
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources and International Innovation Center for Forest Chemicals and Materials,
Nanjing Forestry University, Nanjing 210037, China
b
Department of Chemical Engineering, University of New Brunswick, Fredericton, New Brunswick, E3B 5A3 Canada

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

Keywords: Incorporating corrosion inhibitors in the formulation of coatings can yield active coatings which are able to
Lignin provide a sustained release of the corrosion inhibitor in the case of emergence of microcrack in the structure of
Corrosion the coating. Herein, we developed bio-based polyurethane sublayer coatings with strong anticorrosion perfor­
Corrosion inhibitor
mances. First, lignin-corrosion inhibitor (LCI) conjugate was obtained through conjugation of nicotinic acid to
Polyurethane
Self-healing
lignin through hydrolytically cleavable ester linkage to afford the steady release of low concentrations of
corrosion inhibitor in case of the emergence of microcracks. Subsequently, solution polyaddition of LCI with
diisocyanates and polypropylene glycol and coating on the stainless steel surface afford the polyurethane
coatings. Coating with a thickness of 16 µm increased the Ecorr from − 481 mV (for bare steel) to + 187 mV and
reduced both Icorr and corrosion rate more than 6700 times. As an added benefit, after creating artificial cracks on
the surface of the coating, the release of corrosion inhibitors gradually increased the impedance value, indicating
a thin barrier layer has formed within the cracks.

1. Introduction are in great demand. Biomass-based materials, in contrast to petroleum-

based materials, are mostly made up of plants, which reduces carbon
Metal corrosion is a common phenomenon in which metal objects are dioxide emissions and dependence on petroleum. In addition to other
damaged through chemical and electrochemical reactions upon contact advantages, bio-based materials are renewable, biodegradable, and cost-
with moisture and oxygen. Globally, corrosion is a severe problem in effective.
many industries, resulting in huge financial losses (Chauhan et al., 2021; Lignin, the most abundant aromatic natural biopolymer on earth,
Salleh et al., 2021). Therefore, as one of the most effective and direct mainly is produced as the by-product of papermaking and biorefineries
anti-corrosion strategies, barrier protective coating has become the main (Laurichesse and Avérous, 2014). It can also be extracted from agri­
choice for industries (Mu et al., 2021; Sharma and Sharma, 2021). Many cultural wastes (such as bagasse and straws) with low production costs
organic and polymer coatings have been used for metal protection such (Arni, 2018; Borrero-Lopez et al., 2018). Due to the presence of a
as polyacrylates (Dararatana et al., 2020; Srikamut et al., 2021), poly­ copious number of OH groups, lignin is considered as a natural polyol.
urethanes (Borrero-López et al., 2020; de Haro et al., 2019), phenolic Practically, lignin has been used as a starting material for fabrication of
resins (Van Nieuwenhove et al., 2020), polyesters (Caretto et al., 2018; bio-based PU coatings (Cassales et al., 2020; Lai et al., 2021; Peng et al.,
Heinrich et al., 2022; Nameer et al., 2019) and epoxy resins (Farzad 2020). The high number of aromatic groups endows the coating with
et al., 2021; Seidi et al., 2020; Zhang et al., 2021). Polyurethanes (PUs) strong hydrophobicity along with UV-blocking ability.
have several unique properties including strong weather resistance, While PUs have been used widely for metal coating, however, the
corrosion resistance, excellent adhesion to metal surfaces, high stability main drawback of classic passive coatings is their sensitivity to aggres­
against various acidic/alkaline media, film-forming properties, and low sive environments that damage the coatings and create microcracks.
production cost, which make them prodigious materials for These microcracks in coating layers are the initial sites for starting
anti-corrosion applications. corrosion. Therefore, in recent years, the development of smart anti-
In light of the increased environmental pollution, bio-based coatings corrosion coatings has become one of the research hotspots in the

* Corresponding authors.
E-mail addresses: [email protected] (F. Seidi), [email protected] (H. Xiao).

https://doi.org/10.1016/j.indcrop.2022.115719
Received 20 February 2022; Received in revised form 18 September 2022; Accepted 21 September 2022
Available online 4 October 2022
0926-6690/© 2022 Elsevier B.V. All rights reserved.
J. Wang et al. Industrial Crops & Products 188 (2022) 115719

anti-corrosion field. To address this issue, corrosion scientists paid mixture of pyridine-d:chloroform-d (1.6:1, v/v), which contained the
special attention to corrosion inhibitors (CIs) (Dariva and Galio, 2014; relaxation additive of chromium (III) acetylacetonate (5.6 mg/mL) and
Popoola, 2019). Corrosion inhibitors are commonly a class of small internal standard of cyclohexanol (9.23 mg/mL). Then, the hydroxyl
molecules that retard the corrosion rate at low concentrations by the groups of lignin or LCI were phosphitylated by addition of 0.1 mL of 2-
formation of a thin protective layer on the surface of metals. While even chloro-4, 4, 5, 5-tetramethyl-1,3,2-dioxaphospholane (TMDP) and
simple mixing of CIs with the coating can retard the corrosion; however, shaking for 15 min at room temperature. After this reaction, the samples
the physical mixing does not provide control release for long-term ap­ were transferred to nuclear magnet tubes for testing. The CHN analysis
plications. Accordingly, the chemical conjugation of corrosion inhibitors was performed using a PerkinElmer 2400 CHNS Organic Elemental
to the coating layers is expected to allow the CIs to be released at Analyzer. The scanning electron microscope (SEM) images from the
controllable rates over a prolonged duration. To the best of our knowl­ surface and cross-section of the coating layers were obtained using
edge, most of the reports to date are based on the conjugation of Regulus 8100 field emission SEM (JEOL, Japan) at an acceleration
corrosion inhibitors to the acrylate-based polymers (Dararatana et al., voltage of 5 kV. X-ray photoelectron spectroscopy (XPS, AXIS UltraDLD,
2018; Seidi and Crespy, 2020; Seidi et al., 2018a) which are not proper Shimadzu, Japan) was used to determine the chemical compositions of
materials for practical anti-corrosion coatings due to their flammability, the surface of lignin-based polyurethane (LPU) coatings, using mono­
weak wear resistance, and poor adhesion to the metals. chromatized Al Kα radiation (hv = 1486.6 eV, 225 W) as an X-ray source
In this research, we developed a lignin-based polyurethane anticor­ with a base pressure of 10 − 9 torr. Survey scan spectra were acquired
rosive coating bearing conjugated nicotinic acid, which is one of the using pass energy of 160 and 1 eV step size. Narrow region scans were
well-received corrosion inhibitors and is particularly effective at inhib­ acquired using pass energy of 40 and 0.1 eV step size. The hybrid lens
iting the propagation of corrosion in microcracks. Nicotinic acid is a model was used in both cases. The analyzed area of all XPS spectra was
green corrosion inhibitor that has been used to protect different types of 300 × 700 µm2. A charge neutralizer was used throughout as the sam­
metals such as Fe (Liu et al., 2021), Cu (Coulibaly et al., 2018), and Zn ples were mounted such that they were electrically isolated from the
(Ju and Li, 2007). The spin casting generates thin coating layers of this sample bar. All spectra were calibrated by C 1 s (284.8 eV). UV− Vis
polyurethane on the surface of steel sheets. The conjugated nicotinic spectrophotometer (UV-1780, Shimadzu, Japan) was used to measure
acid can gradually release upon contact with water which is especially the UV− Vis absorption spectra of samples. Electrochemical impedance
important to prevent the initiation of corrosion in microcrack sites. The spectroscopy (EIS) and potentiodynamic polarization diagram were
presence of lignin as a key component of PU also makes the coating obtained by electrochemical workstation (CS310H, Wuhan corrtest,
partially green and environmentally friendly. China).

2. Experimental section 2.3. Synthesis of lignin-corrosion inhibitor (LCI) conjugate

2.1. Materials In a 100 mL round-bottom flask, 35 mL of N, N-dimethylacetamide

(DMAc), and 10.0 g of dried dealkaline lignin were mixed and heated at
Dealkaline lignin (Mw 2600 g/mol, PDI 1.1, Fig. S1), nicotinic acid 120 ◦ C for 10 min. Then, 3.5 g of anhydrous LiCl was added to the
(95 %), N,N-dimethylacetamide (DMAc, AR, 99.0 %,), N,N- mixture and gently cooled down to room temperature to obtain a dark
dimethylformamide (DMF, AR, 99.5 %,), dimethyl sulfoxide (DMSO, brown solution. Finally, 8.0 mL pyridine and 5.0 g nicotinoyl chloride
AR, 99.5 %,), thionyl chloride (SOCl2, AR, 99.0 %,), lithium chloride were added to the lignin solution. After stirring for 12 h at room tem­
(LiCl, AR, 99.0 %,), pyridine (AR, ≥99.0 %), 4,4`-diphenylmethane perature, the product was precipitated by pouring into isopropanol. The
diisocyanate (MDI, ≥99.6 %), triethylamine (Et3N, 99.5 %), poly(pro­ obtained solid was separated by centrifuge and washed several times
pylene glycol) (PPG, 99 %, MW:400)，acetone(AR，99.9 %)，isopro­ with methanol. The obtained LCI was dried at room temperature to
pyl alcohol (99.7 %) were purchased from Shanghai Aladdin produce 11.51 g of brown powder which was kept at ambient
Biochemical Technology Co., Ltd. Cold rolled steel with dimension of 20 conditions.
mm × 20 mm × 0.8 mm and composition (wt%) 99.295 % Fe, 0.5 % Mn,
0.12 % C, 0.04 % P, and 0.045 % S, was employed as the substrate for 2.4. Preparing of lignin-based polyurethane (LPU) coatings
coating. Prior to coating, the pieces of substrate were sequentially pol­
ished with SiC sandpapers (2000Cw), cleaned with deionized water Lignin-based polyurethane (LPU) coatings were prepared by the
(18.3 MΩ cm-1) and ethanol, and then dried under ambient conditions. step-growth polyaddition between LCI and MDI in the presence of
Nicotinoyl chloride was prepared by reaction of nicotinic acid with five polypropylene glycol (PPG) as a diol plasticizer. LCI and PPG are,
times of thionyl chloride according to the literature (Wang et al., 2005). respectively, hard and soft polyol segments in the polyurethane
Phosphate buffer solutions (PBS) with concentration 0.2 M at different formulation whereas MDI is a well-known hard diisocyanate. The
pHs were prepared using H3PO4 and NaOH solutions as precursors. polyurethane formation was performed under homogenous condition by
Lignin was acetylated by acetic anhydride: pyridine (1:1 v/v) mixture dissolving all reagents in DMF (or DMSO, as a green solvent) in the
which increases its solubility in organic solvent; afterward, the molec­ presence of triethylamine catalyst. The formulations of casting solutions
ular weight determination in DMF showed. are summarized in Table 1. In a typical experiment, 100 mg of dried
lignin-corrosion inhibitor (LCI) was stirred in 500 µL of N, N-dime­
2.2. Analytical tools thylformamide (DMF) at room temperature for 12 h to obtain a ho­
mogenous solution. Then, various amounts of MDI and PPG (according
The Fourier transform infrared (FT-IR) and attenuated total reflec­ to Table 1) along with 10 µL of triethylamine were added to the mixture
tance Fourier transform infrared (ATR-FTIR) spectra of the samples were and stirred for 10 min to afford a slightly viscous solution. Afterward,
taken using a VERTEX 80 V spectrophotometer (Bruker, Germany) with the resultant mixture was coated on the surface of a pre-cleaned steel
an attenuated total reflectance accessory (scans = 16, energy scanning sheet (20 × 20 × 0.8 mm3) by spin-casting (12 s at 500 rpm and then 60 s
from 400 to 4000 cm− 1, resolution = 4 cm− 1). For the FT-IR spectra of at 2500 rpm). Finally, the coating was allowed to be cured at 105 ◦ C for
the samples, KBr was used for dilution of the samples and the spectra 1 h.
were recorded from the KBr/samples disks. The 31 P NMR spectra of the
samples were obtained using a Bruker 600 M AVANCE III HD (Bruker 2.5. Contact angle measurement
Biospin, Switzerland) at room temperature in CDCl3/pyriding-d5.
Briefly, 20 mg of lignin or LCI powder was mixed in 0.5 mL solvent A contact angle analyzer (T200-Auto3 plus, Biolin Scientific,

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J. Wang et al. Industrial Crops & Products 188 (2022) 115719

Table 1
Formulation of the casting solutions applied for preparing lignin-based polyurethane (LPU) coatings.
Sample LCI MDI PPG NCO:OHequivalent ratio Et3N DMF*

mg wt% mg wt% mg wt% mg wt% mg wt%

LPU-1 100 15.6 60 9.37 0 0 1.83:1 7.3 1.14 473 73.9

LPU-2 100 16.1 40 6.45 0 0 1.22:1 7.3 1.18 473 76.3
LPU-3 100 16.7 20 3.33 0 0 0.60:1 7.3 1.22 473 78.8
LPU-4 100 16.4 20 3.27 10 1.69 0.51:1 7.3 1.20 473 77.5
LPU-5 100 16.1 20 3.22 20 3.22 0.44:1 7.3 1.18 473 76.3
LPU-6 100 15.9 20 3.17 30 4.76 0.39:1 7.3 1.16 473 75.0
*
DMSO can be used as a green solvent instead of DMF.

Sweden) was chosen to measure the hydrophilicity of LPU coatings. For 3. Result and discussion
each measurement, 5 µL deionized (DI) water was put on the surface of
the coating and the contact angle was recorded after 10 s contact with The general strategy for the conjugation of the corrosion inhibitor to
the surface. Triplicate measurement was performed and the average of lignin and then fabrication of corresponding polyurethane coatings is
the contact angle was provided as the final results. Additionally, an depicted in Fig. 1a. Lignin, as the natural polyaromatic polyol, has the
image of the drop in contact with the desired sample surface was inherent capability to be applied for the fabrication of polyurethanes by
recorded by a digital camera.

2.6. Evaluation of the anti-corrosion performance of LPU coating

The anti-corrosion performance of the LPU coatings was evaluated

by determining the electrochemical impedance spectroscopy (EIS) and
potentiodynamic polarization using CS310H electrochemical worksta­
tion in 3.5 wt% NaCl aqueous solutions at ambient temperature. To do
this, a conventional three-electrode system composed of saturated silver
chloride (AgCl) electrode (reference electrode), platinum (Pt) electrode
(counter electrode), and uncoated steel or steel-coated samples (as
working electrode) was applied. The area of the working electrode
exposed to the electrolyte was 0.8 cm2. The procedure for the fabrication
of working electrode from the steel sheets with surface area of 0.8 cm2 is
described in Supporting information (Fig. S2). For the EIS measure­
ments, the measured frequency range was 105–10-2 Hz and the sinu­
soidal amplitude was 10 mV. The potentiodynamic polarization was
measured at a scanning rate of 0.5 mV s-1 with scanning potentials from
− 0.1–0.1 V.

2.7. Release test of the corrosion inhibitor

Release profiles of the corrosion inhibitor from the LPU coatings

were obtained from the powder form of the LPU material. In the same
way, as for LPU coating, the addition polymerization of LCI, MDI, and
PPG was carried out in triethylamine/DMF. The obtained crosslinked
LPU was washed several times with acetone and dried at ambient tem­
perature, and then ground into fine powder form. 28 mg of LPU powder
was charged to the dialysis bag (MWCO: 500D, Nominal Flat Width: 10
mm) and immersed in 5 mL of 0.2 M phosphate buffer solution (PBS)
with pH = 3.0 or 10.0 at ambient temperature. Over different time in­
tervals, 500 µL of the release medium was taken and replaced by 500 µL
of the fresh buffer. The amount of the released corrosion inhibitor in
each sample was determined by measuring the UV-Vis spectrum at λmax
= 261 nm.

2.8. Evaluating the self-repairing properties

To evaluate the self-repairing properties of the LPU coatings, several

scratches with approximate lengths of 2 mm were created on the surface
of coatings using an injection needle (needle outside diameter = 0.6
mm). Afterward, the coatings were immersed in a 3.5 wt% NaCl solution Fig. 1. (a) Schematic of the conjugation of corrosion inhibitor to the lignin and
at ambient temperature for 0, 2, 4, and 8 h. At these time intervals, by the fabrication of lignin-based polyurethanes coatings (LCI: lignin-corrosion
using an electrochemical impedance spectrometer (EIS), it was deter­ inhibitor conjugate, MDI: 4,4`-diphenylmethane diisocyanate). (b) FTIR
mined whether the LPU coatings formed a thin barrier layer on the spectra of lignin and lignin-corrosion inhibitor conjugate and ATR-FTIR spec­
scratched areas as a result of the released corrosion inhibitors. trum of lignin-based polyurethane coating.

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J. Wang et al. Industrial Crops & Products 188 (2022) 115719

its polyaddition with various types of commercially available iso­ esterification. Furthermore, the shoulder of non-conjugated C– –O
cyanates. Accordingly, various types of lignin-based polyurethanes have groups at 1720 cm-1 (in LG) is converted into a separate small peak at
been developed (Bergamasco et al., 2022; Cao et al., 2020; Ma et al., LCI due to the esterification of some of the alcoholic OH groups of LG
2021; Wang et al., 2021, 2019). However, partial conjugation of the which generate the non-conjugated ester groups. Therefore, the in­
hydroxyl groups of lignin with corrosion inhibitors can provide a polyol tensity of the signal is increased and appears as an individual signal.
precursor with the capability for the fabrication of effective anticorro­ The degree of the functionalization of lignin with the corrosion in­
sive layers. Notably, the conjugation through hydrolytically cleavable hibitor was determined from the elemental analysis. The CHN analysis
linkages can provide a controllable release of the corrosion inhibitor of the lignin showed 48.62, 4.24, and 0.15 wt%, respectively for C, H,
on-demand upon contact with water. Under aggressive environmental and N; whereas the corresponding values for LCI were 52.43, 4.23, and
conditions, microcracks may form on the coating as a result of damage to 3.0 wt%, respectively. By comparing the amount of nitrogen between LG
the coating. These microcracks are the initial locations for the starting of and LCI, the amount of the conjugated corrosion inhibitor in LCI was
corrosion. Corrosion inhibitors released into the environment can form a estimated to be around 23 wt%.
thin barrier layer on these microcracks and delay corrosion. The structure of utilized lignin before and after functionalization
with corrosion inhibitor was further characterized with 31 P NMR
(Fig. 2. and Table 2) to determine the content of aliphatic OH, aromatic
3.1. Synthesis and characterization of lignin-corrosion inhibitor (LCI)
OH, and COOH groups (Carlos de Haro et al., 2019). Based on the 31 P
conjugate
NMR results, the contents of the aliphatic and aromatic OH groups in the
structure of pristine lignin are 1.65 and 2.95 mmol/g which were
The lignin-corrosion inhibitor (LCI) conjugate was synthesized by
reduced, respectively, to 0.90 and 1.70 mmol/g after conjugation with
the reaction between dealkaline lignin and nicotinoyl chloride through
nicotinic acid. Totally, it is shown that the numbers of the OH groups are
the formation of the hydrolyzable ester linkages. In the FT-IR of neat
lignin (LG) (Fig. 1b), the characteristic peaks of LG include a weak
shoulder at 1720 cm-1 which is related to the low content of non- Table 2
conjugated C– – O groups. The signal of conjugated C– – O at around The content of different types of OH groups in the structure of lignin (LG) and
1655 cm-1 is overlapping with the signal of the aromatic rings at around lignin-corrosion inhibitor (LCI) calculated from 31 P NMR.
1600 cm-1 to make a broad signal. The strong band at 1150 cm-1 is LG ppm range OH type mmol/g
ascribed to the ether groups (C-O). The broad band at 3460 cm-1 is
149–144 Aliphatic -OH 1.65
related to the OH stretching vibration and the signal at 2940 cm-1 is 144–139.8 S/C ph. -OH 0.98
attributed to the C-H symmetrical vibrations of CH2 groups. The reaction 139.8–136 Non ph. -OH 1.97
of the LG with nicotinoyl chloride leads to the esterification of some 135.4–132 -COOH 0.70
LCI ppm range OH type mmol/g
phenolic and alcoholic OH groups of LG which respectively produce
149–144 Aliphatic -OH 0.90
conjugated and non-conjugated ester linkages. Comparison of the FT-IR 144–139.8 S/C ph. -OH 0.45
spectra of LCI with LG clearly shows an increased intensity at around 139.8–136 Non ph. -OH 1.27
1640 cm-1 which is related to an increase in the number of aromatic 135.4–132 -COOH 0.62
rings in LCI and the generation of more conjugated C– – O groups upon

Fig. 2. 31 P NMR spectra of (a) lignin (LG) and (b) lignin-corrosion inhibitor (LCI).

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J. Wang et al. Industrial Crops & Products 188 (2022) 115719

reduced from 4.6 mmol/g for lignin to 2.60 mmol/g for LCI. In the other the main characteristic peaks in the neat lignin. The new peak with
words, 2.0 mmol/g of the OH groups are functionalized by conjugation binding energy 289.3 eV in Fig. 3e is related to the O-C– – O indicating
with the corrosion inhibitor. Indeed, conjugation of 2.0 mmol OH per the presence of ester groups. Conjugation through the ester linkage in­
one gram of lignin leads to the result of the conjugation of around 20 wt creases the content of the C–– O group in the LCI structure. Comparing
% nicotinic acid in LCI. However, as mentioned before, the elemental the C 1 s core-level spectra of LCI (Fig. 3e) with that of lignin (Fig. 3b)
analysis showed the amount of the conjugated corrosion inhibitor in LCI clearly shows a higher intensity of C– – O bond in LCI than lignin. The
was 23 wt%. However, we believe the results from the elemental anal­ increase in the C–– O content was further proved by the comparison of
ysis are more precise since the results from NMR can be somehow the O 1 s core-level spectra of LCI (Fig. 3f) with that of lignin (Fig. 3c)
affected by the integration method and also by adjusting the baseline of (khalilifard and Javadian, 2021).
the NMR spectrum. Therefore, all of the calculations were performed
based on 23 wt% conjugation of the nicotinic acid in LCI.
3.2. Synthesis and characterization of lignin-based polyurethane (LPU)
Further confirmation on the conjugation of corrosion inhibitor to
coatings
lignin was achieved by comparison of the XPS results of LCI with neat
lignin (LG). Fig. 3a-c revealed the presence of C–
– O, C-O, C-C, and C-H as
The lignin-based polyurethane (LPU) coatings were prepared by the

Fig. 3. XPS spectra of lignin (LG), lignin-corrosion inhibitor (LCI) conjugate, and lignin-corrosion inhibitor polyurethane (LPU) coating.

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J. Wang et al. Industrial Crops & Products 188 (2022) 115719

polyaddition polymerization between LCI and methylene diphenyl dii­ By further increasing the PPG content to 20 mg, the micropores then
socyanate (MDI) in DMF in the presence of triethylamine. The gelation disappeared, producing a smooth surface. While increasing the PPG
point of the mixture was around 15 min. Therefore, stirring the reaction content to 30 mg improved the smoothness of the surface, however, a
mixture for 10 min afford a slightly viscous solution which was applied higher content of PPG is corresponding to a lower content of LCI, which
directly for the spin casting on the surface of steel sheets. The curing can negatively affect the anticorrosion performance of the coating.
between isocyanate groups and hydroxyl groups was completed upon Furthermore, it negatively affects the gel content of the LPU coating.
heating for 1 h at 105 ℃. Therefore, the optimum formulation for fabrication of a smooth coating
Recording the ATR-FTIR spectrum of LPU coating and comparison with high content of LCI consists of 20 mg MDI, 20 mg PPG, and 100 mg
with the FTIR of the LCI clearly shows the significant reduction in the LCI, leading to the coating denoted as LPU-5.
intensity of the hydroxyl groups at 3460 cm-1, thus confirming the Meanwhile, the thickness of the coating was estimated from the
consumption of the majority of the OH groups upon reaction with the cross-sectional SEM images. The coatings containing 10–30 mg of PPG
isocyanate groups of MDI. Additionally, in the area of carbonyl groups, exhibited almost similar thicknesses. The cross-section SEM image of the
two signals appeared. One of the signals is related to the non-conjugated LPU-5 (Fig. 4f) showed a thickness of approximately 16 µm. Addition­
ester groups of LCI at 1720 cm-1 and a new one at around 1705 cm-1 is ally, there was no delamination of the coating layer from the steel sur­
ascribed to the urethane linkage generated in LPU. The significant in­ face due to the excellent interface compatibility which is a critical factor
crease in the signal at around 1520 cm-1 is due to the inserted new ar­ in retarding the corrosion via isolating oxygen, water molecules, and
omatic groups originating from MDI. Furthermore, the spectrum of LPU other corrosive chemicals from the metal substrate.
showed no signal for isocyanate groups at 2260–2280 cm-1 indicating
almost complete consumption of isocyanates in MDI through reaction 3.4. Wetting properties of the LPU coating surfaces
with OH groups of LCI.
Furthermore, the XPS analysis of LPU also confirmed the successful Water contact angle (WCA) measurements were conducted to study
formation of the polyurethane coatings. Comparing the C 1 s core-level the wettability of the LPU coatings. As shown in Fig. 4g, the WCA of the
spectra of LPU-5 (Fig. 3h) with that of LCI (Fig. 3e) revealed new C-N uncoated steel is 44.54 , which is increased to 77.40 for LPU-3, indi­
◦ ◦

and O– – C-N signals at 285.6 and 287.4 eV, respectively, which are due cating the hydrophobicity of LPU due to the presence of high aromatic
to the formation of urethane linkage. More importantly, the deconvo­ content in its structure. Furthermore, the incorporation of 10 mg PPG
lution of N 1 s spectra of LPU (Fig. 3j) showed two contributions at 399.1 endows more hydrophobicity to the coating surface with WCA 95 .
◦

and 400.3 eV which, respectively, are attributed to C-N and N-H groups Further increase in the PPG content reduced the WCA to around 82 .
◦

of the urethane linkages (Ramezanzadeh et al., 2015). Probably, when the content of PPG is higher than 10 mg, some of the OH
Additionally, the gel contents of the LPU samples were determined groups either from PPG or LCI remain unreacted during the curing
by shaking 50 mg of each sample with 3 mL DMF overnight and then process which makes the surface less hydrophobic. Furthermore, the
removal of DMF after centrifuge. The solid was washed again with DMF contact angle of the thin films of neat lignin, LCI, and LPU at different
and then dried at 100 oC to reach a constant weight. Clearly, by pHs using PBS buffer solutions was determined to evaluate the stability
decreasing the MDI and increasing the PPG the gel content was of the coating, especially under mild alkaline conditions. The results of
decreased (Table 3). The gel contents of the samples ranged between contact angle at pHs 6.0, 7.0, and 8.0 are depicted in Fig. S3. The high
79% and 94% when DMF was used as the extracting solvent. However, content of hydroxyl and carboxyl groups make neat lignin highly
in the presence of water the amount of the residual solid or insoluble gel wettable with contact angle below 10o at all pHs. Practically, the thin
fraction was much higher, ranging from 96 % to 99 %. Practically, water film of neat lignin was completely dissolved at pH 8.0. However, partial
is the solvent in the environment as the corrosive medium, and the re­ esterification of the OH groups with nicotinic acid reduced the hydro­
sults clearly confirm the stability of the coating in the presence of water. philicity by affording the contact angle of around 75o, 45o, and 42o,
respectively, at pHs 6.0, 7.0, and 8.0 after 200 s. The increase in the
3.3. SEM observation of the coatings hydrophilicity at higher pH is probably due to the deprotonation of
COOH groups in the LCI structure. Accordingly, lignin samples with
Fabrication of coatings without cracks, pores, and defects is critical lower COOH content can provide better coating hydrophobicity espe­
in anticorrosion coatings to prevent the diffusion of moisture and oxy­ cially under alkaline conditions. Finally, the contact angle of the LPU-5
gen into the metal surface. Accordingly, studying the morphology of the sample was around 82o, 50o, and 47o, respectively at pHs 6.0, 7.0 and
coatings is important to confirm the fabrication of smooth and uniform 8.0 indicating an increase in hydrophobicity upon polyurethane for­
coating layers. In the absence of PPG, microcracks, micropores, and mation. Additionally, the LPU sample was stable at all three pHs without
aggregations were observed in the structure of the coatings (Fig. 4a, b) delamination from the metal surface. Indeed, the LPU coatings in this
probably due to the highly aromatic and rigid structure of both lignin work provide fair hydrophobicity to retard the moisture from the surface
and MDI. Additionally, high contents of MDI (60 mg, Fig. 4b) generated of the coated metal. However, there are reported coatings bearing si­
severe aggregation, whereas at a low content of MDI (20 mg, Fig. 4a) lanes and fluorinated groups which provide super-hydrophobicity with
only microcracks and micropores appeared in the coating structure. At contact angle > 150o. Our goal here is not to provide a super­
MDI contents less than 20 mg, no crosslinked structure could be ob­ hydrophobic coating but to provide bio-based coatings with fair hy­
tained. Therefore, the MDI of 20 mg was selected as the optimum dosage drophobicity that can release corrosion inhibitor in the case of the
in the formulation for the fabrication of coatings. PPG can act as a emergence of microcracks in the coating structure.
plasticizer and reduce the rigidity of the coatings. Indeed, by adding a
small content (10 mg) of PPG to the coating formulation, microcracks 3.5. Release profiles of corrosion inhibitor
disappeared completely; however, there were still a lot of micropores.
The cleavage of the ester linkage and the release of the corrosion
inhibitor were evaluated by immersing the powder form of LPU-5 in
Table 3
The residual solid of different types of LPU coating after extraction by DMF or buffer solutions. Practically, the release rate from the films is slow due to
water. the small contact area between LPU with water; therefore, the powder
form of the LPU was used to accelerate the release rate. Release under
sample LPU-1 LPU-2 LPU-3 LPU-4 LPU-5 LPU-6
harsh acidic (pH 3) and basic (pH 10) conditions were evaluated to
Gel content% (DMF) 93.5 92.1 90.2 87.5 86.3 78.7 simulate the harsh environmental corrosive medium. It is reported that
Gel content% (water) 99.5 98.9 98.1 97.8 97.1 96.0
the cleavage of ester bonds under basic conditions is faster than in acidic

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J. Wang et al. Industrial Crops & Products 188 (2022) 115719

Fig. 4. SEM images of the surface of (a) LPU-3, (b) LPU-1, (c) LPU-4, (d) LPU-5, (e) LPU-6, and (f) the cross-section of LPU-5. (g) Water contact angels (WCAs) of steel
substrate before and after coating with different LPUs.

conditions (Seidi et al., 2018b). The released amount of the corrosion subsequently prompts the slow release of corrosion inhibitors due to
inhibitor was calculated by following the UV calibration curves of direct contact with water.
nicotinic acid at pHs 3.0 and 10.0. As can be seen from Fig. 5, after one
week around 4 % corrosion inhibitor was released from LPU-5 at pH 3
whereas around 13 % was released at pH 10 during the same period. 3.6. Anticorrosive properties of the LPU coatings
Slow release of the corrosion inhibitor can guarantee the long-term
stability of the coating against corrosion by continuous production of Electrochemical impedance spectroscopy (EIS) was used to investi­
low concentrations of corrosion inhibitors. It is worth noting herein that gate the anticorrosive behavior of the LPU coatings. The AC impedance
due to the hydrophobic structure of LPU, diffusion of water into the bulk spectrum, modeled by the equivalent circuit diagram, is shown in Fig. 6a
structure of LPU is retarded and most of the released corrosion inhibitors and fitted by Z view software. The obtained fitting data are shown in
are the ones near the surface of the powder form of LPU which has more Table 4. In the equivalent circuit diagram, Rs is the resistance in the
access to water. This is important for the practical application of LPU as solution, Rc is a coating resistor (approximate to the Rct), CPEc is a
coating since the release is mainly induced from the cracked areas where constant phase angle element, and the impedance value of a CPE can be
the LPU coating can be exposed to water readily. The LPU coating must expressed by the following formula (Zhang et al., 2019).
be applied as a sublayer to prevent the leaking of corrosion inhibitors
ZCPE = 1/Y0 (jω)n
from the surface areas of the coating layer. The presence of microcracks
where Y0 is the admittance of the constant phase element, n is the CPE
empirical exponent (the system behaves as a pure capacitor at n = 1, and
as a resistor at n = 0), j is an imaginary number, and ω is frequency. The
barrier layer resistance (Rc) of each sample was obtained from the fitting
results.
As can be seen in Fig. 6b, the capacitive arc of uncoated samples in
the Nyquist plot is small and close to a circle, which reveals the solution
charge transfer behavior. The results indicated that the metal surface
was corroded significantly after the immersion in NaCl aqueous solution
for 1 h. In contrast, the Nyquist plots of the LPU coatings (Fig. 6b) show
a single capacitive reactance arc characteristic; and the capacitive arcs
of LPU-4, LPU-5, and LPU-6 in the Nyquist plot are close to a straight
line, which remains almost unchanged after 8 h immersion, revealing
the excellent short-term corrosion resistance of LPU-4, LPU-5, and LPU-
6. The radius of the capacitive anti-arc is often used to evaluate the
corrosion resistance of the coating. The larger the radius, the greater the
resistance of charge transfer and the more difficult for the corrosion
reaction to proceed. Among three LPU samples, LPU-5 coating showed
the best performance. The micropores in the structure of LPU-4 can
Fig. 5. Release profile of corrosion inhibitor from the powder form of LPU-5 accelerate the diffusion of water, salt, and oxygen into the metal surface
formulation at pHs 3.0 and 10.0 in 0.2 M PBS solutions. and therefore, initiate corrosion. On the other side, the content of LCI as

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J. Wang et al. Industrial Crops & Products 188 (2022) 115719

Fig. 6. (a) Equivalent circuit model used to fit the EIS experimental data. EIS evaluation of corrosion resistance and PDP curves of uncoated steel, LPU-4, LPU-5 and
LPU-6 in 3.5 wt% NaCl solution (b) Nyquist plots, (c) Bode impedance plots, (d) Bode phase plots, (e) PDP curves.

Fig. 6c, the impedance value at low frequency (|Z|0.01HZ) slightly

Table 4
increased from 4.4 × 104 Ω cm2 for LPU-4–1.3 × 105 Ω cm2 for LPU-5,
Equivalent circuit diagram parameter value.
however, the impedance value of LPU-6 decreased to 3.8 × 104
sample Rs CPE-T CPE-P Rc Error (%) Ω cm2. Moreover, the impedance value of the uncoated sample
(Ω cm2) (F cm-2) (F cm-2) (Ω cm2)
(1.1 × 102 Ω cm2) is much lower than those of LPU-4, LPU-5, and LPU-6.
uncoated 3.6 1.1 × 10-3 0.83719 306 0.95 Slanted lines are observed at high-middle frequency, which can be
LPU-4 79.5 6.1 × 10-5 0.50924 1.0 × 105 7.72
interpreted by the double layer capacitance (cdl) behavior. Overall,
LPU-5 48.3 1.5 × 10-5 0.54557 1.6 × 105 3.55
LPU-6 11.6 6.7 × 10-5 0.58746 3.5 × 104 5.79 LPU-5 showed the best anti-corrosion performance due to the formation
of a defect-free coating along with the presence of high content of
corrosion inhibitors in its formulation. The phase angle diagram
the main anticorrosive component in LPU-6 is less than that in LPU-5, (Fig. 6d) shows that there is no time constant in the middle and low
therefore, the resistance of LPU-6 against corrosion is lower compared frequency region, indicating that the LPU coating has good barrier
to LPU-5. For the Bode-impedance plots of the LPU coatings (Fig. 6c), the properties and no charge transfer occurs on the surface of the metal
impedance modulus at low frequency (|Z|0.01 Hz) is another way to sheet.
evaluate the anticorrosion ability of coatings. Generally, a larger |Z| in Further useful information about the anticorrosive properties of LPU
low frequency indicates better corrosion resistance. As can be seen from coatings was obtained by performing the potentiodynamic polarization

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J. Wang et al. Industrial Crops & Products 188 (2022) 115719

(PDP) measurements in 3.5 wt% NaCl concentration as the corrosive XPS results (Fig. 8), Fe2O3 and FeOOH are the main corrosion products.
medium. Prior to measurements, the samples were immersed in the Additionally, the XPS results show the presence of C-C, C-N, Fe-N, and C-
corrosive medium for about 30 min, allowing them to get stable open H linkages in the scratch location which is due to the interaction of the
circuit potential (OCP) values. Corrosion current density (Icorr) and po­ released corrosion inhibitor (nicotinic acid) with Fe on the unveiled
tential (Ecorr) which can be obtained from the PDP curves are important metal surface. The SEM of the scratched area (Fig. 9) after being exposed
parameters for evaluating the anticorrosive performance of coatings. A to the corrosion medium clearly shows the formation of a layer that
smaller Icorr and larger Ecorr typically correspond to better corrosion combines the corrosion products with the layer generated by the inter­
resistance. Fig. 6e shows the PDP curves of uncoated and coated steel action of released nicotinic acid with Fe.
sheets after immersing in 3.5 wt% NaCl solution for 2 h. As shown in
Table 5, the Icorr and Ecorr of uncoated steel were determined to be 3.9. Anti-corrosion mechanism
8.69 × 10-5 A cm-2 and − 481 mV, whereas the LPU-4 and LPU-5 and
LPU-6 showed better corrosion resistance than the uncoated sample. The anticorrosion mechanism is associated with two factors that
However, the Icorr of LPU-5 (1.29 × 10-8 A cm-2) is smaller than that of retard the corrosion of the metal by the LPU coating: (1) inherent
LPU-4 and LPU-6 (4.81 × 10-7 A cm-2 and 2.35 × 10-7 A cm-2), and the anticorrosion property of the LPU coating through the interaction be­
Ecorr of LPU-5 (122 mV) is more positive than that of LPU-4 and LPU-6 tween the functional groups of the LPU coating with the metal surface
(− 22.5 mV and − 107 mV), indicating that LPU-5 possesses the stron­ and also through the oxygen and water barrier created by the LPU on the
gest anticorrosive performance. Moreover, the corrosion rate (CR) of metal surface. Practically, presence of pyridine group of corrosion in­
LPU-5 (1.52 × 10-4 mm year-1) is over 6700, 37, and 18 times lower than hibitor in the structure of LPU coating, along with the phenolic OH
the values for the uncoated metal (1.02 mm year-1), LPU-4 (5.56 × 10-3 groups in the lignin structure, improve the adsorption capacity of LPU
mm year-1) and LPU-6 (2.75 × 10-3 mm year-1), respectively, demon­ resin on the steel surface and is the key to improve the corrosion resis­
strating the fiercer corrosion resistance behavior of LPU-5. tance of the LPU coating. (2) The in-situ released corrosion inhibitor in
the case of emergence of microcracks. The interaction of the LPU coating
3.7. Self-healing properties of the LPU coatings with the metal surface can be somehow monitored by comparing the AT-
FTIR of the LPU powder with LPU coated on the Fe (Fig. 10). The main
It is well-known that corrosion inhibitors can generate a nanometric functional groups in the LPU coating that have direct interaction with
barrier layer on the surface of metals to retard the corrosion. The LPU the metal surface are the polar groups including OH, C– – O, and nitrogen

coatings act as a long-term reservoir of corrosion inhibitors. The groups. The signal of the OH group of LPU after coating on the steel
released corrosion inhibitors are especially important to retard the surface has been shifted from 3460 to 3350 cm-1. Additionally, there is a
corrosion from microcracks. The formation of a thin film of corrosion small shift of the carbonyl group from 1730 to 1725 cm-1. The shifts
inhibitors on the unveiled metal surface can be considered as a type of toward lower wavenumbers in the FTIR spectrum confirm the weak­
self-healing in coating layers. To evaluate the self-healing properties of ening of the corresponding linkages due to their interaction with the
LPU coatings, the EIS test was carried out on the LPU-5 after generating metal surface. Also, there are shifts in the aromatic area from around
several scratches on the coating surface. Nyquist and Bode plots are 1635–1600 cm-1 which can be attributed to the interaction of aromatic
shown in Fig. 7. The corrosive electrolyte can easily reach the metal rings in lignin with the metal surface.
surface in the scratched locations. The impedance modulus at low fre­ For the second mechanism which is related to the released corrosion
quency (0.01 Hz) was also used as the indicator for coating protective inhibitor, XPS was used to characterize the scratched layer on the LPU
ability. As can be seen, in the initial stages after the generation of coating exposed to 3.5%wt NaCl solution as the corrosion medium.
scratches the impedance value decreased rapidly after immersion in the Fig. 8 shows the high-resolution XPS spectra of the major elements (C
corrosive medium. The impedance value had the lowest value 1 s, O 1 s, N 1 s, and Fe 2p3/2). In Fig. 8a, the peak located at 285.0 eV
(1.1 × 102 Ω cm2) at the beginning of immersion. A gradual increase in can be attributed to the C–C, C– – C, and C–H aromatic bonds, and the

the impedance value was observed as the immersion time increased peak at 286.3 eV may be associated with the presence of C–N and C– –N

from 2 h (3.1 × 102 Ω cm2) to 8 h (4.1 × 102 Ω cm2). The capacitive bonds in the heterocyclic ring. The peak at 288.6 eV may be ascribed to
arcs are enlarged as prolonged immersion, which indicates that the C–– N+ structures, resulting probably from the protonation of the =N–

impedance of the LPU coating is increasing. The reason is related to the structure in the pyridine ring of corrosion inhibitor. Similarly, as shown
released corrosion inhibitors which can interact with the unveiled metal in Fig. 8b, there are three peaks in O 1 s spectrum, corresponding to
surface in the cracks sites and generate a thin barrier film on the metal FeO/Fe2O3 (530.9 eV), FeOOH (531.6 eV), and C– – O (533.0 eV),

surface. Indeed, the corrosion inhibitor conjugated in LCI played a respectively. As shown in Fig. 8c, the N 1 s spectrum consists of three
protective role and achieved a certain level of self-healing. peaks at 399.4 eV, 400.7 eV, and 401.5 eV. The first peak is attributed to
C–N and the unprotonated N atoms (=N- structure) in the pyridine ring,
while the second peak is mainly ascribed to the N-Fe bond due to the
3.8. Corrosion products coordination of nitrogen in the pyridine ring with the steel surface. The
last peak at 401.4 eV is probably due to the oxidized nitrogen that
To determine the corrosion products, some artificial scratches were originates from the protonation of nitrogen in the pyridine ring, which
created on the surface of the coating and then exposed to the corrosion leads to a positive polarization of the nitrogen atom and increasing in
medium (3.5 wt% NaCl solution). The XPS on the scratch was deter­ the binding energy. The Fe 2p3/2 spectrum (Fig. 8d) can be deconvo­
mined afterward to reveal the possible corrosion products. Based on the luted into three peaks at 710.1, 712.3, and 714.0 eV that could be
attributed to N-Fe, Fe2O3, and FeOOH. All of these XPS results clearly
Table 5 demonstrate the interaction of the released corrosion inhibitor with the
Corrosion current density (Icorr) and potential (Ecorr), corrosion rate (CR) for metal surface. Despite the release of the corrosion inhibitor was already
uncoated, LPU-4, LPU-5 and LPU-6. confirmed from the UV experiment, the XPS results, however, further
sample Icorr Ecorr CR confirmed the interaction of the released corrosion inhibitor with metal
(A cm-2) (mV vs. Ag/AgCl) (mm year-1) surface, which generates a thin layer for corrosion protection.
uncoated 8.69 × 10-5 -481 1.02
LPU-4 4.81 × 10-7 -22.5 5.65 × 10-3 4. Conclusion
LPU-5 1.29 × 10-8 187 1.52 × 10-4
LPU-6 2.35 × 10-7 -107 2.75 × 10-3
A smart lignin-based sublayer coating with strong anticorrosive

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J. Wang et al. Industrial Crops & Products 188 (2022) 115719

Fig. 7. Nyquist and Bode plots of LPU-5 in 8 h immersion in 3.5 wt% NaCl solution.

Fig. 8. XPS spectra of a scratched line in the LPU-5 coating after 10 h immersion in 3.5 wt% NaCl solution.

performance and the ability to release the corrosion inhibitor upon artificial cracks in the coating could produce a thin barrier layer to
contact with water was developed. Following the partial conjugation of reduce the corrosion rate which is considered as a type of self-healing
the OH groups of lignin with nicotinic acid, a green corrosion inhibitor, behavior. This coating must, however, be used as a sublayer coating to
spin casting with various amounts of 4,4`-diphenylmethane diisocya­ prolong its life and prevent corrosion inhibitors from leaking out.
nate (MDI) in DMF solvent afford the corresponding polyurethane
coatings. Due to the aromatic rigid structure of lignin, the addition of Funding
polypropylene glycol, as a plasticizer component, could improve the
smoothness of the coating. Under the optimum conditions, the coating This study was supported by Provincial Key Lab of Pulp and Paper
with a thickness of 16 µm raised the Ecorr from − 481 mV (for uncoated Science and Technology and Joint International Research Lab of
steel) to + 187 mV and declined both Icorr and corrosion rate more than Lignocellulosic Functional Materials, Nanjing Forestry University; the
6700 times. Furthermore, the release of corrosion inhibitors from National Nature Science Foundation of China (Grant No.: 31730106,

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J. Wang et al. Industrial Crops & Products 188 (2022) 115719

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polymers. Prog. Polym. Sci. 39, 1266–1290. https://doi.org/10.1016/j.
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The authors declare that they have no known competing financial Liu, X., Pan, X., Lu, M., Sun, Y., Wang, Z., Zheng, Y., 2021. Nicotinic acid derivatives as
interests or personal relationships that could have appeared to influence corrosion inhibitors for mild steel in hydrochloric acid solutions: an experimental
and computational chemistry study. J. Adhes. Sci. Technol. 35, 63–80. https://doi.
the work reported in this paper. org/10.1080/01694243.2020.1787934.
Ma, X., Zhang, C., Gnanasekar, P., Xiao, P., Luo, Q., Li, S., Qin, D., Chen, T., Chen, J.,
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