Progress in Organic Coatings 139 (2020) 105472

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Progress in Organic Coatings

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

Cashew nut shell liquid terminated self-healable polyurethane as an T

effective anticorrosive coating with biodegradable attribute
Tuhin Ghosh, Niranjan Karak*
Advanced Polymer and Nanomaterial Laboratory, Department of Chemical Sciences, Tezpur University, Tezpur, Assam, 784028, India

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

Keywords: Formulation of smart polyurethane (PU) using renewable resources as the raw materials with desired properties
Bio-based resources is a troublesome task. Thus, in this context, different compositions containing PUs were synthesized using few
Hydrophobic bio-derived raw materials like cashew nut shell liquid, modified polyol of dimer acid-glycerol and sunflower oil
Self-healing based monoglyceride along with other components like bis(hydroxyalkyl)poly(dimethylsiloxane), poly(ε-ca-
Anticorrosive
prolactone)diol, 2,4/2,6-toluene diisocyanate and isophorone diisocyanate. The structure, morphology and
Biodegradable
surface characteristics of the synthesized PUs were well-characterized using Fourier transform infrared spec-
troscopy, 1H and 13C nuclear magnetic resonance spectroscopy, scanning electron microscopy and X-ray dif-
fraction technique. The synthesized PUs showed adequate mechanical and thermal properties along with good
surface hydrophobicity (static contact angle: 112.3–121.2°), excellent microwave responsive self-healing (within
72−89 s) and biodegradable attributes along with good corrosion resistance property (corrosion rate:
8.76 × 10−5 mm/y). Most interestingly, this PU also sustains its anti-corrosive nature even after healing from
mechanical damage and reduces the corrosion rate of a corroded mild steel plate 300 times more than the bare
plate. Therefore, the studied bio-based PU has huge potential and paves a new direction in the field of smart
anticorrosive material.

1. Introduction industry containing a number of reactive phenolic derivatives (car-

Polyurethane (PU) is an important class of polymers containing
thermodynamically incompatible segments of hard and soft domains in
a single polymeric matrix and can be synthesized by a facile one-pot
technique using readily available starting materials [1,2]. Versatility in
feedstock’s and tunable properties as per the need, make this polymer
advantageous over the other commonly used synthetic polymers. But
the major concern associated with PU synthesis is excessive use of
petroleum-based feedstocks as the starting materials (diisocyanates,
polyols and chain extenders) which cause various hazardous impact on
the environment and health issues [3]. Therefore, the rapid depletion of
the fossil fuels and their gradual increment in price triggered the use of
bio-renewable resources for the synthesis of PU [4]. Among various bio-
derived raw materials, vegetable oils (sunflower, peanut, castor, lin-
seed, corn, soybean oil etc.) received huge attentions for the synthesis
of PU due to their unique structural architecture, reasonable price and
ease of necessary chemical modification [5–7].
In recent years, the pericap fluid extracted from cashew nut, known
as cashew nut shell liquid (CNSL) is successfully used as a building
block for PU [6]. Generally, CNSL is a waste product of the cashew food
danol, cardol, 2-methyl cardol and anacardic acid) with highly hydro-
phobic aliphatic chains [8–10]. Prior art literature advocates that the
CNSL is mainly used to obtain resol and novolac which are routinely
used as a thermoset resins for the fabrication of biocomposites [11].
However, CNSL is also used for the development of sustainable PU with
desired properties. For example, Liu et al. developed the synthesis of
UV-curable coating containing multiarmed cardanol (one of the com-
ponents of CNSL) based acrylates [12]. Wang and Zhou reported the
synthesis of mechanically tough PU coating using cardanol based
polyols [13]. Kathalewar reported the synthesis of isocyanates free PU
coating using diglycidyl ether of cardanol [14]. Eventhough, they used
greener method but very low mechanical performance of PUs limited
their applications. Suresh and Kishanprasad developed different kinds
of di/triol which further reacted with methylene diphenyl diisocyanate
(MDI) for the development of PU [15]. Suresh reported the synthesis of
rigid PU foam using cardanol modified polyol [16]. Though all these
reports depict successful synthesis but their complicated modification
process of cardanol limit their uses. Moreover, most of the reports were
found to be silent about their mechanical properties which ultimately
determined their practical applications as an active surface coating

⁎
Corresponding author.
E-mail address: karakniranjan@gmail.com (N. Karak).

https://doi.org/10.1016/j.porgcoat.2019.105472
Received 31 July 2019; Received in revised form 23 November 2019; Accepted 30 November 2019
Available online 06 December 2019
0300-9440/ © 2019 Elsevier B.V. All rights reserved.
T. Ghosh and N. Karak
[17–19].
Furthermore, corrosion of the metal substrate is the biggest chal-
lenge and economic burden encountered by both government and pri-
vate industries [17]. Billions of dollars were spent every year to protect
these metal-based articles. As per the report, India losses 4–5% and USA
losses 6.2% of total GDP due to corrosion [20]. Therefore, the devel-
opment of anticorrosive polymeric coating is very much necessary to
prevent such huge loss and to extend the service life of metallic pro-
ducts. From, the very beginning, PU is widely used as a surface coating
material due to its inborn versatility and favorable properties. These
properties can be tailored easily by manipulation of the structures and
compositions. Further, properties like surface hydrophobicity and self-
healing properties can also be achieved by proper design of them which
can be added as extra advantages in the field of the anticorrosive
coatings by prolonging their service life [21].
Therefore, the aim of the present work is to design a mechanically
tough PU using some bio-derived raw materials like modified polyol of
dimer acid-glycerol (DAGP, as branch generating unit), monoglyceride
of sunflower oil (MG, as a chain extender) and CNSL (as chain termi-
nating agent). Moreover, to reduce the surface energy and to provide
sufficient rigidity, crystallinity, good flexibility in the PU matrix bis
(hydroxyalkyl)poly(dimethylsiloxane) (BHPDMS) and poly(ε-capro-
lactone)diol (PCL) were also used as the building blocks. As per our
knowledge, this is the first report in which both sunflower oil and CNSL
were used to develop self-healing, anticorrosive PU coating. The
structural, physical, morphological and thermal properties of the syn-
thesized PUs were investigated using Fourier transform infrared (FT-IR)
and nuclear magnetic resonance (NMR) spectroscopies, gel permeation
chromatography (GPC), scanning electron microscopy (SEM), thermo-
gravimetric analyzer (TGA) and differential scanning calorimetry
(DSC). The mechanical properties and special properties like surface
hydrophobicity and self-healing were also evaluated. The anticorrosive
performance of the coatings was also determined to emphasize the
usefulness of the materials. In addition, the biodegradation of the
synthesized PUs was also studied to highlight their potential as an ef-
fective environmental friendly surface coating materials.
2. Experimental section
2.1. Materials
DA (average molecular weight (Mn) ∼570 g/mol), PCL
(Mn∼2000 g/mol), sunflower oil and isophorone diisocyanate (IPDI)
were procured from Sigma-Aldrich, USA. Glycerol and calcium oxide
(CaO) were purchased from Merck, India. BHPDMS (Mn∼5600 g/mol)
and 2,4/2,6-toluene diisocyanate (TDI) were obtained from Sigma-
Aldrich, Japan and Merck, Germany, respectively. DA and sunflower oil
were dried in a vacuum oven at 60 °C for 12 h before use. Other che-
micals were used as received. para-Toluene sulfonic acid (p-TSA) was
obtained from SRL, Mumbai, India. Xylene was procured from Merck
(India) and used after normal distillation. CNSL (hydroxyl value:
374.5 mg KOH/gm) was provided by Asian Paints, India and used after
vacuum drying. It is also necessary to mention that the CNSL was ob-
tained by the solvent extraction technique by the manufacturer. DAGP
and MG were prepared as reported in our earlier report [2].
2.2. Synthesis of PU containing CNSL (PU-CNSL)
Predetermined amounts of PCL (2 g, 2 mM), BHPDMS (0.56 g,
0.2 mM) and DAGP (0.075 g, 0.1 mM) were placed in a three-neck glass
reactor (100 mL) fitted with a mechanical stirrer. The other two necks
were tightly sealed with a Teflon septum and a nitrogen inlet.
Afterwards calculated amount (1 mL) of xylene was added to the re-
action mixture using a syringe to maintain the solid content of the re-
action mixture near about 75%. Then the temperature of the reaction
mixture was gradually increased to 50 °C to melt the PCL using a
2
Progress in Organic Coatings 139 (2020) 105472
controlled temperature oil bath and subsequently required amount of
TDI (0.27 g, 1.6 mM) was added under continuous stirring condition
(300 rpm). Then the temperature was raised to 85 ± 5 °C and con-
tinued for 4.5 h to obtain desired viscosity. Resulted viscous mass was
cooled to room temperature and treated as the prepolymer of PU. In the
next step, MG (0.407 g, 1.15 mM) and required amount of IPDI (0.44 g,
2 mM) were added into the prepolymer followed by the addition of
4.4 mL xylene to maintain ∼50% solid content. Again, the temperature
of the reaction was further increased to 110 ± 5 °C and continued for
3 h under continuous stirring. Then predetermined amount of CNSL
(0.69 g, 2.3 mM) was added to the reaction mixture under vigorous
stirring (450 rpm) and continued for 1.5 h to obtain PU-CNSL-1. The
completion of the reaction was supported by the butylamine test and
solubility test, indicating no gel formation. The obtained product was
cast on Teflon sheets and the residual solvent was allowed to evaporate
under ambient condition to obtain a dry film for the evaluation of
different properties. The precipitated PU product was used for other
(NMR, viscosity etc.) analyses. Simply following the above described
procedure, other two PUs were synthesized using 1.045 g and 1.393 g of
CNSL, separately, keeping all of the components as they were and en-
coded as PU-CNSL-2 and PU-CNSL-3. The exact compositions of the
synthesized PUs are provided Table S1 of supporting information (SI).
2.3. Instrumentation and testing methods
2.3.1. Determination of physical properties
The specific gravity of the dry PU-CNSLs was determined using by
the standard ASTM (D7932) method. The viscosity (specific) of the as
prepared PUs was evaluated using Ubbelohde viscometer as per the
ASTM D4020 method using Tetrahydrofuran (THF) as a solvent. The
number average molecular weight (Mn) and weight average molecular
weight (Mw) and polydispersity index (PDI) of the PU-CNSLs were
evaluated using gel permeation chromatography (GPC, Waters, UK)
equipped with a refractive index (2414) and 515 HPLC pump. The
eluent (THF) used at flow rate of 0.75 mL/min and linear polystyrene
was as standard for the analysis.
2.3.2. Structural characterization
The FT-IR spectra of the synthesized PU-CNSLs were recorded using
Perkin Elmer FT-IR spectrometer (Frontier MIR-FIR, USA) in attenuated
total reflection (ATR) mode over the range of 4000−400 cm−1.
Presence of different types of proton and carbon was verified using a
400 MHz Nuclear Magnetic Resonance (NMR) spectrophotometer
(JEOL, Japan). Deuterated DMSO was used as the solvent and trimethyl
silane (TMS) was used as the internal standard to record the NMR
spectra. Further, the degree of crystallinity of the samples was scruti-
nized using a Bruker D8 FOCUS XRD machine (AXS, Germany) fitted
with Cu-Kα radiation source over the range of 2θ = 5 to 70°. The d-
spacing value of the synthesized PUs was evaluated using Bragg’s
equation:
d = nλ/2sinθ (1)
where, λ = wavelength of the used X-ray, θ = diffraction angle,
d = distance between lattice plane from which the X-ray diffracted and
n = positive integer (1).
2.3.3. Determination of mechanical properties
Tensile properties (tensile strength, elongation at break and
toughness) of the PU-CNSL strips with a dimension of
0.5 × 10 × 50 mm3 were measured using a WDW-10 Universal tensile
machine (UTM, Jinan, China) equipped with 0.5 kN load cell. Tensile
properties of all the samples were analyzed at room temperature with a
crosshead speed of 50 mm/min. Scratch hardness of the dried strips
under dynamic and static condition was evaluated using a scratch
hardness tester (Sheen Instrument Ltd, UK) and Shore A hardness tester
T. Ghosh and N. Karak
Scheme 1. Plausible synthesis route of PU-CNSL.
(Shenn, China) respectively. Further, the falling weight method was
used to access the impact resistance property of the synthesized PU-
CNSLs. A weight of 0.85 kg attached with impact tester (S.C. Dey & Co,
Kolkata) was allowed to fall on the coated steel plate from different
heights (limit:1 m) and the impact resistance value as energy per unit
thickness was reported as a maximum height up to which the film was
not damaged. All the aforementioned experiments were carried in tri-
plicate and the average results were reported.
2.3.4. Determination of thermal properties
Thermal stability of the synthesized PU-CNSLs was investigated
thermogravimetrically using a Perkin Elmer thermogravimetric ana-
lyzer (TGA-4000, USA) over the range of 32–720 °C at a heating rate
10 °C/min under ultra pure N2 atmosphere (flow rate:30 mL/min).
Different thermal transition temperatures of the PU-CNSLs were scru-
tinized using Differential scanning calorimetry (DSC). Perkin Elmer
DSC-6000 (USA) instrument was used over the temperature range of
−70 °C to 120 °C under ultra pure N2 atmosphere by following a
heating (heating rate: 5 °C/min), cooling (cooling rate: 10 °C/min) and
heating (heating rate: 5 °C/min) cycle.
2.3.5. Surface hydrophobicity test
Surface hydrophobicity was measured as the static contact angle
(SCA) of the water droplets which were placed on the surface of the
dried PU-CNSL strips. For each case, water droplets were placed in five
different places of the strips and the average result was considered.
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Progress in Organic Coatings 139 (2020) 105472
2.3.6. Self-healing test
Self-healing ability of the synthesized PU-CNSLs against mechanical
damage was investigated simply by cutting the strips in a transverse
direction using a razor blade and exposed under microwave radiation
(500 W). The healing efficiency was assessed by measuring the ratio of
the tensile strengths of the damaged strip after healing to before da-
mage as given below.
Healing efficiency (%) = [Tensile strength (healed film)/ Tensile
strength (initial)] × 100 (2)
2.3.7. Corrosion resistance test
Electrochemical corrosion resistance properties were determined to
understand the corrosion resistance ability of the coatings, using an
electrochemical work station (Autolab PGSTAT302 N, Metrohm, UK)
attached with three electrode system, namely platinum (Pt) wire as the
counter electrode, coated mild steel (MS) plate as the working electrode
and a saturated calomel electrode (silver electrode) as the reference
electrode. During the study coated MS plate of surface area: 1 cm2 was
used as a working electrode and 3.5% NaCl solution was used as a
corrosion medium. All the above mentioned experiments were carried
in triplicate and the average results were reported.
Effective healing process of the coating was also checked by simply
making a cross mark on the coated plate by a razor blade which was
subsequently healed under MW. Afterwards, potentiodynamic polar-
ization (PDP) and electrochemical impedance spectroscopy (EIS)
T. Ghosh and N. Karak
Fig. 1. ATR-FTIR spectra of PU-CNSLs.
measurements were carried out to further support the healing process.
2.3.8. Biodegradation test
Gram negative (Pseudomonus aeruginosa) and Gram positive (Bacillus
subtilis) bacterial strains were used to study the biodegradation char-
acteristic of the synthesized PU-CNSL strips. At first a medium con-
taining 25 g Luria Bertani Broth (Miller, Himedia) in 1 L demineralized
water was prepared. The obtained medium was sterilized under a
pressure of 103.5 kPa for 15 min at 120 °C in an autoclave and then
allowed to cool under room temperature. Using the above sterilized
medium, bacterial strains were cultured separately inside an incubator
maintaining constant temperature (37 °C) for 48 h. Then 100 μL (con-
taining approximately 108 microbes/mL) cultured bacterial strain was
added separately in each culture tubes containing 10 mL of the above
sterilized Luria Bertani broth and sterilized films of the synthesized PU-
CNSL. Afterwards all the culture tubes were left for incubation for a
specified period of time (5 weeks) and the degradation of PU films was
monitored by measuring the optical density (OD) of the medium every
week. All the samples were examined in triplicate and the average re-
sults were reported. Further, the surface images of the films before and
after degradation were also taken using SEM (JEOL JSM-6390LV).
3. Results and discussion
3.1. Synthesis of PU containing CNSL (PU-CNSL)
As displayed in Scheme 1, PU-CNSLs were prepared using two-step
one pot pre-polymerization technique [2]. The formation of iso-
cyanates-terminated pre-polymer through the rearrangement reaction
of diisocyanates (TDI) in the presence of reactive diols (PCL, BHPDMS)
and branching units (DAGP) was observed in the initial step. The excess
isocyanate is necessary to gain isocyanate terminated pre-polymer
(supported by FTIR spectra as reported in our earlier report) in the first
step [22]. Further, the increasing viscosity of the reaction medium with
time also support the formation of polymeric product termed as pre-
polymer. For further chain extension, predetermined amounts of MG
and IPDI were added to the reaction medium in the second step. It is
also relevant to mention that a less reactive diisocyanate (IPDI) was
used in the second step of the reaction to avoid gel formation. Further,
50% solid content of the reaction mixture in the second step also
minimizes the gelation tendency of the reaction. Moreover, to maintain
the overall -NCO/-OH ratio ∼1, stoichiometric amount of CNSL con-
taining reactive phenolic –OH group was added to the reaction medium
to obtain CNSL terminated PU chains. Competition of the reaction was
confirmed by measuring the amount of free isocyante using butylamine
test and absence of characteristic –NCO peak in FTIR spectra. Different
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Progress in Organic Coatings 139 (2020) 105472
compositions containing PUs were synthesized with a variable amount
of CNSL, maintaining the overall NCO/OH ratio ∼1, to obtain the best
composition.
3.2. Physical properties
Different physical properties (color, solubility, specific gravity, so-
lution viscosity and molecular weight) were evaluated as per the
standard methods and corresponding values are summarized in Table
S2 of SI. All the synthesized PU strips appeared as reddish brown in
color. This color might be due to the presence of intense reddish brown
color of the CNSL present in the structure of the PUs [23]. Most inter-
estingly, it is noted that the synthesized PUs were soluble in most of the
common organic solvents like dimethylformamide, dimethylsulfoxide,
tetrahydrofuran, dimethylacetamide, acetone etc. even in xylene,
chloroform, dichloromethane, etc. but totally insoluble in hexane,
methanol, ethanol etc. A large number of polar functional groups (ester,
urethane, hydroxyl etc.), long aliphatic chains and three-dimensional
globular architecture of the synthesized PUs are responsible for such
good solubility in the aforementioned solvents [24]. Further, the PUs
also exhibited specific gravity in the range of 1.43-1.27 and decreases
with the increase of CNSL content. Mainly, the structure of CNSL con-
tents long aliphatic chains, thus with the increase of CNSL content the
free volume of the PU matrix increases (also supported by mechanical
property as well as XRD and DSC studies). As a result, synthesized PUs
followed a decreasing trend in specific gravity. Further, the solution
viscosity for the synthesized PUs was found in the range of 0.287 to
0.265. The viscosity of the synthesized PUs strongly depends on the
molecular weight. Higher the Mw (Table S2), higher is the solution
viscosity for the polymer with the same structure. Thus PU-CNSL-1 with
the highest value of Mw showed higher solution viscosity [2,25].
3.3. Structural characterization
3.3.1. FTIR analysis
The expected structure of the synthesized PUs was supported by
ATR-FTIR spectra as shown in Fig. 1. The band at 2270 cm−1 for free
isocyanate groups was not observed, which clearly indicates the com-
pletion of the reaction. The band appeared in the range of
3200−3500 cm−1 is due to H-bonded NeH stretching. Further, sig-
nificant bands (cm−1) at 1725 for combination of both carbonyl (C]O)
and amide I stretching, 1530 for -N-C stretching and -N-H bending
(amide II), 1243-1200 for in-plane bending vibration of NeH (amide
III) bond, and 1185-1160 for CeN stretching, -O-C stretching were also
found in the spectra. Presence of the abovementioned bands correspond
to the formation of urethane (-NH-(C]O)-O-) linkage in the synthe-
sized PUs [3,8,26]. Few other bands centered at 2933-2863, 1600 and
1470, 1259, 1094 and 1018 cm−1 assigned to the asymmetric and
symmetric stretching of methylenic C–H groups, C]C stretching of
aromatic ring present in TDI and CNSL, -CH3 bending vibration of
BHPDMS, asymmetric and symmetric stretching of Si-O-Si bond, re-
spectively. Moreover, the bands at 870 and 800−690 cm-1 represent
the bending vibration C-H group and stretching vibration Si-C bond
present n the structure of BHPDMS [25].
3.3.2. NMR analysis
Generally, the prediction of the structure of the synthesized PU with
very high molecular weight is a very troublesome task. Because higher
molecular weight generates intricate coiled architecture, as a result, a
slight change was observed in the chemical environment of a similar
kind of protons/carbons.
From 1H NMR (Fig. 2a) study it was found that the chemical shift
values at δ = 0.12 (a), 0.89 (b), 0.92 (c), 0.94 (d), 1.05 (e) and 2.16 (f)
ppm correspond to the terminal methyl (-CH3) protons present in the
structure of BHPDMS, DAGP, MG, IPDI and TDI moieties present in the
structure of the synthesized PU. Further, the chemical shift values at
T. Ghosh and N. Karak
Fig. 2. (a) 1H and (b)
δ = 1.21 (g) and 1.32 (h) assigned to the methylenic protons of long
aliphatic chains of MG, DAGP and PCL. Further the chemical shift va-
lues at δ = 2.03 (i), 1.58 (j) and 2.32 (k), 2.57 (l), 3.66 (m), 4.16 (n)
and 4.03 (o) ppm assigned to the α-methylenic protons with respect to
double bond, β- and α-methylenic protons with respect to ester car-
bonyl, methylenic protons between two double bond, methine (-CH)
protons of IPDI and the two different methylenic protons of glycerol
unit, α- and β-methylenic protons with respect to ester oxygen re-
spectively were observed. In addition the signals at δ = 5.02–5.09 (p)
ppm assigned to the methine protons of glycerol unit. Further, the
protons attached with aliphatic (present in MG, DAGP, CNSL) and cy-
cloaliphatic (present in DAGP) double bond carbons found at δ = 5.38
(q) and 6.62 (r) ppm. Aromatic protons of CNSL and TDI moiety ap-
peared in the range between δ = 7.12–7.65 (s) ppm [15,27]. The re-
maining most two deshielded protons found at δ = 8.78 (t) and 9.25 (u)
ppm, attributed to the urethane protons (-N-H) attached with IPDI and
TDI [2].
Progress in Organic Coatings 139 (2020) 105472
13
C NMR spectra of PU-CNSL-1.
Similarly, 13C NMR spectral analysis (Fig. 2b) revealed the presence
of different types of carbon as predicted in the proposed structure. The
chemical shift values at δ = 14.02 (a), 14.34 (b), 16.02 (c), 19.81 (d),
22.44 (e), 29.24 (f) and 31.48 (g) ppm correspond to methyl carbon of
BHPDMS, DAGP, MG, CNSL, TDI and IPDI moieties, respectively [25].
Further, the chemical shift values at δ = 21.26 (h), 24.61 (i) and 25.5
(j), 28.3 (k), 28.61 (l), 33.87 (m), 27.18 (n), 63.51 (o), 63.97 (p) and
68.80 (q) ppm ascribed to the methylenic carbon near terminal methyl
group, β and γ methylene protons with respect to the carbonyl carbon, δ
methylenic carbon with respect to the carbonyl carbon, α methylenic
carbon with respect to double bond, α methylenic carbon with respect
to carbonyl carbon, methylenic carbon between two double bond,
methylene and methine carbons of glycerol unit respectively. Further,
the chemical shift for the aromatic ring carbon (unsubstituted), double
bond carbon of MG and CNSL, double bond carbon of cyloaliphatic ring
of DAGP, substituted aromatic carbon attached to -NHCOO- group,
substituted aromatic carbon attached to -O(C]O)NH- group, ester
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T. Ghosh and N. Karak Progress in Organic Coatings 139 (2020) 105472

Fig. 3. (a) XRD patterns (b) stress-strain curves (c) TGA curves and DTG curves (inset) and (d) DSC curves of PUs.

carbonyl carbon were observed at δ = 113.13–125.95 (r), matrix. As a consequence of high free volume, sequential arrangement
128.58–130.19 (s), 134.5–137.6 (t), 144.2 (u), 157.7 (v) and 173.02 of PCL segments disturbed which results in poor crystallinity. Further,
(w) ppm [15]. However, some of the peaks (r, v) are displayed in the broad peak appeared in the range of 12.3° is due to amorphous
maximized form due to their very low intensity in the NMR spectrum. BHPDMS moiety. Presence of peaks for both PCL and BHPDMS seg-
ments clearly depict the presence of microphase separation in the
synthesized PUs [30].
3.3.3. XRD analysis
From the XRD analysis (Fig. 3a) it is clearly evident that all the
synthesized PUs showed a sharp peak at 2θ = 21.4° (d spacing of
3.4. Mechanical properties
4.14 Å) and 23.5° (d spacing of 3.78 Å). The appearance of such peaks
corresponds to the (110) and (200) planes of the orthorhombic unit cell
Generally, mechanically properties of synthesized PUs were gov-
of PCL moiety [28,29]. Further, the degree of crystallinity of the syn-
erned by several factors like molecular weight, crystallinity, chain en-
thesized PUs was calculated by taking the area ratio under the crys-
tanglement, physicochemical crosslinking, primary and secondary in-
talline peak to the overall area under the curve. From the tabulated
teractions etc. [1]. Different mechanical properties like tensile
results (Table 1) it is clear that overall crystallinity decreases sharply
properties, scratch resistant under dynamic and static condition, impact
(also supported by decreasing intensity pattern) with the increase of
resistant were evaluated and the results are furnished in Table 1. From
CNSL content, even after using a similar amount of PCL (2 mM) for the
the stress-strain curves (Fig. 3b), it is evident that the synthesized PUs
synthesis of above-mentioned PUs. The presence of long aliphatic
exhibited moderate tensile strength (5.74-2.7 MPa) which is attributed
chains of CNSL eventually increases the overall free volume of the
to the high molecular weight (∼104 order) and crystallinity of PUs.
Higher the molecular weight, higher is the possibility of physico-
Table 1
Crystalline and mechanical properties of PU-CNSLs.
chemical interaction between the polar functional groups (ester, ur-
ethane, carboxylic etc.) of the structure of PUs which provide sufficient
Properties PU-CNSL-1 PU-CNSL-2 PU-CNSL-3 rigidity to the synthesized PU [2]. Moreover, the overall crystallinity
Crystallinity (%) 14.93 12.37 7.58 also plays a crucial role and provides an adequate amount of intrinsic
Tensile strength (MPa) 5.74 ± 0.4 3.56 ± 0.3 2.7 ± 0.3 rigidity to PUs. Due to this reason, PU-CNSL-1 with a higher degree of
Elongation at break (%) 296 ± 20 238 ± 12 211 ± 10 crystallinity (confirmed from XRD results) showed comparatively better
Toughness (MJ/m3) 15.50 ± 0.5 7.59 ± 0.2 4.6 ± 0.2 results than the other two PUs (PU-CNSL-2 and PU-CNSL-3). Moreover,
Scratch hardness (kg) 3.2 ± 0.1 2.2 ± 0.1 1.6 ± 0.1
the presence of long aliphatic chains and an extensive number of sec-
Shore A hardness 48 ± 2 42 ± 1 34 ± 4
Impact resistance (kJ/m) 15.3 ± 0.2 12.9 ± 0.5 12.5 ± 0.4 ondary interactions including H-bonding, π-π interaction etc. in the
structure of the synthesized PUs also provide good flexibility without

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T. Ghosh and N. Karak Progress in Organic Coatings 139 (2020) 105472

any deformation. However, the obtained tensile properties are much
higher than other reported polymers containing CNSL [12,24]. Syn-
thesized PUs also exhibited adequate toughness which ascribed to the
combined effect of moderate tensile strength and flexibility. From the
table, it is also evident that the tensile strength, elongation at break and
toughness of PUs decrease with the increase of CNSL content from PU-
CNSL-1 to PU-CNSL-3. Intrinsic plasticization effect of long aliphatic
chain of CNSL is responsible for such decrement in tensile properties.
Similarly, hardness under the dynamic condition and static condition
also follows the same trend which clearly indicates that the toughness
of the PUs decreases simultaneously with the increasing amount of
CNSL.
Moreover, the synthesized PUs showed good impact resistance va-
lues. In fact, this property strongly depends on the load transferring
ability in between the polymeric chains mainly from the soft segment to
the hard segment and the rigidity of the PU matrix [31]. During the
time of applied impact, flexible units absorb the energy and quickly
dissipate it by transferring to the hard segments (aromatic moiety
present in TDI and CNSL), present in the same polymeric backbone.
These hard segments absorb the energy and help to maintain the
structural integrity after impact without any failure. Thus PU-CNSL-1
showed more impact resistance ability as it possesses more compact and
rigid structure compared to the other two PUs.
3.5. Thermal properties
Thermostability of the synthesized PUs was assessed using TGA
thermograms and corresponding first derivative (DTG) curves as shown
in the Fig. 3c. DTG curves revealed that the synthesized PUs underwent
a multi-step degradation pattern and the degradation temperatures are
furnished in Table 2. The initial degradation (Ton) was found in the
range of 251−269 °C which corresponds to the degradation of long
aliphatic chains present in the structure of MG, CNSL and DAGP
[12,25]. The second step degradation peak temperature was found in
the range of 358−364 °C which is related to the chain scission of ur-
ethane, ester linkages and degradation of cycloaliphatic rings of DAGP
[24]. The third step which was also considered as the step for maximum
rate of degradation (TMAX), occurred in the range of 405−413 °C. Such
degradation corresponds to the degradation of thermostable aromatic
rings present in the structure of TDI and CNSL. The forth degradation
temperature corresponds to the thermal cleavage of most thermostable
Si-O-Si bond present in the structure of BHPDMS.
Further, the melting temperature (Tm) and heat of crystallization
(ΔHc) of the PCL segments present in the structure of PUs are evaluated
from the DSC curves as shown in Fig. 3d and the corresponding values
are reported in Table 2. From the tabulated results it is clearly evident
that the Tm value of the PCL segments decreases dramatically with the
increase of the CNSL amount. Such decrease in Tm is attributed to the
presence of long aliphatic chains in CNSL which directly increase the
free volume of the PU matrix. Higher the free volume, lower is the
Table 2
Thermal properties, SCA, healing efficiency and healing time of PU-CNSLs.
Parameter PU-CNSL-1 PU-CNSL-2 PU-CNSL-3
Ton (°C) 269 251 258
Second degradation peak 358 364 358
temperature (°C)
Third degradation peak temperature 414 405 413
(°C)
Forth degradation peak temperature 456 452 452
(°C)
Tm (°C) 65.2 51.3 50.2
ΔHc (J/g) 20.28 17.03 14.49
SCA (°) 112.3 ± 1 115.8 ± 0.6 121.2 ± 0.5
Healing efficiency (%) 94.7 86.3 82.8
Healing time (s) under MW (500 W) 72 ± 5 81 ± 3 89 ± 2
temperature for melting. Moreover, Tm of PUs is also governed by the
crystallinity. High degree of crystallinity leads to compact ordered ar-
chitecture [29] as a consequence, higher temperature is needed to melt
the ordered structure. From the DSC study, it is also evident that ΔHc
value (Table 2) for PU-CNSL-1 was slightly higher than the other two
PUs. Higher the value of ΔHc, higher is the crystallinity. As per the
literature PCL is considered as 100% crystalline with a ΔHc value
136.08 J/g (32.4 cal/g) [32]. Thus PU-CNSL-1 with a higher degree of
crystallinity possesses higher Tm compared to the other two PUs.
However, the obtained crystallinity from ΔHc value is almost similar to
the crystallinity reported by XRD patterns.
3.6. Surface hydrophobicity study
The hydrophobic nature of the synthesized PU-CNSL strips was
confirmed by measuring the water contact angle under static condition
(inset of Fig. 4a, b and c) and corresponding values are reported in
Table 2. Generally, the surface with SCA greater than 90° considered as
a nonwetting surface [33]. Hence from the reported results, it is clear
that all the PUs exhibited nonwetting phenomena with SCA in the range
of 112.3° to 121.2°. Such kind of nonwetting characteristic is attributed
to the low surface energy of BHPDMS and nonpolar nature of long
aliphatic hydrocarbon chains of MG and CNSL which present as a
structural component in the PUs [34]. Moreover, the presence of
crystalline PCL and BHPDMS in the same polymeric backbone generates
structural inhomogeneity which results in papillary hill-like structures
(Fig. 4a, b and c) in micro/nanoscale on the surface [35–37]. As a re-
sult, significant amount of air is entrapped in between these micro/
nanoscale structures which act as air cushion beneath the water droplet
and increase the SCA by minimizing liquid-solid interface [38–40].
From the tabulated results, it is noted that SCA of PUs increases sur-
prisingly with the increase of the amount of CNSL. This increasing trend
of SCA is accredited to the presence of long aliphatic chains of CNSL
which increases with the increase of CNSL content from PU-CNSL-1 to
PU-CNSL-3.
3.7. Self-healing property
As displayed in Fig. 4d, damaged PU-CNSL-1 strip was effectively
healed and recovered its original set of properties after the application
of a suitable stimulus (MW). Most interestingly, tensile properties of the
healed samples resemble with the pristine as displayed in the stress-
strain curves (Fig. 4e) and corresponding healing efficiency values are
furnished in Table 2. Such kind of healing is possible only because of
the diffusion of polymeric chains in the damage site [41]. Briefly, upon
exposure to a suitable stimulus, some polar functional groups start to
vibrate their dipoles after absorbing the energy. The heat generated
from such vibration is enough for softening the soft segments (mainly
PCL) present in the structure [2,29]. Hence, a rapid Brownian motion
occurred in between the soft segment which leads to the diffusion of the
polymeric chains at the damaged site. Upon removal of the stimulus,
melted soft segments recrystallize and heal the crack surface efficiently.
At the same time, strong supramolecular interactions (H-bonding, di-
pole-dipole and π-π interactions) present in the structure of PUs par-
tially help to regain their initial property [41].
Generally, healing in the synthesized PUs is governed by some im-
portant parameters like the ratio of hard to soft segments, molecular
weight of the soft segments, crystallinity, glass transition and melting
temperatures. [41]. But in our study, the amount of hard and soft
segments and crystallinity are the predominating factors among the
abovementioned parameters. From Table S1 it is cleared that the
amount of hard segment (wt%) increases with the increase of CNSL
content from PU-CNSL-1 to PU-CNSL-3. Presence of excess amount of
hard segment acts as a physical barrier and prohibited the flowing
ability of the soft segments during the time of healing. As a result, the
time required for healing gradually increases with the increase of CNSL

7
T. Ghosh and N. Karak Progress in Organic Coatings 139 (2020) 105472

Fig. 4. (a, b, and c and insets) represent the surface roughness of PU-CNSL-1, PU-CNSL-2, PU-CNSL-3 and SCA on the corresponding surface (d) SEM images of the
PU-CNSL-1 surface during healing and (e) representative stress–strain profiles of PU-CNSL-1 before damage and after healing with different repeating cycles.

content (Table S1). Further, PU-CNSL-1 showed a higher degree of
crystallinity for the PCL segment which generally melts and re-
crystallizes during the time of healing. The combined attribute of these
factors is the main reason behind the efficient (Healing efficiency:
94.7%) and ultrafast (within 72 s under MW) self-healing behavior of
PU-CNSL-1.
3.8. Anticorrosion study
Corrosion resistance property of the synthesized PU-CNSL-1 coated
MS plate was investigated in 3.5 % NaCl solution for a period of 96 h.
Overall study was carried out using PU-CNSL-1, as it showed superiority
in mechanical and self-healing behavior compared to other two PUs.
Different electrochemical parameters like corrosion current density
(Icorr), corrosion potential (Ecorr), corrosion rate and polarization re-
sistance (Rp) values were evaluated from Tafel plots (Fig. 5a) and
corresponding results are presented in Table 3. From the results, it is
clear that the synthesized PU showed excellent corrosion resistance
performance and the results (mainly corrosion rate) are much better
than the prior art literatures values [20,35,42]. At the very beginning of
the reaction, MS plate showed the lowest Ecorr (-1.027 V) and the
highest Icorr (1.7 × 10−4 A/cm2) value. Origination of pitting corrosion
on the MS plate immediately after immersion in the salt solution, is the
main reason for such poor corrosion resistant behavior [17]. Whereas in
the coated MS plate, Ecorr value (-0.469 V) shifted towards a more po-
sitive direction compared to the bare MS plate which endorsed the
decrease of anodic reaction (mainly the oxidation of iron). As a result,
Icorr value of the coated steel plate (6.65 × 10-9 A/cm2) depressed sig-
nificantly. Further, it is also noted that the MS plate exhibited RP value
of 84.91 ohm whereas the RP value for coated MS plate is 8.76 × 105
ohm. This huge increase in RP value clearly indicates that the coating
acts as a physical barrier and appreciably resists the corrosion of the MS

Fig. 5. (a and b) Tafel and Nyquist plots of bare MS plate and PU-CNSL-1 coated MS pate at different time intervals, (c and d) Tafel and Nyquist plots of bare MS plate
and PU-CNSL-1 coated MS pate after healing and (e and f) Tafel and Nyquist plots of corrode MS plate after coating.

8
T. Ghosh and N. Karak
Table 3
Corrosion parameters of the bare MS plate, PU-CNSL-1 coated MS plate, PU-CNSL-1 coated MS plate after healing and PU-CNSL-1 coated corrode MS plate at different
time intervals.
Materials Time Icorr
(h) (A/cm2)
MS plate 0 1.7 × 10−4
PU-CNSL-1 coated MS plate 0 6.65 × 10−9
48 1.41 × 10−8
96 1.969 × 10−7
PU-CNSL-1 coated MS plate after healing 0 6.94 × 10−9
48 1.16 × 10−8
96 2.57 × 10−7
PU-CNSL-1 coated corrode MS plate 0 5.85 × 10−7
plate from the corrosive medium. Generally, the synthesized PU acts as
a wall in between the plate and corrosive medium [17]. Therefore, the
toughness of the wall is an important factor which significantly controls
the penetration of the corrosive ions to get in touch with the MS plate.
From Table 1 it is evident that PU-CNSL-1 showed adequate toughness
which makes the coatings tough to penetrate by the corrosive ions.
Moreover, the PU also showed intrinsic hydrophobic behavior due to
micro/nano scale roughness as described earlier. Such rough archi-
tecture entrapped a huge amount of air and hence penetration of cor-
rosive ions through the coating is very difficult [35]. Combinations of
both these factors dramatically reduce the corrosion rate.
From the study, it is also noticed that Ecorr value of the coated MS
plate decreases slowly from -0.469 V to -0.517 V and the corresponding
Icorr value increases simultaneously with the increase of immersion
time. This is due to the diffusion of conductive ions into the PU-CNSL-1
coating through pinholes [20]. Formation of such pinholes is also evi-
dent by the decreasing trend in Rp values from 8.76 × 105 to
3.82 × 105 ohm with immersion time. Results of such diffusion of
corrosive ions into coating slightly increase the corrosion rate.
The Nyquist plots (Fig. 5b) of the coated MS plate obtained from EIS
measurements in different time interval (0 h, 48 h, 98 h) showed
semicircle throughout the study but the diameter of that semicircle
decreases with the increase of immersion time which clearly indicates
the diffusion of the corrosive ions into the coating [42]. From the fit and
simulation studies of the Nyquist plots, it is also found that the pore
resistance (Rpore) of MS plate is 0.509 ohm whereas the Rpore of the
coated plate MS plate is 309 × 103 ohm. Generally, Rpore defines the
extent of the porosity of the coating. Higher the value of Rpore, stronger
is the electrical resistance characteristic of the coatings against corro-
sive ions. Due to this very low Rpore value, bare MS plate is unable to
resist the corrosion activity immediate after immersion in the salt so-
lution whereas the coated MS plates showed good anticorrosion activity
for longer periods of immersion time. Noticeably, Rpore of the coated MS
plates decreases with the increase of immersion time which is accre-
dited to the slow and progressive diffusion of electrolyte flux through
the coatings.
Most interestingly, synthesized PU coated MS plates also retain good
corrosion resistance property (Ecorr: −0.571 V, Icorr: 6.94 × 10−9 A/
cm2, corrosion rate: 8.07 × 10−5 mm/y) even after healing from me-
chanical damage. Tafel plots of the healed PU coated MS plates are
displayed in Fig. 5c and their corresponding values in different time
interval are furnished in Table 3. Effective healing of the damaged PU
surface under a suitable stimulus is responsible for maintaining such
good corrosion resistant performance. Even though, the healed coating
acts as an active shield but the RP and Rpore value depressed drastically
compared to the coated MS plate without any cut as described earlier.
Further, a huge reduction is observed in the semicircle diameter of the
Nyquist plot as shown in Fig. 5d. Presence of microscopic cracks in the
damaged site even after healing makes the coating slight permeable
towards the corrosive medium and increases the corrosion rate.
All the above results depicted good anticorrosive nature of the
Progress in Organic Coatings 139 (2020) 105472
Ecorr Corrosion rate Polarization resistance Pore
(V) (mm/y) (RP) Resistance (Rpore)
(ohm) (ohm)
−1.027 2.0534 84.91 0.509
−0.469 7.72 × 10−5 8.76 × 105 309 × 103
−0.479 1.63 × 10−4 4.88 × 105 197 × 103
−0.517 2.22 × 10−3 3.82 × 105 128 × 103
−0.571 8.07 × 10−5 3.47 × 105 67.2 × 103
−0.724 1.35 × 10−4 5.49 × 105 47.7 × 103
−0.592 2.9 × 10−3 7.4 × 104 17.3 × 103
−0.694 6.8 × 10−3 2.7 × 104 10.8 × 103
synthesized PUs. But the problem associated with our day to day life is
to resist the corrosion of metal which already underwent corrosion
under normal atmospheric condition. Thus to check the corrosion re-
sistant ability of PU, a corrode MS plate was coated with the synthe-
sized PU and projected for electrochemical study. Tafel and Nyquist
plots of the PU coated corrode MS plates in different time intervals are
shown in Fig. 5e and f. Displayed results showed that after coating the
corrosion rate of the MS plate decreases almost 300 times which seems
to be very good. Not only the corrosion rate, but the corresponding RP
and Rpore values were also found to be very high than the bare MS plate.
Strong barrier property of the synthesized PU acts as a spacer in be-
tween MS plate and salt solution. As a consequence oxidation process of
the metal plate decreased significantly which results good anticorrosive
performance. But after a certain time interval, corrosion resistivity
decreases significant amount. Presence of corrosion products below the
coatings leads to improper adhesion which favors for further corrosion
with detachment of the coating from the MS plate.
3.9. Biodegradation study
Degradation of PUs after its useful service life is one of the most
important properties owing to strict environmental regulations [43]. In
this article, the McFarland turbidity method was used to evaluate the
biodegradability of the PU strips under the exposure of Gram positive
and Gram negative bacteria strains [25,44]. Degradation under the
exposure of Gram negative bacteria is more effective and hence the
corresponding results are shown in Fig. 6. From the biodegradation
study, it is clearly evident that the synthesized PU strips underwent a
significant amount of degradation after 5 weeks of incubation as shown
in Fig. 6a. Such degradation is attributed to the presence of hydrolyz-
able ester and urethane linkages present in the structure of PUs
[2,45,46]. Generally, the biodegradation of the PU strips occurred
through a systematic pathway. Initially, the microorganisms cannot
attach directly to the PU surface. Rather they excrete extracellular en-
zymes that adhered to the PU surface through physicochemical inter-
action and depolymerize the PU chains into smaller fragments. Such
kind of depolymerization leads to bulk surface erosion and makes the
surface more accessible for the microorganisms [43,47,48]. SEM images
(Fig. 6b and c) before and after biodegradation clearly support the
aforementioned statement. This small carbon and nitrogen-rich poly-
meric fragments act as catabolite to the microorganism and further
degraded to gaseous products (mainly CO2), water and biomass [45].
From the OD curve it is clear that PU-CNSL-3 is more susceptible to-
wards biodegradation compared to the other two PUs. Again, lower
degree of crystallinity and higher free volume of PU-CNSL-3 matrix are
the main reasons behind the improved biodegradability.
4. Conclusion
In conclusion, different compositions containing PUs were effi-
ciently synthesized from bio-derived raw materials like cashew nut
9
T. Ghosh and N. Karak
Fig. 6. (a) Growth curve of P. aeruginosa on the PUs, (b and c) represents the SEM images of the PU-CNSL-1 before and after degradation.
shell liquid, sunflower oil modified monoglyceride and polyol of mod-
ified dimer acid-glycerol through a facile polymerization pathway. The
current study demonstrated the benefit of bio-based units for the
synthesis of PU and tailoring the structure-property relationship
through the minute compositional variation. The study also revealed
the effect of free volume as created by the long aliphatic chains of PU
and its influence on the mechanical and thermal properties.
Additionally, the study also demonstrated the effect of surface rough-
ness on hydrophobicity, which can be further manipulated by the
variation of amount of CNSL. In addition, the synthesized PUs showed
intrinsic ultrafast self-healing behavior through the segmental mobility
of the soft segment along with excellent corrosion resistance property.
Most interestingly, the synthesized PUs underwent degradation under
microbial exposure. Therefore, the studied PUs can be used as a pro-
mising sustainable material for different potential advanced applica-
tions.
Supporting information
The composition of the reactants for the synthesis of PUs and other
parameters, and physical properties of the PUs.
Author contribution statement
The first author, Tuhin Ghosh executed the experimental work and
writing of the manuscript. The corresponding author, Niranjan Karak
helps in design the work and supervised the overall work for publica-
tion.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgment
The authors express their gratitude to the research project assistance
given by DST, India through the grant No. EMR/2016/001598, dated
04-Jan-2017.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.porgcoat.2019.
105472.
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