Progress in Organic Coatings 105 (2017) 18–28

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Progress in Organic Coatings

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Enhancement of anti-corrosive performances of cardanol based amine

functional benzoxazine resin by copolymerizing with epoxy resins
Deepak M. Patil, Ganesh A. Phalak, S.T. Mhaske ∗
Department of Polymer Surface Engineering, Institute of Chemical Technology, Mumbai, 400019, India

a r t i c l e i n f o a b s t r a c t

Article history: The bio-based amine functional benzoxazine (Bnz) resin was synthesized from cardanol, N,N’-Bis(2-
Received 29 March 2016 aminoethyl)ethane-1,2-diamine and paraformaldehyde by the Mannich condensation reaction. The
Received in revised form 17 October 2016 additional amine functionality in Bnz resin was introduced by using multi functional amine (N,N’-
Accepted 19 October 2016
Bis(2-aminoethyl)ethane-1,2-diamine) to react with monofunctional cardanol. The synthesized amine
functional Bnz resin was chemically analyzed for amine value by volumetric titration method. The
Keywords:
Fourier Transform Infrared spectroscopy (FTIR) and 1 H-Nuclear Magnetic Resonance (1 H NMR) spec-
Bio-based
troscopy used to illustrate the structure of amine functional Bnz resin. The synthesized Bnz resin was
Functional
Benzoxazine
copolymerized with conventional epoxy resins to prepare Poly(Benzoxazine-co-Epoxy) coatings for anti-
Anti corrosive corrosive application. The network formation of Bnz and epoxy resins was monitor by FTIR analysis.
Poly(Benzoxazine-co-Epoxy) The Poly(Benzoxazine-co-Epoxy) coatings have shown good mechanical, chemical, and solvent resis-
tance properties as compared to the crosslinked Polybenzoxazine coating. Further, gel content and
water absorption of Poly(Benzoxazine-co-Epoxy) and Polybenzoxazine coatings were also studied. The
cured coatings were evaluated for thermal behavior by thermogravimetric analysis (TGA). The corrosion
resistance properties of coatings were investigated by salt spray and electrochemical analysis.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction to overcome the negative aspect, incorporation of the additional

Benzoxazine (Bnz) resin is nitrogen containing heterocyclic ring
and it is good alternative to high-performance phenolic resin for
heat resistance applications. Bnz resin is characterized by the pres-
ence of a Mannich base bridge and it is synthesized from a phenolic
compound, formaldehyde and amines via Mannich-like condensa-
tion reaction. The Bnz resins may be viscous or thin liquid product
and thermal energy is required to activate the cationic ring-opening
polymerization. The Bnz resin does not generate any byproduct or
volatiles during the polymerization reaction [1–5]. The Bnz resin is
well known for excellent mechanical, electrical, and thermal prop-
erties and hence, gained recent attention by number of authors [6].
Polybenzoxazine coating has numerous application opportunities
in various fields such as the high temperature coating, automo-
tive, flame-retardants coating and electronic industries [7,8]. But,
Polybenzoxazine coating is not favorable for the coating applica-
tion due to the high curing temperature and brittleness of the film,
∗ Corresponding author.
E-mail addresses:
deepakpatil.udct@gmail.com (D.M. Patil), ganesh.phalak@yahoo.com (G.A. Phalak),
st.mhaske@ictmumbai.edu.in, stmhaske@gmail.com (S.T. Mhaske).
functional group in Bnz resin structure such as amine, cyano, and
hydroxyl can be done. The extra functionality incorporated into
the Bnz resin may be achieved by utilizing the multifunctional
phenolic molecule with a monoamine, or with a multifunctional
amine paired with a mono-phenol [9–15]. This extra functionality
of Bnz resin is utilized to synthesize the Bnz-composites or Bnz-
copolymer with various resins to enhance the properties [16–19].
The most of the Bnz resin is synthesized from petroleum based
raw materials and they have number of health related issues. Com-
paratively, renewable materials are easy to handle with no or
less toxicity and health hazards. Number of authors have pub-
lished papers on Bnz resin synthesis from the bio-based materials
such as diphenolic acids [20] vanillin [21,22] cardbisphenol [23],
guaiacol[24] and eugenol [25,26]. Amongst these, Cardanol as a
renewable material is a lot appealing. Cardanol is based on cashew
nutshell liquid (CNSL), a natural, non-food chain, and annually
renewable biomaterial. Cardanol is a reddish brown viscous liq-
uid extracted from a soft honeycomb structure inside the cashew
nutshell. Cardanol, is obtained by vacuum distillation of “cashew
nut shell liquid” (CNSL), which is an alkyl phenolic oil contained in
the spongy mesocarp of the cashew nut shell from the cashew tree
Anacardium occidentale L. [27]. Therefore, cardanol and its deriva-
tives, are becoming important starting materials having possible

http://dx.doi.org/10.1016/j.porgcoat.2016.10.027
0300-9440/© 2016 Elsevier B.V. All rights reserved.
 D.M. Patil et al. / Progress in Organic Coatings 105 (2017) 18–28
industrial utilizations, such as antioxidants, stabilizers, flame retar-
dants and resins [28–31]. Recently, cardanol has been widely used
to synthesize the benzoxazine resin for various applications. The
aniline and cardanol used to synthesize a benzoxazine monomer
and then blended it with bisphenol-A benzoxazine. The study of
the rheological, thermal, viscoelastic and mechanical properties
showed that cardanol-based benzoxazine improved the toughness
of the blends. Unfortunately, the thermal properties of the blends
were significantly reduced because of the monofunctional struc-
ture of cardanol-based benzoxazine [32–35]. In order to improve
the various properties of the Polybenzoxazine coating, it is essential
to incorporate the variable functionality into the Bnz resin back-
bone.
Corrosion of metal causes enormous financial losses and addi-
tionally reduces our natural resources. It is a critical issue all over
world and protective coatings are applied in most of the case for the
anti-corrosive application. The most of them are synthesized from
the petroleum based raw materials, whose use steadily reduced in
many countries due to their toxicity to environment [36,37]. These
environmental concerns have increased demand for bio-based raw
materials to synthesize the coating for anti-corrosive application. In
present work, we utilize the bio-based material to synthesize amine
functional Bnz resin. The amine functional Bnz resin was synthe-
sized by react the monofunctional cardanol with multifunctional
amine to incorporate the amine functionality in Bnz resin back-
bone. The added amine functionality was utilized to copolymerize
Bnz resin with various epoxy equivalent weight (EEW) epoxy resins
to prepared Poly(Benzoxazine-co-Epoxy) coatings. The changes in
performance properties of coating were studied such as mechani-
cal, chemical, solvent resistance, gel content and water absorption.
The enhancement in corrosion resistance properties of coatings
were studied by salt spray and electrochemical analysis.
2. Experimental
2.1. Raw materials
N,N’-Bis(2-aminoethyl)ethane-1,2-diamine, sodium sulfate and
paraformaldehyde were lab grade chemicals procured from SD Fine
Chemicals Ltd. Mumbai, India and were used as supplied. Cardanol
(cardolite NC-700) was provided by Cardolite Specialty Chemi-
cals Ltd., Manglore, India. Epotec YD 127 resin (EEW = 180-188
gm/eq; It is an unmodified liquid epoxy resin with medium vis-
cosity produced from bisphenol-A and epichlorohydrin.) received
from Aditya Birla Chemicals Ltd, India. Epoxy resin with various
EEW (EEW = 270–310 gm/eq, 450–550 gm/eq) received from Grand
Polycoats Co. Pvt. Mumbai, India. Xylene, butanol and chloroform
were purchased from SD Fine Chemicals Ltd. Mumbai, India.
2.2. Synthesis of amine functional Bnz resin
The solvent free synthesis of amine functional Bnz resin from
paraformaldehyde, N,N’-Bis(2-aminoethyl)ethane-1,2-diamine
and Cardanol is shown in Scheme 1 and detailed procedure is
described below. A four-neck flask was charged with cardanol
(0.114 mol, 34.73 gm) and paraformaldehyde (0.229 mol, 6.87 gm)
at room temperature assembled with a thermometer, dean stark
apparatus, nitrogen inlet and a mechanical stirrer. The reaction
mixture was mechanically stirred at 500 rpm and then drop wise
addition of N,N’-Bis(2-aminoethyl)ethane-1,2-diamine (0.057 mol,
8.38) was done over the period of 30 min. Then reaction mix-
ture temperature was increased gradually up to 95–100 ◦ C and
maintained for next 4 h. During this period, once the red color
reaction mixture turned into dark maroon color, heating of reac-
tion mixture was stopped, and temperature was brought down to
19
Table 1
Formulation of Polybenzoxazine and poly(benzoxazine-co-epoxy).
Sr. No. Base resin EEW of Epoxy Coating code
resin (gm/mole)
1 Bnz resin – Polybenzoxazine
2 Bnz resin 180 Bnz 180
3 Bnz resin 310 Bnz 310
4 Bnz resin 500 Bnz 500
room temperature. The maroon color liquid product was dissolve
in chloroform and repeatedly washed with water to remove the
unreacted diamine and paraformaldehyde. The organic layer was
dried over anhydrous sodium sulfate and the product was filtered.
Chloroform removed by using a rotary evaporator (Yield Cal. 87%)
and synthesized resin was characterized for amine value, FTIR and
1 H NMR analysis.
2.3. Coating preparation
The MS panel was cleaned by using solvent to remove oil, grease
and subsequently panel surface scrubbed by using sand paper.
Epoxy equivalent weight (EEW) of epoxy resins was determined
by using ASTM D1652–11 and mixed with Bnz resin on equivalent
weight basis in 1:1 wt ratio. The formulation is given in Table 1.
The xylene: butanol mixture (70:30 by volume) was added into
the formulated Bnz-epoxy resin mixture to reduce viscosity for
proper application. The mixed formulations was applied on the MS
panel by flow coating method and thermally cured at 200 ◦ C for
3 h (Scheme 2). The coating uniformity was checked by dry film
thickness (DFT) measurement. The coatings were characterized for
various properties such as mechanical, chemical resistance, solvent
resistance, water absorption, gel content and corrosion resistance
properties.
3. Characterization
3.1. Chemical analysis
The amine value (AV) of prepared amine functional Bnz resin
was determined by titration method [38]. The known weight
of the resin sample was entirely dissolved in 100 ml of neu-
tral isopropanol. The above solution’s titration carried out with a
standardized HCl solution (0.5 N) and bromocresol green used as
indicator. The AV was calculated by following equation Eq. (1).
B.RXNX56.1
AmineValue = (1)
Ws
Where, B.R. = burette reading, N = normality of HCl, Ws = weight of
sample
The epoxy equivalent weight (EEW) of the conventional epoxy
resins were determined by the volumetric titration method [39].
The EEW of the resin was calculated by using Eq. (2).
1000XW
EEW = (2)
(B − S) XN
Where, B = blank titration reading; S = sample titration reading;
N = normality of the titrant; W = weight of the sample.
3.2. Instrumentation
3.2.1. FTIR analysis
The chemical structure of amine functional Bnz resin was identi-
fied by Fourier Transform Infrared (FTIR) Spectroscopy on a Bruker
ATR USA. The FTIR analysis of cured Poly(Benzoxazine-co-Epoxy)
coatings were carried out by preparing the pellets with potassium
bromide (KBr). The 0.2% to 1% of the coatings concentration was
20 D.M. Patil et al. / Progress in Organic Coatings 105 (2017) 18–28

Scheme 1. Synthesis reaction of amine functional Bnz resin.

Scheme 2. Curing reaction of amine functional Bnz and epoxy resins.

 D.M. Patil et al. / Progress in Organic Coatings 105 (2017) 18–28
maintained in KBr pellets. The spectra recorded on a Bruker ATR
spectrophotometer, USA in the 600–4000 cm−1 wavelength range.
3.2.2. 1 H NMR analysis
The supportive confirmation of chemical structure was given by
1 H-Nuclear Magnetic Resonance (1 H NMR) spectroscopy. 1 H NMR
spectra of the product was analyzed using Bruker DPX 800 MHz
spectrophotometer with dimethyl sulphoxide (DMSO) as solvent.
3.2.3. Thermogravimetric analysis
Thermogravimetric analysis (TGA) of coating sample was con-
ducted on Perkin Elmer TGA 4000 instrument under nitrogen
atmosphere. Thermal analysis was monitored in the 40–800 ◦ C
temperature range with 20 ◦ C/min heating rate.
3.3. Coating characterization
Coatings were evaluated for mechanical (Adhesion, Hardness,
Flexibility and Impact resistance properties), chemical (acid, alkali),
solvent scrub resistance, water absorption, gel content and corro-
sion resistance (Salt spray and Electrochemical analysis) test.
3.3.1. Mechanical properties
Coating adhesion to metal substrate was examined by cross-cut
[40] and pull off adhesion test [41]. The conical mandrel tester was
used to determine the flexibility of coatings [42] and the capacity
of a coating material to survive a high force in a short period is
studied by impact resistance tester [43]. The impact resistance test
was carried out through dropping a 2 lb weight ball from maximum
height of 60 cm and weight dropped onto the coated surface (for-
ward impact) and on the reverse of the panel with reference to the
coated surface (reverse impact). Hardness properties of coatings
were examined by pencil [44] and scratch hardness (IS-104) test.
3.3.2. Chemical properties
Chemical resistance tests of the coatings were performed in
sodium hydroxide (5% w/v) and hydrochloric acid (5% v/v) solu-
tions. Both tests were carried out separately for 24 h at ambient
temperature and the edges of the coated panels was sealed with
adhesive tape. The coating surface was analyzed for physical change
in coating appearance [45].
3.3.3. Solvent scrub resistance
The resistivity of the coating to the solvents was studied by scrub
resistance test using xylene, acetone and methanol solvent. The sol-
vent rub resistance done for maximum 200 cycles [46]. The coatings
were examined for changes such as discoloration or softening.
3.3.4. Gel content
DMSO: Xylene (50:50 by volume) solvent mixture used to deter-
mine the gel content of cured coatings. For this purpose, coating
accurately weigh (Wd) on sensitive weight balance and dip into
the solvent for the period of 24 h [52]. Then, the coating was to
separate out and dried in oven until constant weight obtained and
weigh the sample (Ww).The gel content was calculated by Eq. (3).
Ww
Gelcontent = X100
Wd
Where, Wd = initial coating weight, Ww = after test coating weight
3.3.5. Water absorption
Water absorption of cured coating was measured by kept the
known weight of coating (Wi) in water at room temperature for
24 h. Next day, coating was made free from water and dried using
21
Table 2
Chemical analysis of functional Bnz resin.
Sample Theoretical amine Practical amine value
value (mg of KOH/gm (mg of KOH/gm of
of sample) sample)
Bnz resin 140.21 125.23
the paper towel and note down the weight of the sample (Wf) [47].
The percentage of water absorption has calculated by using Eq. (4).
(Wf − Wi)
Waterabsorption (%) = X100 (4)
Wi
Where, Wi = initial weight, Wf = final weight
3.3.6. Corrosion resistance properties
3.3.6.1. Salt-spray test. The corrosion resistance of the coating was
evaluated by the salt spray test as per ASTM B-117. The salt spray
test apparatus consists of a closed testing chamber, where the
coating was exposed to 3.5 wt% aqueous sodium chloride (NaCl)
solution. The exposed coating has studied for corrosion spreading
or blistering along the crosscut [61].
3.3.6.2. Electrochemical analysis. The tafel polarization curve of
coated panel was conducted in 3.5 wt.% aqueous NaCl solution as an
electrolyte at a room temperature and the area of coating exposes
to the electrolyte is 7 cm2 on Versa STAT-3 instrument (AMETEK,
Princeton AppliedResearch, Oak Ridge, TN). The coated plate used
as a working electrode, while Pt and Saturated Calomel Electrode
(SCE) were used as counter and reference electrodes.
4. Result and discussion
In our work, we utilized renewable resource, Cardanol as
base material to synthesize the amine functional Bnz resin for
anti-corrosive application. Cardanol based amine functional Bnz
resin was synthesized via Mannich condensation reaction of
hydroxyl groups of cardanol with N,N’-Bis(2-aminoethyl)ethane-
1,2-diamine and paraformaldehyde (Scheme 1). The calculated
amine value (AV) of synthesized amine functional Bnz resin is given
in Table 2. The practically calculated AV is near to the theoreti-
cal AV, hence we can say that the Bnz resin carry the secondary
amine group in their backbone. The added amine functionality is
utilized to overcome the Polybenzoxazine coating drawback by
modify the Bnz resin backbone with epoxy resins. The epoxy mod-
ified Polybenzoxazine coatings has sustained the enough hardness
and flexibility at same time. This can be attributed to the excellent
balance maintained between the softer segments of long aliphatic
chains of epoxy resin and the hardness offered from high crosslink
structure of Polybenzoxazine coating.
4.1. FTIR analysis
The structure of amine functional Bnz resin is characterized by
FTIR analysis as shown in Fig. 1. The FTIR spectrum show band at
925 cm−1 is attributed for the unsaturation (C C) of alkyl side chain
of cardanol. The amine functional Bnz resin show significant bands
at 1270 cm−1 , 1112 cm−1 and 992 cm−1 are attributed for asym-
(3) metric, symmetric stretching of C O C and trisubstituted benzene
ring of benzoxazine resin respectively [2]. The amine functional
Bnz resin spectrum show the peak at 1370 cm−1 and 3287 cm−1
attributed for C N and N H stretching respectively. The bands at
2851 cm−1 , 2923 cm−1 and 3008 cm−1 are owing to the asymmet-
ric and symmetric stretching vibrations of CH2 of oxazine ring as
well as alkyl side chain of cardanol. The characteristic absorption
band of cardanol in the range 3300–3500 cm−1 due to the phenolic
22 D.M. Patil et al. / Progress in Organic Coatings 105 (2017) 18–28
Fig. 1. FTIR spectra of amine functional Bnz resin.
hydroxyl group is absent in amine functional Bnz resin spectra33 .
The above FTIR spectrum, suggests that conversion of cardanol into
the Bnz resin is complete and we can also conclude that cardanol
based Bnz resin has amine functionality.
4.2. 1H NMR analysis
The 1 H NMR analysis of amine functional Bnz resin is as shown
in Fig. 2. The triplet and doublet peak are assigned at 7.1 ppm and
6.60 ppm for the aromatic protons respectively. The NMR spectrum
shows singlet characteristic oxazine ring protons at 3.70 ppm and
4.80 ppm for Ar CH2 N and Ar O CH2 N respectively[22,48].
The proton at Ar O CH2 N shifts down side in spectrum due to
the deshielding effect of oxygen and nitrogen. The peak at 5.85 is
due to vinyl bond (C CH) protons of long alkyl side chain originally
present in cardanol. The peak attribution at the down field is due to
the movement of the electrons in the pi bond of the carbon–carbon
double bond [49]. The sharp peak is observed at 3.35 ppm for the
amine proton. The peak at 2.65 ppm corresponds to the methylene
protons adjacent to the aromatic ring. The other peaks in the range
of 1.5–2.4 ppm are assigned to the methylene protons attached to
long alkyl side chain present in cardanol. Thus from the 1 H NMR
spectrum data, it may be confirmed that amine functional Bnz resin
was successfully synthesized.
4.2.1. Crosslinked network formation of Bnz and epoxy resins
The network formation reaction of Poly(Benzoxazine-co-epoxy)
coatings is monitored by FTIR analysis [Fig. 3]. From Fig. 3, we can
observe that after heating the Bnz and epoxy resin mixture the
characteristic absorption band at 992 cm−1 assigned to trisubsti-
tuted benzoxazine ring almost disappeared [50,51]. In addition,
disappearance of N H stretching band at around 3287 cm−1 is
observed followed by the appearance of OH stretching at around
3300–3400 cm−1 . It confirmed that the secondary amine open the
oxirane ring of epoxy resin and this observation suggests reaction
between Bnz and epoxy resin has taken place39 . Hence, we can con-
clude that the amine functional Bnz resin reacts with epoxy resins
to form crosslinked Poly(Benzoxazine-co-epoxy) coatings.
5. Coating characterization
5.1. Mechanical properties
The brittleness of the film is the main disadvantage of Poly-
benzoxazine coating and hence it has limited application area. The
properties of Polybenzoxazine coating observed to be improved by
copolymerization with more flexible epoxy resins of various EEW
and obtained results are given in the Table 3. Flexibility of Poly-
benzoxazine coating was checked by the conical mandrel test, film
is broken at 2 mm. The Poly(Benzoxazine-co-Epoxy) coatings show
the improved flexibility as compared to Polybenzoxazine coating.
This could be attributed to the presence of long aliphatic chains
and hydroxyl group along the chain length of epoxy resin. Coat-
ing adhesion with metal substrate was examined by crosscut and
pull off adhesion test. The coatings show 100% adhesion to the
metal substrates as measured by the crosscut adhesion method.
The adhesion strength of coating on metal substrates was evaluated
with pull off adhesion test. The Poly(Benzoxazine-co-Epoxy) coat-
ings show the better adhesion value than Polybenzoxazine coating.
It is mainly attributed to the free secondary hydroxyl groups and
long aliphatic chains of the epoxy molecules. This free hydroxyl
group forms the hydrogen bonds with metal surface and enhance
the adhesion properties. Further, pencil and scratch hardness tests
were carried out to study the hardness properties of coating. All
Poly(Benzoxazine-co-Epoxy) coatings show the higher hardness
properties as compared to the Polybenzoxazine coating. The trend
observed could be correlated to the highly cross-linked network
structure and higher hardness properties. In Poly(Benzoxazine-co-
Epoxy) coatings, amine groups of Bnz resin react with oxirane ring
of epoxy resin and created three-dimensional cross-linked struc-
ture. Hence, the penetration of the needle into the coating was
becoming difficult. As well, epoxy-amine reaction was generat-
ing the secondary hydroxyl group along the backbone chain and
that form the hydrogen bonds with one another. The Bnz-180
copolymerized coating has highest hardness properties as com-
pared the other copolymerize coatings and this could be attributed
as Bnz-180 have more number of epoxy rings and hence more
cross-linked structure. All coatings show the pencil hardness above
3H and this could be attributed to the high crosslinked density.
Response of coatings to the rapid deformation is a most important
characteristic and it was studied by the intrusion and extrusion
impact test. The Polybenzoxazine coating has broken at 110 and
90 lb.cm for intrusion and extrusion impact test respectively.
The Poly(Benzoxazine-co-Epoxy) coatings show the best response
the rapid deformation at 120 cm lb for intrusion and extrusion
impact tests. This could be attributed to the excellent balance
maintained between the softer segments of long aliphatic chains
of epoxy resin molecules and the hardness offered from cross-
linked structure of Poly(Benzoxazine-co-Epoxy) coatings. From
the above study, Poly(Benzoxazine-co-Epoxy) coatings has shown
good performance for all mechanical properties as compared to the
Polybenzoxazine coating.
5.2. Chemical resistance
Acid and alkali resistance of Polybenzoxazine and
Poly(Benzoxazine-co-Epoxy) coatings were evaluated by immer-
sion method for 24 h. All coatings show no softening or adhesion
loss after the 24 h test. But, some change in appearance in
term of gloss values is observed as given in Table 4. The
gloss value of Polybenzoxazine coating was decrease in more
percentages as compared to the Poly(Benzoxazine-co-Epoxy)
coatings. This could be due to the dual cross-linked structure
formed in cured Poly(Benzoxazine-co-Epoxy) coatings [52]. Hence,
 D.M. Patil et al. / Progress in Organic Coatings 105 (2017) 18–28 23

1
Fig. 2. HH NMR analysis of Cardanol and amine functional Bnz resin.

Table 3
Mechanical characterization of Polybenzoxazine, Bnz 180, Bnz 310 and Bnz 500 coatings.

Coating Polybenzoxazine Bnz 180 Bnz 310 Bnz 500

DFT (Micron) 75–85 80–85 70–80 70–85

Cross-cut adhesion 5B 5B 5B 5B
Pencil hardness 3H 5H 6H 4H
Scratch hardness (gm) 2700 3400 3000 3100
Flexibility (mm) 2 mm 0 mm 0 mm 0 mm
Impact resistance (lb.cm) Intrusion 110 120 120 120
Extrusion 90 120 120 120
Pull of adhesion Test (MPa) 1.54 2.08 1.84 1.82
24 D.M. Patil et al. / Progress in Organic Coatings 105 (2017) 18–28

Table 4
Chemical resistance of polybenzoxazine, Bnz 180, Bnz 310 and Bnz 500 coatings.

Coating Initial Gloss @ 600 After immersion test After immersion test
(acid) Gloss @ 600 (base) Gloss @ 600

Polybenzoxazine 102.13 85.85 91.34

Bnz 180 102.67 93.65 100.15
Bnz 310 99.30 87.85 97.80
Bnz 500 90.60 82.45 87.20

Fig. 5. Thermogravimetric analysis of Polybenzoxazine, Bnz 180, Bnz 310 and Bnz
Fig. 3. FTIR spectra of Bnz resin and Bnz 180, Bnz 310, Bnz 500 coatings. 500 coatings.

Table 5
Thermo gravimetric analysis of Polybenzoxazine, Bnz 180, Bnz 310 and Bnz 500
coatings.

Coating Td5 (◦ C) Td30 (◦ C) % Char Yield

Polybenzoxazine 193.34 448.75 17.41

Bnz 180 342.14 431.6 8.81
Bnz 310 263.63 423.34 7.79
Bnz 500 314.12 421.12 7.35

other molecules; which can be considered as effective physical

cross-linker. The diffusion of solvent into the Poly(Benzoxazine-co-
Epoxy) coatings becomes difficult. Hence, significantly improved
solvent resistance of the Poly(Benzoxazine-co-Epoxy) coatings is
observed.

5.4. Thermogravimetric analysis

The thermal stability of coatings was studied by TGA anal-

Fig. 4. Solvent scrub resistance test of Polybenzoxazine, Bnz 180, Bnz 310 and Bnz
500 coatings after 200 cycle.
Poly(Benzoxazine-co-Epoxy) coatings show the efficient resistance
to acid and alkali than Bnz coating.
5.3. Solvent scrub resistance
All coatings were characterized for solvent scrub resistance
and loss of gloss in coatings after 200 cycles is observed (Fig. 4).
Poly(Benzoxazine-co-Epoxy) coatings show the excellent resis-
tance to the solvent scrub compared to the Polybenzoxazine
coating; since these coating have high cross-linked coating struc-
ture. Further, the free hydroxyl groups present in the epoxy
resin molecules create a hydrogen bonding in itself or with
ysis under nitrogen atmosphere and results shown in Fig. 5.
The result was recorded as a weight loss of coating as func-
tions of temperature. The values of 5 wt% (Td5%), 30 wt% (Td30%)
loss degradation temperature and residual wt% (char yield) at
800 ◦ C are listed in Table 5. From Fig. 5, it is observed that
upto 350 ◦ C the thermal stability of Poly(Benzoxazine-co-Epoxy)
coatings higher than the Polybenzoxazine coating. The weight
loss of the Poly(Benzoxazine-co-Epoxy) coatings is less than 10%
where as the Polybenzoxazine coating show degradation of 12%.
The results can be attributed due to the Poly(Benzoxazine-co-
Epoxy) coatings have more crosslinking density compared to
the Polybenzoxazine coating. The cross-linked density of coating
increases with increasing functional group and high cross-linked
network has high thermal stability. The Poly(Benzoxazine-co-
Epoxy) coatings have Polybenzoxainze and amine-epoxy cured
dual crosslinked structure in backbone. But, at temperature above
400 ◦ C Poly(Benzoxazine-co-Epoxy) coatings have rapid weight
 D.M. Patil et al. / Progress in Organic Coatings 105 (2017) 18–28
Table 6
Ecorr vs SCE, Icorr, Corrosion rate and Corrosion Resistance Efficiency value of coatings in 3.5% NaCl solution.
Coating Ecorr vs SCE (mV) Icorr (␮A)
Metal −717.45 19.60
Polybenzoxazine −777.97 4.284
Bnz 180 −255.85 0.011
Bnz 310 −389.80 0.017
Bnz 500 −617.55 0.361
Fig. 6. Gel content of Polybenzoxazine, Bnz 180, Bnz 310 and Bnz 500 coatings.
loss as compared to the Polybenzoxazine coating. As the epoxy resin
concentration increased in Poly(Benzoxazine-co-Epoxy) coatings
the aliphatic chain density also get introduced into the cross-linked
structure. The aliphatic chains have less thermal stability as com-
pared to the aromatic structure [19]. The above study shows that,
Poly(Benzoxazine-co-Epoxy) coatings have good thermal stability
upto 400 ◦ C compared to Polybenzoxazine coating.
5.5. Gel content
The gel content of Polybenzoxazine and Poly(Benzoxazine-
co-Epoxy) coatings are shown in Fig. 6. The gel content of
Polybenzoxazine, Bnz180, Bnz310, and Bnz500 coatings is 94.25,
95.45, 95.05 and 94.85 respectively. The results show that
Poly(Benzoxazine-co-Epoxy) coatings have higher value of gel con-
tent than Polybenzoxazine coating. In Poly(Benzoxazine-co-Epoxy)
coatings, the amine functional group of Bnz resin reacts with epoxy
ring and increase the three-dimensional cross-linked structure.
However, the crosslink density is related to the number of func-
tional groups present in molecules and more the functional groups
higher are the cross-linked density. Hence, the Bnz-180 coating has
higher gel content than a Bnz-310 and Bnz-510 coating.
5.6. Water absorption
Water absorption by a coating is a major factor affecting its
corrosion resistance efficiency and hence, it is most important
property in corrosion resistance application. The water absorp-
tion by Polybenzoxazine and Poly(Benzoxazine-co-Epoxy) coatings
with time was studied and percentage of water absorbed plotted
against time in Fig. 7. The percent water absorption of Polybenzox-
azine, Bnz 180, Bnz 310, and Bnz 500 coatings is 1.45, 0.87, 0.96
and 1.02 respectively. The amount of water absorbed in the coat-
ing depends on both the nature of the film and crosslinking density.
The decreased water absorption percentage in Poly(Benzoxazine-
co-Epoxy) coatings may be attributed due to the highly packed
three-dimensional cross-linked coating structure. Hence, absorp-
tion of water becomes difficult in cross-linked coatings.
25
Corrosion Rate Corrosion resistance
(mm/y) Effeciency (%)
3.257*10−2 0
7.119*10−3 78.16
1.803*10−5 99.94
2.794*10−5 99.91
5.994*10−4 98.15
Fig. 7. Water absorption test of Polybenzoxazine, Bnz 180, Bnz 310 and Bnz 500
coatings.
5.7. Electrochemical analysis
The electrochemical study of Polybenzoxazine, Bnz 180, Bnz 310
and Bnz 500 coatings included: corrosion current (Icorr), corrosion
potential (Ecorr), corrosion rate (CR) and corrosion resistance effi-
ciency (Fig. 8). The electrolyte used for the analysis was 3.5 wt%
NaCl solution and the coated and uncoated panel were used as
working electrodes. The tafel polarization curve was constructed
by measuring Potential vs I. The corrosion potential (Ecorr) and
corrosion current (Icorr) of different coatings was obtained by the
Tafel extrapolation method. Extrapolation of these curves in their
linear regions to the point of intersection provides both the Ecorr
and Icorr. The faster corrosion rates generally correspond to more
negative Ecorr and the larger Icorr while the more positive Ecorr
and the smaller Icorr mean a slower corrosion process [53–55].
According to values obtained for the tafel polarization curve Icorr is
19.80 ␮A, 4.2844 ␮A, 0.3616 ␮A, 0.0174 ␮A and 0.0109 ␮A for bare
metal, Polybenzoxazine, Bnz 500, Bnz 310 and Bnz 180 coatings
respectively. The corrosion rate and corrosion resistance efficiency
is calculated by using Eq. (5) and (6) respectively.
Icorr.K.EW
Corrosionrate = (5)
D.A
Where Icorr = corrosion current (A), K = constant, EW = equivalent
weight (in g/equivalent), D = density (g/cm3 ), A = Exposed sample
area to electrolyte (cm2 ), CR is in millimeter per year (mmpy).
Icorr − Icorr (C)
E (%) = X100 (6)
Icorr
Where, E (%) = corrosion resistance efficiency; Icorr and Icorr (C)
were the corrosion current values in the absence and presence of
the coatings, respectively.
The Ecorr, Icorr, corrosion rate and corrosion resistance effi-
ciency value is summarized in Table 6. The value shows that
corrosion rate (CR) and corrosion resistance efficiency of Bnz 180 is
less than Polybenzoxazine, Bnz 310 and Bnz 500 coatings. The above
study show that Bnz 180 coating has better corrosion resistance
properties compared to the Polybenzoxazine, Bnz 310 and Bnz 500
coatings. This could be attributed to the presence of cross-linked
26 D.M. Patil et al. / Progress in Organic Coatings 105 (2017) 18–28
Fig. 8. Tafel Polarization curve for bare metal, Polybenzoxazine, Bnz 180, Bnz 310 and Bnz 500 coatings in 3.5 wt% NaCl solution at 25 ◦ C.
density and aliphatic chain of epoxy resin in coatings; hence, barrier
properties of the coating increase to corrosive species. The diffu-
sion paths for the corrosive species become difficult, which help
to increase the corrosion resistance performance of the coating. In
addition, secondary hydroxyl groups form hydrogen bonds with
metal surface and decreases the permeability of the oxygen and
corrosive species as well as increases the adhesion of the coating
to the metal surface [56–58]. The data demonstrated that Poly-
benzoxazine coating corrosion resistance performance improved
by co-polymerizes with epoxy resins and coatings shows cathodic
corrosion resistance properties.
5.8. Salt spray test
The corrosion and rust formation on carbon steel involves sev-
eral steps of oxidation and reduction processes as given below [59].
From the reactions, it can be concluded that H2 O and O2 are neces-
sary for the corrosion of metal. Effective corrosion prevention can
be achieved if H2 O or O2 is prevented from accessing the surface of
the metal substrate [60].
Fe → Fe2+ + 2e−
Fe2+ → Fe3+ + 1e−
O2 (g) + 2H2 O+4e- → 4OH-
2Fe2+ (aq)+ O2 (g)+2H2 O → 2FeOOH+2H+
The salt spray analysis of each coating systems has been carried
to evaluate anticorrosive resistance of coatings. The images of each
coating panel before and after salt spray test are shown in Fig. 9a
and b respectively. It is clearly seen from Fig. 9b; Polybenzoxazine
coating show poor anticorrosive properties after 750 h compared to
the Poly(Benzoxazine-co-Epoxy) coatings. The Poly(Benzoxazine-
co-Epoxy) coatings show no more spreading of corrosion along the
crosscut. This could be due to the dual cross-linked network forma-
tion in Poly(Benzoxazine-co-Epoxy) coatings and the suppression
of permeation of water along the cross-cut by the dense dual cross-
linked network formed by cured coatings. Additionally, the free
hydroxyl groups present along the chain in epoxy resin chemi-
cally adsorb onto the metal surface leading to enhanced coating
adhesion with metal substrate. Therefore, transport rate of water
along the crosscut of the coating reduces significantly. The corro-
sion reactions taking place across the metal–electrolyte interface
can be inhibited correspondingly. This passive layer gives rise in
the improvement of the anticorrosive resistance properties as com-
pared to Polybenzoxazine coating [62]. We conclude from above
study that, the corrosion rate is decreased in Poly(Benzoxazine-co-
Epoxy) coatings as compared to Polybenzoxazine coating.
6. Conclusion
The bio-based Bnz resin consisting amine functionality was syn-
thesized from cardanol a byproduct of cashew nut shell industry.
To enhance the coating performance, amine functional Bnz resin
was successfully copolymerized with various epoxy resins. The
thermal stability of cured coatings was studied by thermogravimet-
ric analysis and poly(Benzoxazine-co-Epoxy) coatings were show
a lower char yield at 800 ◦ C compared to Polybenzoxazine coat-
ing. Poly(Benzoxazine-co-Epoxy) coatings display high chemical
and solvent resistance properties compared to the Polybenzoxazine
coating and this could be due to the dual cross-linked network. The
mechanical properties of Polybenzoxazine coating are improved by
copolymerization with more flexible and functional epoxy resins.
The electrochemical analysis and salt spray test of coatings show
the corrosion rate of poly (Benzoxazine-co-Epoxy) coating has a
lower value than the Polybenzoxazine coating. From the above
study, poly (Benzoxazine-co-Epoxy) coatings observed to be suit-
able for metal surface for high performance anticorrosive coating
application.
 D.M. Patil et al. / Progress in Organic Coatings 105 (2017) 18–28
Fig. 9. a) Caoating surface before the salt spray test in 3.5% NaCl solution; (a) Polybenzoxazine, (b) Bnz 180, (c) Bnz 310, (d) Bnz 500. b) Coating surface after 750 h. salt spray
test in 3.5% NaCl solution; (a) Polybenzoxazine, (b) Bnz 180, (c) Bnz 310, (d) Bnz 500.
Acknowledgment
The authors thank Cardolite Speciality Chemicals Ltd., Manga-
lore, India for providing NC-700 sample.
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