See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/278049564

Fatty acid based waterborne air drying epoxy

ester resin for coating applications

Article in Progress in Organic Coatings · October 2015

DOI: 10.1016/j.porgcoat.2015.05.012

CITATIONS READS

3 519

4 authors, including:

Dr Ashish Pratap Singh R. Baloji Naik

Bhabha Atomic Research Centre Defence Research and Development Organis…
2 PUBLICATIONS 4 CITATIONS 9 PUBLICATIONS 18 CITATIONS

SEE PROFILE SEE PROFILE

All content following this page was uploaded by R. Baloji Naik on 03 July 2015.

The user has requested enhancement of the downloaded file.

 Progress in Organic Coatings 87 (2015) 95–105

Contents lists available at ScienceDirect

Progress in Organic Coatings

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

Fatty acid based waterborne air drying epoxy ester resin

for coating applications
Ashish Pratap Singh, G. Gunasekaran ∗ , C. Suryanarayana, R. Baloji Naik
Naval Materials Research Laboratory, Shil-Badlapur Road, P.O-Anandnagar, Ambernath 421506, India

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

Article history: High performance water soluble epoxy ester resin was synthesized by partially reacting bis-phenol A
Received 23 March 2015 based epoxy resin with different fatty acids. The resultant epoxy ester resin was then reacted with
Received in revised form 25 April 2015 diethanol amine. These resins were characterized by FTIR, NMR, DSC and TGA. Further, the prepared
Accepted 18 May 2015
epoxy esters were neutralized using phosphoric, lactic, acetic and hydrochloric acids to make them water
soluble. Mild steel panels were coated with the water soluble epoxy ester resins and their performance
Keywords:
were evaluated by monitoring adhesion, tensile, scratch hardness, bend and impact resistances. The
Waterborne
corrosion resistance properties of the coatings were evaluated by salt spray, seawater immersion and
Acid value
Anticorrosive coatings
electrochemical impedance spectroscopy. It is observed that phosphoric acid neutralized tung oil fatty
Fatty acids acid based epoxy ester has better mechanical and anticorrosive properties than the rest of the water
soluble polymers.
© 2015 Published by Elsevier B.V.

1. Introduction atmospheric oxygen into carbon hydrogen (C H) bonds adjacent

Environmental concerns, governmental directives, technical
and economic factors have stimulated research to develop environ-
ment friendly coatings with low or no VOC content [1,2]. Depletion
of fossil fuels used in the paint formulations and their high cost
along with serious environmental hazards forces industries to
search for cheaper, eco-friendly and renewable resources like plant
resins and vegetable oils. Vegetable oil based waterborne (WB)
resins generally use water as solvent [3,4]. They are non-toxic, non-
flammable, odourless and eco friendly in nature due to their low
VOC contents. Besides this, abundant availability of water as solvent
and renewable nature of vegetable oils are additional advantages
[5–7]. The development of WB resin materials from vegetable oils
is a challenging task due to their hydrophobic nature. The most
common way to solubilize a vegetable oil in water is to introduce
highly hydrophilic ionic groups such as carboxyl, amine, anhydride
or amide and subsequent neutralization with acid or base [8–16].
In WB coating systems, the curing of resin takes place through
auto-oxidation i.e. the addition of atmospheric oxygen in the resin
followed by cross-linking. This process begins with insertion of
∗ Corresponding author. Tel.: +91 251 2623158; fax: +91 251 2623004.
E-mail address: gunanmrl@gmail.com (G. Gunasekaran).
to double bonds within the unsaturated fatty acid. The formed
hydro-peroxides undergo cross-linking reactions resulting in the
formation of bonds between neighbouring fatty acids in the resin
molecules.
Aigbodion et al. [17,18] reported the preparation of WB coating
from maleinated and fumarised rubberseed oil. Fish oil and linseed
oil modified polyurethane dispersion (PUD) have shown good coat-
ing properties as reported by Nimbalker and Athawale [19]. The
fish oil PUD exhibited good impact resistance, adhesion and flex-
ibility. Tung oil modified soyabean alkyd emulsions prepared by
Wang et al. [20] have shown good hydrolytic stability with glossy
films. Several other workers were also reported the use of deriva-
tives of WB alkyds, polyurethane dispersions [21] and waterborne
oil-acrylates [22] for preparation of WB coatings.
Most of the vegetable oil based waterborne coatings reported
in the literature cures at higher temperature and mainly used for
decorative purposes only due to their lower mechanical and anti-
corrosive properties. In the present work the synthesized WB resin
has a epoxy moiety to increase the anticorrosive property of resin,
fatty acid from vegetable oils and di-ethanolamine (DEA) for mak-
ing the resin soluble in water as well as to cure at room temperature.
The composition of fatty acid and DEA were standardized to get bet-
ter mechanical properties. Fatty acids from tung oil, linseed oil and
dehydrated castrol oil were used for the preparation of waterborne

http://dx.doi.org/10.1016/j.porgcoat.2015.05.012
0300-9440/© 2015 Published by Elsevier B.V.
96 A.P. Singh et al. / Progress in Organic Coatings 87 (2015) 95–105
Fig. 1. Synthesis of tung oil fatty acid.
epoxy ester resins. Their physico-mechanical, thermal behaviour
and corrosion resistance properties were studied in detail and com-
pared with each other.
2. Materials and methods
2.1. Materials
Bisphenol A epoxy resin (epoxy equivalent weight 450) was pur-
chased from Ciba Geigy, India. Linseed oil, tung oil and dehydrated
castrol oil were supplied by M/s Jayant Oil Mill, India. Rest of the
chemicals were purchased from Merck, India. All the chemicals
were used as received without any further purification.
2.2. Preparation of fatty acids
900 g tung oil was taken in a four-necked round bottom flask
fitted with mechanical stirrer, condenser and thermometer. NaOH
solution prepared by dissolving 120 g of sodium hydroxide in
500 ml of water/methanol (1:1 v/v) mixture was added slowly
under stirring to the reaction mixture. After complete addition,
the reaction mixture was maintained at 75–80 ◦ C under constant
stirring till the formation of homogeneous mixture. Thereafter, the
reaction mixture was cooled to room temperature, poured into a
saturated NaCl solution and washed with water to remove reaction
byproduct such as glycerol and monoglyceride. Then, dry sodium
sulfate was added in the reaction mixture to remove the trace
amount of water. The reaction scheme for the formation of tung
oil fatty acid (TOFA) from tung oil is shown in Fig. 1. Linseed oil
fatty acid (LOFA) and dehydrated castrol oil fatty acid (DCOFA) were
prepared adopting the same procedure.
2.3. Synthesis of waterborne epoxy ester
Waterborne epoxy ester based on different fatty acids (LOFA,
TOFA & DCOFA) were synthesized using epoxy resin, fatty acid, di-
ethanolamine and neutralized using phosphoric, lactic, acetic and
hydrochloric acids. The schematic diagram for the synthesis of air
drying waterborne epoxy resin neutralized with phosphoric acid
is shown in Fig. 2. One mole fatty acid (LOFA) and 0.85 mole of
epoxy resin with epoxy equivalent weight of 450 (bi-functional)
were taken in a four necked round bottom flask fitted with mechan-
ical stirrer, condenser, thermometer and nitrogen gas inlet. The
reaction mixture was heated at 140 ◦ C in presence of pTSA cata-
lyst for 4 h under nitrogen atmosphere. The reaction was monitored
using FTIR and acid value. When the acid value reaches below 10 mg
KOH/g of resin, the reaction was cooled to room temperature. The
synthesized resin was reacted with 0.7 mole di-ethanolamine at
65 ± 2 ◦ C for 1 h, neutralized with phosphoric acid solution and stir-
ring continued for 6 h. The prepared waterborne resin was dried
using cobalt based driers (blend of lead (0.3% of metal), cobalt
(0.03% of metal) in the ratio 10:1 (Lead: cobalt)). This cobalt and
lead based driers are most extensively used for drying waterborne
coatings [23–27]. The viscosity and non volatile matter (NVM) of
resin were adjusted with water. Similar procedure was adopted for
the synthesis of acid neutralized waterborne epoxy ester containing
TOFA and DCOFA.
3. Characterization
3.1. Acid value
Acid value of resin was determined as per ASTM D 1639-90 by
titrating resin sample against standard alcoholic KOH using potas-
sium hydrogen phthalate as a primary standard. Acid value (Z) was
calculated using the following equation:
56.1 × A × 0.1
Z= × 100 (1)
B
where A is the volume of KOH consumed (ml) and B is the weight
of sample (g).
3.2. FTIR spectroscopy
FTIR spectrophotometer (Thermo Electron Corporation Nicolet
5700) was used for the characterization of fatty acids and epoxy
esters. The liquid samples were spread over KBr pellets and FTIR
spectra were recorded in transmittance mode at a resolution of
4 cm−1 . The final FTIR spectra is the average of 32 scans.
3.3. NMR spectroscopy
1 H NMR spectra were recorded using Bruker 500 MHz model
Nuclear Magnetic Resonance Spectrometer. The solution of fatty
acids in CDCl3 were prepared with tetra methyl silane (TMS) as
internal standard for the measurement of NMR spectra.
3.4. Thermal analysis
Thermal properties of the epoxy ester resins were deter-
mined by using TA Instruments (Model-Q100) differential scanning
calorimeter. Measurements were carried out at a heating rate of
10 ◦ C min−1 under nitrogen atmosphere. Thermal stability of the
polymers was studied using TA Instruments (Model-Hi-Res. TGA
2950) thermo gravimetric analyzer at a heating rate of 10 ◦ C min−1
under nitrogen atmosphere up to 800 ◦ C.
3.5. Storage stability of resin
Storage stability of resins was determined as per method given
in ASTM D-D1849-95(2004). This test method covers the change in
consistency and certain other properties that may take place when
liquid paint of either the solvent-reducible or water-reducible type
is stored at a temperature above 0 ◦ C (32 ◦ F). The samples were
observed for any skinning, corrosion, odour of putrefaction, ran-
cidity, souring, lower layer rigidity, consistency and the presence
of lump or streaks in the brushed films.
3.6. Preparation of free films
Waterborne epoxy ester resins were coated on methyl cellulose
precoated glass plates using a motorized film applicator (Model
No. 335/1 Erickson) containing 400 ␮m clearance blade. The epoxy
 A.P. Singh et al. / Progress in Organic Coatings 87 (2015) 95–105 97

Fig. 2. Synthesis of the waterborne epoxy ester.

ester coated glass plates were kept in a dust-free chamber for dry-
ing of the films. After 7 days, the films were peeled off from plates,
washed thoroughly under running water to remove methyl cellu-
lose layer and dried at ambient temperature.
3.7. Tensile strength
Tensile strength of the films was determined as per ASTM D-
882-97. Dry film of size 100 mm × 15 mm were conditioned at 50%
relative humidity for 24 h and examinated using the Universal Ten-
sile Testing Instrument (Lloyd, Model-LR30K) under a strain rate
of 20 mm min−1 . All the tests were performed at 27 ± 2 ◦ C and the
results are expressed in mega Pascal (MPa). Ten specimens were
tested for their tensile strength and the presented result is an aver-
age of the values obtained from five specimens.
3.8. Determination of impact resistance, flexibility and scratch
resistance
Impact resistance of the coatings was determined as per ASTMD
2794 by using Impact tester (ERICHSEN GMBH & CO, D-5870, Model
304). The coated mild steel specimen with 75 ± 10 ␮m film thick-
ness was subjected to an impact of 0.908 kg load, dropped from
65 cm height. The test area was examined for cracking and loss of
adhesion of coating. The flexibility of coating was carried out as per
ASTM D 552-93a by using ¼ dia Conical mandrel tester (Sheen Inst
98 A.P. Singh et al. / Progress in Organic Coatings 87 (2015) 95–105
Ltd.). The scratch resistance test of coatings were determined as per
BS 3900.
3.9. Adhesion strength
Adhesion strength was determined as per method described
in Indian Standard IS: 101 (pull-off method). The method
was modified by reducing the area of one dolly to facilitate
the de-bonding of coating from one side. Measurements were
carried out using a Universal Testing Machine (Lloyd, Model-
LR30K). Epoxy ester coated burnished mild steel specimens of
size 150 mm × 100 mm × 1.5 mm with a dry film thickness of
75 ± 10 ␮m were used for adhesion test. For each coating, ten spec-
imens were tested and adhesion strength was calculated from the
average of five higher readings.
3.10. Evaluation of resistance to corrosion
Anticorrosive properties of developed coatings were assessed
by evaluating their resistance to corrosion in salt spray and
sea water exposure as per ASTM B117-09 and ASTM D1748-10.
WB resin coated clean and rust free mild steel panels of size
150 mm × 100 mm × 1.5 mm with average film thickness of coating
is 75 ± 10 ␮m were used for corrosion resistance measurement. The
edges of coated specimens were sealed using molten wax before
exposure.
3.11. Electrochemical impedance spectroscopy (EIS)
EIS has been used to study the corrosion mechanism of devel-
oped coatings. The EIS measurement was carried out using Gamry
CMS 300 electrochemical impedance system. Three electrode cell
assembly having coated panel area of 22.5 cm2 as working elec-
trode, large Pt mesh as counter electrode, saturated Calomel
electrode as reference electrode and 100 ml 3.5% NaCl solution as
electrolyte was employed. A sine wave of 10 mV (r.m.s) was applied
across the cell. The measurements were made in the frequency
range of 50 kHz–0.02 Hz. EIS study was carried out on samples after
different exposure intervals at ambient temperature.
4. Results and discussion
4.1. FTIR spectroscopy
The FTIR spectra of the developed resins and precursor materi-
als are shown in Fig. 3a and b. The carbonyl (C O) stretching peak
appearing at 1746 cm−1 in the spectra of tung oil (Fig. 3a) indicates
the presence of ester linkages. After hydrolysis, the peak for ester
group in tung oil disappeared and a peak for acid group appeared at
1704 cm−1 . It confirms the hydrolysis of tung oil and formation of
fatty acid TOFA. The appearance of peak at 915 cm−1 and 1730 cm−1
for oxirane ring and C O stretching frequency of epoxy ester link-
ages confirmed the formation of TOEE. Similarly, the FTIR spectra of
linseed oil, LOFA, LOEE, dehydrated castrol oil, DCOFA and DCOEE
were recorded and found to be similar to tung oil, TOFA and TOEE
(Spectra not shown). The FTIR spectra of LOEE, TOEE and DCOEE
are shown in Fig. 3b. The peaks seen at 1730 cm−1 and 915 cm−1 in
the spectra are due to the presence of ester group and epoxy ring
between the esterification reaction of fatty acids and epoxy resin
respectively. It confirms the conversion of LOEE & DCOEE. Forma-
tion of epoxy ester resin was also confirmed by measuring its acid
value. The calculated acid value for all epoxy ester resins was below
10 KOH/mg indicating the reduction of acid groups in epoxy esters.
4.2. NMR spectroscopy
Synthesized epoxy resins with various fatty acids were further
characterized using 1 H-NMR spectroscopy and the respective spec-
tra are shown in Fig. 4a–c. In the 1 H-NMR spectrum of epoxy ester
resin, the peaks at 0.9, 1.2, 1.3 and 1.5 ppm are characteristics for
CH3 and CH2 groups present in the fatty acid moiety in epoxy
ester resin. The peaks at 2.7 and 5 ppm correspond to the protons of
oxirane ring and hydroxyl group of epoxy ester resin respectively.
The peaks at 6.8 and 7.3 ppm are characteristic of HC CH of fatty
acid chain and aromatic protons of epoxy resin. The above data
confirms the formation of TOEE.
4.3. Thermal properties of films
Thermal properties of epoxy ester resins were determined as per
method described in Section 3.4. TGA thermograms of LOEE, TOEE
and DCOEE epoxy ester resins (Fig. 5a) showed similar degradation
pattern which is attributed to their similarity of structure. How-
ever, they exhibited different degradation temperatures due to the
presence of varying amount of unsaturated moiety present in each
resin. A second step in weight loss rate of the LOEE, DCOEE and
TOEE epoxy ester resins appears at temperatures, between 285 to
400 ◦ C, 275 to 400◦ C and 300 to 450 ◦ C, respectively corresponding
to the thermo oxidative degradation. The observed weight loss in
TOEE at higher temperature is attributed to the presence of higher
amount of conjugated unsaturated moiety.
Glass transition temperatures (Tg ) were calculated from DSC
thermograms of LOEE, DCOEE and TOEE epoxy ester resins (Fig. 5b)
and were found to be 20.79, 30.02 and 34.04 ◦ C, respectively. The
observed Tg values of all the three epoxy esters are very close to
each other, in accordance with the similar basic chemical structure
of the resins. Among the epoxy esters, TOEE has showed the high-
est Tg due to the presence of higher conjugated unsaturation in the
tung oil fatty acid moiety of TOEE, which imparts rigidity to the
epoxy resin.
4.4. Mechanical properties
Tensile strength of the epoxy ester coatings was determined as
per the method described in Section 3.7 and the respective results
are shown in Fig. 6. It is observed that the tensile strength of TOEE
is 6 MPa which is higher compared to LOEE and DCOEE. This is due
to the presence of higher amount of conjugated unsaturation in the
TOEE, which would increase the cross-link density of the film.
Clear coating compositions of all the epoxy ester resins neutral-
ized with various acids were coated on mild steel specimens and
were evaluated for scratch and impact resistance characteristics as
per standards described in Section 3.8. The results are presented
in Table 1. The scratch resistance of various acid neutralized LOEE,
TOEE and DCOEE are in the range of 0.7–1.0, 1–1.5 and 0.6–0.8 kg.
The superior performance of TOEE is clearly due to the higher cross-
link density. Among the acids used, phosphoric acid neutralized
resins showed higher scratch resistance than the other acids. This
may be due to the presence of phosphate which converts iron oxide
present in the interphase to iron phosphate and blendes in the
coating films. HCl neutralized resins showed lower scratch resis-
tance, may be due to reduction in cross link density by chloride
ions present in the resin. Impact test results also show that phos-
phoric acid neutralized epoxy resins passed the impact of 0.908 kg
of load dropped from 65 cm height. All the coating samples with
LOEE, TOEE and DCOEE neutralized with phosphoric, lactic, acetic
and hydrochloric acids passed the bent in a manderal with diameter
of ¼ (Table 1). This flexibility is attributed to the presence of long
hydrocarbon flexible chain containing fatty acids, which reduced
the brittleness of epoxy ester.
 A.P. Singh et al. / Progress in Organic Coatings 87 (2015) 95–105 99

Fig. 3. FTIR Spectra of (a) Tung oil, TOFA and TOEE (b) DCOEE, TOEE and LOEE

Pull-off adhesion strength was determined as per method
described in Section 3.9 and the results are presented in Table 1.
It can be seen from Table 1 that the adhesion strength of resins
neutralized using phosphoric acid is higher than other acid neu-
tralized epoxy esters. Among the various epoxy esters studied,
TOEE showed higher adhesion strength. The increase in adhe-
sion strength of TOEE neutralized using phosphoric acid may be
attributed to the formation of iron phosphate passive films at metal
coating interface and presence of higher amount of polar linkages
such as ester, acid as well as higher unsaturation in tung oil fatty
acid compared to the rest of the fatty acids. The higher amount
of polar group and unsaturation makes TOEE to form stronger
bonding with metal surface and thereby enhance the adhesion
strength of coating. On the other hand, HCl neutralized resins
100 A.P. Singh et al. / Progress in Organic Coatings 87 (2015) 95–105

1
Fig. 4. H NMR spectra of (a) LOEE, (b) DCOEE and (c) TOEE.

showed poor adhesion strength due to the presence of chloride
ions which enhances the metal corrosion at the coating metal inter-
phase, thereby decreasing the adhesion of coating on the metal
surface.
4.5. Storage stability of resins
The clear coating compositions were evaluated for their stor-
age stability as per method described in Section 3.5. The epoxy
ester based on LOEE, TOEE, and DCOEE were neutralized with
phosphoric acid and stored for six months under ambient stor-
age conditions. The resultant resins were evaluated for their
stability and performance characteristics. Separation and settling
were not observed. Marginal change in viscosity (Table 2) was
noticed. Despite presence of moisture and phosphate, no foul-
ing was observed. The above evidences show that these resins
have high storage stability which is prerequisite of a good coating
system.
 A.P. Singh et al. / Progress in Organic Coatings 87 (2015) 95–105 101

Fig. 5. (a) TGA thermograms and (b) DSC curves of LOEE, TOEE and DCOEE.

4.6. Anticorrosive properties
Anticorrosive properties of LOEE, TOEE and DCOEE neutralized
with different acids were evaluated by following two methods.
4.6.1. Accelerated corrosion test
Burnished mild steel panels coated with various acid neutralized
LOEE, TOEE and DCOEE were exposed to salt spray and seawater for
600 h to evaluate the resistance to corrosion. Assessment of these
coatings on these panels were quantified by assigning numbers
from 0 to 10, to rank the severity of corrosion, in accordance with
ASTM D 610-01 and the respective results are shown in Table 3.
Photographs of the panels exposed for 600 h in salt spray chamber
are shown in Fig. 7.
TOEE resin neutralized with phosphoric acid showed supe-
rior corrosion resistance compared to other compositions. This
may be attributed to the good adhesion strength of the coat-
ing films resulting from the formation of iron phosphate passive
films and higher number of valence bonds between polar groups
present in the resin and metal surface at metal coating interface.
The TOEE resin neutralized with phosphoric acid exhibited higher
resistance to corrosion as compared to other compositions under
seawater exposure condition also. The change in colour of dif-
ferent coatings is probably due to the water absorption. Onset
of corrosion in TOEE-Lactic acid, TOEE-Acetic acid and TOEE-HCl
coatings was noticed after 400 h of exposure in salt spray and
the severity increased with time. On the other hand, first cor-
rosion spot in TOEE-Phosphoric acid coating was observed only
after 600 h of exposure in seawater. Higher corrosion resistance
102 A.P. Singh et al. / Progress in Organic Coatings 87 (2015) 95–105

Fig. 6. Tensile strength of epoxy ester.

Table 1
Mechanical properties of coating based on resins LOEE, TOEE and DCOEE resins neutralized with phosphoric acid, lactic acid, acetic acid and hydrochloric acid.

Resins Acids Adhesion, MPa Scratch hardness (Kg) Impact test Drying time (h) Flexibility

Surface dry Hard dry

Phosphoric 8.5 1 Pass 1 22 Pass

Lactic 5.7 0.8 Fail 1 26 Pass
LOEE
Acetic 6.1 0.8 Fail 1 24 Pass
Hydrochloric 5.4 0.7 Fail 1 25 Pass

Phosphoric 10.8 1.5 Pass 1 19 Pass

Lactic 8.2 1 Fail 1 24 Pass
TOEE
Acetic 8.5 1.2 Fail 1 22 Pass
Hydrochloric 7.8 1 Fail 1 24 Pass

Phosphoric 9.5 0.8 Pass 1 24 Pass

Lactic 7.4 0.6 Fail 1 28 Pass
DCOEE
Acetic 7.6 0.7 Fail 1 26 Pass
Hydrochloric 6.9 0.6 Fail 1 28 Pass

Table 2
Storage stability of phosphoric acid neutralized LOEE, TOEE and DCOEE resins stored for 6 months under ambient storage conditions. (ASTM-D1849-95(2004)).

Test characteristic LOEE TOEE DCOEE

Initial Final Initial Final Initial Final

Viscosity at 25 ◦ C, Poise 27 30 43 45 47 51
Settling/Separation No No No No No No
Fouling No No No No No No
Change in appearance No No No No No No

of TOEE-Phosphoric acid based coating compared to other coat-
ings may be attributed to the formation of iron phosphate passive
films at metal coating interface and the higher cross linking den-
sity resulting from the large number of conjugated double bonds
present in TOEE. This leads to the formation of a compact film
thereby reducing the ingress of ionic species towards the sub-
strate.
4.6.2. Electrochemical impedance spectroscopy (EIS)
In order to obtain quantitative information about the kinetics
of iron corrosion in presence of WB protective coating, the electro-
chemical process taking place on coated panels at the open-circuit
potential was examined by electrochemical impedance spec-
troscopy (EIS) at various intervals. EIS measurements of the coated
steel at its open circuit potential after 1–25 days of immersion in

Table 3
Corrosion resistance properties of various coatings exposed in salt spray and sea water.

Resins Resistance to corrosion, after 600 h of exposure (rating: 0, severe corrosion; 10, no corrosion/no blistering)

Salt spray Sea water

Lactic acid Acetic acid Phosphoric Hydro chloric Lactic acid Acetic acid Phosphoric Hydro chloric
acid acid acid acid

LOEE 2 2 7 3 3 4 8 4
TOEE 3 4 8 4 3 3 9 4
DCOEE 2 2 5 2 3 3 6 3
 A.P. Singh et al. / Progress in Organic Coatings 87 (2015) 95–105 103

Fig. 7. Various acid neutralized tung oil fatty acid modified epoxy resin (TOEE) coated panels after 600 h of exposure in salt spray chamber.

1000
Zim (M ohm cm 2)

1 day
5 days
800 10 days 1 day
15 days
5 days
Zim (M ohm cm2)

20 days
25 days 10 days
600
0 15 days
0 10 20
400 Zre (M ohm cm 2) 20 days
25 days

200

0
0 200 400 600 800 1000 1200 1400
Zre (M ohm cm2 )

Fig. 8. Nyquist plots of mild steel coated with phosphoric acid neutralized TOEE immersed in 3.5% NaCl for various immersion period.
104 A.P. Singh et al. / Progress in Organic Coatings 87 (2015) 95–105

Fig. 9. Simulated and experimental EIS results using (a) one and (b) two time constant equivalent circuit models.

3.5% NaCl solution were performed. Nyquist representations for dif- the corrosion of TOEE neutralized with phosphoric acid coated steel
ferent immersion period for TOEE neutralized with phosphoric acid in 3.5% NaCl solution is controlled by a charge-transfer process. A
coating at 25 ◦ C are shown in Fig. 8. The fact that impedance dia- small distortion was observed in some diagrams, this distortion
grams have an approximately semicircular appearance shows that has been attributed to frequency dispersion. It is clear from all

1
Volume fraction of water absorbed

0.8

0.6

0.4 TOEE-Phosphoric acid

TOEE-Acetic acid
0.2 TOEE-Lactic acid

TOEE-Hydrochoric acid
0
0 10 20 30
Exposure duration (day)

Fig. 10. Rp vs. immersion time for various acid neutralized TOEE coated mild steel Fig. 11. Volume fraction of water absorbed by various acid neutralized TOEE coated
panel in 3.5% NaCl solution. mild steel panel in 3.5% NaCl solution vs. immersion.
 A.P. Singh et al. / Progress in Organic Coatings 87 (2015) 95–105
plots that the impedance response of mild steel in the test solution
was significantly changed with immersion period. The diameter
of the capacitive loop is approximately equal to the value of the
charge-transfer resistance of the process of corrosion reaction and
is associated with the corrosion resistance ability of the films in
3.5% NaCl solution. The diameters of the capacitive loop decreased
on increasing the immersion period and were indicative of the
degree of the corrosion progress. Single capacitive semicircles were
noticed for phosphoric acid neutralized TOEE till 15 days immersion
period and further increasing the immersion period, two capacitive
semicircles were noticed indicting that pores opened up after 15
days of immersion.
To analyze the EIS plots, single and two time constant equiv-
alent circuit models shown in Fig. 9 (inset) were used. Rs , Rpo
and Rp are resistance of solution, pores and polarization. Qc and
Qdl are the constant phase elements of coating and double layer.
The experimental and simulated data using single (Fig. 9a) and
two time constant equivalent circuit models (Fig. 9b) are in good
agreement with each other. The Rp deduced from the analysis of
Nyquist diagram were plotted with respect to immersion period
for TOEE neutralized with various acids and shown in Fig. 10.
Rp decreases with immersion period for all the coatings and this
behaviour is attributed to the initiation of corrosion on the coated
metal/solution interface. The initial Rp of all the coatings are
close to 109  cm2 . However, the decrease in Rp was deep for
TOEE-Lactic acid, TOEE-Acetic acid and TOEE-Hydrochloric acid
compositions. Bierwagen reported [28] that polarization (Rp ) value
for an excellent coating lies between 109 and 1010  cm2 , whereas
for a good coating it lies between 106 and 109  cm2 . The coat-
ing is considered poor, if Rp value is less than 106  cm2 . The
initial Rp value of TOEE-Phosphoric acid, TOEE-Lactic acid, TOEE-
Acetic acid and TOEE-Hydrochloric acid coating compositions are
1.1 × 109 , 9.4 × 108 , 8.5 × 108 and 8.1 × 108  cm2 and it reduced
to 1.1 × 107 , 3.2 × 106 , 2.12 × 106 and 9.12 × 105  cm2 after 15
days of immersion. This indicates that TOEE-HCl coating fails at
15 days of immersion. Further increasing the immersion period,
the Rp values of all the TOEE coatings except TOEE-phosphoric acid
decreased below 106  cm2 which indicates their failure. The grad-
ual decrease in Rp value for these coatings during exposure period
may be attributed to the loss of barrier properties due to perme-
ation of electrolyte. This indicates that the above coatings have lost
their protective nature after 20 days of exposure. The Rp value of
TOEE-Phosphoric acid coating was found to be 3 × 106  cm2 after
25 days exposure indicating that this coating will be suitable for
long term corrosion protection.
The capacitance of coating is a measure of water permeation
into the coating. The capacitance of the coating increases on water
permeation due to the charge develops at the coating electrolyte
interphase. The water uptake of coating in terms of volume fraction
of water absorbed (W) was calculated from coating capacitance (Cc )
by using following equation [29].
log(Ct /Co )
W=
log 80
where, Ct is coating capacitance after time “t” and C0 is coating
capacitance after 1 days of exposure. The dielectric constant of
water is 80. The relative volume fraction of water absorbed by
the various acid neutralized TOEE coatings is plotted against the
immersion period and shown in Fig. 11. It is observed that water
uptake of TOEE-Phosphoric acid coating is less compared to the rest
View publication stats
105
of the compositions. The lesser water up take of TOEE-Phosphoric
acid coating composition may be attributed to the formation of iron
phosphate passive films at metal coating interface and high cross
linked intact film on metal substrate resulting in enhancement of
barrier property of the TOEE-Phosphoric acid coating.
5. Conclusions
Water soluble fatty acid based epoxy ester resins were syn-
thesized and characterized by FTIR and NMR spectroscopy. Glass
transition temperature and thermal stability of polymer showed
formation of water soluble fatty acid based epoxy ester resin. Coat-
ing prepared using TOEE-phosphoric acid showed good adhesion,
mechanical and anticorrosive properties compared to the rest of the
compositions. The excellent corrosion resistance shown by TOEE-
Phosphoric acid is due to the high cross linked intact film on metal
substrate and the formation of iron phosphate passive films at
metal surface-coating interphase. The developed polymer can have
application in the area of eco-friendly WB decorative as well as
anticorrosive coatings.
Acknowledgements
Authors thank Dr. R. S. Hastak, Director, NMRL for his valuable
suggestion and also permission to carry out this work. We would
also like to thank Mr. N. G. Malvanker, NMRL for his help in testing
the samples.
References
[1] K.D. Weiss, Prog. Polym. Sci. 22 (1997) 203–245.
[2] J. Lindeboom, Prog. Org. Coat. 34 (1998) 147–151.
[3] M.Y. Shah, S. Ahmad, Prog. Org. Coat. 75 (2012) 248–252.
[4] D. Shikha, P.K. Kamani, M.C. Shukla, Prog. Org. Coat. 47 (2003) 87–94.
[5] V.D. Athawale, R.V. Nimbalkar, J. Am. Oil Chem. Soc. 88 (2011) 159–185.
[6] D.I. Caglar, E. Basturk, B. Oktay, M.V. Kahraman, Prog. Org. Coat. 77 (2014)
81–86.
[7] D. Ramesh, T. Vasudevan, Prog. Org. Coat. 66 (2009) 93–98.
[8] S.A. Chen, J.S. Hus, Polymer 34 (2776) (1993).
[9] T.A. Grotenhuis, U.S. Pat. 3, 156 (1964) 576.
[10] Surface Coatings, vol. 1-OCCA, Australia-Chapmann and Hall Ltd., London, 1963.
[11] H.C. Beachell, C.P. Ngocson, J. Appl. Polym. Sci. 8 (1964) 1089.
[12] Y. Nakae, Assignors to Nippon paint Co., Ltd. U.S. Patent, 5,597,861 (1997) 28.
[13] S.B. Lee, J. Gummeson, Patricia Ball and George Vaughu Solutia Inc.730, in:
Presented at International water-borne, high solids and powder coatings, Sym-
posium, March 1–3, New Urleans, LA, USA, 2000.
[14] J.J. Gummeson, D.E. Erickson, Am. Paint Coat. J. 25 (1998) 15.
[15] K. Raghupathy, Thesis submitted to Madurai Kamaraj University, Tamil Nadu,
(India). 1991, p. 43.
[16] A. Hasan, Surf. Coat. Inter Part B Coat. Trans. 84 (B2) (2001) 91.
[17] A.I. Aigbodion, F.E. Okiemien, E.O. Obazaa, I.O. Bakare, Prog. Org. Coat. 46 (2003)
28–31.
[18] A.I. Aigbodion, F.E. Okiemien, E.U. Ikhuoria, I.O. Bakare, E.O. Obazaa, J. Appl.
Polym. Sci. 89 (2003) 3256–3259.
[19] R.V. Nimbalkar, V.D. Athawale, J. Am. Oil Chem. Soc. 87 (2010) 1035–1045.
[20] C. Wang, F.N. Jones, J. Appl. Polym. Sci. 76 (2000) 105–114.
[21] Y.S. Hu, Y. Tao, C.P. Hu, Biomacromolecules 2 (2001) 80–84.
[22] Y. Lu, R.C. Larock, Biomacromolecules 8 (2007) 3108–3114.
[23] J.H. Bieleman, in: J.H. Bieleman (Ed.), Additives for Coatings, Wiley/VCH, Wein-
(3) heim, 2000, p. 202.
[24] R.G. Middlemiss, D.J. Olszanski, Am. Paint. Coat. J. 35 (1993) 78.
[25] M.D. Soucek, T. Khattab, J. Wu, Prog. Org. Coat. 73 (2012) 435–454.
[26] J.M. Behr, US Patent 0250976 (2008).
[27] R. Chakraborty, M. Thatte, M. Soucek, J. Coat. Technol. 6 (2009) 471–481.
[28] G.P. Bierwagen, L. He, J. Li, L. Ellingson, D.E. Tallman, Prog. Org. Coat. 39 (2000)
67–78.
[29] S.K. Singh, S.P. Tambe, G. Gunasekaran, V.S. Raja, D. Kumar, Corros. Sci. 51 (2009)
595–601.