Anticorrosion performance of zinc ferrite pigmented lignin/phenol

epoxy novolac resin based coating

AHMED Murtala Musa1,2,a, NASRI Noor Shawal1,b *,HAMZA Usman Dadum3,c,
MOHAMMED Jibril3,d,GARBA Abdurrahman4,e and MOHD Zain Husna1,f
1
Sustainability Waste-To-Wealth Unit, UTM-MPRC Institute for Oil and Gas, Energy Research
Alliance, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia.
2
Chemical Engineering Department, Faculty of Engineering, University of Maiduguri, P.M.B. 1069
Maiduguri, Borno, Nigeria.
3
Chemical Engineering Department, Faculty of Chemical Engineering, Universiti Teknologi
Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia.
4
Faculty of Science, Technology and Human Development, University Tun Hussein Onn Malaysia,
86400 UTHM Parit Raja, Johor. Malaysia
a
muriahmed@yahoo.com bnoorshaw@petroleum.utm.my, cusmandhamza@gmail.com,
d
jibrilmuhammad@gmail.com, eagarba2008@yahoo.com, fhhusnae@yahoo.com

Keywords: Bio-oil, corrosion, epoxy, coating, zinc ferrite, lignin

Abstract. Corrosion in most processing equipment has always been a key research area. It is an
important threat that needs to be prevented and controlled. Application of epoxy-based coatings
on the surfaces of metallic parts is among the preventive measures but it is toxic and expensive. In
this work, the anticorrosion performance of zinc ferrite pigmented bio-based epoxy-novolac
coatings was studied. Initially, bio-based novolac resins were prepared by condensation from the
reaction between phenol, bio-oil phenolic fractions and formaldehyde in an acidic medium. The
prepared novolac was later transformed to epoxide with epichlorohydrine and 30 percent sodium
hydroxide solution. The final coating formulation was obtained by mixing the prepared epoxy with
zinc ferrite (a nontoxic anticorrosion pigment) and solvent. Anticorrosion tests using the formulated
coatings and two other conventional coatings for comparison were conducted by simulating actual
field conditions in a closed autoclave loop system that used 3 percent sodium chloride and water
medium. The results showed that the zinc ferrite pigmented bio-based formulated coatings are
very efficient in protecting the substrates since they exhibit similar protection ability with the
conventional ones. The prepared epoxy can be said to be an eco-friendly and cheap source of
resin for coating formulation that will reduce production cost and negative environmental effects as
compared to conventional materials

Introduction
The need to adequately and efficiently transfer energy or fuel for energy production can be found in
a wide range of systems such as chemical, refinery, biological, electronics and petrochemical
systems. After some operational period, surfaces of the equipment used for the transfer of the heat
or fuel may no longer be in the same condition found upon installation. The surfaces can become
coated with deposits from the process or cooling streams or become coated with corrosion products
which can crates additional resistance to the heat transfer and a decrease in performance. Corrosion
is the disintegration of an engineered material into its constituent atoms due to chemical reactions
with its surroundings [1,2]. Disintegration implies deterioration of physical properties of the
material. This can be a weakening of the material due to a loss of cross-sectional area, it can be the
shattering of a metal due to hydrogen embrittlement, or it can be the cracking of a polymer due to
sunlight exposure [1].

Coating on the surfaces of metallic parts is among the preventive measures. The use of
polymer materials for the production of high performance coating has evolved and matured into a
cost-effective remedy to reduce typical fouling and corrosion problems intrinsic to various
processing equipment. These polymeric materials have superior mechanical, thermal and
anticorrosive characteristics ideally suitable for adverse environmental conditions [3]. On the other
hand, most of the coating materials are toxic and harmful to the environment [3]. As such, recycle
waste materials or biomass in general, is a promising option for coating agents (chemicals).
Chemicals produced from such resources can be safe and environmentally friendly [4].

The objective of this study is test the anticorrosion performance of zinc ferrite pigment bio-
based epoxy novolac resin based coating with the view of having a formulation that would be highly
anticorrosive and eco-friendly.

Materials and Methods

Fractionation of bio-oil. The bio-oil was first separated into water- soluble (light) and insoluble
(heavy) components by mixing the bio-oil with water at 2:1 V/V ratio under ambient condition [5].
It employed the use of magnetic stirrer where the measured amount of water was gradually added to
the bio-oil which was in vigorously stirred condition for 3hours. It was then allowed to stand for 24
hours and after which the bio-oil was separated into two phases.
Synthesis of Novolac Resin. The bio-based novolac resin was prepared by condensation reaction
between phenol, bio-oil phenolic fraction and formaldehyde in acidic medium. This was synthesized
in a 2.0L glass reactor equipped with a thermometer, reflux condenser and a stirrer. The pH was
adjusted to 2.0 with aid of 0.1M HCl (used as catalyst) and the contents was heated to 90°C with
constant stirring. The required amount (1mole) of formaldehyde (37% formaline solution) was
added over a period of 2.5 hours through a dropping funnel. The mixture was then stirred for an
additional 30 minutes. Finally the water was removed under vacuum [6].

Epoxidation of Novolac Resin. The novolac resins prepared above was then reacted with
epiclorohydrine and 30% NaOH solution was later added to the reaction vessel over a period of
2.5hrs. The content was then washed with hot water in order to completely remove any salt that will
be formed during the reaction. The epoxidation process was conducted in a 2.0L glass reactor
equipped with a thermometer, reflux condenser and a stirrer. Finally the residual moisture in the
resin was removed under vacuum [6].

Coating formulation. A typical coating is composed of binders, carriers, pigments and additives.
Binders provide the major properties to the coating while the carriers (solvents and/or water) adjust
the viscosity of the coating for application [9]. Pigments impart specific properties to a coating such
as corrosion resistance and colour. In this study, the coating composition was formulated by
incorporating the prepared resins (epoxy-novolac) and zinc ferrite pigment with the curing agent
(Phthalic anhydride). The nomenclatures for the coating used in the test are as follows:-CA-
Laboratory prepared coating (solvent-borne); CB- Laboratory prepared coating (water-borne);
CSA- Commercial coating 1(zinc-rich); CSB- Commercial coating 2.

Measurement of Corrosion Rate. Initially all the plates used for the test were cleaned
mechanically ( by 400# abrasive paper), degreased using acetone to remove all the oxidized surface
and impurities, rinsed and pickled with hydrochloric acid solution at 1:1 dilution, and finally rinsed
with de-ionized water and oven-dried. Thereafter, weight loss method which is a simple test for
measuring corrosion is adopted. The weight loss from the testing plates was obtained by first
measuring the initial weights (W1) of the empty cleaned plates. It was followed by measuring the
weights of the dry coated plates (W2) and finally measuring the weights of the plates after the
corrosion test (W3). This final measurement was done after removing the corrosion products from
the plates. The coating solution was applied on the metallic plates by flow coating method and left
in air for 3 h to evaporate the solvent. The coating samples were thermally cured in an oven to have
a uniform coating thickness of about 20-30 µm measured in accordance with ASTM D4138-94. The
following expressions were used to assessed the corrosion rate [7].

(1)

or Where the values for variables are; A= 10cm2 , D= 7.85g/cm3 (for carbon steel)
and since the area is in cm2 then corrosion rate constant, K=3.45x106 in order to get the CR in mills
per year (mpy). Therefore,

(2) or (3)

Results and Discussions

Fractionation of bio-oil. The separation operation was performed in order to separate the relatively
stable top emulsion phase containing water soluble chemicals and light oily components which are
mostly alkenes and low molecular lignin and precipitate the heavy oil of the bottom layer. The
bottom fraction is a mixture of large oily molecule characterized by high viscosity and water
insoluble (heavy oil). The heavy oil yield from this experiment was about 20 % of bio-oil while that
of the light oil was about 80 %.
Corrosion rate. The results indicate that as time increases, corrosion rate also increase due to
continuous dissolution of iron ion from the plate. The corrosion rate is faster in brine medium than
the that of water. This may be due to the presence of chloride in NaCl. The summary of the results
are presented in Figures (1-4).

CB
CA
CB
2 0.25 CSA
CA CSB
CSA
CSB 0.2
1.5
w e ig h t lo s s ( g )

w e ig h t l o s s ( g )

0.15

1
0.1

0.5
0.05

0
0 50 100 150 200 250 300 350 400 450 500 0 100 200 300 400 500 600 700 800
time(hr) time(hr)

(a) (b)
Figure 1.Variation of weight loss with time of coated plates in (a) water (b) brine medium
400
CB 600
CA CB
350
CSA CA
CSB 500 CSA
300 CSB
c o rro s io n ra te (m p y )

250 400
c o r r o s io n r a t e ( m p y )

200
300

150
200
100

100
50

0 0
0 100 200 300 400 500 600 700 800 900 1000 0 100 200 300 400 500 600 700 800 900 1000
time(hr) time(hr)

(a) (b)
Figure 2. Variation of corrosion rate with time of coated plates in (a) water (b) brine medium
 (a) (b)
Figure 3. Comparison of corrosion rate of the different coatings in (a) water (b) brine medium

(a) (b)
Figure 4. Uncoated plates corrosion behavior showing (a) weight loss (b) corrosion rate
The coating performance on various coated and uncoated (blank) plate in terms of weight loss and
corrosion rate was analysed. As indicated in Figures 1-4, it was observed that coating the metals
with any of the coatings provide a significant protection against corrosion when compared with the
blank plates. It was also observed the corrosion rate is faster under the brine medium which may due
to chlorine presence.
Conclusion
No visible corrosion products were seen on the surface of the unscratched area of the coated panels
at the end of the all the tests. Corrosion products were seen mainly on scratched area of the coated
panels. Corrosion is lower in the case of commercial coating 1, 2 and the solvent based bio-based
epoxy-novolac coated panels than the water-borne epoxy and blank (uncoated).
Acknowledgement
This study was supported by Ministry of Education through the University Research Grant
(Q.J130000.2509.06H79) provided by Universiti Teknologi Malaysia, Johor Bahru.
References
[1] G., Vourlias, N. Pistofidis, G. Stergioudis, E. Polychroniadis, D. Tsipasa, Corrosion
mechanism under accelerated atmospheric conditions. Journal of Optoelectronics and
Advanced Materials, 6(2004) 315-320.
[2] A. Y. Musa, Corrosion protection of Al alloys: Organic coatings and inhibitors. in: R.S.
Razavi, (Eds), Recent researches in corrosion evaluation and protection, InTech, Rijeka,
Croatia, 2012, pp17.
[3] J. A. Kehr, Fusion-Bonded Epoxy (FBE): A foundation for pipeline corrosion protection.
NACE(2003).
[4] Y. Xu, M.A. Hanna, L. Isom, “Green” Chemicals from renewable agricultural biomass, The
Open Agriculture J, 2 (2008) 54-61
[5] L.F. Zilnik, A. Jazbin.ek, Recovery of renewable phenolic fraction from pyrolysis oil,
Separation and Purification Technol, 86(2012) 157–170
[6] J. Xu, J. Jiang, W. Lv, Preparation of novolacs using phenolic rich components as partial
substitute of phenol from biomass pyrolysis oils, Bull. Chem. Soc. Ethiop, 24 (2010) 251-
257
[7] Information on http://www.metalsamples.com