Progress in Organic Coatings 112 (2017) 127–132

Contents lists available at ScienceDirect

Progress in Organic Coatings

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

Cellulose nanofibers to assist the release of healing agents in epoxy coatings MARK
a,⁎ a a a,b
Poornima Vijayan P , Aisha Tanvir , Yara Hany El-Gawady , Mariam Al-Maadeed
a
Center for Advanced Materials, Qatar University, P.O. Box 2713, Doha, Qatar
b
Materials Science and Technology Program, Qatar University, P.O. Box 2713, Doha, Qatar

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

Keywords: Epoxy monomer and amine curing agents were immobilized on cellulose nanofibers (CNF). Obtained epoxy
Self-healing immobilized CNF (EiCNF) and amine curing agent immobilized CNF (AiCNF) were characterized using Fourier
Epoxy coating transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy
Cellulose nanofiber (SEM). The mechanism and nature of interaction in EiCNF and AiCNF were elucidated. While chemical inter-
Immobilization
action was observed between amine curing agent and CNF, only physical interaction exists between epoxy
monomer and CNF. Preliminary investigation of self-healing ability of epoxy coating incorporated in both EiCNF
and AiCNF was carried out. The dual healing agents supported on CNF were effective in imparting self-healing
ability to epoxy coatings.

1. Introduction excellent mechanical properties [19]. The numerous hydroxyl groups

Polymer coatings are widely used to protect metal structures from
corrosion. Polymer coatings are usually incorporated with fillers to
further improve their corrosion protection ability [1,2]. Any mechan-
ical damage on these polymer coatings can increase the chances of
triggering corrosion. Hence, the ability of polymer coatings to repair
mechanical damages by themselves can improve the life span of the
metal under protection. There are various methods adopted by re-
searchers to induce self-healing in polymers [3–6]. Among various
techniques used to achieve self-healing ability, the one based on the use
of reservoirs for the safe encapsulation and release of healing agents is
most promising. Micro/nano polymer capsules [7–9], inorganic nano-
tubes [10,11] and mesoporous materials [12] are effective reservoirs
for the storage of healing agents/corrosion inhibitors. Core-shell fibers
encapsulated with healing agents were fabricated using coaxial elec-
trospinning [13,14]. The healing agent- dicyclopentadiene (DCPD) was
successfully enwrapped into polymer fibers of polyacrylonitrile (PAN)
using co-axial electrospinning method.
In search of finding easier and ecofriendly methods, chitosan [15]
and cellulose nanofibers [16,17] have been reported as efficient green
reservoirs for corrosion inhibitors. Cellulose is an abundant poly-
saccharide that consists of β (1-4) linked D-glucose units [18]. It is one
of the most promising nature-derived nanomaterials owing to its ex-
traordinary mechanical properties combined with its sustainable
nature. The abundance of OH groups on the surface of cellulose favors
the formation of hydrogen bonding, causing the cellulose chains to
assemble in highly ordered structures, which in turn results in its
present on cellulose make it compatible with hydrophilic polymers, and
to be used as a mechanical reinforcing agent [20–23]. Apart from their
use as reinforcing fillers, cellulose derivatives such as cellulose nano-
crystals (CNC) can be used for enzyme immobilization and drug de-
livery purposes [24]. Yabuki et al. [16,17] reported that cellulose na-
nofibers act as pathways to release corrosion inhibitors into damaged
areas on epoxy coatings over carbon steel substrate. According to this
study, cellulose nanofibers deformed and shortened in the presence of
water, thereby facilitating the release of corrosion inhibitors into the
scratched area.
In order to recover the damage on the host epoxy coating with a
matching chemical entity, a two-component self-healing system based
on reservoirs of epoxy monomer and curing agent is required [24].
Green reservoirs like cellulose nanofibers have not yet been used to
store and release epoxy monomer and curing agents.
This research reports on the possibility of using cellulose nanofibers
to assist the release of epoxy monomer and curing agent upon damage
of epoxy coatings. The advantage of using dual healing agents such as
epoxy monomer and curing agents is the recovery of damaged area with
the matching chemical entity as the epoxy coating matrix. This work
aims to immobilize both epoxy monomer and amine curing agent on the
surface of cellulose nanofibers to utilize them to heal the damage in
epoxy coatings.

⁎
Corresponding author.
E-mail addresses: poornimavijayan@qu.edu.qa, poornimavijayan2007@gmail.com (P. Vijayan P).

http://dx.doi.org/10.1016/j.porgcoat.2017.07.008
Received 8 May 2017; Received in revised form 16 June 2017; Accepted 18 July 2017
0300-9440/ © 2017 Elsevier B.V. All rights reserved.
P. Vijayan P et al.
2. Experimental
2.1. Materials
The epoxy resins used for the study are Epon 826 and Epon 815C.
Epon 815C is a diluted (with butyl glycidyl ether) form of Epon 826.
Amine curing agent used is Diethylenetriamine (Epikure 3223). The
epoxy resin and curing agent were purchased from Miller-Stephenson
Chemical Co., USA. Polished carbon steel plates are used as substrates
for coating. Commercially available cellulose (fibers) from Sigma-
Aldrich was used as the source for cellulose nanofiber synthesis.
2.2. Methods
2.2.1. Preparation of cellulose nanofibers
CNF was prepared using a previously reported one-step method
[25]. The starting biomass was added to 1 M solution of ammonium per
sulphate (APS). The mixture was heated to 60 °C for 16 h to yield a
suspension of CNFs. The suspension was centrifuged at 10,000 rpm for
10 min which resulted in the formation of a CNF pellet. This pellet was
repeatedly washed and centrifuged until it reached a pH of 4. It was
then sonicated to break-down any CNF agglomerates and neutralized
using a 1 M NaOH solution. Finally, the suspension was lyophilized to
yield a white powder. The TEM images of obtained cellulose nanofibers
are shown in Fig. 1. The obtained cellulose is in the form of nanofiber
rather than nanocrystal reported by Leung et al. [25].
2.2.2. Immobilization of epoxy monomer and amine curing agent on
cellulose nanofiber
0.1 g of cellulose nanofibers were added to epoxy (Epon 815C) and
the mixtures were incubated at room temperature (shaking for 24 h).
Similarly, 0.1 g of cellulose nanofibers in amine curing agent was in-
cubated at room temperature (shaking for 24 h). The incubated samples
centrifugated and washed with excess ethanol. The resulting cellulose
nanofibers were named as epoxy immobilized CNF (EiCNF) and amine
curing agent immobilized CNF (AiCNF).
2.2.3. Preparation of self-healing epoxy coating on carbon steel
Both EiCNF and AiCNF were dispersed in epoxy monomer (Epon
826) using ultra-sonication for 10 min. The obtained homogeneous
mixture was mixed with stoichiometric amount of curing agent
Fig. 1. TEM images of cellulose nanofibers.
128
Progress in Organic Coatings 112 (2017) 127–132
(100:10.9). The resulting mixture was coated on polished carbon steel
substrate and cured for 24 h at room temperature to get uniform
coating of approximately ∼300 μm thickness. The coating was named
as Epoxy/EiCNF/AiCNF. Steps involved are schematically shown in
Fig. 2.
2.3. Experimental techniques
Fourier transform infrared spectroscopic (FTIR) studies of the CNF,
EiCNF and AiCNF were carried out from 4000 to 600 cm−1 using the
FT-IR Frontier (PerkinElmer) instrument. The thermal stability of CNF,
EiCNF and AiCNF were analyzed using TGA Pyris 4000 from 30 °C to
800 °C at a heating rate of 10 °C/min. Benchtop scanning electron mi-
croscopy (JCM 6000, Jeol) was used to observe CNF with and without
immobilization of resin and curing agent. The accelerated salt immer-
sion test was carried out to determine the self-healing and corrosion
resistance of the coatings. Cross-scratches were made on the coating
surface using a scalpel. The prepared coatings were immersed in 10 wt
% salt solutions to observe the corrosion process in different time in-
tervals for two weeks.
3. Results and discussions
3.1. Scanning electron microscopy
Initially, the evidence of immobilization of epoxy monomer and
curing agent on CNF was obtained from morphological analysis. Fig. 3
shows the SEM images of cellulose nanofibers, EiCNF and AiCNF. The
CNFs appear to be aggregated while the surface is smooth (Fig. 3a). On
the other hand, the surface of EiCNF and AiCNF is covered with excess
material (Fig. 3b and c). This indicated that the CNF effectively im-
mobilized both epoxy and the curing agent on its surface.
3.2. Fourier transform infrared spectroscopic analysis
Infrared spectroscopic analysis was used to identify the nature and
mechanism of immobilization of both epoxy monomer and curing agent
on cellulose nanofibers. Initially, the interaction between amine curing
agent and cellulose nanofiber was investigated. Fig. 4 shows the FTIR
spectrum for CNF, amine and AiCNF. Cellulose nanofibers exhibited a
broad absorption band between 3500 and 3000 cm−1, which represents
OeH stretching vibration of the OH groups [26]. In AiCNF, this OeH
stretching remained unchanged indicating the absence of reaction with
amine groups. CeH stretching vibration of cellulose was observed
around 2900 cm−1 [27]. Bands at 1058 cm−1 and 898 cm−1, assigned
to CeO stretching and the glycosidic linkages were observed, both of
which are characteristic of the cellulose structure [28]. The presence of
carboxyl groups on CNF was confirmed by the presence of the
stretching vibration of C]O at 1730 cm−1 [25]. For AiCNF, new peaks
at 1560 cm−1 and 1640 cm−1 were observed which suggested the
formation of amides as a result of the reaction between C]O in CNF
with amine. The peak seen at 1560 cm−1 represents the NeH bend
found in primary amides, whereas the peak at 1640 cm−1 confirmed
the presence of C]O as a result of the amide linkage [29]. As suggested
previously [30], the formation of stable amide linkage between car-
boxylated CNF and amine can offer the storage of curing agent in CNF
for self-healing purpose. Moreover, the OeH band at 1430 cm−1 in CNF
shifted to a higher wavelength of 1480 cm−1 in amine immobilized
CNF suggesting that hydrogen bonds between carboxyl groups were
broken to form the amide linkage. The presence of sharper bands in
3300–3500 cm−1 region indicated the existence of unreacted amine
group in the curing agent. It is expected that the unreacted amine and
newly formed amide functionalities would be reactive for healing
process.
Similarly, Fig. 5a and b shows the FTIR spectrum for CNF, epoxy
monomer and EiCNF. The band in the region 3300–3500 cm−1 from the
P. Vijayan P et al. Progress in Organic Coatings 112 (2017) 127–132

Fig. 2. The steps involved in the preparation of self-healing epoxy coating.

Fig. 3. SEM images of (a) cellulose nanofiber (b) epoxy immobilized cellulose nanofibers and (c) amine immobilized cellulose nanofibers.

Fig. 4. FTIR for (a) cellulose nanofiber, amine immobilized cellulose na-
nofiber and diethylenetriamine curing agent.

eOH group in cellulose retained in epoxy immobilized cellulose na-
nofiber suggested the absence of chemical reaction between epoxy
monomer and cellulose nanofiber. The characteristics peaks in epoxy
such as 915 cm−1, 861 cm−1 (epoxide ring), 1509 cm−1 (Aromatic
C]C stretching) and 829 cm−1 (]CH, para substituted aromatic)
present in the epoxy immobilize CNF samples indicated the presence of
adsorbed epoxy monomer on the CNF surface. FTIR studies showed no
indication of chemical interaction between CNF and epoxy monomer,
concluding that the immobilization of epoxy monomer on CNF is purely
by physical interaction.

129
P. Vijayan P et al. Progress in Organic Coatings 112 (2017) 127–132

Fig. 5. FTIR for cellulose nanofiber, epoxy immobilized cellulose nanofiber and epoxy; (b) is the details of (a).

Fig. 6. (a) TGA and (b) DTA curves of cellulose nanofiber, epoxy, amine, epoxy immobilized cellulose nanofiber and amine immobilized cellulose nanofiber.

Fig. 7. Photographs of (a) epoxy coating and (b)

epoxy/EiCNF/AiCNF coating after 14 days of im-
mersion in 10 wt% NaCl solution.

3.3. Thermogravimetric analysis (TGA)
Fig. 6 shows TGA and DTA curves of neat cellulose nanofibers, pure
epoxy, AiCNF and EICNF. An initial weight loss in the region 25–100 °C
occurs for CNF, which is due to evaporation of loosely bound surface
water [30]. This initial weight loss due to water evaporation is also
visible in both EiCNF and AiCNF samples. In case of CNF, major de-
gradation occurred at around 250 °C, which is attributed to thermal
depolymerization of hemicellulose and cleavage of glycosidic linkages
[31]. The major degradation peak for EiCNF appeared around 280 °C,
which is in between that of pure epoxy (382 °C) and CNF (250 °C). This
degradation behavior of EiCNF clearly indicated strong physical ad-
sorption of epoxy monomer on cellulose surface which restricted the
mobility of the cellulose backbone. The major degradation peak for
amine is at 196 °C. At the same time, EiCNF showed multiple peaks.
Peak at 191 °C is due to the degradation of unreacted amine on the
surface of CNF. A duplet at 282 °C and 317 °C are due to the degrada-
tion of amide functionality on CNF and CNF backbone respectively.

130
P. Vijayan P et al.
Thermal stability of AiCNF is less when compared to EiCNF. At 150 °C,
the EiCNF lost 9.52% of its weight compared to 15.75% for AiCNF. At
350 °C, weight loss of 52.39% and 62.02% occurred for EiCNF and
AiCNF respectively. However, after 550 °C, both materials exhibited
similar thermal degradation.
3.4. Accelerated salt immersion test
The ability of EiCNF and AiCNF to assist the self-healing process in
epoxy coating was demonstrated by accelerated salt immersion test.
Fig. 7 shows the photographs of scratched control epoxy coating and
epoxy/AiCNF/EiCNF coating after immersing in 10 wt% NaCl solution
for 14 days. Corrosion took place along the scratch in the control epoxy
coating, whereas, in the epoxy/AiCNF/EiCNF coating the scratch was
absolutely free from corrosion due to the possible self-healing ability.
Moreover, penetration of water in between the coating and substrate is
evident in the control epoxy coating. On the other hand, the presence of
CNF in epoxy/AiCNF/EiCNF coating appeared to enhance the adhesion
between the coating and substrate and thereby prevented water pene-
tration, this improvement in adhesion is visible through the difference
in corrosion on each of the substrates. The self-healing process in
epoxy/EiCNF/AiCNF can be explained based on the mechanism pro-
posed by Yabuki et al. [16,17]. Once the coating is damaged, the cel-
lulose nanofibers present in the damaged site deform in the presence of
water and thereby release the epoxy monomer into the scratched area.
Thus released epoxy monomer reacts with eNH2 or amide group pre-
sent in the AiCNF to form an epoxy network to recover the scratch.
Fig. 8 illustrates the entire self-healing process in epoxy/EiCNF/AiCNF
coating. As the CNF deformed in the presence of water, the EiCNF lo-
cated near the scratch released epoxy monomer. The released epoxy
monomer reacts with nearby AiCNF. Since this self-healing mechanism
operates only in the presence of water, the present self-healing coating
cannot be used for outdoor metal structures.
4. Conclusion
Both epoxy monomer and amine curing agents were successfully
immobilized on the surface of cellulose nanofibers. FTIR studies re-
vealed that epoxy monomer physically adhered to the surface of CNF.
Meanwhile, amine curing agent established chemical reaction with CNF
to form active amide groups while leaving some unreacted amine
groups. Epoxy coating incorporated with both EiCNF and AiCNF
showed self-healing ability. EiCNF present in the damaged site de-
formed in the presence of water and thereby released epoxy monomer
into the scratch. The released epoxy monomer reacted with eNH2 or
amide groups present in the AiCNF to form an epoxy network to heal
the scratch.
131
Progress in Organic Coatings 112 (2017) 127–132
Fig. 8. Schematic digram showing the self-healing
mechanism in epoxy/EiCNF/AiCNF coating.
Acknowledgements
This paper was made possible by PDRA grant # PDRA1-1216-13014
from the Qatar National Research Fund (a member of Qatar
Foundation). The findings achieved herein are solely the responsibility
of the authors.
References
[1] A.B. Radwan, A.M. Mohamed, A.M. Abdullah, M.A. Al-Maadeed, Corrosion pro-
tection of electrospun PVDF-ZnO superhydrophobic coating, Surf. Coat. Technol.
289 (2016) 136–143.
[2] E.M. Fayyad, K.K. Sadasivuni, D. Ponnamma, M.A. Al-Maadeed, Oleic acid-grafted
chitosan/graphene oxide composite coating for corrosion protection of carbon steel,
Carbohydr. Polym. 151 (2016) 871–878.
[3] W.D. Yang, S. Meure, D. Solomon, Self-healing polymeric materials: a review of
recent developments, Prog. Polym. Sci. 33 (2008) 479–522.
[4] T.C. Mauldin, M.R. Kessler, Self-healing polymers and composites, Int. Mater. Rev.
55 (2013) 317–346.
[5] J.A. Syrett, C.R. Becer, D.M. Haddleton, Self-healing and self-mendable polymers,
Polym. Chem. 1 (2010) 978–987.
[6] E.M. Fayyad, M.A. AlMaadeed, A. Jones, A.M. Abdullah, Evaluation techniques for
the corrosion resistance of self-healing coatings, Int. J. Electrochem. Sci. 9 (2014)
4989–5011.
[7] B.J. Blaiszik, N.R. Sottos, S.R. White, Nanocapsules for self-healing materials,
Compos. Sci. Technol. 68 (2008) 978–986.
[8] B.J. Blaiszik, M.M. Caruso, D.A. McIlroy, J.S. Moore, S.R. White, N.R. Sottos,
Microcapsules filled with reactive solutions for self-healing materials, Polymer 50
(2009) 990–997.
[9] Y. Zhao, W. Zhang, L. Liao, S. Wang, W. Li, Self-healing coatings containing mi-
crocapsule, Appl. Surf. Sci. 258 (2012) 1915–1918.
[10] P.P. Vijayan, M.A. Al-Maadeed, TiO2 nanotubes and mesoporous silica as con-
tainers in self-healing epoxy coatings, Sci. Rep. 6 (2016).
[11] P.P. Vijayan, Y.M.H. El-Gawady, M.A. Al-Maadeed, Halloysite nanotube as multi-
functional component in epoxy protective coating, Ind. Eng. Chem. Res. 55 (2016)
11186–11192.
[12] E.V. Skorb, D. Fix, D.V. Andreeva, H. Möhwald, D.G. Shchukin, Surface-modified
mesoporous SiO2 containers for corrosion protection, Adv. Funct. Mater. 19 (2009)
2373–2379.
[13] S. Sinha-Ray, D.D. Pelot, Z.P. Zhou, A. Rahman, X.F. Wu, A.L. Yarin, Encapsulation
of self-healing materials by coelectrospinning emulsion electrospinning, solution
blowing and intercalation, J. Mater. Chem. 22 (2012) 9138–9146.
[14] X. Wu, A. Rahman, Z. Zhou, D.D. Pelot, S. Sinha-Ray, B. Chen, S. Payne, A.L. Yarin,
Electrospinning core-shell nanofibers for interfacial toughening and self-healing of
carbon-fiber/epoxy composites, J. Appl. Polym. Sci. 129 (2013) 1383–1393.
[15] M.L. Zheludkevich, J. Tedim, C.S.R. Freire, S.C.M. Fernandes, S. Kallip, A. Lisenkov,
A. Gandini, M.G.S. Ferreira, Self-healing protective coatings with “green” chitosan
based pre-layer reservoir of corrosion inhibitor, J. Mater. Chem. 21 (2011)
4805–4812.
[16] A. Yabuki, T. Shiraiwa, I.W. Fathona, pH-controlled self-healing polymer coatings
with cellulose nanofibers providing an effective release of corrosion inhibitor,
Corros. Sci. 103 (2016) 117–123.
[17] A. Yabuki, A. Kawashima, I.W. Fathona, Self-healing polymer coatings with cellu-
lose nanofibers served as pathways for the release of a corrosion inhibitor, Corros.
Sci. 85 (2014) 141–146.
[18] E. Sjöström, Wood Chemistry: Fundamentals and Applications, Academic Press, San
Diego, 1993.
[19] S. Kalia, A. Dufresne, B.M. Cherian, B.S. Kaith, L. Avérous, J. Njuguna,
E. Nassiopoulos, Cellulose-based bio- and nanocomposites: a review, Int. J. Polym.
Sci. 8 (2011) 1–35.
[20] K.-Y. Lee, Y. Aitomaki, K. Oksman, L.A. Berglund, A. Bismarck, On the use of na-
nocellulose as reinforcement in polymer matrix composites, Compos. Sci. Technol.
P. Vijayan P et al.
105 (2014) 15–27.
[21] C. Miao, W.Y. Hamad, Cellulose reinforced polymer composites and nanocompo-
sites: a critical review, Cellulose 20 (2013) 2221–2262.
[22] K. Deshmukh, M.B. Ahamed, R.R. Deshmukh, S.K.K. Pasha, K.K. Sadasivuni,
A.R. Polu, D. Ponnamma, M.A. Al-Maadeed, K. Chidambaram, Newly developed
biodegradable polymer nanocomposites of cellulose acetate and Al2O3 nano-
particles with enhanced dielectric performance for embedded passive applications,
J. Mater. Sci.: Mater. Electron. 28 (2017) 973–986.
[23] A.A. Issa, M.A. Al-Maadeed, A.S. Luyt, M. Mrlik, M.K. Hassan, Investigation of the
physico-mechanical properties of electrospun PVDF/cellulose (nano)fibers, J. Appl.
Polym. Sci. 133 (2016).
[24] X. Liu, H. Zhang, J. Wang, Z. Wang, S. Wang, Preparation of epoxy microcapsule
based self-healing coatings and their behavior, Surf. Coat. Technol. 206 (2012)
4976–4980.
[25] A.C.W. Leung, S. Hrapovic, E. Lam, Y. Liu, K.B. Male, K.A. Mahmoud, J.H.T. Luong,
Characteristics and properties of carboxylated cellulose nanocrystals prepared from
a novel one-step procedure, Small 7 (2011) 302–305.
132
Progress in Organic Coatings 112 (2017) 127–132
[26] A. Kaushik, M. Singh, Isolation and characterization of cellulose nanofibrils from
wheat straw using steam explosion coupled with high shear homogenization,
Carbohydr. Res. 346 (2011) 76–85.
[27] A. Mandal, D. Chakrabarty, Isolation of nanocellulose from waste sugarcane ba-
gasse (SCB) and its characterization, Carbohydr. Polym. 86 (2011) 1291–1299.
[28] R.C. Sun, J. Tomkinson, Y.X. Wang, B. Xiao, Physico-chemical and structural
characterization of hemicelluloses from wheat straw by alkaline peroxide extrac-
tion, Polymer 41 (2000) 2647–2656.
[29] A.P. Mangalam, J. Simonsen, A.S. Benight, Cellulose/DNA hybrid nanomaterials,
Biomacromolecules 10 (2009) 497–504.
[30] C. Borsoi, M.V.G. Zimmernnam, A.J. Zattera, R.M.C. Santana, C.A. Ferreira,
Thermal degradation behavior of cellulose nanofibers and nanowhiskers, J Therm.
Anal. Calorimetry: Int. Forum Therm. Stud. 126 (2016) 1867–1878.
[31] L.B. Manfredi, S.R. Exequiel, M.W. Przybylak, A. Vázquez, Thermal degradation and
fire resistance of unsaturated polyester, modified acrylic resins and their composites
with natural fibres, Polym. Degrad. Stab. 91 (2006) 255–261.