Industrial Crops and Products 76 (2015) 215229

Contents lists available at ScienceDirect

Industrial Crops and Products

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

Recent advances in vegetable oils based environment friendly

coatings: A review
Eram Sharmin a,b, , Fahmina Zafar a,c , Deewan Akram a,d , Manawwer Alam e ,
Sharif Ahmad a
a

Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia (A Central University), New Delhi 110 025, India
Department of Pharmaceutical Chemistry, College of Pharmacy, Umm Al-Qura University, Makkah Al-Mukarramah, PO Box 715, Postal Code: 21955,
Saudi Arabia
c
Inorganic Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia,New Delhi 110 025, India
d
Department of Chemistry, Faculty of Science, Jazan University, P.O. Box 2097, Jazan, Saudi Arabia
e
Research CentreCollege of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
b

a r t i c l e

i n f o

Article history:
Received 17 January 2015
Received in revised form 6 June 2015
Accepted 9 June 2015
Keywords:
Vegetable oils
Coatings
Environment friendly
High solids
Waterborne
Hyperbranched
UV curable

a b s t r a c t
The overarching goal worldwide for the scientic community is sustainable development today, for an
everlasting sustainable and green tomorrow. The strategy includes (i) harvesting renewable resources
instead of fossil fuels, (ii) using environment friendly routes, and (iii) engineering material degradation
pathways operating under reasonable time frames. The concept revolves around the focal point of Green
or Sustainable Chemistry. In the world of coatings, the idea has already made its debut in the form of
environment friendly technologies-low or no solvent, high solids, hyperbranched, water borne and UV
curable coatings, utilising monomers/polymers derived from renewable resources. Vegetable oils [VEGO]
constitute Mother Natures most abundant, cost-effective, non toxic, and biodegradable resource. They
have been traditionally used for several non-food applications mainly coatings since primitive times.
Today, the implementation of the modern technologies coupled with the full edged use of VEGO based
monomers or polymers in the eld as raw materials, is an excellent effort toward sustainable future
in the world of coatings globally. The review highlights some state-of-the art-modications of VEGO as
environment friendly-low or no solvent, high solids, hyperbranched, water borne and UV curable coatings.
The article provides a handy overall vision of VEGO based environment friendly coatings on a single
platform. These approaches can be well employed on those oils that are non-edible, non-medicinal and
are left unexplored, unutilised or underutilised to date, thus adding value to an unutilised or underutilised
sustainable resource.
2015 Elsevier B.V. All rights reserved.

Contents
1.
2.
3.
4.
5.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
VEGO and their chemical transformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
Low solvent or zero solvent coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
High solids [HS] coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
Hyperbranched [HYP] coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220

Abbreviations: BMF, butylated melamine formaldehyde; CasO, castor oil; DGEBA, diglycidyl epoxy of bisphenol A; DMPA, dimethylol propionic acid; DPE, dipentaerythritol;
FAD, fatty amide diol; HS, high solids; HYP, hyperbranched; HBPA, HYP polyamine; HPU, HYP polyurethane; LinO, linseed oil; MFO, Mesua ferrea oil; MG, monoglycerides; MMT,
montmorillonite; MWCNT, multiwalled carbon nanotubes; NC, nanocomposites; HEFA, N,N-bis(2-hydroxyethyl)fatty amide; PAA, poly(amido amine); PANI, polyaniline;
PCD, poly(-caprolactone) diol; PEsterA, polyesteramide; PU, polyurethanes; RSO, rubberseed oil; SoyO, soybean oil; SunFO, sunower oil; TDI, toluene-2,4-diisocyanate;
TO, tung oil; UV, ultra violet; VEGO, vegetable oils; VOC, volatile organic compounds; VOMM, VO macro-monomer; WB, waterborne; WPU, waterborne polyurethane.
Corresponding author at: Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia (A Central University), New Delhi 110025, India.
Fax: +91 11 26981717/Department of Pharmaceutical Chemistry, College of Pharmacy, Umm Al-Qura University, Makkah Al-Mukarramah, PO Box 715, Postal Code: 21955,
Saudi Arabia.
E-mail address: eramsharmin@gmail.com (E. Sharmin).
http://dx.doi.org/10.1016/j.indcrop.2015.06.022
0926-6690/ 2015 Elsevier B.V. All rights reserved.

216

6.
7.
8.

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

WB coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
Radiation curable coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
Future perspectives and summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
Appendix A.
Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227

1. Introduction
In the past two decades, research and development efforts have
undergone vast changes globally, due to the ever growing consumer expectations of good quality and performance coupled with
lower cost, escalating prices of petro-based chemicals due to the
fear of depleting stocks by the end of twenty rst century, concerns
related to energy consumption and environmental contamination
(improper waste management, greenhouse effect, health problems), regulations such as Clean Air Act Ammendment, 1990 and
rapid innovations. These challenges related to predictions, regulations and innovations have forced the coatings industry to change
its gears worldwide and resulted in the exploration and utilization
of sustainable alternatives to chemicals derived from petro-based
products (Lochab et al., 2014). The researchers in industry and
academia are actively engaged to explore and formulate new strategies to meet the mandatory limits through the tapping of our green
gold-the naturally available resources primarily:(i) to cut off the increasing raw material costs of the petro-based
products
(ii) to develop environmentally benign formulations
(iii) to expedite their post-service degradation
(iv) to add value to an otherwise waste material
As a consequence, some environmentally friendly or green
technologies have evolved, with special emphasis being laid on the
excessive utilization of renewable resources such as vegetable oils
[VEGO] and also reducing or eliminating the use of volatile organic
compounds [VOC]. Considering the vast amount spent on corrosion and its mitigation programs worldwide, we understand that
the proper utilization of our domestically abundant sustainable
resources such as VEGO thriving on our acres of agricultural lands
may prove as silver lining, in this regard (Balachandran et al., 2013;
Miller, 2014). This review article describes the recent advances
in the modications and applications of VEGO as environment
friendly protective coatings, role of VEGO based components in
governing the properties of these coatings, and further encourages
the application of these approaches on non-edible and nonmedicinal VEGO, adding value to a waste or unutilized sustainable
resource.
2. VEGO and their chemical transformations
VEGO constitute a broad class of sustainable resources rendering a plethora of value added functional materials. They comprise
one of the most important components of biomass. They are triesters of glycerol and fatty acids (saturated and unsaturated).
VEGO mainly consist of triglycerides as major (9398 wt%) and
diglycerides, monoglycerides and phosphoglycerides as minor
components. VEGO and their derivatives nd applications in coatings owing to their unique structural attributes and tendency to
form lms (depending upon their unsaturated portion). Considering their degree of unsaturation, described by their iodine value,
VEGO are classied as drying (iodine value > 130), semi-drying
(100 < iodine value < 130) and non-drying (iodine value < 100)as
in linseed oil [LinO], soybean oil [SoyO] and palm kernel oil,

respectively (Alam et al., 2014; Xia and Larock, 2010). Usually, drying or semi-drying oils are used in surface coatings. Non-drying
oils may also be utilized for the purpose by the incorporation
of suitable entities (e.g., hydroxyls) or modiers (vinyls, acrylics,
acrylic co-polymers) in oil backbone, through chemical reactions
to transform them as lm formers. In virgin oils, longer drying
times are required while the lms formed do not meet the desirable physico-mechanical and corrosion resistance performance.
Consequently, several chemical transformations are carried out
through the important functionalities and active sites of VEGO
such as hydroxyls, oxiranes, double bonds, allylic carbons, esters,
alpha carbon to the ester group and others. About 90% reactions
occur at carboxyl functionality while the rest involve unsaturation sites (Gunstone, 2001). Some of them have been exemplied
in Fig. 1. VEGO undergo glycerolysis reaction resulting in the formation of monoglycerides or diglycerides that are used as raw
materials in the production of alkyds. Amidation (base catalysed)
is carried out at carboxyl functionality, producing fatty amide
diols/polyols that serve as starting material for the development
of polyesteramides [PEsterA] and polyetheramides. Another much
explored important reaction is transesterication reaction also
occurring at carboxyl functionality. Epoxidation and hydroxylation
reactions occurring at double bonds of VEGO produce epoxies and
poyols, respectively. The former render strong thermosets when
cured by suitable curing agents such as amines, acids, amides,
while the latter yield polyester and polyurethane [PU] coatings
on treatment with acid/anhydride or isocyanates. Maleinization,
acrylation, vinylation, hydrohalogenation are few other examples
involving reactions at double bonds of VEGO (Ahmad et al., 2004;
Lligadas et al., 2013; Maisonneuve et al., 2013; Miao et al., 2014;
Montero de Espinosa and Meier, 2011; Mosiewicki and Aranguren,
2013).
The coatings obtained from fossil fuel derived petro-based
chemicals such as vinyls, acrylics, epoxies, PU, polyesters and
others, are often (i) costly, (ii) toxic, (iii) hazardous after use (nonbiodegradable), and (iv) may require ample of hazardous solvents
during processing and coating applications, thus causing environmental contamination and health hazards on exposure. VEGO
derivatives are generally devoid of these drawbacks bearing advantages of cost effectiveness, non-toxicity, biodegradability, requiring
no or low solvents due to their inherent uidity characteristic.
VEGO coatings are available for specic uses as antimicrobial,
biocompatible, biodegradable, corrosion protective, architectural,
decorative, electrical insulating, paper packaging, and self-healing
coatings. However, due to long aliphatic hydrophoebic chains, they
are often low on mechanical strength, lack toughness and are water
insoluble (Bordes et al., 2009; Lligadas et al., 2010). Thus to further augment the performance of VEGO coatings, and to compete
with their petro-based counterparts, several innovative and stateof-the-art modications have been accomplished in the eld.
3. Low solvent or zero solvent coatings
VEGO chains are exible due to the the presence of long aliphatic
fatty acid chains. VEGO derivatives generally serve as solvents or
reactive diluents in coatings, often in combination with commercial
resins, and themselves participate in chemical reactions occurring

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

217

Fig. 1. Chemical reactions of VEGO.

during drying or curing or crosslinking reactions forming inherent

part of the nal material (Ahmad et al., 2011; Czub, 2006; Das and
Karak, 2009; Ghosal et al., 2013; Muturi et al., 1994; Sharmin et al.,
2011, 2010).
The research is focused on the development of VEGO based coatings using zero solvent or low solvent approach. This means
during synthesis and coating formulation, either completely eliminating the use of solvent or introducing only minimum amount
of solvent for dilution, to offset the effect of high viscosity often
achieved in due course of chemical reactions, as a result of increase
in crosslinking and viscosity, which restricts the free mobility of
polymer chains, during polymerisation.
Ahmad et al. and Zafar et al., prepared solventless PEsterA and
metal containing PEsterA from Linum ussiatatissimum or Linseed Oil
[LinO], taking advantage of inherent uidity of VEGO chains (Fig. 2).
The synthesis of PEsterA is generally accomplished by chemical
reaction between N,N-bis(2-hydroxyethyl) fatty amide (obtained
by base catalysed amidation of VEGO) and phthalic anhydride or
phthalic acid as raw materials, in presence of on organic solvent
(e.g., xylene). However, during synthesis of PEsterA under solvent
free conditions, self catalysed direct esterication reaction takes
place at temperature lower than the melting points of both the
monomers used as raw materials, owing to (i) good uidity of N,Nbis(2-hydroxyethyl) fatty amide in which phthalic anhydride is
dissolved, and (ii) solvent free condition allowing better proximity
of the reactants with each other facilitating the reaction to occur
at relatively lower temperature (Ahmad et al., 2007; Zafar et al.,
2011). In solvent free synthesis of metal [Zn (II), Mn (II), Co (II), Cu
(II)] containing PEsterA, the mechanism involved (self catalysed)
additionelimination mechanism at the carbonyl double bond of
the carboxylic acid group of PEsterA chain. The presence and content of metal also governed the synthesis reaction time due to the
catalytic effect of the metal itself. The results obtained were based

on the extent of occupancy of d orbitals of the metals. Co (II) and Cu

(II) containing PEsterA were prepared in lower reaction time due to
their partially lled d orbitals (d7 and d9 ) which conferred higher
reactivity as compared to Mn(II) having half lled (d5 ) d orbitals,
associated with higher stability and lower reactivity. Similar results
were also observed in drying times/curing behavior of coatings.
PEsterA containing Co (II) and Cu (II) metals (with higher number of
unlled d orbitals) were cured faster compared to Mn (II) containing
PEsterA (half lled d orbitals) due to higher reactivity of the former.
The curing behavior in metal containing solvent free PEsterA was
a result of cross-linking of polymeric chains through coordination
of metals with donor groups of the polymer such as oxygen, nitrogen and double bond, contrary to the curing mechanism of plain
VEGO based PEsterA which involves slow lipid autoxidation process that further requires driers to accelerate the curing process
(Ahmad et al., 2007; Zafar et al., 2007, 2011). Akram et al. (2008,
2010a,b) developed LinO and castor oil [CasO] based boron containing PU coatings for corrosion protection using minimum amount of
solvent (used in the second step of reaction, i.e., PU formation, only
to offset the effect of high viscosity and complexity of the inherent
PU structures) with good physico-mechanical and chemical resistance against alkali, acid, tap water and xylene, and also thermal
stability upto 220 C.
Karak and Das prepared nanocomposite blends of Mesua ferrea oil [MFO] based epoxy and commercial epoxy with nanoclay
as modier cured with poly(amido amine) hardener for use
as coatings. The combination produced miscible system with
good compatibility of either matrix. The hardener simultaneously
reacted with oxirane rings present in either epoxy resin, allowing
for better compatibility of the two matrices, and proper interaction of nanoclay. The cumulative effect of commercial and VEGO
epoxies, respectively, as well as nanoclay, can be observed in
the improved scratch hardness, impact resistance, exibility and

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E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

Fig. 2. Synthesis of PEsterA from VEGO (in the absence and presence of solvent).

adhesion of the nanocomposite coatings (Das and Karak, 2009).

It can be seen that MFO epoxy served as the binder, diluent and
also modier to offset the brittleness (drawback) of commercial
epoxy, owing to its long (exible) aliphatic alkyl chains rendering toughness. Thus, MFO based epoxy acted as an ingredient as
well as reactive diluent in nanocomposite preparation. Sharmin
and coworkers described the in situ preparation of LinO based
polyol nanocomposite as a raw material for polyester and PU
coatings, with LinO polyol as organic matrix and metal acetate
as inorganic precursor by facile solventless, one-pot chemical
reaction (Sharmin et al., 2013). LinO polyol is formed by the
hydroxylation reaction of LinO; it bears hydroxyl groups chemically
inserted (via epoxidation followed by hydroxylation) at unsaturation sites of LinO (Sharmin et al., 2007). Thus, LinO based
polyol not only served the purpose of solvent due to its inherent uidity characteristic, but also as matrix providing functional
groups for the chemical reaction), and also as stabilizer (prevent-

ing agglomeration of nanoparticles) for the preparation of metal

oxide nanoparticles from metal acetate and hydroxyls of LinO
polyol, resulting in the formation of nano-sized metal oxide particles producing nanocomposite (Sharmin et al., 2015, 2013). In situ
preparation of SiO2 nanoparticles was carried out in polyol matrix
using tetraethoxyorthosilane as inorganic precursor and CasO and
LinO based polyols as organic matrices, respectively, by zero solvent approach (Akram et al., 2010a,b; Sharmin et al., 2011). The
prepared coatings were scratch resistant, impact resistant, glossy
and exibility retentive (Akram et al., 2008, 2010a,b; Sharmin et al.,
2011).
4. High solids [HS] coatings
The drive towards HS coatings is initiated and fostered by
environmental regulations. Epoxy, alkyd and PU based coatings
are currently representing the major part of HS coatings in the

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

219

Fig. 3. VEGO based HYP polyester.

protective coatings market. Paints with more than 80% solids

content by volume are generally referred to as HS paints; those
with 6070% solids content can also be called HS paints. These systems contain a higher percentage of solids paints and lower solvent
content than conventional solvent-borne coatings (Chattha and van
Oene, 1982; Haseebuddin et al., 2009). Efforts are also being made
to develop 100% solids PU and PU urea coatings.
HS coatings have lower solvent emissions as well as other technical benets besides bearing closer resemblance to conventional
systems with improved performance and durability, making them
readily acceptable in applications. In HS coatings, narrow molecular weight distribution is attained to lower solution viscosity with
a more homogeneously cross-linked network (Lindeboom, 1997).

The lowering of viscosity can be achieved by increasing oil chain

length (of binder) that lowers the molecular weight and also introduces more unsaturation content (due to C C of oil). However, an
adverse consequence of lowering the molecular weight and viscosity of HS coatings is poor stabilization properties and drying
behavior of coatings (Zabel et al., 1999). To overcome this problem, conventional solvents in HS coatings are partially replaced by
reactive diluents that function as diluents during the formulation
of coatings and during curing, form an integral part of the coating.
Often driers are used to promote drying in thick lms (Bhabhe and
Athawale, 1997; Das and Karak, 2009; Lindeboom, 1997).
HS alkyds from Glycine max or SoyO and dehydrated
CasO fatty acid combinations with varying percentage of

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E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

dipentaerythritol [DPE] (as multi-functional polyol to introduce

branching) have been synthesized with 80% solids in mineral turpentine oil and characterized for their physicochemical, optical,
thermal and mechanical properties. The increased DPE content
introduced good branching, cross linking, and increased the corrosion protection performance, improved gloss and thermal stability
of the alkyd coating (Haseebuddin et al., 2009).
Air drying HS alkyd paints provide environmental as well as economical benets (Lindeboom, 1997). Alkydacrylic hybrids having
nal solids content of 7580% were prepared by dropping alkyd
resin into an acrylic dispersion (Jowkar-Deriss and Karlsson, 2004).
Different liquid structures were produced depending on the mode
of addition of the surfactant to the system. To improve upon the
drying characteristics of HS alkyd paints, thiolene reaction was
carried out, which can assist their oxidative drying. Fast drying HS
alkyd paints were thus obtained by using visible light photoinitiators and/or cobalt free metal catalysts (Klaasen and van der Leeuw,
2006).
VEGO polyols have relatively high molecular mobility, contain
pendant dangling chains, which lead to relatively low glass transition temperatures (Tg) and a low modulus. Kong and coworkers
produced polyols, Liprols, by epoxidation/hydroxylation of VEGO
(Canola, Helianthus annuus L. or Sunower oil [SunFO], Camelina,
Linola 2090 ax and NuLin 50 ax crude oils) followed by transesterication reactions of the glycerides with diols (1,2 propane
diol and 1,3 propane diol). Such polyols on treatment with an
isocyanate produced PU coatings which were HS in nature. Such
coatings showed good adhesion due to chemical interaction and
mechanical interlocking at the interface. Also, few pendant chains,
low molecular weight and high functionality are another important
factors contributing to good performance of these coatings. The solvent free approach also improved hydrophobicity of coatings by
increasing of cross-linking density (Kong et al., 2013).
A good HS coating material should have acceptably low viscosity without compromising on performance characteristics of the
material. This is achieved by the use of reactive diluents, increasing oil chain length, and narrower molecular weight distribution.
A diluent decreases the viscosity of the material and eventually
becomes an integral part of the coating after drying (since it
participates in drying reactions). The lowering of molecular weight
is achieved by increasing of fatty acids contents or increasing the
ratio of OH/COOH groups. However, a homogenous network cannot
be formed and overall coating properties are deteriorated. Increasing oil chain length often results in loose packing of molecules (due
to unsaturation). Low molecular weight resins often exhibit slow
drying and sagging. So, to overcome these drawbacks, along with
the reduction of molecular weights in the resins, a simultaneous
increase in molecular branching was performed; it was preferred
to obtain resins with well-dened highly branched structure.
5. Hyperbranched [HYP] coatings
The dendritic polymersdendrimers, HYP polymers and dendrigrafts are preferred over HS resins. The dendrimers involve
isolation and purication steps and are costly relative to HYP
polymers, which combine lower manufacturing costs and single step polymerization. The principal concept of HYP polymers
reports back to the works of Flory and Kienle past several decades,
which later on graduated to more elaborated building blocks (van
Benthem, 2000).
Star and HYP polymers show improved drying and performance
characteristics over HS alkyds; these are synthesized in single step
and are less costly than their other counterparts. The low viscosities
of the nal product allow for easier lm formation and the low VOC
content attribute to the environment friendliness (Bat et al., 2006;

and Szewczyk, 2002).

Lindeboom, 1997; Manczyk

HYP polymers have many advantages over their linear analogs.

HYP polymers have higher solubility, lower hydrodynamic diameter and lower melt as well as solution viscosity, and high
reactivity compared to their linear counterparts owing to their
compact, non-entangled and highly branched structures with
large numbers of active functional groups on the periphery
(Deka and Karak, 2009a,b). Due to their highly functionalized
three-dimensional globular non-entangled inimitable architectural
features and unique properties coupled with their single-step
preparative techniques, these macromolecules are considered as
advanced polymeric materials. Chattopadhyay and Raju (2007)
have described the structures and properties of HYP polyols,
polyesters, PU, and others. Bat and coworkers prepared HYP
polyester using DPE as core molecule and dimethylol propionic
acid [DMPA] twice, as chain extender, to obtain HYP derivative
with peripheral hydroxyl groups. The latter was further reacted
with CasO fatty acid, LinO fatty acid and benzoic acid, to obtain
HYP of second, third and fourth generation (Fig. 3). VEGO content
provided reduced viscosity and increased hardness to the coatings, which showed good abrasion resistance, adherence to the
substrate, excellent gloss and exibility (Bat et al., 2006). Radiation curable material was synthesized by Samuelsson et al. (2004),
from a hydroxy functional HYP polyether onto which an epoxy
functional fatty acid, vernolic acid, was attached, polymerized with
vernolic acid methyl ester as reactive diluents; the results were
compared with a model oil based trimethylol propane [TMP] lms
(structurally similar but with no polyether core), which showed
lower Tg value and softness after polymerization. In another
publication by Karakaya et al. (2007) DPE (core molecule) was
transesteried with CasO and a mixture of CasO and LinO and
esteried with DMPA. The obtained HYP resin was treated with
melamine formaldehyde; the coatings prepared therefrom showed
excellent adhesion, gloss, exibility, impact and abrasion resistance.
Urethane acrylates with different degrees of acrylation were
obtained by the reaction of partially modied HYP polyesters and
different amounts of acrylate-isocyanate adduct from equimolar
amounts of isophorone diisocyanate and 2-hydroxyethyl acrylate.
Here, HYP of the second and the third pseudo-generation were
synthesized from DMPA and TMP; the modication of the OH endgroups was carried out with isononanoic acid and SoyO fatty acids
in separate reports by Dzunuzovic et al. (2006). Tall oil fatty acids
based HYP alkyd resin prepared from fourth generation hydroxylated HYP polyester through acid catalysis exhibited excellent
adhesion, exibility, drying time, gloss and chemical resistance
(Murillo et al., 2010, 2011).
In a recent work, the drawbacks of epoxy resins such as brittleness or low toughness and nonbiodegradability were overcome
by preparing a HYP epoxy from CasO modied HYP polyester
polyol and in situ-generated diglycidyl ether of bisphenol A
[DGEBA]. Here, biodegradation and exibility were conferred by
the VEGO chains. HYP structure as well as the aromatic (epoxy) and
aliphatic (VEGO chains) constituents collectively imparted good
toughness to the coatings, increasing the free volume between
molecules (due to steric effect) in the three-dimensional network
(De et al., 2014). Hyperbranched polyurethane [HPU], polyester,
alkyd and hyperbranched polyesteramide [HPEsterA] coatings
were produced from MFO, CasO, and SunFO. A VEGO derivative as biobased chain extender is treated with another chain
extender, isocyanate and a multi-functional amine by A2 + B3
approach (Fig. 4; Kalita and Karak, 2014). The produced materials
showed good thermostability, ame retardancy, hardness, chemical resistance, higher tensile strength, impact resistance, scratch
hardness, exibility retention than their linear counterpart owing
to the stronger intra- and intermolecular secondary interactions,
hydrogen bonding, chain entanglements and compact conned

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

221

Fig. 4. Synthesis of VEGO based HPU.

[Reprinted (adapted) with permission from Kalita and Karak (2014). Biobased hyperbranched shape-memory polyurethanes: effect of different vegetable oils. J. Appl. Polym.
Sci. 131, 3957939586.]. Copyright 2013. John Wiley and Sons.

geometry, collectively. Good exibility retention was offered by

the fatty chains of the parent VEGO, within the highly branched
structure and the presence of larger void spaces which offer easier movement of chains in HYP material relative to the linear
counterpart (Bao et al., 2013; Das et al., 2013; Deka and Karak,
2009a,b; Karak et al., 2009; Konwar and Karak, 2009; Mahapatra
and Karak, 2007; Pramanik et al., 2013a,b,c; Rana et al., 2013;
Kalita and Karak, 2014). SunFO based HPU were prepared by Das
et al. (2013) by following A2 + B2 + B4 approach. SunFO based MG,
PCD, and butanediol were treated with TDI such that hydroxyl
terminated prepolymer (A2 ) was formed. In the next step this prepolymer or diol was treated with pentaerythritol (B4 ) and TDI
to produce HPU. Similarly, a linear PU analog was also prepared
by the addition of BD in place of PE. HPU showed higher tensile
strength, impact resistance, scratch hardness, exibility retention
than its linear counterpart owing to the stronger intra- and intermolecular secondary interactions, hydrogen bonding, chain entanglements and compact conned geometry of HPU, collectively

Good exibility retention was offered by PC component and

MG chains of SunFO within the highly branched structure and
the presence of larger void spaces which offer easier movement of chains in HPU relative to the linear PU (Das et al.,
2013).
Nanocomposites [NC] of VEGO based HYP polymers have been
prepared for some advanced applications demanding high mechanical strength, good adhesion, chemical resistance, thermostability,
low water vapor permeability and others, with different nanoreinforcements such as Octadecylamine-modied montmorillonite
clay (MMT) nanoclay, silver nanoparticles, Multiwalled Carbon
nanotubes (MWCNT), polyaniline [PANI] nano bres, Functionalised reduced graphene oxide (f-RGO), and others. It can be well
interpreted that the properties of HYP depend upon the type of
VEGO as parent precursor, chain extender, isocyanate, and the type
of nano-reinforcement employed. HYP are much sought after materials for surface coating applications due to their unique properties
and reduced viscosity (Table 1 and Fig. 5 ).

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E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

Table 1
Environment friendly nanocomposite coatings from VEGO.
S.No.

Type

Modiers

Properties

References

1.

HPU from MFO

MMT nanoclay

Deka and Karak (2010, 2011)

De and Karak (2014) De et al.
(2014)

2.

HPU from MFO

Silver nanoparticles and clay

3.

HPEsterA from CasO (Fig. 5)

MWCNT

4.

HPEsterA from CasO

PANI nano bres

5.

HPU from CasO

f-RGO

6.

WPU from CasO:

Organoclay

7.

WPEsterA from LinO

MMT nanoclay

8.

UV curable Acrylated LinO

TiO2 nanoparticles

Light weight, transparency,

exibility characteristic, good
tensile strength, scratch
hardness, impact resistance,
low water vapor loss, higher
thermal stability
Good thermal stability and
mechanical properties, long
dispersion stability, small
particle size, narrow size
distribution along with good
antimicrobial efcacy against
E. coli, S. aureus, P. aeruginosa
and C. albicans producing
antimicrobial coatings
Improved tensile strength,
shape memory, enhanced
biodegradability, and no
cytotoxicity; with good
antimicrobial efcacy against S.
aureus and B. subtilis
Mechanically strong, thermally
stable, antistatic materials due
to the interfacial interaction of
PANI nanobers with the HYP
PEA matrix
Improved tensile strength and
toughness, good thermal
stability and electrical
conductivity
Enhanced mechanical and
thermal performance due to
strong interfacial interactions
between ller and matrix
Improved scratch hardness,
impact resistance, exibility,
chemical resistance (in acid,
alkali, salt and water, and
thermal stability)
Improved hardness, impact
resistance, glass transition
temperature, thermal stability,
and bactericidal effect against
S. aureus and E. coli

6. WB coatings
The term WB is applied to those coating systems that primarily use water as the solvent or sometimes upto 80% water
with small amount of other solvents such as glycol ethers.
They are classied as: watersoluble/waterreducible (solutions),
waterdispersible/colloidal (dispersions) and emulsions (latex)
paints. The physical properties and performances of each type
mentioned above depend upon the choice of the resin. Generally,
hydrophilic groups are inserted in oil chains that yield the polymer water dispersible. The polymer derivatives commonly used
are vinyls, two-component acrylics, epoxies, polyesters, styrenebutadiene, amine-solubilized, carboxyl-terminated alkyd and PU.
Interest in WB materials arises due to their non-polluting, easy
to handle, quick drying, economic and environmentally friendly
nature (Athawale and Nimbalkar, 2011; Dara et al., 2009; Gndz
et al., 2002, 2004; Shah and Ahmad, 2012). The synthesis of WB
coatings is a challenging task due to hydrophoebic nature of VEGO
triglyceride chains.
WB alkyds based on non or semi-drying VEGO generally do not
show good drying tendency at room temperature. Consequently,
driers are added to achieve drying of coatings. However, in most
of the cases, proper drying and good performance is achieved only
by baking the coatings at elevated temperatures. Aigbodion et al.

Deka et al. (2010a) Karak et al.

(2010) Konwar et al. (2010)

Deka et al. (2010b) Pramanik

et al. (2013a,b,c) (Fig. 5)

Pramanik et al. (2014,

2013a,b,c)

Thakur and Karak (2014b,a)

Gurunathan et al. (2015)

Zafar et al. (2015)

Diez-Pascual and Diez-Vicente,

(2015)

have synthesized WB alkyds based on Rubberseed oil [RSO] for

coating applications (Aigbodion et al., 2003a,b; Aigbodion and
Pillai, 2001). RSO was rst maleinated or fumarized and then
treated with glycerol to yield its monoglyceride derivative; the latter was chemically reacted with phthalic anhydride and the acid
functionalities of the nal product were neutralised with amine.
The modied alkyd resins had lower VOC than their corresponding
virgin counterparts. They showed good water, brine and acid resistance while fair alkali resistance attributed to the presence of ester
linkages. Heated RSO and alkyd resins were evaluated as binders in
air drying solvent and WB coatings.
WB alkyds are more chemical resistant than their solvent-borne
counterparts (Aigbodion and Pillai, 2000). To further improve the
performance of WB alkyds, Saravari et al. prepared alkyds from
monoglycerides derived from interesteried product of palm and
tung oil [TO], along with carboxyl functionalized acrylic copolymers (butyl methacrylate and maleic anhydride) in place of di- or
polybasic acids; the unreacted carboxyl groups could be neutralized
by a base to give water reducible alkyds. Films were obtained by
baking at 190 C; these showed good water, acid and alkali resistance (Saravari et al., 2005). In some instances, proper air-dried
lms could not be obtained, thus, driers were added and lms
with good exibility, adhesion, impact strength, water, acid and
alkali resistance were obtained by baking at elevated temperatures

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

223

Fig. 5. Synthesis of FAD-MWCNT.

[Reprinted (adapted) with permission from Pramanik et al. (2013). Biofunctionalized multiwalled carbon nanotube: a reactive component for the in situ polymerization of
hyperbranched poly(ester amide) and its biophysico interfacial properties. J. Phys. Chem. C. 117, 2509725107.]. Copyright 2013. American Chemical Society

(Aigbodion et al., 2003a,b; Aigbodion and Pillai, 2000, 2001; Wu

et al., 2004).
In another example by Kamani and research group, maleinated
Rice bran oil fatty acids were used for curing of DGEBA epoxy
in presence of co-solvents and additives. These could be utilized
for varnishes suitable for electrophoretic deposition and dipping
(Shikha et al., 2003). An excellent review has appeared on VEGO
based WB coatings by Nimbalakar and Athawale wherein the
authors provided a brief overview of WB alkyds, alkyd emulsions,
WB urethanes and hybrid dispersions (Athawale and Nimbalkar,
2011). Water reducible Canola oil alkyd has shown better thermal,
chemical and coating properties relative to its pristine counterpart (Nimbalkar and Athawale, 2010). Pathan and Ahmad (2013a,b)
recently prepared WB alkyd from SoyO and CasO. They followed
traditional method of glycerolysis of SoyO and CasO, forming
MG, followed by esterication of MG with phthalic acid producing alkyd resin, and simultaneously treatment of SoyO and
CasO alkyd with triethylamine, rendering WB alkyd. It was further
treated with butylated melamine formaldehyde [BMF], which acted
both as crosslinker and modier because curing with BMF led to
simultaneous inclusion of s-triazine ring into WB alkyd backbone
(Fig. 6). The latter drastically improved the corrosion resistance
behaviour of modied alkyd coatings. The coatings showed good

hydrophobicity as investigated by contact angle measurements

(contact angle values ranging from 8395 ). The coatings also

showed good scratch hardness, impact resistance and exibility
retention characteristic because of good crosslinking of chains,
excellent adhesion with the substrate and hardness conferred
by the s-triazine ring. The latter also improved the antibacterial behaviour of WB alkyd relative to plain alkyd against both
Staphylococcus aureus and Escherichia coli, though slightly better against S. aureus because in the latter the polyglycogen outer
layer is sufciently loosely packed and allows for the deep penetration of the polymer, while the cell wall of Gram negative
bacteria is surrounded by an additional outer membrane with a
bilayer phospholipids structure, which offers a supplementary barrier and obstructs the penetration of a wide range of antimicrobial
agents into the cell. They also investigated the corrosion resistance
behavior of VEGO based WB alkyd by potentiodynamic polarisation and electrochemical measurements techniques for the rst
time. The mechanism of corrosion protection involved the formation of highly crosslinked hydrophobic surface which repelled
the corrosive media and prevented corrosion of the underlying
substrate. The polar groups of WB alkyd oriented towards the
substrate promoted adhesion and also facilitated the protection
phenomenon.

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E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

Fig. 6. VEGO based waterborne alkyd.

New chlorinated rapeseed oil polyol based waterborne

polyurethane [WPU] was synthesized and used to modify glycerol plasticized starch lms. Plasticized starch was miscible with
WPU only below 20 wt% of WPU, attributed to the intermolecular
hydrogen bonding interactions between starch and WPU. The lms
formed were biodegradable with improved physical properties (Lu
et al., 2005). In a report by Mohamed et al. (2001) epoxidized SoyO
was treated with methyl amine; the formed adduct was characterized by FTIR analysis, further emulsied and added to different
emulsion paint formulations using styrene/acrylic copolymer as
binder for emulsion paint. The role of soy epoxy-methyl amine
adduct as corrosion inhibitor for carbon steel was also investigated and compared with the results obtained with lead chromate.

It was found that paint containing 0.5% of methylamine adduct

provided better protection to carbon steel than those containing
25% of lead chromate with good exibility and chemical resistance
(Mohamed et al., 2001). In another report, Aglan et al. used the same
inhibitor with different binders, i.e., Styrene [ST]/acrylic copolymer
and water soluble alkyd resin and also investigated their corrosion
inhibition mechanism (Badran et al., 2002). All the systems showed
good adhesion, hardness, ductility, acid and alkali resistance. ST/
acrylic copolymer lms showed lower water uptake values than
alkyds. These paints were free from any heavy metal or VOC.
Polymeric dispersants have been prepared from CasO fatty acids
for WB paint applications (Dara et al., 2009). In another publication,
SoyO was treated with phosphoric acid, hydrolysed, neutralized

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

with organic base to obtain aqueous dispersions. The phosphorylated polyols obtained were used as a component in WB coatings
with superior corrosion resistance performance (Guo et al., 2006).
WPU and waterborne polyesteramide [WPEsterA] are prepared
with VEGO based diol/polyol, chain extenders such as dimethylol
propionic acid, N-methyl diethanolamine, a diisocyanate, phthalic
anhydride, and an amine for further neutralization (Gurunathan
et al., 2015; Ren et al., 2015; Zafar et al., 2015). WPU coatings have
shown good storage ability, low cost, and potential biodegradability
(Ni et al., 2010). Another approach involve macro or miniemulsion
polymerization of acrylic monomers in presence of VEGO polymers (Hu et al. 2015; Lu and Larock, 2007, 2008, 2010; Wang and
Jones, 2000; Akbarinezhad et al., 2009; Quintero et al., 2006). To
further improve the performance WB nanocomposites have also
been developed (Table 1).

7. Radiation curable coatings

Conventional thermoset coating formulations are generally
cured through thermal crosslinking and polymerization processes,
often in presence of catalysts (to initiate curing reactions), and solvents or water. Radiation curable coating formulations are free of
solvents or water; curing is initiated by a catalyst or photoinitiator by irradiation with ultra violet [UV] or visible light. They
require low curing energy, show high curing efciency and are
ecologically compliant as no VOC or water are required for such
formulations. The process involved is considered clean and green
UV curing technology is applicable at ambient temperature, thus,
it can be applied to thermally sensitive molecules. The photopolymerisation can be accomplished by polyaddition of double bonds
under radical or cationic initiation or by cycloaddition of photosensitive molecules or chromophores (Fig. 7) (Fertier et al., 2013).
Typical raw materials used in UV curing are (i) oligomers (e.g.,
acrylates, unsaturated polyesters), (ii) monomers (reactive diluents), (iii) photoinitiators, and (iv) additives. Acrylated oligomers
are generally used in UV-cure coatings owing to their relatively
higher reactivity and lower volatility. Styrene due to its volatility is
replaced with higher molecular weight and functionality reactive
diluents to increase reactivity, line speed, and mechanical properties. Acrylated resins such as epoxy acrylates, polyether acrylates,
urethane acrylates, polyester acrylates, and silicone acrylates are
generally preferred over methacrylated ones due to higher cure
rates and lower oxygen inhibition. An optimum composition of
coating material as well as UV curing time is required to obtain
coatings of desirable performance, e.g., good adhesion, scratch
resistance, impact resistance, abrasion resistance, exibility, optical transparency, and others (Chen et al., 2010; Fertier et al., 2013;
Gianni et al., 2009; Han et al., 2007; Nebioglu and Soucek, 2007;
Rengasamy and Mannari, 2014; Smitha et al., 2013; Wan Rosli et al.,
2003; Wouters et al., 2004).
One of the most important VEGO derivative used for UV curable coatings are epoxies, both naturally available such as in oils
of Vernonia galamensis, Euphorbia lagascae, and chemically synthesized from various oils, e.g., LinO, SoyO, palm and other oils
(Zovi et al., 2011). VEGO derivatives such as CasO, Lesquerella
and Vernonia oil macromonomers have been used in radiation
curable architectural coatings, which were glossy, hard and welladherent to substrates (Kolot and Grinberg, 2004; Soucek et al.,
2004; Thames and Yu, 1999; Thames et al., 1996). VEGO epoxies
cure by cationic polymerization in presence of suitable photoinitiators as reported by Crivello and Thames et al. The coatings obtained
possess good adhesion, impact resistance, UV stability, gloss retention, and corrosion resistance (Thames and Yu, 1999; Thames et al.,
1996). Soucek and Crivello have carried out synthesis and photopolymerization of epoxidized oil (Crivello and Narayan, 1992;

225

Wu et al., 1999; Zou and Soucek, 2004, 2005). Similarly, radiation curable HYP resin based on epoxy functional fatty acids was
reported by Johansson and coworkers (Samuelsson et al., 2004).
Acrylated LSO coatings have shown good exibility and adhesion
on metal substrates (Thames et al., 1996). Thiolene UV curable
coatings have been prepared by Rawlins et al. (Black and Rawlins,
2009). The alcoholysis of tobacco seed oil in combination with polyhydroxyl compounds gave polyols. PU from the resulting polyols
were further reacted with hydroxyethyl methacrylate to produce
UV urethane acrylate coatings with excellent performance (Patel
et al., 2008). The inuence of cashew nut shell oil, epoxidized SoyO,
CasO, and dioctyl phthalate on the photocrosslinking kinetics of UV
curable mixtures containing an o-cresol novolac epoxy resin, a biscycloaliphatic diepoxide monomer, and a triarylsulfonium salt as a
cationic photoinitiator has been studied by Hien et al. (2011). They
have also carried out the cationic photopolymerization of a mixture
of epoxy resin modied by TO in the presence of a triarylsulfonium
salt after 1.2 s of exposure under a light intensity of 250 mW/cm2
and storage in the dark for a few hours. UV cured coatings containing the optimum amount of the VEGO or VEGO epoxy showed
the best performance. These may nd applications as adhesives
as well as decorative and protective coatings (Hien et al., 2011).
Decker et al. (2001) have studied the cationic photocrosslinking
of DGEBA resin with epoxidized SoyO. In their investigation, they
found that the formulation with an optimum content of the components proceeded substantially with faster curing than that of the
neat DGEBA.
UV cured HYP coatings showed good mechanical and thermal
properties; the former were more dependent on the degree of acrylation than molar mass (Dzunuzovic et al., 2006). Chen et al. have
reported the coating performance of acrylated epoxidized SoyO
based UV curable coating material prepared by the inclusion of
acrylated sucrose and commercial HYP acrylates. The coatings containing both the modiers showed good performance; those with
HYP acrylates showed good hardness, adhesion, solvent resistance
and glass transition temperature, while the ones with acrylated
sucrose exhibited improved toughness, but reduced water resistivity and thermal stability of the coatings (Chen et al., 2011; Wu
et al., 2011). Acrylated SoyO epoxy based UV curable coatings,
with biobased gallic acid cross linking agent have shown highly
improved coating properties in terms of pencil hardness, wear
resistance and adhesion (Ma et al., 2014). Recently, to further augment the performance, UV curable nanocomposites have also been
developed as antimicrobial coatings (Table 1).

8. Future perspectives and summary

VEGO are abundantly available, easy to procure and cost effective sources of nature. These hone unique natural functional
attributes and potential biodegradability that symbolize them
inevitably as established raw materials toward renewable feedstocks for environment friendly materials. Although the use of
VEGO in paints and coatings is decades old and well studied,
today emphasis is being laid on research pertaining to modications of these materials to introduce novel properties for improved
performance, environment friendliness at affordable costs. The
multi-step reactions are involved in the synthesis of VEGO based
monomers/polymers at elevated temperatures and times, consuming ample of solvents. The coatings obtained also consist of complex
synthesis and cure schedules with longer curing times and temperatures. The long drying times and high curing temperatures often
impair the quality of the nal product and yield. Thus, efforts must
be taken toward the development of low or solvent free materials
rendering VOC free coatings, i.e., cutting off the use of solvents during processing, formulation and application of coatings. The solvent

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E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

Fig. 7. VEGO based UV curable acrylic polyol.

free reactions under microwave irradiations may provide remedies

to some of the drawbacks such as poor yield due to inhomogenous heating (under conventional conditions) and longer synthesis
times. Another alternate may be the enzymatic synthesis approach.
In HYP polymers, it is proposed that as a green material, the core
molecule should also be biobased in origin, unlike the present synthetic ones. If an oil based core molecule is well developed, it will
surely be of advantageously reduced viscosity, which will facilitate
the complete elimination of the use of solvents and reactive diluents in HYP coatings. WB coatings have been developed from VEGO
generally prepared in water along with some co-solvent. Efforts
should be directed to achieve 100% water solubility of VEGO polymers, offering several advantages especially towards applications
as green VEGO coatings. To improve upon the performance characteristic of VEGO coatings blending with commercially available
polymers is the simplest method to reach a synergistic platform
at both cost and performance levels. Conventional curing agents,
drying agents, diluents and modiers must be replaced by their
environment friendly renewable resource based counterparts. The
approach presented in the article must be employed on those oils
that are non-edible and non-medicinal to add value to a waste or
unutilized material.

The manuscript provides an insight into the world of VEGO

as potential candidates for environment friendly materials. They
yield value added materials by simple chemical reactions, which
nd plethora of applications, especially as protective coatings. The
greater utilization of the aforementioned non-depletable, domestically abundant and reliable resources over conventional resources
of energy is expected to have less deleterious/hazardous impact on
environment at a stable price and may cut off the annual expenses
incurred on processing and purchase of materials. The state-of
the-art-modications in the eld are expected to promote both academic and industrial research on industrial (non-food) applications
of VEGO, focussing on both crop-oriented and product-oriented
research and to further establish VEGO as workhorses of polymer
materials, particularly the coatings industry. Thus followed and
implemented, we are sure to enter the promising era of 100% green
coatings.
Acknowledgements
Dr. Eram Sharmin is thankful to the Council of Scientic and
Industrial Research, New Delhi, India, for Senior Research Associateship against Grant No. 13(8464-A)/2011-Pool. Dr. Fahmina

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

Zafar is thankful to the University Grants Commission, India for

Dr. D. S. Kothari Post Doctoral Fellowship, Ref. # F.4/2006(BSR)/13986/2013(BSR) with Prof. Nahid Nishat. Dr Deewan Akram is
thankful to the Council of Scientic and Industrial Research,
New Delhi, India for Senior Research Fellowship against Grant
No.9/466(0122) 2K10-EMR-I.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.indcrop.2015.06.
022

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