Article

High Performance Polymers

1–7
Curing of epoxy/alkyd blends in ª The Author(s) 2018
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DOI: 10.1177/0954008318784635
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Nurshafiza Shahabudin1,2, Rosiyah Yahya2,3,

Seng Neon Gan3 and Faridah Sonsudin1

Abstract
Self-healing of polymeric material using microcapsules has been developed to repair microcracks within the materials. The
self-healing character is reflected from the curing behavior of the material. In this work, curing study of alkyd/epoxy blend
was carried out by replacing part of amine hardener with alkyd in the epoxy formulation. The inclusion of alkyd in the
epoxy blend resulted in higher degree of curing and higher thermal stability compared to the alkyd-free blend, as evi-
denced from higher heat of reaction values of differential scanning calorimetry and maximum degradation temperature at
379 C, respectively. Self-healing reaction of epoxy coating as evaluated by Fourier-transform spectroscopy revealed that
the 914 cm 1 peak attributed to C–O–C of epoxy has decreased, as the epoxide group was consumed in the reaction.
Appearance of a new peak at 1631–1632 cm 1 in the cured coating confirmed that the epoxide has reacted with the
carboxylic acid group of alkyd to form ester.

Keywords
Self-healing, alkyd, palm oil, epoxy, blend, curing

Introduction The introduction of self-healing functionality into pro-

tective epoxy coating is a better alternative for long-term
The failure of many polymers begins from microcracks
corrosion protection of metallic structures.5 A self-healing
formed within the materials.1 The undetected or inacces-
epoxy coating system was first introduced by Toohey et al.
sible microcracks made early repair unavailable. The
when they included microvascular networks into an epoxy
microcracks will then propagate until failure occurs, and
coating. The networks release the healing agent when
consequently will result in major losses. Traditional
cracks occur, thus repaired the cracks.6 A concept of self-
repairs such as welding and patching are limited to visible
healing using a drying oil was introduced in low molecular
damages and only applicable when the failure has already
epoxy coating. Cracks in a paint film were healed when
occurred or worsened. Furthermore, frequent inspection is
needed as these methods are neither autonomic nor instan- linseed oil was released from microcapsules ruptured under
taneous.2 Self-healing materials were introduced about 17 simulated mechanical action. The linseed oil-healed area
years ago 3 to overcome these limitations and intense was found to prevent corrosion of the substrate.7 In another
research in this field has been going on for the past
decade. Self-healing or self-repairing in materials is
1
demonstrated by the ability to regain original properties Centre for Foundation Studies in Science, University of Malaya, 50603,
lost during external damage. Partial recovery of the Kuala Lumpur, Malaysia
2
main functionality of the material can also be considered Centre for Ionics University of Malaya, Department of Physics, Faculty of
Science, University of Malaya, 50603, Kuala Lumpur, Malaysia
as a self-healing ability.4 Among the various methods, 3
Department of Chemistry, Faculty of Science, University of Malaya,
self-healing can be achieved particularly via the 50603, Kuala Lumpur, Malaysia
microcapsules-based technique, where the healing agent
is loaded into a matrix material by microcapsules. When Corresponding author:
microcracks occur, the microcapsules will break and Nurshafiza Shahabudin, Centre for Foundation Studies in Science
University of Malaya, 50603 Kuala Lumpur, Malaysia; Centre for Ionics
release the healing agent to polymerize or cure after react- University of Malaya, Department of Physics, Faculty of Science,
ing with the embedded catalyst, or even with the matrix University of Malaya, 50603 Kuala Lumpur, Malaysia.
host itself. Email: [email protected]
2 High Performance Polymers XX(X)

work, a coating utilizing Diels–Alder (DA) reaction method to observe the heat release during the curing pro-
demonstrated thermally reversible self-healing property cess. Amino resin is most commonly used as epoxy curing
from 50 C to 150 C, and that the best temperature of the agent, such as 2,7-diaminofluorene (DAF)/epoxy system18
DA reaction was 80 C. The self-healing efficiency of and amino derivatives/CYCOM 970 epoxy system which
furanyl-terminated resin with a cross-linker in this work are commonly used laminates of aircraft structure.19
showed healing efficiency of up to 88% after staying at In addition, Fourier-transform infrared (FTIR) spectro-
80 C for 12 h.8 scopy can be used to monitor the progress of healing at
In general, the microcapsules carrying healing agent molecular level, where certain bonds appear or disappear
must be able to withstand the conditions of high tempera- in the course of the self-healing reactions.20 FTIR was used
tures during the epoxy resins application. Besides, the pre- to monitor the extent of conversion of cyanate ester group
ferred healing agent should be reasonably priced. Thus, the in self-healing system, consisting of cyanate ester and
introduction of less expensive and more environmental poly(phenylene oxide) resins. 21 FTIR studies were
friendly components would be beneficial. employed to follow the curing process of the resin blends
An alkyd resin, a bio-based and relatively cheap healing reported in several works.13,22,23 Here, attenuated total
agent derived from renewable palm oil, was proposed as a reflectance (ATR)-FTIR was employed to confirm whether
healing agent for epoxy matrix as described in previous the alkyd participates in curing reaction in the epoxy
work.9 Alkyd is a very versatile material due to its compat- coating.
ibility with a number of polymers such as nitrocellulose,
chlorinated and cyclized rubber, and many resins such as
phenolic, epoxy, amino, silicone, hydrocarbon, and acrylic.
Materials and methods
Alkyd resins can also be designed to suit a broad range of
applications by changing the oil length and modifying the A selected alkyd, AlkydPKO65, was synthesized as
chain stopping agents and the related resins.10 It can also be described in previous work9 with acid value of 15 mg KOH
tailored to have functionalities such as carboxylic and g 1. The epoxy resin used was Epikote 240, which is a low-
hydroxyl groups that are used in cross-linking reactions viscosity resin with an epoxy molar mass of 185–190 g/
with other resins. equivalent. Epikure F205 (cycloaliphatic amine) was used
Epoxy and alkyd are blended to obtain improved prop- as the curing agent. Both the epoxy and curing agent were
erties over the individual resin, usually for coating appli- from Hexion Inc., Columbus, Ohio, USA. All materials
cation. Blending can be physical or chemical, to achieve were used as received. Figure 1 shows the plausible chem-
the combined superior properties. Several works have stud- ical structures of epoxy and alkyd resins used.
ied the blending of alkyds and epoxies, their characteristics
and performance in coatings. Coatings with better drying
DSC study of epoxy/alkyd blends
time, hardness, flexibility, and gloss, among others, were
reported by blending a nahar seed oil-based alkyd with Epoxy/alkyd blends were prepared as listed in Table 1.
epoxy.11 A palm oil-based alkyd have also been used to They were cured in DSC and the curing reactions were
blend with epoxy, also meant for coating applications.12,13 studied. Approximately, 15–16 mg samples were sealed
Assanvo et al. used a Ricinodendron heudelotii oil-based in TZero aluminum hermetic pans and measurements were
alkyd blended with epoxy resin to improve the performance made using a DSC Q20 (TA Instruments, New Castle,
of coatings.14 All these works showed good compatibility Delaware, USA). Samples were cured in the DSC by ramp-
of the blending and have improved the coating properties. ing the temperature to 80 C and held isothermally for 10
In different application, a Jatropha curcas oil-based alkyd/ min, followed by quick cooling. Then, they were scanned
epoxy blend was used as bio-reinforced composites and has from 25 C to 200 C at 20 C min 1 to observe the curing
been reinforced with expanded graphite.15 Palm oil-based process. Experiments were done with nitrogen flow of 50
alkyds were also found to be compatible with epoxidized mL min 1. Data were processed using Q series 5.4.0 Uni-
natural rubber and formed some cross-linking, which could versal Analysis 2000 (TA Instruments, New Castle, Dela-
modify the properties of rubber compounds.16 ware, USA).
In order to design a healing mechanism for self-healing
epoxy coating, it is important to study the reactions within
Thermogravimetric analysis (TGA) of epoxy/alkyd
the alkyd and epoxy blends. In this work, the blends were
studied using differential scanning calorimetry (DSC) to
blends
analyze the curing reaction. The two-part epoxy resin sys- Approximately, 5 mg of the cured blends was analyzed
tem is commonly used, where the uncured resin and the using simultaneous thermal analyzer (STA 6000, PerkinEl-
curing agent are mixed. On the other hand, in a one-part mer, Waltham, Massachusetts, USA). They were scanned
system, the curing agent is encapsulated and the curing of from 30 C to 800 C at 10 C min 1 in a nitrogen environ-
the epoxy resin was studied using DSC.17 DSC is a useful ment at a flow rate of 20 mL min 1.
Shahabudin et al. 3

Figure 1. Chemical structure of epoxy and AlkydPKO65 resins.

Table 1. Formulations of epoxy/alkyd blends. Preparation of epoxy coating

Eq. wt ratio of Epoxy resin (Epikote 240) of 1 g was weighed in a small
Sample epoxy/amine/alkyd Epoxy (g) Amine (g) Alkyd (g) beaker. Alkyd-loaded microcapsules of 0.20 g in weight (12
wt%) were added to the resin and were carefully stirred, fol-
Control 1/1/0 1 0.58 0
EA1 1/0.8/0.02 1 0.44 0.39
lowed by the addition of 0.44 g amine hardener. A control of
EA2 1/0.8/0.01 1 0.44 0.20 neat epoxy coating was prepared without any microcapsules.
EA3 1/0.7/0.01 1 0.39 0.20 The mixture was stirred carefully using a spatula. Next, they
were dropped into silicone rubber molds with approximately
Eq. wt: equivalent weight.
10  4 cm2 dimension and were sandwiched with another

Figure 2. Overlays of dynamic DSC scan of neat epoxy and epoxy/alkyd blends. DSC: differential scanning calorimetry.
4 High Performance Polymers XX(X)

Table 2. Curing temperature characteristics from DSC and TGA.

Curing temperature profile ( C)

TGA analysis
Samples Start Onset Maximum End Integration,
H (J g 1) Maximum degradation temperature ( C)

Control 64 81 135 200 68 370

EA1 65 77 138 196 62 382
EA2 70 77 136 196 68 373
EA3 62 75 136 196 69 379

DSC: differential scanning calorimetry; TGA: thermogravimetric analysis.

Figure 3. TGA curves of neat epoxy and epoxy/alkyd blends. TGA: thermogravimetric analysis.

similar mold to obtain a thin layer of coating. Low pressure observed to be exothermic. From Table 2, the epoxy/alkyd
was applied on top of the molds and the mixture was left to blends can be cured rapidly at a temperature of 136–138 C.
cure overnight at room temperature. Thin layer of transpar- The heat of reaction (
H) can be calculated from the normal-
ent coatings were obtained. The coats were analyzed using ized area of the exothermic peak. Generally, in a resin/hard-
ATR-FTIR, before being scratched with a razor blade. ener system, the larger heat of reaction indicates the higher
After scratching, the coats were re-scanned using ATR- degree of cure. The
H of epoxy/alkyd blend 1 (EA1) blend
FTIR to observe any changes. The samples were heated was significantly lower than that of the control epoxy,
at 100  C for 2 h and reanalyzed using ATR-FTIR to whereas epoxy/alkyd blend 2 (EA2) and epoxy/alkyd blend
observe any difference. The coatings that were scratched 3 (EA3) blends showed almost similar value indicating sim-
and cured were also microscopically inspected using a ilar degree of cure as the control. Comparing the onset cure of
digital microscope (AnMo Electronics, Taiwan). EA2 and EA3 blends, EA3 blend showed lowest onset of
curing temperature, with highest degree of cure. Thus, with
the inclusion of alkyd, epoxy/alkyd blends showed lower
Results and discussion onset curing temperature from the epoxy control, which sug-
DSC analysis of the blends gests the influence of alkyd in the curing process.

To probe the viability of the curing reactions between the

epoxy and alkyd resins, small amounts of alkyd were blended
Thermal stability of the cured blends
with epoxy with different equivalent weight of hardener The overlaid TGA curves of neat epoxy system and the
(Table 1). Figure 2 shows the curing profiles of epoxy/alkyd epoxy/alkyd blends are given in Figure 3 and the maximum
blends with the neat epoxy as control, whereby the curing is degradation temperatures are tabulated in Table 2. Neat
Shahabudin et al. 5

Figure 4. FTIR spectra of (a) alkyd; epoxy coating with 12 wt% of B2 microcapsules: (b) cured at room temperature for 24 h (c) ditto;
scratched (d) ditto; scratched and cured at 100C for 2 h (e) neat epoxy coating. FTIR: Fourier transform infrared.

epoxy started to degrade at approximately 120 C with max-

imum degradation at 370 C, while the epoxy/alkyd blends
were more thermally stable and started to degrade at 329–
347 C with maximum degradation at 379–382 C. The
inclusion of alkyd in the epoxy blends has increased the
thermal stability of epoxy. This higher degradation tem-
perature could possibly be due to some cross-linking reac-
tions between alkyd and epoxy.

FTIR analysis of the coating

FTIR studies were carried out to follow curing process of the
resin blends such as those reported in several papers.13,22,23
Here, ATR-FTIR was employed to confirm whether the alkyd
participates in the healing process from the curing reactions in
the epoxy coating. Figure 4 shows the curing of the alkyd and
epoxy in the coating as monitored using FTIR spectroscopy.
The peak at 914 cm 1 attributed to epoxy is observed in the
microcapsules-loaded partially cured coating (Figure 4(b)
and (c)). This indicates that there is still unreacted epoxy in
the system to cross-link with the alkyd upon capsules rupture.
When the coating was scratched (i.e. the microcapsules rup-
tured) and heated at 100 C for 2 h, the peak at 914 cm 1 Figure 5. Plausible curing reaction of (a) alkyd and epoxide group
disappeared suggesting the consumption of the epoxide group to form ester bond and (b) alkyd and amine hardener to form
(Figure 4(d)). Similar observation was obtained for the con- amide bond.
trol epoxy coating (Figure 4(e)), showing that epoxy group
has also been consumed upon reaction with amine. The Microscopic analysis of the coating
appearance of new ester peak at 1732 cm 1 and the disap-
pearance of carbonyl peak at 1727 cm 1 in healed coating From microscopic inspection, the scratched coating
show that the ester bond between alkyd and epoxy has formed showed a certain amount of recovery (Figure 6(b)). After
during the curing time (2 h at 100 C). The plausible healing being cured at elevated temperature, the scratches became
reaction occurred in the coating is shown in Figure 5. less obvious, suggesting that curing has occurred between
6 High Performance Polymers XX(X)

Figure 6. Digital microscopic images of epoxy coating embedded with microcapsules (a) after being scratched with razor and (b) after
being cured at 100 C for 2 h.

the alkyd released from the ruptured microcapsules with References

the unreacted epoxy and amine hardener present in the 1. Kessler MR. Polymer Matrix Composites: A Perspective for a
coating. This result further supports the curing evidence Special Issue of Polymer Reviews. Polym Rev 2012; 52: 229–233.
given by the FTIR results above. 2. Hia IL, Vahedi V and Pasbakhsh P. Self-healing polymer
composites: prospects, challenges and applications. Polym
Rev 2016; 56(2): 225–261.
Conclusion 3. White SR, Sottos NR, Geubelle PH, et al. Autonomic heal-
ing of polymer composites. Nature 2001; 409(6822):
The blend with equivalent molar ratio of epoxy/amine/ 794–797.
alkyd equals to 1/0.7/0.01 exhibited the highest cure. The 4. Zheludkevich M. Self-healing anticorrosion coatings. In:
thermal stability of epoxy/alkyd blends was higher than Ghosh SK (ed) Self-healing materials: fundamentals, design
that of the neat epoxy blend, indicating that the presence strategies, and applications. Weinheim: Wiley-VCH Verlag
of alkyd has resulted in higher degradation temperature. GmbH & Co. KGaA, 2009; 101–140.
From FTIR results, the healing of epoxy coating can be 5. Vijayan P and AlMaadeed M. ‘Containers’ for self-healing
performed with the help of heat at 100 C for 2 h. The epoxy composites and coating: trends and advances. Exp
healing is suggested to have occurred from the reaction Polym Lett 2016; 10(6): 506–524.
of carboxylic of alkyd with the epoxide of epoxy. 6. Toohey KS, Sottos NR, Lewis JA, et al. Self-healing materi-
als with microvascular networks. Nat Mater 2007; 10(6):
581–585.
Declaration of Conflicting Interests
7. Suryanarayana C, Rao KC and Kumar D. Preparation and
The authors declared no potential conflicts of interest with respect
characterization of microcapsules containing linseed oil and
to the research, authorship, and/or publication of this article.
its use in self-healing coatings. Prog Organic Coat 2008;
63(1): 72–78.
Funding 8. Wang X, Zhao K, Huang X, et al. Preparation and properties
The authors disclosed receipt of the following financial support of self-healing polyether amines based on Diels–Alder rever-
for the research, authorship, and/or publication of this article: This sible covalent bonds. High Perform Polym 2018; 2018:
work was supported in parts by the Ministry of Science, Innova- 0954008317750727.
tion and Technology Malaysia (MOSTI) through 03-01-03- 9. Shahabudin N, Yahya R and Gan S. Microcapsules filled with
SF0874 grant and Ministry of Higher Education Malaysia a palm oil-based alkyd as healing agent for epoxy matrix.
(MOHE) through FP052-2016 grant. Polymers 2016; 8(4): 125.
Shahabudin et al. 7

10. Hofland A. Alkyd resins: from down and out to alive and 17. Fang W, Jun X, Jing-wen W, et al. Study on curing kinetics of
kicking. Prog Org Coat 2012; 73(4): 274–282. a diglycidyl ether of bisphenol A epoxy resin/microencapsu-
11. Dutta N, Karak N and Dolui S. Alkyd–epoxy blends as multi- lated curing agent system. High Perform Polym 2012; 24(8):
purpose coatings. J Appl Polym Sci 2006; 100(1): 516–521. 730–737.
12. Issam A, Khizrien AN and Mazlan I. Physical and mechanical 18. Ghaemy M and Barghamadi M. Nonisothermal cure kinetics
properties of different ratios of palm oil-based alkyd/epoxy of DGEBA with 2, 7-diaminofluorene. J Appl Polym Sci
resins. Polym Plast Technol Eng 2011; 50(12): 1256–1261. 2009; 112(3): 1311–1318.
13. Ong HR, Khan MMR, Ramli R, et al. Effect of CuO nano- 19. Chen C, Li Y, Gu Y, et al. An improved simplified approach
particle on mechanical and thermal properties of palm oil for curing kinetics of epoxy resins by nonisothermal differ-
based alkyd/epoxy resin blend. Proc Chem 2015; 16: ential scanning calorimetry. High Perform Polym 2017;
623–631. 2017: 0954008317693291.
14. Assanvo EF, Gogoi P, Dolui SK, et al. Synthesis, character- 20. Peterson AM, Jensen RE and Palmese GR. Reversibly cross-
ization, and performance characteristics of alkyd resins based linked polymer gels as healing agents for epoxy amine
on Ricinodendron heudelotii oil and their blending with thermosets. ACS Appl Mater Int 2009; 1: 992–995.
epoxy resins. Ind Crops Prod 2015; 65: 293–302. 21. Yuan L, Huang S, Hu Y, et al. Poly(phenylene oxide) mod-
15. Gogoi P, Boruah M, Bora C, et al. Jatropha curcas oil ified cyanate resin for self-healing. Polym Adv Technol 2014;
based alkyd/epoxy resin/expanded graphite (EG) rein- 25(7): 752–759.
forced bio-composite: Evaluation of the thermal, mechan- 22. Cakić SM, Ristić IS, Jašo VM, et al. Investigation of the
ical and flame retardancy properties. Prog Org Coat 2014; curing kinetics of alkyd–melamine–epoxy resin system. Prog
77(1): 87–93. Org Coat 2012; 73(4): 415–424.
16. Lee SY, Gan SN, Hassan A, et al. Reactions between epox- 23. Oh JH, Jang J and Lee SH. Curing behavior of tetrafunctional
idized natural rubber and palm oil-based alkyds at ambient epoxy resin/hyperbranched polymer system. Polymer 2001;
temperature. J Appl Polym Sci 2011; 120(3): 1503–1509. 42(20): 8339–8347.