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Materials Today: Proceedings 3S (2016) S88 – S95
Abstract
This paper describes the encapsulation procedure of an alkyd resin derived from palm oil. The palm oil-based alkyd having
carboxylic and hydroxyl moieties can be tailor-made to suit the intended application. Microencapsulation process was done using
poly(urea-formaldehyde) (PUF) resin as shell material. The microcapsules obtained were free-flowing, with 80 -90 % core
encapsulated, and are intended to be used in self-healing material development. The functional groups of alkyd and shell material
were observed using ATR-FTIR. DSC analysis shows melting peaks and glass transition of PUF and alkyd in the microcapsules.
TGA analysis indicated that the shell of the microcapsules was thermally stable up to 250°C. FESEM examination showed that
the microcapsules had rough outer surface.
1. Introduction
Recently, self-healing process utilizing microcapsules as carriers of healing agent has been an interesting topic
that has attracted many researchers and the number of related publications has been growing fast. Many healing
mechanisms have been studied and the healing agents encapsulated, such as dicyclopentadiene (DCPD), 5-
* Corresponding author. Tel.: +603 7967 4241; fax: +603 7967 4193 .
E-mail address: sngan@um.edu.my
2214-7853 © 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Selection and Peer-review under responsibility of Conference Committee Members of 5th International Conference on Functional
Materials & Devices (ICFMD 2015).
doi:10.1016/j.matpr.2016.01.012
Nurshafiza Shahabudin et al. / Materials Today: Proceedings 3S (2016) S88 – S95 89
ethylidene-2-norbonene (ENB), siloxane-based, epoxy, glycidylmethacrylate (GMA) and unsaturated polyester just
to name a few. The latest, extensive reviews have been provided by Hillewaere and Du-Prez, 2015 [1] and Zhu et al.,
2015 [2] on the self-healing designs, reactions and preparations. Yang et al., 2015 [3] has provided a review on the
chemical and physical aspect of self-healing materials.
It is of interest to study the potential role of a selected palm oil-based alkyd which contains a certain controlled
amount of hydroxyl and carboxylic groups capable of reacting with epoxy groups [4]. This alkyd provides a usage
of natural material as a self-healing agent. Therefore, in this work, we presented an encapsulation method of the
alkyd using poly(urea-formaldehyde) (PUF) resin. This is an attempt to produce alkyd-containing microcapsules to
be used in this attractive and rapid-growing field of self-healing materials.
2.1. Materials
Urea, and 1-octanol were purchased from ACS Sigma-Aldrich while formaldehyde (37 % aqueous) was from
Systerm. Ammonium chloride was from Fluka. 1, 3-dihydroxybenzol (resorcinol) and ethylene maleic anhydride
(EMA) copolymer (Mw 400 000) were from Riedel de-Haen. Refined, bleached and deodorized palm kernel oil
(PKO) and glycerol were obtained from Emery Oleochemicals (M) Sdn. Bhd. Phthalic anhydride (PA) was from
Hanwha Chemical, Korea and lithium hydroxide was from JT Baker, US. All materials were used as received.
The selected alkyd has an oil-length of 65 %, and an acid number of 17 mg KOH/ g. Details of its synthesis and
characterization were described elsewhere [4].
An aqueous solution of EMA was prepared by dissolving 0.625 g of EMA in 125 ml of water in a 500 mL beaker
at ambient temperature. Designated amount of alkyd was poured into the aqueous solution to form emulsion by
stirring at 300-500 rpm. 2.50 g urea was added to the emulsion, followed by 0.25 g ammonium chloride and 0.25 g
resorcinol. The emulsion was adjusted to pH 3.5 by adding a few drops of 10 % sodium hydroxide solution.
Generally about 3-6 drops (< 0.3 ml) were used and had not caused significant change in the total volume. 6.35 g of
formaldehyde solution (37 %) was added into the mixture. Temperature of the water bath was raised to 55°C. After
about 4 h of reaction, a white slurry has formed. The stirring was reduced to 200 rpm and the slurry was allowed to
cool down to room temperature overnight. The product was washed with distilled water to remove unreacted
chemicals and finally rinsed with ethanol. It was filtered under suction and dried under the fan for 1 h. The
microcapsules were separated according to different sizes using sieves (Endecotts, certified acc. to BS410, ISO
3310) with mesh sizes of 50, 150, 200, 300 and 500 microns. Microcapsules of a size larger than 500 microns were
discarded.
The yield of the microcapsules was calculated from the weight of the dried product over the total weight of
capsules-forming raw materials. The amount of alkyd in microcapsules was determined by solvent extraction
method. The microcapsules were ruptured with a pestle in a mortar. A mixture of acetone and ethanol was used to
extract and dissolve the core. The insoluble shell was filtered and thoroughly washed and dried at 70°C for 24 h in a
vacuum oven. The microcapsules core content was calculated using the equation 1, where W s refers to the weight of
sample and Wm refers to the weight of the insoluble shell:
Infrared spectra of the samples were collected from an attenuated total reflectance-Fourier transform infrared
spectrometer (ATR-FTIR) (Nicolet 6700 FTIR, Thermo Scientific). Spectra were recorded for the range of 4000-
450 cm-1 at 4 cm-1 resolution with 4 scans. The spectra of intact microcapsules, the extracted shell and core materials
90 Nurshafiza Shahabudin et al. / Materials Today: Proceedings 3S (2016) S88 – S95
The morphology and shapes of microcapsules were examined using a handheld digital microscope (AnMo
Electronics, Taiwan) at 50x and 200x magnifications. The average diameter of microcapsules was determined on
data sets of more than 250 particles as recommended by Yuan and Liang [5]. To examine the external morphology
of the shell of microcapsules, field-emission scanning electron microscopy (FESEM) was used (FEI Quanta FEG
450, USA). The capsules were mounted on a single-stub sample holder and the analysis was carried out under
vacuum using an electron acceleration voltage of 5.0 kV.
The reaction mechanisms involved in the formation of the PUF shell had been reported by many other
researchers. Typically in the preparation, a low molecular weight pre-polymer was formed from the condensation of
urea and formaldehyde at the initial stage. Subsequently, the prepolymer deposits onto the surface of the dispersed
core material and polymerize to form the shell [6,7].
isolated as stable free flowing microcapsules. Presumably the higher concentration of EMA leads to higher solution
viscosity. Thus, insufficient PUF prepolymer was able to be deposited onto the alkyd droplet, and consequently, thin
shell was formed.
Fig. 1. Size distribution (left) and digital microscopic images of microcapsules (50x magnification) (right), prepared at different agitation rates
(rpm): (a) 500; (b) 400; (c) 300.
92 Nurshafiza Shahabudin et al. / Materials Today: Proceedings 3S (2016) S88 – S95
Fig. 2. Digital microscopic images of microcapsules (200x magnification) synthesized at different EMA concentration (wt. %):
(a) 1.0; (b) 2.5; (c) 5.0.
Fig.3 shows the infrared red spectra of A2 microcapsules, which has all the characteristic peaks of PUF and
alkyd. The alkyd’s characteristic peak at 1730 cm-1 corresponds to the carbonyl group. The characteristic peaks of
PUF are seen at 2900 & 2800 cm-1, 1600 cm-1 and 1500 cm-1 which correspond to C-H, NH and C-N respectively.
The O-H of alkyd and N-H of amine appear at 3200 to 3500 cm-1. A1 and A3 also show characteristic peaks as
exhibited by A2.
Nurshafiza Shahabudin et al. / Materials Today: Proceedings 3S (2016) S88 – S95 93
Fig. 3. Infrared peaks of PUF/alkyd microcapsules with alkyd core and PUF shell.
DSC thermograms of A1-A3 shows glass transition (Tg) and melting (Tm) peak which correspond to the Tg and Tm
of the encapsulated alkyd, and the PUF shell (Fig. 4). The Tg of A2 is at -13.1°C, which is closely resembling that of
the alkyd. At higher temperature range, a sharp melting peak is seen at 148qC that corresponds to the melting of
PUF. A similar observation was found in A1 and A3 microcapsules, which show the Tg of alkyd at -10qC and -13qC
respectively. A1 and A3 show melting peaks at 155qC and 132qC respectively, which were attributed to the melting
of PUF shell.
Fig. 4. DSC thermogram of A1, A2 and A3 microcapsules with extracted shell and neat core.
94 Nurshafiza Shahabudin et al. / Materials Today: Proceedings 3S (2016) S88 – S95
Fig.5 shows the thermal degradations of A2 (microcapsules), the alkyd and the PUF shell. A2 was thermally
stable up to 250°C and subsequently decomposed completely within the range of 260-450qC. Degradation of PUF
occurs around 220-300qC, while the alkyd has started to break down around 250qC. The thermal degradations of the
core and shell have occurred in overlapping temperature ranges, consequently TGA could not be used to determine
the amount of core and shell accurately. The TGA data of the other samples were summarized in Table 2. A1 and
A3 capsules were thermally stable up to 250°C and 230°C respectively and the similar trend of degradation as of A2
capsules was observed. 50% weight loss occur at around 350qC for all microcapsules.
As shown in Fig. 6a, the free-flowing microcapsules were spherical in shape, and have rough outer surface. Fig.
6b shows the multi-layered PUF formed from PUF nanoparticles embedded in the layers of the shell (Fig.6c).
Nurshafiza Shahabudin et al. / Materials Today: Proceedings 3S (2016) S88 – S95 95
Fig. 6. FESEM micrographs of PUF/alkyd microcapsules (a) 800x; (b) 2500x; (c) 12000x. Scale bar (μm): (a) 100 (b) 40 (c) 10.
Instrument setting HV at 5.00 kV at low vacuum.
4. Conclusion
The selected palm oil-based alkyd has been encapsulated by the PUF resin. Using a suitable agitation rate and
emulsifier concentration, free-flowing microcapsules with up to 40 % yield could be obtained. The microcapsules
were thermally stable up to 250°C and had a rough outer surface. The microcapsules have encapsulated 80-90 %
alkyd by weight. This work provides an approach for making the alkyd microcapsules which could be used as the
healing agent for epoxy matrix.
Acknowledgements
This work is supported by the Ministry of Science, Technology and Innovation, Malaysia (MOSTI) and
University of Malaya under 03-01-03-SF0874 and PG050-2014A grants. N.S. acknowledges the Ph.D scholarship
by the Ministry of Higher Education, Malaysia (MOHE).
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