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The Journal of The Textile Institute

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Preparation and textile application of poly(methyl


methacrylate-co-methacrylic acid)/n-octadecane
and n-eicosane microcapsules

Sennur Alay Aksoy, Cemil Alkan, M. Selda Tözüm, Sena Demirbağ, Ruhan
Altun Anayurt & Yusuf Ulcay

To cite this article: Sennur Alay Aksoy, Cemil Alkan, M. Selda Tözüm, Sena Demirbağ, Ruhan
Altun Anayurt & Yusuf Ulcay (2017) Preparation and textile application of poly(methyl methacrylate-
co-methacrylic acid)/n-octadecane and n-eicosane microcapsules, The Journal of The Textile
Institute, 108:1, 30-41, DOI: 10.1080/00405000.2015.1133128

To link to this article: https://doi.org/10.1080/00405000.2015.1133128

Published online: 19 Jan 2016.

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The Journal of The Textile Institute, 2017
VOL. 108, NO. 1, 30–41
http://dx.doi.org/10.1080/00405000.2015.1133128

Preparation and textile application of poly(methyl methacrylate-co-methacrylic


acid)/n-octadecane and n-eicosane microcapsules
Sennur Alay Aksoya, Cemil Alkanb, M. Selda Tözüma, Sena Demirbağa, Ruhan Altun Anayurtb and Yusuf Ulcayc
a
Textile Engineering Department, Süleyman Demirel University, Isparta, Turkey; bDepartment of Chemistry, Gaziosmanpaşa University, Tokat, Turkey;
c
Textile Engineering Department, Uludağ University, Bursa, Turkey

ABSTRACT ARTICLE HISTORY


In this study, a series of microencapsulated phase change materials with poly(methyl methacrylate-co- Received 8 July 2015
methacrylic acid) P(MMA-co-MAA) shell and n-octadecane or n-eicosane core were synthesized by emulsion Accepted 9 December 2015
polymerization method. The aim was to produce microencapsulated n-alkanes having functional groups
KEYWORDS
on their outer surface, so that functional groups would help increasing physical interactions between Microencapsulated PCMs;
microcapsules and fiber surface. Therefore, methyl methacrylate (MMA), ethylene glycoldimethacrylate functional group; textile;
(EGDM), and methacrylic acid (MAA) were copolymerized in oil phase of n-alkane. FT-IR results proved the heat storage; n-alkanes
successful synthesis of P(MMA-co-MAA) shell of microencapsulated n-alkanes. The DSC results indicated
that the microencapsulated n-alkanes have considerable latent heat storage capacity in a range of
58–145  J/g. The average melting and freezing temperatures of the microencapsulated n-alkanes were
measured as 27 and 26 °C for n-octadecane and 36 and 35 °C for n-eicosane, respectively. The microcapsules
were of spherical and compact shape with particle sizes between 15 and 32 μm. The microcapsules on
the cotton fabric applied by pad-dry-cure method were found highly durable and they showed sufficient
stability upon several washings and rub fastness. Thermo-regulating properties of the fabrics were declared
as a result of thermal history measurements.

Introduction encapsulation studies for thermal energy storage focused on the


encapsulation of n-alkanes and paraffin waxes (Alay, Alkan, &
Fundamental principles of textile science and technology have
Göde, 2011; Alay, Göde, & Alkan, 2011; Alkan, Sarı, Karaipekli,
been increasingly employed for the manufacturing of innovative
& Uzun, 2009; Cho, Kwon, & Cho, 2002; Kim & Kim, 2005;
textile products with sensing, adapting, and reacting capabilities
Önder, Sarıer, & Çimen, 2008; Sarier & Onder, 2007; Zhang &
in the last decades. Thermal adaptive textiles having heat storage
Wang, 2009).
and thermo-regulation property is an example of such innova-
The type and constitution of the shell and core materials
tive materials. These novel textile materials containing PCMs
determines the properties such as thermal and mechanical sta-
have become important as a insulation material, because of their
bilities, particle size and its distribution, and chemical reactivity.
automatic acclimatizing properties according to the environment
Selection of shell material is done according to the application
and body temperature.
requirements for the expected properties as the type of prepara-
PCMs are thermal energy storage materials which can store
tion is selected according to the shell material. Recently, micro-
and release latent heat during their phase transformations at a
encapsulation of paraffin waxes in different shells have been tried
certain temperature interval. The type of phase change is gener-
using mini emulsion, interfacial polycondensation, suspension,
ally melting–crystallization in thermal energy storage systems,
and sol–gel process (Chen, Chen et al. 2012; Chen, Yu et al.,
and the materials are so-called as solid–liquid PCMs (Erkan,
2012; Ma, Chu, Li, & Tang, 2012; Wang, Shi, Xia, Zhang, & Feng,
2004; Mondal, 2008). Among the organic and inorganic solid–
2012; Zhang, Wang, & Wu, 2010; Zhang, Sun, Wang, & Wu, 2011;
liquid PCMs, linear long chain hydrocarbons or paraffin waxes
Zhang, Bon et al., 2012; Zhang, Tong et al., 2012). Additionally,
are especially preferred due to their properties such as nontox-
some researches focused on the preparation of microcapsule with
icity, chemically inertness, and high energy storage capacity.
functional reactive groups on the shell surface to improve the
Upon changing chain length, phase change temperature of the
interfacial bond or adhesion between microcapsules and sub-
material can be adjusted for possible application fields such as
strate (PCT/IB2006/050605; Wang, Li, Hu, He, & Liu, 2009).
textiles and building. (Erkan, 2004; Jin, Wang, Liu, & Yang, 2008;
Improving the adhesion and interfacial bond of microcapsules
Mondal, 2008; Shilei, Guohui, Neng, & Li, 2007). The liquid
with substrate is one of the major factors for textile application to
handling problems of solid–liquid PCMs have been overcome
get durable applications. Therefore, this study focused on prepar-
by macro- or micro-size encapsulation. Microcapsules are tiny
ing microencapsulated paraffin by a shell with functional group
particles with a core material surrounded by a coating or shell
used as textile additives.
(Zhang, Tao, Yick, & Wang, 2004). In the literature, most of the

CONTACT  Sennur Alay Aksoy  sennuralay@sdu.edu.tr


© 2016 The Textile Institute
THE JOURNAL OF THE TEXTILE INSTITUTE   31

PCMs are usually applied to textiles in three different Preparation of microencapsulated PCMs
manners; they are embedded into coating compounds (Kim
In the preparation of microencapsulated PCMs (MPCMs),
& Cho, 2002; Koo, Choe, & Park, 2009; Koo, Park, Choe, &
­oil-in-water emulsion polymerization technique was used (Altun-
Kim, 2008; Sánchez, Sánchez-Fernandez, Romero, Rodríguez,
Anayurt, Arslan, Kahraman-Dögüscü, Alkan, & ­Alay-Aksoy,
& ­Sánchez-Silva, 2010; Sanchez-Silva, Rodriguez, Romero, &
2013). N-Octadecane and n-eicosane were the core materials
Sanchez, 2012), applied to fabrics by exhaustion and impregna-
of microcapsules. The shell was P(MMA-co-MAA) with three
tion processes (Alay, Alkan et al., 2011; Alay, Göde et al., 2011;
different compositions. The first step of emulsion polymerization
Shin, Yoo, & Son, 2005), or incorporated into fiber geometry by
was to emulsify the core material, monomers, and cross-linker
spinning (Bryant, 1999; Zhang, Wang, Tao, & Yick, 2005; Zhang,
in distilled water by stirring at 10,000 rpm. In this step, 50 g of
Wang, Tao, & Yick, 2006).
n-octadecane or n-eicosane, 50 g of MMA, 10 g EGDM, 5 g of
The incorporation of microencapsulated n-alkanes to tex-
Triton X100, and 0.5, 2.5, or 5 g of MAA monomer (for 3 com-
tiles is an old task but has continually growing interest. In this
positions, respectively) were added to 200  ml of water. Then,
study, production of PMMA microcapsules of n-octadecane and
the mixture was heated to 50 °C. A 0.5 g of ammonium persul-
n-eicosane with methacrylic acid functional groups on their
fate, and 4 mL of ferrous sulfate heptahydrate was dropped to
surface were prepared because that they were expected to inter-
the emulsion medium to initiate polymerization reaction. After
act with textiles effectively by electrostatic interactions or to
half an hour, post initiators of 0.25 g of sodium thiosulfate and
react easily with bridging chemicals to form chemically bonded
tert-butyl hydro peroxide solution were added and temperature
structures. Therefore, microcapsule application to the textiles
was increased to 80 °C. The polymerization was continued by
that was durable to washing and mechanical effect such as fric-
stirring at 500 rpm for 5 h. Prepared microcapsules were washed
tion could be carried out. The preparation, characterization, and
and dried at 40 °C in vacuum oven. The abbreviated names and
thermal energy storage properties of P(MMA-co-MAA) shell
recipes of microcapsules were tabulated in Table 1.
and n-alkane core microcapsules with three different shells to
show the composition effect and with two different n-alkanes
to differentiate the effect of the core type were performed. The Analysis of MPCMs
core type shows the applicability of the particles at their phase
The synthesis of MPCMs was proven using FTIR spectrometer
temperatures also. Cotton weaving fabrics were treated with the
(Jasco 430 FT-IR). The number of scan and resolution of the
prepared microcapsules with a resin cross-linker by a conven-
spectra was adjusted as 16 and 4 cm−1, respectively. Phase tran-
tional pad-dry-cure process. The treated fabrics were character-
sition temperatures and enthalpies of microencapsulated PCMs
ized morphologically, and the laundering and rubbing durability
were determined using a DSC instrument (Perkin-Elmer Jade).
was evaluated for practical use.
The samples were heated at a rate of 10 °C/min between the −5 °C
and 80 °C under a constant stream of nitrogen at a flow rate of
Materials and methods 60 mL/min. Thermal stability of the MPCMs was investigated
using a TGA instrument (Perkin-Elmer TGA7) at a scanning
Material rate of 10 °C/min in a static air atmosphere. The morphology of
Methyl methacrylate (MMA, Merck), methacrylic acid (MAA, the MPCMs was determined using a POM instrument (Leica EP
Fluka), and ethylene glycol dimethacrylate (EGDM) were 50). The mean particle size and PSD of the microcapsules were
treated with NaOH solution prior to use to remove the inhib- analyzed using a PSD analyzer instrument (Malvern MS2000E).
itor. N-Alkanes (n-octadecane and n-eicosane, Alfa Aesar), During particle size analysis, dried microcapsules were mixed
ferrous sulfate heptahydrate, ammonium persulfate, and Triton with water and homogenized using a mechanical homogenizer
X-100 were used as received in the synthesis of microcapsules. A at a rate of 10,000 rpm for 45 min.
70% tert-butyl hydro peroxide (Merck) and sodium thiosulfate
(Sigma-Aldrich) were used as post initiators without purifica- Application of the MPCMs to the fabrics
tion. A modified dimethyloldihydroxyethylene urea-based resin
(Fixapret Resin F-ECO®, BASF) was used as cross-linker to fix In this study, P(MMA-co-MAA)/n-octadecane-2, P(MMA-co-
the microcapsules to the fabric. Fixapret Resin F-ECO catalyzed MAA)/n-octadecane-3, P(MMA-co-MAA)/n-eicosane-2, and
by MgCl2. Undyed, woven 100% cotton fabric (55 yarns per cm P(MMA-co-MAA)/n-eicosane-3 microcapsules were applied to
in warp direction and 28 yarns per cm in weft direction) with cotton fabrics by pad-dry-cure method. MPCMs were homog-
the weight of 112 g/m2 was desized, scoured, and bleached by enized in a NaCl salt solution of water by stirring at a speed of
the supplier. 10,000 rpm using a homogenizer (IKA Ultra Turrax T25) for

Table 1. The abbreviated names of MPCMs and their shell and core constitutions.
Abbreviated names of MPCMs MMA/MAA/EGDM/n-alkane weights (g) Core material
P(MMA-co-MAA)/n-octadecane-1 50/0.5/10/50 n-octadecane
P(MMA-co-MAA)/n-octadecane-2 50/2.5/10/50
P(MMA-co-MAA)/n-octadecane-3 50/5.0/10/50
P(MMA-co-MAA)/n-eicosane-1 50/0.5/10/50 n-eicosane
P(MMA-co-MAA)/n-eicosane-2 50/2.5/10/50
P(MMA-co-MAA)/n-eicosane-3 50/5.0/10/50
32   S. ALAY AKSOY ET AL.

one hour. The fabric samples were impregnated to the aqueous Characterization of the fabrics
dispersion of microcapsules for 1 h, and then Fixapret Resin
In order to investigate the fixation and durability of microcap-
F-ECO and a catalyst were added. After 30 min, the impreg-
sules on cotton fabrics, treated fabrics were washed in an aqueous
nated fabrics were passed through squeezing rolls under 2 bar
solution containing 4  g/L standard detergent (non-phosphate
pressure and 2  rpm using foulard, dried at 80  °C for 5  min
ECE standard detergent without optical brightness) according to
and then cured at 120  °C for 1  min. The concentrations of
TS EN 20105-C06: 2001/A2S program at 40 °C for 30 min using
the microcapsules were 60  g/L with respect to the weight of
a Gyrowash washing machine (James H. Heal, Gyrowash Model
the dried microcapsules. The concentration of Fixapret Resin
415). Laundering durability was tested up to washing 1, 5, 10, and
F-ECO and MgCl2 was 60 and 15 g/L, respectively. The NaCl
20 cycles. The rubbing test was carried out using a standardized
salt of 1 g/L was used to increase adhesion between the cellulose
Crockmeter (James H. Heal & Co. Ltd) according to TS 717 EN
and microcapsules.
ISO 105-X12. The face side and back side of MPCMs-treated
samples were rubbed for 10 cycles at a pressure of 9 N under
dry condition.
The presence of the microcapsules on the fabric specimens
sputtered-coated with a thin layer of gold was observed using a
scanning electron microscope (LEO 440 Computer Controlled
Digital Instrument). The chemical structure of the microcapsule
applied fabric clarified by FTIR spectrometer (Jasco 430 FT-IR).
The number of scan and resolution of the spectra was adjusted
as 16 and 4 cm−1, respectively. Fabric samples were ground and
mixed with KBr to make pellets.
Textiles containing MPCMs have thermo-regulation effect
resulting from heat absorbed and released by the core PCM.
Hence, measurement of thermo-regulation effects of the fab-
Figure 1. Schematic drawing of the T-history instrument. rics containing MPCMs was carried out using a thermal history

Figure 2. FT-IR spectra of P(MMA-co-MAA)/n-octadecane (on left) and P(MMA-co-MAA)/n-eicosane (on right) ((a) MAA, (b) MMA, (c) paraffin, (d)–(f) microcapsules having
1, 5 and 10% MAA, respectively) (Altun-Anayurt, 2014).
THE JOURNAL OF THE TEXTILE INSTITUTE   33

(T-history) system (Figure 1). The setup of the T-history system Cabeza, & Mehling, 2003; Yinping et al., 1999). The temper-
designed at the ZAE-Bayern (Lázaro et al., 2006) was modified. ature of an air enclosure was controlled by a thermostat that
This T-History method was proposed by Yinping, Yi, and Yi was connected to a 40-watt lamp which provides the heat to
(1999) and improved by various authors (Günther, Hiebler, the air enclosure. There was an insulated polyurethane box (air
Mehling, & Redlich, 2009; Lázaro et al., 2006; Marin, Zalba, enclosure) which the fabric and thermal camera were placed in.

Figure 3. DSC curves of microencapsulated n-octadecane (a)–(c) and n-eicosane (d)–(f) by P(MMA-co-MAA) shell containing 1, 5, and 10% MAA, respectively.
34   S. ALAY AKSOY ET AL.

The system was composed of a thermal camera (Fluke Ti100 OH and carboxyl groups, respectively, the cotton fabrics can be
Thermal Imager) measured surface temperature of the fabric, more attractive material for microcapsules having hydrophilic
and temperature sensor measured the temperature of air enclo- property.
sure and a data-logger (Ahlborn MA25903S Data-logger). The
emission value of the thermal camera was adjusted to 0.94 during Thermal properties of the MPCMs
measurement.
The cooling effect of MPCMs on the fabrics was investigated Determination of thermal properties of the MPCMs was
by temperature rise. The method was based on comparing the studied using DSC curves presented in Figure 3. The energy
temperature evolution of the sample fabric which was treated storage and release capacity and phase change temperatures of
with microcapsule and the untreated reference fabric relative to the MPCMs obtained from DSC curves were given in Table 2.
the empty boxes. During measurement, the sample or reference According to the measurements, the melting and crystalliza-
fabrics were placed in insulated box. Then, the temperature in tion temperatures were 27.3 and 26.4 °C for the P(MMA-co-
air enclosure was increased instantaneously. The temperature of MAA)/n-octadecane-1, respectively, and 27.3 and 26.1 °C for
the sample or the reference and air enclosure were all recorded the P(MMA-co-MAA)/n-octadecane-2 and 3 microcapsules,
simultaneously. The sample and reference fabric were in the same respectively. The phase change characteristics of the micro-
sizes. Before measurements, both of reference and sample fab- encapsulated composites were close to those of n-octadecane
rics were conditioned pursuant to heat releasing temperature (at that have melting point of 28.2  °C and crystallization point
0 °C). Evaluation of thermal history results was carried out by of 25.4  °C. It was also shown from Table 2 that the melting
comparing the temperature differences of the treated fabric to and crystallization latent heats were measured to be 94.2 and
the reference fabric. −87.7 J/g for the P(MMA-co-MAA)/n-octadecane-1, 58.7 and
−56.1 J/g for the P(MMA-co-MAA)/n-octadecane-2, 70.6 and
−65.4  J/g for the P(MMA-co-MAA)/n-octadecane-3. It can
Results and discussion be clearly seen form Figure 3 and Table 2 that the total latent
FT-IR spectroscopy analysis of MPCMs heats of P(MMA-co-MAA)/n-eicosane microcapsules-1-3 for
melting were measured to be 107.7 J/g at 36.3 °C, 145.8 J/g at
FT-IR spectra of P(MMA-co-MAA)/n-octadecane and P(MMA- 36.1 °C, and 86.3 J/g at 36.1 °C, respectively. The latent heats
co-MAA)/n-eicosane microcapsules were presented in Figure 2. released by the MPCMs were measured as 101.4 J/g at 35.5 °C,
As seen in the Figure, the spectra of microcapsules showed 134.7 J/g at 35.4 °C, and 78.9 J/g at 35.0 °C. According to the
absorption peaks between 2915–2946 cm−1 and 2848–2859 cm−1 DSC results, all of MPCMs were found as promising thermal
for C–H stretching of paraffin waxes. The peaks at 1459 and energy storage materials for textile applications.
1388 cm−1 are also characteristic C–H bonding vibration peaks
of the paraffin proving the presence of paraffin in microcapsule Thermal stability of MPCMs
structure (Liu & Lou, 2015). The IR spectra of microcapsules also
showed completion of the addition reaction between the MMA To investigate the thermal stability of the MPCMs, TGA analyses
and MAA monomers by the disappearance C=C stretching peak were carried out. Figure 4 shows TGA and differential thermo-
at 1639 cm−1 in the spectra of MMA and at 1631 cm−1 in the spec- gravimetric analysis (DTG) curves of MPCMs by various shell
tra of MAA. The appearance of C=O (carbonyl) peak at around materials. Straight and dashed lines were TGA and DTA curves,
1729–1731 cm−1 in spectra of microcapsules, which was shown respectively. TGA data of the MPCMs with P(MMA-co-MAA)
at 1741 cm−1 and at 1698 cm−1 in the spectra of MMA and MAA shell and n-octadecane and n-eicosane core were summarized
monomers, respectively, was also evidence of copolymer forma- in Table 3. According to the collected data, MPCMs degraded in
tion. Moreover, broad band appearing at 3600–3350 cm−1 in the 3 steps with an initial weight loss of about 19–32% from 100 to
spectra of microcapsules was –OH stretching band of carboxylic 200 °C, resulting from the evaluation of n-octadecane (Qiu, Li,
acid group of MAA in microcapsule shell material. According to Song, Chu, & Tang, 2012). Probably, the shell of MPCMs broke
the FT-IR analysis, the MPCMs contained n-alkanes and have down simultaneously during n-octadecane release from the sys-
functional carboxylic acid group at the same time. Adhesion tem. And then the weight decreased from 275 to 420 °C in two
between the two materials increases depending on similarity of sharp steps because of the decomposition of the shell. The sec-
their chemical structure (Alay, Alkan et al., 2011). Since both ond and third step degradations must be for EGDM and MMA
cotton cellulose and P(MMA-co-MA) copolymer shell have polar release from the structure. Because that the functional monomer

Table 2. Thermal energy storage properties of MPCMs (Altun-Anayurt, 2014).


Microcapsule Melting enthalpy (J/g) Melting temperature (°C) Crystallization enthalpy (J/g) Crystallization temperature (°C)
n-Octadecane 215.4 27.8 −212.9 24.6
P(MMA-co-MAA)/n-octadecane-1 94.2 27.3 −87.7 26.4
P(MMA-co-MAA)/n-octadecane-2 58.7 27.3 −56.1 26.1
P(MMA-co-MAA)/n-octadecane-3 70.6 27.3 −65.4 26.1
n-Eicosane 276.7 36.7 −274.2 31.5
P(MMA-co-MAA)/n-eicosane-1 107.7 36.3 −101.4 35.5
P(MMA-co-MAA)/n-eicosane-2 145.8 36.1 −134.7 35.4
P(MMA-co-MAA)/n-eicosane-3 86.3 36.1 −78.9 35.0
THE JOURNAL OF THE TEXTILE INSTITUTE   35

was soluble also in water as it was in monomer phase, its percent- together with EGDM or MMA and not monitored as a sepa-
age in MPCMs was too low and its degradation was expected to rate degradation step. Also some of MMA and EGDM released
be occurring about the same temperatures as the other acrylic simultaneously leading to undetermination of the steps clearly.
monomers in the medium. It was thought that it released According to the TGA analysis of P(MMA-co-MAA)/n-eicosane

Figure 4. TGA curves of the P(MMA-co-MAA)/n-octadecane-3 (on the top) and P(MMA-co-MAA)/-n-eicosane-3 (on the bottom) microcapsules.
36   S. ALAY AKSOY ET AL.

microcapsules, thermal decomposition took place in 3 stages too. Morphology of MPCMs


The first step degradation started at 120 °C which was caused by
Particle morphology has a big influence on the physical prop-
the decomposition of n-eicosane. In this step, weight loss % val-
erties of the substances. It is well known that the smaller the
ues were 41, 54, and 31% for P(MMA-co-MAA)/n-eicosane-1-3
particles, the better the heat transfer is. In spite that organic
microcapsules, respectively. Mass loss in the first step of ther-
materials are not good conductors of heat, the extended
mal degradation process increased as the paraffin content in
surface area of small particles make them interact with the
microcapsules increased. The P(MMA-co-MAA) degraded in
environment thermally. Also spherical particles have a good
two steps at almost 200–240 °C and 410–420 °C. Degradation
mechanical constraint. Figure 5 shows the POM images of
processes were completed at around 410  °C in the microcap-
P(MMA-co-MAA)/n-octadecane and P(MMA-co-MAA)/n-
sules. P(MMA-co-MAA)/n-alkane microcapsules had easily dis-
eicosane microcapsules. The small size, unimodal particle size
tinguishable three-step thermal degradation process similar to
distribution and spherical shapes are very common in micro-
the degradation of microcapsules with PMMA shell crosslinked
capsules produced using emulsion polymerization technique.
using EGDM, which stated that degradation steps of hydrophilic
POM images showed that P(MMA-co-MAA) microcapsules
monomer overlapped and dissolved in the degradation steps of
had the expected geometrical profile.
the shell (Alkan, Sarı, & Karaipekli, 2011; Alkan et al., 2009).

Table 3. Degradation characteristics of MPCMs (Altun-Anayurt, 2014).


Microcapsules Degradation temperature interval (°C) Weight loss %
P(MMA-co-MAA)/n-octadecane-1 100–200 (1st step) 32
200–275 (2nd step) 6
275–420 (3rd step) 61
P(MMA-co-MAA)/n-octadecane-2 100–200 (1st step) 19
200–275 (2nd step) 4
275–420 (3rd step) 46
P(MMA-co-MAA)/n-octadecane-3 100–175 (1st step) 26
175–275 (2nd step) 8
275–425 (3rd step) 67
P(MMA-co-MAA)/n-eicosane-1 120–225 (1st step) 41
225–275 (2nd step) 7
275–420 (3rd step) 51
P(MMA-co-MAA)/n-eicosane-2 120–240 (1st step) 54
240–275 (2nd step) 4
275–410 (3rd step) 41
P(MMA-co-MAA)/n-eicosane-3 120–220 (1st step) 31
220–275 (2nd step) 6
275–410 (3rd step) 62

Figure 5. POM images of the P(MMA-co-MAA)/n-octadecane-1-3 (on the top) and P(MMA-co-MAA)/n-eicosane-1-3 (on the bottom) microcapsules ((a) and (d) 1% MA; (b)
and (e) 5% MAA; (c) and (f)10% MAA) (Altun-Anayurt, 2014).
THE JOURNAL OF THE TEXTILE INSTITUTE   37

Particle size and size distribution analysis of MPCMs the particle size distributions were narrow as shown in Figure 5.
According to the particle size measurement, it was concluded
The particle size and particle size distribution (PSD) of the
that all microcapsules have uniform and suitable particle sizes
PCMs were analyzed using a particle size analyzer with a
and PSD for textile applications. In literature, small-size capsules
dynamic laser scattering detector. Figure 6(a)–(c) and (d)–(f)
having mean particle size of 1–50 μm are recommended. Particle
shows the particle size distribution graphics of P(MMA-co-
size and size distribution of microencapsulated PCMs affect the
MAA)/n-octadecane-1-3 and P(MMA-co-MAA)/n-eicosane-1-3
spin-ability of polymer melts or solutions and the mechanical
microcapsules, respectively. Capsule size of P(MMA-co-MAA)/
properties of thermal regulating fibers. To overcome such prob-
n-octadecane-1 vary mostly from 1 to 40  μm, and they have
lems, the diameter of PCM microcapsules should be less than
mean particle size of 32.04 μm as the particle size of P(MMA-co-
10 μm (Boan, 2005; Jıang, Song, Ye, & Xu, 2008). The small par-
MAA)/n-octadecane-2 and P(MMA-co-MAA)/n-octadecane-3
ticle diameter provides relatively large surface area enabling heat
varies between 2–40 μm and 1–40 μm, respectively. The mean
transfer occur much easily. Thus, the rate of reaction of PCM to
particle size of the microcapsules was measured as 27.7 and
external temperature variations becomes very high.
32.5 μm, respectively.
According to Figure 6(d)–(f), particles size of P(MMA-
co-MAA)/n-eicosane-1-3 microcapsules varied by 1–40, and
SEM analysis results of the MPCMs-treated fabrics
1–20 μm, and the mean particle size were 29.6, 16.4, and 15.4 μm,
respectively. The average particle sizes measured by particle size Figure 7 shows the SEM photographs of the P(MMA-co-MAA)/
instrument were higher than the particle sizes observed by POM n-octadecane-3 microcapsule-treated fabrics that were washed
because of aggregation of nanosized MPCMs. In the meantime, for 5–20 laundering cycles and tested with rubbing test. The

Figure 6. Particle size distribution curves of the P(MMA-co-MAA)/n-octadecane-1–3 and P(MMA-co-MAA)/n-eicosane-1–3 microcapsules ((a) and (d) 1% MAA; (b) and (e)
5% MAA; (c) and (f) 10% MAA) (Altun-Anayurt, 2014).
38   S. ALAY AKSOY ET AL.

peaks of encapsulated paraffin on the fabric. These are evidence


of the presence of microcapsules in the structure of the fabrics.

T-History results of the MPCM-treated fabrics


Cooling effect by heat absorption of microencapsulated n-oc-
tadecane or n-eicosane on the fabric was detected by T-history
measurements. Heat absorption of MPCMs on the fabric leads
to a cooling effect during melting process of PCMs. To deter-
mine the cooling effect, the treated and untreated fabrics firstly
were conditioned at a low temperature (0 °C) and then placed
in heated box (50 °C), next the temperature on the fabrics was
recorded every 30 s. In the beginning, the temperature inside box
(air enclosure) decreased because of the cold fabrics placed in.
Additionally, the first temperature recorded on the fabrics was
reached to 33–34 °C due to time losing during the placement of
the fabrics into the box.
According to the Figures 10(a) and (b), there were
slight differences at a temperature of 33–40  °C between
the untreated (reference fabric) and treated fabrics with
microcapsules containing n-eicosane. But from 40  °C, the
temperature curves began to display considerable differ-
ences, particularly in the range of 40.6–44.5  °C, which
corresponds to two minutes after the start of test. The
maximum temperature difference reached up to 3.1  °C for
the fabric treated with P(MMA-co-MAA)/n-eicosane-3
while it was 2.3  °C for the fabric treated with P(MMA-co-
MAA)/n-eicosane-2 microcapsules. Additionally, the temper-
ature measured on the treated fabric was always lower than
that of the reference sample during all the measurement times,
which showed good thermo-regulatory effects of PCM on
Figure 7. SEM images of the fabrics treated with P(MMA-co-MAA)/n-octadecane-3 the fabric. However, the thermo-regulating effect decreased
microcapsule using Fixapret F-ECO resin (a) rubbing test applied, (b) 5 cycles
washed, (c) 10 cycles washed, and (d) 20 cycles washed. after 10 times washings, especially for the fabric treated with
P(MMA-co-MAA)/n-eicosane-2 microcapsules.
From Figure 10(c) and (d), it was seen that a significant tem-
spherical-shaped microcapsules were observed on the fabric sur- perature difference was shown up at around 36 °C for the fabric
face after repeated laundering. This is the proof of the successful treated with capsules containing n-octadecane. The maximum
fixation between textile substrate and the microcapsules and the temperature difference for the fabric treated with P(MMA-co-
microcapsule stability after washing and rubbing processes were MAA)/n-octadecane-3 and P(MMA-co-MAA)/n-octadecane-2
verified. The PCM microcapsules in the treated samples were compared to untreated fabric was determined as 4 and 2.6 °C,
mainly located at the spaces between fibers and the fiber surface. respectively. These differences were measured after 4 min from
Some of the microcapsules were broken and some caved with the starting of the test. Similarly, the temperature measured on
increasing laundering. the treated fabric was always lower than that of the reference
sample during all measurement time and the thermo-regulat-
FT-IR spectroscopic analysis results of the MPCMs-treated ing effect was decreased after 10 times washings, particularly
fabrics for the fabric treated with P(MMA-co-MAA)/n-octadecane-2
microcapsules.
The H-bonding O–H stretching vibration band near 3348 cm−1 According to the T-history test results, the untreated fabrics
in the spectra of untreated cotton fabric decreased after micro- had the largest temperature increasing rate, whereas this rate was
capsule application since the hydrogen bonds between the OH slower for the fabrics with microcapsules. It was concluded that
groups of the cellulose were weaker in microcapsule-bonded the fabrics treated with microcapsules had thermal regulating
cellulose (Figure 8). The diminution in the number of ter- effect and could change the temperature gradually. In this study,
minal OH groups of cellulose confirmed the chemical bond it was also determined that thermo-regulating effect of the fabrics
between the cellulose and microcapsules by means of a cross- treated with microcapsules improved with the higher hydrophilic
linker (Fixapret Resin F-ECO), shown in Figure 9. The peaks at MAA monomer content of the shell copolymer of microcapsules.
around 1720 cm−1 in the spectra of the microcapsule incorpo- This result proved that microencapsulated paraffin on the fabric
rated cellulose fabric were characteristic carbonyl (C=O) peak, provided thermo-regulation property depending on adhesion
which appeared around 1729–1731 cm−1 in spectra of micro- and binding amount of the microcapsules to the fabric instead
capsules. The peaks near 1456–1460 cm−1 were characteristic of the heat storage capacity of microcapsules.
THE JOURNAL OF THE TEXTILE INSTITUTE   39

Figure 8.  FT-IR spectra of the untreated (a); P(MMA-co-MAA)/n-eicosane-2 incorporated (b); P(MMA-co-MAA)/n-eicosane-3 incorporated (c); P(MMA-co-MAA)/n-
octadecane-2 incorporated (d); P(MMA-co-MAA)/n-octadecane-3 incorporated (e) fabrics.

Figure 9. Schematic representation of chemical bonds formed between the microcapsule and cellulose by means of cross-linker.
40   S. ALAY AKSOY ET AL.

Figure 10. T-History results of the fabrics treated with P(MMA-co-MAA)/n-eicosane-3 (a); P(MMA-co-MAA)/n-eicosane-2 (b); P(MMA-co-MAA)/n-octadecane-3 (c) and
P(MMA-co-MAA)/n-octadecane-2 (d) microcapsules.

Conclusion Disclosure statement


Preparation and characterization of n-octadecane or n-eicosane No potential conflict of interest was reported by the authors.
core and P(MMA-co-MAA) shell MPCMs were performed to
reveal application potential as textile thermal comfort additives. Funding
Spectroscopic and morphological results confirmed encapsula-
tion in spherical P(MMA-co-MAA) particles. According to the This work was supported by Scientific and Technological Council of
Turkey [Project no: 111M484].
FT-IR analysis, microcapsules had methacrylic acid functional
groups to interact with fiber surface physically or chemically
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