Thermochimica Acta 662 (2018) 135–148

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Development of heat storing poly(acrylonitrile) nanofibers by coaxial T

electrospinning
⁎
Ezgi C.B. Noyana, Emel Ondera, , Nihal Sarierb, Refik Aratb
a
Istanbul Technical University, Faculty of Textile Technologies and Design, 34437, Gumussuyu, Taksim, Istanbul, Turkey
b
Istanbul Kultur University, Faculty of Engineering, 34158, Bakirkoy, Istanbul, Turkey

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

Keywords: New thermal energy storage materials were developed as poly(acrylonitrile) (PAN) nanofibers with encapsulated
Energy materials phase change materials (PCMs). Sixteen samples composed of PAN shells and PEG or PEGME cores, and one
Nanocomposites control sample composed of only a PAN shell, were manufactured by coaxial electrospinning. SEM images re-
Thermal properties vealed the formation of randomly distributed, distinct nanofibers with smooth surfaces and cylindrical shapes
Electrospinning
along their lengths. FTIR results confirmed bicomponent nanofiber structures and TGA results demonstrated
their thermal stabilities. Phase change performances of nanofibers were repeatedly examined by DSC analyzes;
heating enthalpies ranged from 38 to 133 J g−1 and from 29 to 60 J g−1 for PAN-PEGs and PAN-PEGME samples,
respectively, corresponding to good encapsulation efficiencies. These remarkable thermal energy storages were
achieved at different melting temperatures (−1 to 60 °C). Textile based sandwich structures containing three
different types of PAN-PCM nanowebs demonstrated enhanced thermal properties and buffering function against
temperature changes in surrounding.

1. Introduction breathability or moisture transport capability in the final products [16].

Growing awareness of energy efficiency, attempts for avoiding en-
vironmental pollution as well as new lifestyle trends towards more
comfortable and well-being products have become the main drivers to
create alternative materials providing enhanced thermal management
solutions [1]. The latent heat storage materials, commonly known as
phase change materials (PCMs), that are capable of absorbing and re-
leasing large quantities of latent heat during solid-solid or solid-liquid
phase transitions, possess significant potential to fulfill the thermal
management requirements for cooling and heating applications in
various research fields and industries such as space heating and cooling
[2], solar energy storage [3], temperature sensitive textiles and clothing
[4], transportation packaging [5], healthcare [6] and electronics etc.
[7].
Various storage processes such as microencapsulation [8,9], shape
stabilization [10,11], foam production [12–14], filling hollow fibers
[15] have been applied to PCMs prior to their integration into different
composites in order to prevent their interaction with the surrounding
medium and their leaching throughout the phase change process, to
increase their mechanical and thermal stabilities and to enhance their
ease of handling [4]. On the other hand, each method has some
drawbacks such as reduced thermal conductivity, softness, flexibility,
Currently, developing new temperature regulating composites pro-
duced by single or coaxial electrospinning with improved thermal,
mechanical and physical performances has received great attention for
endorsing the applicability of PCMs [17–19]. Electrospun form stable
PCMs exhibit remarkable advantages, such as forming a large surface
area with the numerous nanofibers, being lightweight, and allowing
direct use in various composites, etc. [20]. The method of single nozzle
electrospinning, concerning with mixing or grafting of PCMs in the host
polymer matrix, is the most common approach for fabricating ultrafine
PCM fibers due to the easiness of electrospinning process. The greatest
disadvantage of single electrospinning is the insufficient encapsulation
and partial leakage of PCM through the fibers causing the PCM’s in-
teraction with the surrounding medium [19]. Over the past decade, the
method of coaxial electrospinning, namely simultaneous electrospin-
ning of two or more different materials into core-shell structured na-
nofibers, has attracted more and more attention [16–18] for en-
capsulating both hydrophilic and oleophilic PCMs in a variety of
polymers, achieving high encapsulation efficiencies, preventing the
leakage of PCMs and enhancing the mechanical properties of the
composite PCM electrospun fibers [19,21]. Bringing in these ad-
vantages, various PCMs and polymers have recently been explored as
core and shell materials in coaxial electrospinning processes to

⁎
Corresponding author.
E-mail address: onderem@itu.edu.tr (E. Onder).

https://doi.org/10.1016/j.tca.2018.02.008
Received 21 November 2017; Received in revised form 10 February 2018; Accepted 14 February 2018
Available online 21 February 2018
0040-6031/ © 2018 Elsevier B.V. All rights reserved.
E.C.B. Noyan et al.
manufacture a number of form-stable PCM nanofibers [22–29].
Among the various organic PCMs, poly(ethylene glycols) (PEGs),
composed of linear dimethyl ether chains with hydroxyl end groups
[He(OeCH2eCH2)neOH], have attracted attention for diverse thermal
storage applications due to their desirable characteristics, such as their
capability for repeatable solid-liquid phase changes at low and mod-
erate temperature intervals, high heat of fusion (ΔHfus), non-volatility,
chemical and thermal stability, solubility both in water and organic
solvents, biocompatibility, non-toxicity and low price [1,30–32]. Poly
(ethylene glycol) methyl ethers (PEGMEs) [CH3e(OeCH2eCH2)neOH],
which are the methyl-terminated (CH3) derivatives of PEGs, also have
suitable characteristics for thermal storage utilization [33]. Along with
the utilization of PEGs in the preparation of nanowebs through single
axial electrospinning [34–37], PEGs have recently been tested as core
material in the production of coaxial electrospun PCMs by Park’s re-
search group [29,38,39], Rezai et al. [28], Sun et al. [24], Chen et al.
[26], Golestaneh et al. [25], Babapoor et al. [40]. They all observed
that the heat capacity values and phase change temperature intervals of
the nanofibers produced through coaxial electrospinning had varied in
a wide range as a function of the molecular weight of PEG selected as
core as well as the concentration, solvent type and pumping rate of PEG
solution.
In the fabrication of coaxial nanofibers of PCMs, various types of
polymers have been tested as shell material such as cellulose acetate
(CA) [26,28], poly(vinyl pyrrolidone) (PVP) [22], poly(vinylidene
fluoride) (PVDF) [27], polyurethane (PU) nanofibers [23,41], poly-
ethylene terephthalate (PET) [25] and polyamide 6 (PA6) [40]. The
results of these studies demonstrated that the average fiber diameter
and fiber length as well as the mechanical properties of nanofibers
dependent on the type of polymer picked as shell, concentration and
pumping rate of polymer solution under given electrospinning condi-
tions.
The use of PAN in the manufacture of electrospun form-stable PCM
nanofibers has recently been studied due to its very good filament
forming properties, high tensile strength and elastic modulus, thermal
stability and low density [42–46]. Ke et al. fabricated a form-stable
composite PCM with the methyl stearate (MES) mixed in the supporting
matrix of PAN (50,000–60,000 g mol−1) using simple electrospinning
method and investigated the composite nanofibrous mats for their
changing thermal and mechanical properties when loaded with various
contents of graphene oxide [47]. Esmaeilzadeh et al. prepared PEG-PAN
nanofibers with different amounts of multi walled carbon nanotubes
(MWCNTs) through single electrospinning [48]. The number of pub-
lished articles concerning with PAN-PCM shell/core structures is lim-
ited as well. Wan et al. studied PAN-co-IA/isopropyl palmitate and
paraffin oil (PCM) sheath/core nano-fibers by coaxial electrospinning,
reporting phase change enthalpies for only PAN-co-IA/isopropyl pal-
mitate nano-fibers but no thermal transition for PAN/paraffin oil nano-
fibers [49]. Very recently, Haghighat et al. studied the encapsulation of
n-alkanes in PVP, PVDF and PAN [50], concluding that PAN solution
was not suitable for embedding n-octadecane into the core.
Although the coaxial electrospinning has become a promising
method to develop form-stable PCMs, the use of PAN in shell/core nano
structures is quite new and the information on their chemical, structural
and thermal phenomena is quite limited. There still exists a knowledge
gap with respect to coaxial electrospinning of PAN and PCMs to develop
diversified dynamic heat storage materials suitable for different in-
dustrial energy applications. More specifically, the coaxial electro-
spinning of PAN-PEG and PAN-PEGME shell/core nanofibers has never
been reported in the previous studies. PEGMEs are good PCM candi-
dates; however, to the best of our knowledge, their thermal properties
have not yet been addressed in this respect despite they provide phase
transitions with considerable heat enthalpies in different temperature
intervals. The objective of the present study is to design and develop
bicomponent nanofibers composed of PAN shells and various PEG and
PEGME cores for use as novel thermal energy storage materials that
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Thermochimica Acta 662 (2018) 135–148
ensure the continuity of the microclimate of the system despite fluc-
tuations in the temperature of the surrounding medium and are suitable
for further manufacturing practices. The shell material of PAN
(150,000 g mol−1) is preferred considering its good thermal, chemical
and fiber forming properties as well as its potential use in both energy
and nanofiber applications. A number of low molecular weight PEGs
(400–2000 g mol−1) are selected due to their perfect thermal proper-
ties, especially the high latent heat of fusions at relatively low and
normal temperatures, chemical stabilities and biodegradability.
Similarly, three PEGMEs (550–5000 g mol−1) for the first time are
chosen regarding the lack of their applications in the shape stabilized
PCM manufacture. The coaxial electrospinning is applied at optimized
processing conditions to produce uniformly shaped bicomponent na-
nofibers. Structural and thermal characterizations of the as-spun na-
nofibers are investigated in depth by using Fourier-transform infrared
spectroscopy (FTIR), differential scanning calorimetry (DSC) and ther-
mogravimetry (TGA). Scanning electron microscopy (SEM) is used to
identify the morphologies of the electrospun PAN-PEG and PAN-PEGME
nanofibers. In addition, to seek the potential use of PAN-PCM nanofi-
bers in textile-based composites, four sandwich-like structures were
developed and characterized for their thermal properties.
2. Experimental study
2.1. Materials
A PAN copolymer, which consists of 99.5% acrylonitrile (AN) and
0.5% maleic anhydride (MAH), (H2CHCN)n, was supplied by Good
Fellow Cambridge Limited (Ermine Business Park, Huntingdon,
England; CAS No: 25014-41-9) in powder form and used as the shell
material in the coaxial electrospinning process. Its average molecular
weight was 150,000 g mol−1, its density was 1.18 g cm−3, and its mean
particle size was 50 μm [51].
Eight different types of organic PCMs were used as core materials in
the same process to enhance the thermal properties of the PAN-based
nanofibers. Poly(ethylene glycols) (PEGs) with molecular weights of
400 g mol−1 (PEG400), 600 g mol−1 (PEG600), 1000 g mol−1
(PEG1000), 1500 g mol−1 (PEG1500) and 2000 g mol−1 (PEG2000)
and PEG methyl ethers (PEGMEs) with molecular weights of
550 g mol−1 (PEGME550), 750 g mol−1 (PEGME750) and
5000 g mol−1 (PEGME5000) along with the chemical reagent dimethyl
acetamide (DMAc, C4H9NO) were purchased from Sigma-Aldrich Inc.
These materials were all technical grade and used without further
purification.
2.2. Coaxial electrospinning of PAN-PCM nanofibers
The PAN-PCM nanofibers were produced using a coaxial electro-
spinning device (Yflow Co., Spain) [52], which was suitable for the
fabrication of shell/core structures in one step. The spinneret of the
device consists of two stainless steel coaxial needles with outer dia-
meters (ODs) of 0.9 and 1.7 mm and inner diameters (IDs) of 0.6 and
1.4 mm, respectively, connected to a reservoir. The grounded flat
stainless steel plate was placed 15 cm from the coaxial nozzles, and a
double polarized system (−30 kV, +30 kV) was used to effectively
collect the nanowebs. The system was equipped with a Taylor cone
visualization system.
To produce electrospun heat storing bicomponent nanofibers, the
shell and core solutions were prepared by separately dissolving PAN
and each of the PCMs in DMAc. To prepare the shell solution, 150 mL of
DMAc and 6% PAN (by weight) were added to a glass sample bottle and
stirred at 500 rpm using a magnetic stirrer at 35–40 °C for 4 h to obtain
transparent solutions. The core solutions were prepared at two different
concentrations: either 40 wt% or 30 wt% PEG in DMAc and either 30 wt
% or 20 wt% PEGME in DMAc. Therefore, the weight ratios of the core
materials in the core/shell compositions (RWcore) were calculated as
E.C.B. Noyan et al. Thermochimica Acta 662 (2018) 135–148

Table 1
Optimized coaxial electrospinning parameters and conditions for the production of PAN-PCM nanofibers.

Sample Code Shell (in DMAc) Core (in DMAc) Shell pump rate (mL h−1) Core pump rate (mL h−1) Injector voltage (kV) Collector voltage (kV)

NF-6PAN (Control) 6% PAN – 0.03 – 7.0 −7.0

NF-PEG400/40 6% PAN 40%PEG400/1%PEG1500 0.06 0.01 6.2 −6.0
NF-PEG400/30 6% PAN 30%PEG400/1%PEG1500 0.04 0.01 6.7 −6.7
NF-PEG600/40 6% PAN 40%PEG600/1%PEG1000 0.05 0.01 6.5 −6.5
NF-PEG600/30 6% PAN 30%PEG600/1%PEG1000 0.04 0.01 6.4 −6.4
NF-PEG1000/40 6% PAN 40%PEG1000 0.04 0.01 6.0 −6.0
NF-PEG1000/30 6% PAN 30%PEG1000 0.04 0.01 6.5 −6.5
NF-PEG1500/40 6% PAN 40%PEG1500 0.02 0.01 6.3 −6.1
NF-PEG1500/30 6% PAN 30%PEG1500 0.04 0.01 6.1 −6.0
NF-PEG2000/40 6% PAN 40%PEG2000 0.04 0.01 6.4 −6.3
NF-PEG2000/30 6% PAN 30%PEG2000 0.05 0.01 6.5 −6.5
NF-PEGME550/30 6% PAN 30%PEGME550 0.04 0.02 6.5 −6.9
NF-PEGME550/20 6% PAN 20%PEGME550 0.04 0.02 7.0 −7.0
NF-PEGME750/30 6% PAN 30%PEGME750 0.04 0.02 7.1 −6.8
NF-PEGME750/20 6% PAN 20%PEGME750 0.05 0.04 8.0 −7.6
NF-PEGME5000/30 6% PAN 30%PEGME5000 0.05 0.02 7.0 −7.0
NF-PEGME5000/20 6% PAN 20%PEGME5000 0.05 0.03 8.1 6.9

0.870 for the nanofiber (NF) samples produced with 40 wt% core so-
lutions, as 0.833 for NF samples produced with 30 wt% core solutions
and as 0.769 for NF samples produced with 20 wt% core solutions,
correspondingly. PEG1500 (1 wt%) and PEG1000 (1 wt%) were added
to the core solutions of PEG400 and PEG600, respectively, to ensure
compatibility between the shell and core solutions and achieve stability
for the electrospinning conditions. Due to their chain lengths, chain
entanglements were improved, and fiber formation was enhanced.
The processing parameters for coaxial electrospinning, which are
summarized in Table 1, were set to ensure Taylor cone formation for
each of the samples specifically after their fine tuning. The inner needle
was used to pump core solution and outer needle was used to pump
shell solution. The injector flow rates were adjusted to
0.01–0.06 mL h−1 to ensure that the core solutions were added at rates
that were one half to one sixth of the flow rate of the shell solution.
Therefore, the shell/core jets were successfully spun by means of an
applied voltage (12–16 kV). Electrospinning was continued for 15 min
at 25 °C. In total, sixteen different types of nanowebs containing a
particular PAN-PCM nanofiber (NF) and one control sample (NF-6PAN)
were produced. To examine the reproducibility, implemented electro-
spinning process was repeated three times (under the same conditions)
for each of the NF-PEG and NF-PEGME samples produced with 40 wt%
PEG and 30 wt% PEGME core solutions, respectively.
2.3. Characterization of shell/core solutions and PAN-PCM nanofibers
attenuated total reflection (ATR) accessory. The morphology and sur-
face characteristics of all prepared nanowebs were analyzed via scan-
ning electron microscopy (SEM) using an EVO® LS 10 model Zeiss type
SEM (LaB6-Tungsten filament) at 5–10 kV. To prepare the SEM sam-
ples, dried nanowebs were placed on standard mounts (15 mm in dia-
meter and 2 mm in depth) under vacuum and coated with a 1–2 nm
thick conductive layer of gold to prevent charging during imaging. The
diameter distributions of the nanofibers were obtained from SEM
images with a 15.00 K magnification via the ImageJ-DiameterJ soft-
ware for 100 nanofibers on average [56].
The thermal properties of the materials and NF samples were in-
vestigated using a Perkin Elmer DSC 4000 differential scanning ca-
lorimeter with an accuracy of ± 0.001 for both temperature and en-
thalpy measurements. A nitrogen flux (20 mL min−1) was used as the
purge gas for the furnace. Temperature scans were run on samples that
had been placed in a closed pan and that weighed 10–15 mg for ten
successive heating and cooling cycles. All samples were brought to
thermal equilibrium at the starting temperature, which was held for
10 min. Then, the samples were heated to the final temperature at a
heating rate of 10 °C min−1, which was held for 10 min. Finally, the
samples were cooled to the starting temperature at a cooling rate of
10 °C min−1. Thermogravimetric (TG) analysis of the samples was
performed from 20 to 800 °C at a heating rate of 10 °C min−1 under a
dry nitrogen atmosphere purged at a rate 20 mL min−1 by a SEIKO
EXSTAR 6200 Model TG/DTA instrument.

Since viscosity, surface tension and electrical conductivity of the
core and shell solutions significantly affect the fiber morphologies in
coaxial electrospinning [53], these solution parameters were measured
correspondingly for each of the solution prepared. Dynamic viscosity
measurements of the shell and core solutions were performed using an
SNB-1 model Stepless Speed Regulation Rotary Display Viscometer at
the shear rate (R) of 60 rpm and at 25 °C [54]. The surface tensions of
the solutions were measured with a Neubert Glass model Traube Sta-
lagmometer according to a previously reported method [55]. Electrical
conductivity measurements of the shell solutions were performed at
25 °C using a Mettler Toledo S80 model Multi Conductometer between
0.001 μS cm−1 and 1000 mS.cm−1. The conductometer was calibrated
with a standard solution (84 μS cm−1), and the cell constant was taken
as ≤0.1.
The Fourier transform infrared (FTIR) transmission spectra of the
shell/core materials and the electrospun nanowebs were recorded be-
tween 4000 and 650 cm−1 at a resolution of 4 cm−1 using a Perkin
Elmer Spectrum 100 FTIR spectrometer equipped with a universal
2.4. PAN-PCM nanofiber applications into textiles
To demonstrate applicability of the bicomponent nanofibers into
textiles and to observe enhanced thermal properties of the final pro-
ducts containing PAN-PCM nanofibers, NF-6PAN (Control) and three
other NF samples, say NF-PEGME550/30, NF-PEG1000/40, NF-
PEG1500/40, were reproduced under the same conditions, provided
that the electrospinning was proceeded for 2 h in order to ensure
compatibilities of the nanowebs with the selected conventional textile
materials. A spunbond textile sheet (STS) composed of 100% polyester
microfibers weighing 25 g m−2, suitable for applications in auto-
mobiles, filtration, home furnishing, and wiper use; and a 50.50 poly-
amide-polyester lining (L) weighing 36 g m−2, suitable for fixation of
partial textile surfaces in the production of fine and soft-handling ap-
parel, were chosen as the base and bonding layers in production of four
sandwich-like structures (see Fig. 1). Each reproduced nanoweb was
placed in between two bonding layers and STS base before inserting
them into a rotating couple. These matrices (sandwich-like structures)

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Fig. 1. Schematic presentation of the designed sandwich-like composite structure.

Table 2
Developed sandwich-like structures containing PAN based nanowebs.

Composite Sample The type of multi-layer structure Weight of textile layers in the sample Weight of nanoweb in the sample Total weight of the composite sample
(g) (g) (g m−2)

A STS/L/NF-6PAN 0.00563 0.01914 244.0

B STS/L/NF-PEGME550/30 0.00608 0.01827 310.0
C STS/L/NF-PEG1000/40 0.00608 0.02378 380.0
D STS/L/NF-PEG1500/40 0.00608 0.00880 190.0

Table 3
Viscosity, surface tension and conductivity results for the shell and core solutions used in PAN-PCM coaxial electrospinning (T = 25 °C).

Sample Code Dynamic Viscosity Surface Tension Conductivity (μS cm−1) Core/shell viscosity Core/shell surface Core/shell conductivity
(Pa s) (mN cm−1) ratio tension ratio ratio

NF-6PAN (Control) 0.53 35.56 17.19 – – –

NF-PEG400/40 0.01 38.62 35.60 0.02 1.10 1.80
NF-PEG400/30 0.01 38.11 52.40 0.02 1.10 2.60
NF-PEG600/40 0.02 37.27 19.74 0.03 1.00 1.00
NF-PEG600/30 0.01 35.28 28.10 0.02 1.00 1.40
NF-PEG1000/40 0.02 35.72 13.77 0.04 1.00 0.70
NF-PEG1000/30 0.01 35.35 15.61 0.02 1.00 0.80
NF-PEG1500/40 0.02 36.76 31.20 0.04 1.00 1.60
NF-PEG1500/30 0.01 35.47 24.60 0.02 1.00 1.20
NF-PEG2000/40 0.03 37.43 14.38 0.06 1.10 0.70
NF-PEG2000/30 0.02 35.61 13.62 0.03 1.00 0.70
NF-PEGME550/30 0.01 34.78 0.88 0.01 1.00 0.04
NF-PEGME550/20 0.01 35.09 0.84 0.01 1.00 0.04
NF-PEGME750/30 0.01 32.85 1.527 0.01 0.90 0.08
NF-PEGME750/20 0.01 33.98 1.424 0.01 1.00 0.07
NF-PEGME5000/30 0.02 30.36 17.44 0.03 0.90 0.87
NF-PEGME5000/20 0.01 31.58 18.60 0.02 0.90 0.93

were then fixed under the pressure of 2.5 bar at 132 °C for 24 s using a
laboratory-type LaStar lining machine. Four types of the studied sand-
wich-like structures are summarized in Table 2, indicating high mass
ratios of the nanowebs in A, B, C and D matrices which were 77%, 75%,
80% and 59%, respectively, so that other layers acted only as sup-
porting material.
The thermal properties of the sandwich-like composite structures, B,
C and D, containing PAN-PCM nanofibers, were analyzed in comparison
of corresponding properties of the composite A, containing NF-6PAN
(PAN hollow nanofibers without PCM in their cores). The parameters of
thermal conductivity, thermal diffusivity, specific heat capacity and
thermal effusivity, listed in Table 7, were measured using a Hot Disc
TPS 2500S model thermal analysis device according to the ISO 22007-
2:2015 standard test method [57]. A hot plate sensor with a diameter of
6.4 mm was placed between two prepared test specimens
(0.5 mm × 2.0 mm × 7.0 mm), and electric power (0.005–0.008 W)
was applied to the sensor for a short period of time (80–160 s) initially
at 23 °C to determine the resistance against a change in temperature
[58,59]. Hot Disc measurements were repeated 5 times for each of the
prepared composites. DSC analyses were conducted as well for this
group of samples.
3. Results and discussion
3.1. Characterization of shell/core solutions
Results of viscosity, surface tension and conductivity measurements
of the shell and core solutions are given in Table 3, which did not show
any significant variation for the samples prepared from the same stock
solution.
The shell solution (i.e., 6 wt% PAN in DMAc) was demonstrated to
be electrospinnable for the manufacture of NF-6PAN (Control). In
general, the viscosities of the core solutions were hundreds of times less
than that of the shell solution, all measured at the constant shear rate of
60 rpm. The concentration of the shell solution (i.e., 6 wt% PAN in
DMAc) and its corresponding viscosity (0.53 Pa s), as well as the con-
centrations of the core solutions, i.e., 40 wt% or 30 wt% PEG (in DMAc)
and 30 wt% or 20 wt% PEGME (in DMAc) and their viscosities (varied
between 0.01–0.03 Pa s), resulted in core/shell viscosity ratios ranging
from 0.01 to 0.06, and thus ensured continuous and beadless fiber
formation. The conditions required for a compound Taylor cone for-
mation were easily achieved when the surface tension values of the core
and shell solutions were of the same order. The core/shell surface
tension ratios ranged from 0.9 to 1.1 for both the PEG/PAN and

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Fig. 2. SEM images of the nanowebs, which contain electrospun bicomponent nanofibers produced from the 6 wt% PAN shell solution and core solutions consisting of PEGs with different
chain lengths (x15.00 K): a) NF-6PAN (Control); b) NF-PEG400/40; c) NF-PEG400/30; d) NF-PEG600/40; e) NF-PEG600/30; f) NF-PEG1000/40; g) NF-PEG1000/30; h) NF-PEG1500/40;
i) NF-PEG1500/30; j) NF-PEG2000/40; k) NF-PEG2000/30; and l) NF-PEG1500/30 (x50.00 K).

PEGME/PAN solutions, demonstrating the low interfacial tension be-
tween these solutions. The electrical conductivity of the shell solution
(i.e., 17.19 μS cm−1) satisfactorily contributed to the encapsulation
process of the core. No additional impact or adverse effect was observed
due to the varying conductivities of the PEG and PEGME solutions.
Thus, the applied parameters of shell and core solutions matched the
requirements for efficient coaxial electrospinning in order to get na-
nofibers of the desired morphology and fineness [53].
3.2. SEM results of PAN-PCM nanofibers
The SEM images of the nanowebs shown in Figs. 2 and 3,
demonstrated randomly distributed and distinct nanofibers with
smooth surfaces and cylindrical shapes along their lengths. In general,
the predetermined concentration of the shell solution (6 wt% PAN in
DMAc) facilitated the production of beadless nanofibers. Free chains
from the core macromolecules were not observed outside of the na-
noweb structures. These results confirmed that encapsulation of the
cores with the shell material can be achieved for all of the samples by
determining the solution characteristics and coaxial electrospinning
conditions. Table 4 summarizes the characteristic nanofiber diameter
distributions obtained from the SEM images shown in Figs. 2 and 3.
The fineness of the control sample (NF-6PAN) was quite remarkable,
with an average of 290 nm and a standard deviation of 105 nm.

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Fig. 3. SEM images of the nanowebs, which contain electrospun bicomponent nanofibers produced from the 6 wt% PAN shell solution and core solutions consisting of PEGMEs with
different chain lengths (x15.00 K); a) NF-PEGME550/30; b) NF-PEGME550/20; c) NF-PEGME750/30; d) NF-PEGME750/20; e) NF-PEGME5000/30; and f) NF-PEGME5000/20.

Table 4
Diameter distributions of the PAN-PCM nanofibers obtained from SEM images with 15.00 K magnification using ImageJ-DiameterJ software.

Sample Code Min. Max. Highest Percentage of the diameters of Nanofiber diameter for 90% of Mean and Standard
(nm) (nm) frequency (nm) the nanofibers ≤500 nm the size distribution (nm) Deviation [x ± σ ] (nm)

NF-6PAN (Control) 34 933 233 97% 415 290 ± 105

NF-PEG400/40 34 1586 724 38% 1000 606 ± 327
NF-PEG400/30 34 1621 448 38% 930 630 ± 265
NF-PEG600/40 34 1517 552 48% 828 524 ± 247
NF-PEG600/30 34 2069 517 46% 980 622 ± 318
NF-PEG1000/40 34 2034 552 44% 870 584 ± 281
NF-PEG1000/30 34 2207 552 25% 1300 775 ± 383
NF-PEG1500/40 34 1655 552 28% 1050 676 ± 271
NF-PEG1500/30 34 1724 448 72% 675 415 ± 237
NF-PEG2000/40 50 2450 50/355 50% 900 654 ± 496
NF-PEG2000/30 34 1546 400 70% 590 424 ± 181
NF-PEGME550/30 34 1724 655 21% 1170 732 ± 326
NF-PEGME550/20 34 2000 552 35% 1060 662 ± 300
NF-PEGME750/30 34 2310 1000 16% 1550 939 ± 431
NF-PEGME750/20 34 1966 690 38% 1050 663 ± 289
NF-PEGME5000/30 34 1300 133/600 56% 630 432 ± 138
NF-PEGME5000/20 34 1700 600 58% 700 455 ± 248

Therefore, 97% of the diameters of the obtained fibers were less than
500 nm. In the shell/core structures, the diameter distribution of each
of the nanofibers was wider due to the coaxial configuration of two
different types of large organic molecules and was affected by the en-
capsulation efficiency of the core by the shell. Most of the distributions
were single mode distributions based on their highest frequencies (e.g.,
552 nm for NF-PEG600/40). Some of the distributions were positively
skewed (e.g., 90% of the fiber diameters in NF-PEG1000/40 were
≤870 nm, with its right-hand tail extending over the micron scale). The
mean nanofiber diameters for all NF samples ranged from 415 to
939 nm (see Table 4).
3.3. FTIR results of PAN-PCM nanofibers
In general, the FTIR results were consistent with the SEM and TG
results. Fig. 4b to f show the FTIR transmission spectra of two specific
NF-PEG samples compared to the IR spectra of the PEG used in the core
and the NF-6PAN control sample. Fig. 5a–c represent similarly arranged
FTIR spectra of the NF-PEGME samples.
Fig. 4a shows the FTIR spectrum of the PAN copolymer (Good
Fellow Corp.) with typical peaks corresponding to the CH2, C^N, C]O,
and C−O groups. The broad band observed at 3440 cm−1 and the small
band located at 1624 cm−1 were due to the stretching vibration of the
eOH and CeOH groups in the O]CeOH groups of MAH in the PAN
copolymer [60,61]. The stretching vibrations of the C−H bonds in the
eCH, eCH2 and eCH3 groups were observed at 2937 cm−1. The band
at 2243 cm−1 was associated with the stretching vibrations of the C^N
bonds, indicating the presence of nitrile groups in the PAN structure
[62]. The small band at 1731 cm−1 corresponded to the C]C double
bond vibration of MAH. The transmission bands at 1247 and
1072 cm−1 were associated with the strong stretching vibrations of the
OeC and C]O bonds in the OeC]O groups in MAH. The strong to
medium intensity bands at 1454 and 1355 cm−1 were caused by
twisting vibrations of the eCH2 and eC^N groups in the PAN chains,

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Fig. 4. FTIR transmission spectra of a) PAN (Good Fellow Corp.); b) NF-6PAN (Control), PEG400, NF-PEG400/40 and NF-PEG400/30; c) NF-6PAN (Control), PEG600, NF-PEG600/40
and NF-PEG600/30; d) NF-6PAN (Control), PEG1000, NF-PEG1000/40 and NF-PEG1000/30; e) NF-6PAN (Control), PEG1500, NF-PEG1500/40 and NF-PEG1500/30; and f) NF-6PAN
(Control), PEG2000, NF-PEG2000/40 and NF-PEG2000/30.

respectively [60,61]. Similar transmission bands were also observed in
the FTIR spectrum of the control sample (NF-6PAN), including
stretching vibrations of the C−H bonds at 2923 cm−1 and stretching
vibrations of the C^N bonds at 2243 cm−1 (See Fig. 4b–f).
The IR spectra of PEG400, PEG600, PEG1000, PEG1500 and
PEG2000, which are shown in Fig. 4b–f, are quite similar to each other
and contain all characteristic transmission bands corresponding to PEG
chains. The bands at 3456–3348 cm−1 corresponded to the eOH groups
in the PEG chains. The characteristic bands at 2884–2865 cm−1 were
associated with the stretching vibration of the eCH2 groups in PEG.
Similarly, the bands at 1466–1455 cm−1 and 1349–1146 cm−1 corre-
sponded to the bending and rocking vibrations of the eCH2 groups,
respectively. The bands at 1105–1094 cm−1, 959–943 cm−1 and
846–841 cm−1 were characteristic of the CeOeC stretching vibrations
in the PEG chains [15]. In addition, the intensity of the transmission
bands of the PEG chains increased with increasing chain length. The
FTIR spectra of PEGME550, PEGME750 and PEGME5000 in Fig. 5a–c
contain the stretching vibrations of the eOH groups in the PEGME
chains at 3482–3472 cm−1 and the stretching vibrations of the eCH2
groups in the PEGME chains at 2881 cm−1 and 2864 cm−1. The char-
acteristic bands at 1466–1456 cm−1 and 1349–1249 cm−1 were due to
the bending and rocking vibrations of eCH2, respectively, and were
also related to the PEGME chains. The bands at 1280 cm−1,
1097–1094 cm−1, 959–944 cm−1 and 848–841 cm−1 were character-
istic of the CeOeC stretching vibrations of the ether groups in the
PEGME chains [63].
All distinctive bands of the PAN and PEG or PEGME groups were
observed in the FTIR spectra of the NF-PEG and NF-PEGME samples,

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Fig. 5. FTIR transmission spectra of PAN/PEGME NFs: a) NF-6PAN (Control), PEGME550, NF-PEGME550/30 and NF-PEGME550/20; b) NF-6PAN (Control), PEGME750, NF-PEGME750/
30 and NF-PEGME750/20; and c) NF-6PAN (Control), PEGME5000, NF-PEGME5000/30 and NF-PEGME5000/20.
which indicated effective trapping of the PEG or PEGME macro-
molecules in the PAN shell. In addition, no phase separation or struc-
tural changes occurred in the nanowebs during electrospinning.
Therefore, successful formation of the shape-stabilized PCM nanofibers
was confirmed. The stretching and bending vibrations of the eC^N
groups in PAN were detected at 2244–2241 cm−1 and
1631–1630 cm−1, respectively. The stretching and bending vibrations
of the eCH3, eCH2 and eCH groups in the PEG, PEGME and PAN
chains were identified by small shifts at 2888–2866 cm−1,
1467–1454 cm−1 and 846–839 cm−1, respectively. The bands at
3503–3431 cm−1 and 1643–1629 cm−1 were associated with the
stretching and bending vibrations of the eOH groups of PEGs and
PEGMEs. The ether groups (H2CeOeCH2) in the PEGs exhibited
stretching vibrations at 1280 cm−1and bending vibrations at
1108–1092 cm−1.
3.4. TGA results of PAN-PCM nanofibers
The thermograms of the core materials and NF samples are shown in
Fig. 6. The thermal decompositions of the PEGs primarily occurred in
one step starting at 310–388 °C and ending at 377–440 °C with little
residue. Similarly, one-step thermal decomposition of the PEGMEs
started at 351–394 °C and ended at 411–425 °C (see Fig. 6a and c). The
onset and end temperatures of these thermal decomposition curves
gradually increased as the PEG and PEGME chain lengths increased.
Relatively lower onset and end temperatures were observed in the
thermogram of PEG2000 (368 °C and 413 °C, respectively), which may
be due to small variations in the chain lengths of the test material.
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Thermochimica Acta 662 (2018) 135–148
These results confirmed that the PCMs were thermally stable and sui-
table for electrospinning applications.
The NF-PEG and NF-PEGME nanofibers exhibited a four-step mass
change pattern in the TG analyses similar to that of PAN (see Fig. 6b
and d). No loss of mass was observed for pure PAN up to 294 °C, which
corresponds to the cyclization of the nitrile groups and evolution of
small molecules, such as NH3 and HCN [64,65]. The first step in the
thermograms of the NF-PEG samples involved some dehydration due to
the hydroxyl groups of the PEG molecules in the core and ended a little
earlier at 260–290 °C. These onset temperatures of the thermal de-
gradations shifted to higher temperatures with the use of PEGs with
longer chain lengths in the NF structures. The thermal decomposition
reactions became more rapid at approximately 325 °C, and mass losses
up to 25% were primarily observed, which were caused by evolution of
PEG oligomers and pyrolytic reactions [11]. A further mass loss of 51%
for PAN occurred at 325–461 °C, which may be due to partial evolution
of NH3(g) and HCN(g) [64,65]. The corresponding TGA curves of the
NF-PEGs exhibited 67–79% mass losses from 325 °C to 412–440 °C. A
steady decrease in the mass was also observed up to 650 °C, corre-
sponding to complete evaporation of the polymer chain fragments from
the PAN fibers. The residues of the NF-PEG structures, as well as that of
PAN, at 650 °C were related to the non-volatile hard segment of the
polymer chains [65] and were 17–29% for NFs and 43% for PAN. The
thermal decompositions of NF-PEGME550/30 and NF-PEGME750/30
began at 163–166 °C, became more rapid up to 290–295 °C due to the
evolution of PEGME, as well as the pyrolytic reactions of PAN, and then
continued with the partial evaporation of the polymeric groups at
319–329 °C. Finally, the decomposition ended with mass losses of
E.C.B. Noyan et al. Thermochimica Acta 662 (2018) 135–148

Fig. 6. TGA results for a) PEGs; b) NF-PEGs; c) PEGMEs; and d) NF-PEGMEs.

Table 5
Phase transition characteristics of different chain length PEGs and PEGMEs obtained from the 2nd and 10th heating-cooling cycles of the DSC analyses (10 °C min−1).

PCM 2nd Heating 2nd Cooling 10th Heating 10th Cooling

Phase transition (°C) ΔH (J g−1) Phase transition (°C) ΔH (J g−1) Phase transition (°C) ΔH (J g−1) Phase transition (°C) ΔH (J g−1)

Tonset Tpeak Tend Tonset Tpeak Tend Tonset Tpeak Tend Tonset Tpeak Tend

PEG400 −16 2 6 77 −13 −17 −22 82 −13 2 6 80 −13 −16 −21 81

PEG600 8 19 23 129 12 7/4 −3 129 11 22 25 133 12 9/4 1 134
PEG1000 30 38 41 155 26 22 14 156 31 39 41 158 28 22 14 158
PEG1500 42 50 53 174 25 22/17 14 175 43 51 54 172 25 21 15 175
PEG2000 51 57 61 165 37 32 28 166 51 58 62 166 37 32 28 166
PEGME550 −6 15 19 129 9 4 −12 127 0 18 22 145 10 6 −22 142
PEGME750 10 31 36 135 25 16 5 130 11 31 36 136 25 16 5 131
PEGME5000 58 66 70 185 43 37 33 181 58 66 70 184 43 38 33 184

65–67% at 650 °C. The thermal decomposition of NF-PEGME5000/30
followed a pattern similar to that of PAN, which became more rapid at
both 290 °C and 419 °C and was complete at 650 °C with 25% residue.
3.5. DSC results of PAN-PCM nanofibers
The DSC analysis of PAN was carried out in a temperature interval
of 0–200 °C, wherein heating and cooling cycles were repeated four
times at 10 °C min−1. The glass transition temperature (Tg) of PAN was
determined to be 127.8 °C based on onset (Tonset) and end (Tend) tem-
peratures of 94.8 °C and 127.9 °C, respectively. This result is consistent
with the given Tg value of 125 °C (for the first heating cycle) for
commercial PAN, and the specific heat capacity (cp) of PAN was de-
termined to be 0.335 J g−1 °C−1 using the differential calculation soft-
ware that accompanies the Perkin-Elmer Pyris DSC. The cp and Tg va-
lues were measured to be 0.573 J g−1 °C−1 and 99.3 °C, respectively,
during the first cooling interval. The transition from the glass phase to
the crystal phase during this fast cooling occurred at lower tempera-
tures [66]. The heating-cooling behavior of PAN stabilized at the be-
ginning of the 2nd heating cycle, and the cp and Tg values during the 4th
heating cycle were measured to be 0.227 J g−1 °C−1 and 101.4 °C, re-
spectively [67].
Table 5 summarizes the phase transition temperatures and en-
thalpies of the PEGs and PEGMEs used as core material in coaxial

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Fig. 7. DSC graphs of NF-PEGs for 10th heating-cooling cycles at 10 °C min−1: a) NF-PEG400/30 and NF-PEG400/40; b) NF-PEG600/30 and NF-PEG600/40; c) NF-PEG1000/30 and NF-
PEG1000/40; d) NF-PEG1500/30 and NF-PEG1500/40; e) NF-PEG2000/30 and NF-PEG2000/40.
electrospinning. As shown from Table 5, peak temperatures during solid
to liquid phase transitions and corresponding ΔH values showed a
gradual increase with the increase in the average molar mass of PEG
and PEGME chains, e.g. PEG400 melted at 2 °C with an enthalpy of
80 J g−1 and PEG1500 melted at 51 °C with an enthalpy of 172 J g−1 in
the 10th heating cycles of the DSC analyses, in accordance with the
literature [1,4]. Super-cooling effects due to the difficulty of crystal-
lizations of PEG and PEGME chains were also observed during solidi-
fication phases, e.g. PEG400 crystallized at −16 °C and PEG1500
crystallized at 21 °C during 10th cooling periods, parallel to the
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Thermochimica Acta 662 (2018) 135–148
literature [1,4]. However, this phenomenon occurred with insignificant
changes in heat absorptions, heat releases and phase transition tem-
peratures of PEG and PEGME cores during the repeated heating-cooling
cycles, indicating thermal cycling stabilities of them. Considering both
phase transition intervals ranging from cold to normal environments
and the high heats of fusion, the studied technical grade PEGs and
PEGMEs were found suitable for the manufacture of heat storing shell/
core nanofibers.
Figs. 7 and 8 and illustrate DSC results for the NF-PEG and NF-
PEGME samples obtained from the 10th heating-cooling cycles. Table 6
E.C.B. Noyan et al.
Fig. 8. DSC graphs of NF-PEGMEs for 10th heating-cooling cycle at 10 °C min−1: a) NF-PEGME550/20 and NF-PEGME550/30; b) NF-PEGME750/20 and NF-PEGME750/30; c) NF-
PEGME5000/20 and NF-PEGME5000/30.
summarizes both phase transition characteristics and electrospinning
efficiencies of them.
DSC analyses results showed that the phase change intervals of these
nanofibers greatly overlapped with those of the PCMs enclosed in their
cores. However, the NF samples exhibited phase transitions in relatively
narrower temperature intervals, which suggests fewer variations in the
molecular conformations of the PEG or PEGME chains surrounded by
the PAN shell. Shifts in the phase change temperatures and slight en-
thalpy changes from the 2nd to 10th heating-cooling cycles observed for
some of the NF samples were associated with the thermal history effects
of the produced nanofibers.
The 10th heating cycle phase change enthalpies varied from 38 J g−1
to 46 J g−1 for NFs produced with 30 wt% PEGs and from 38 to
133 J g−1 for NFs produced with 40 wt% PEGs, each of which occurred
in a specific temperature interval. Adding1 wt% PEG1500 and 1 wt%
PEG1000 to the cores of PEG400 and PEG600 did not affect the phase
change intervals of NF-PEG400/40, NF-PEG400/30, NF-PEG600/40 or
NF-PEG600/30 significantly even though this addition did contribute to
the formation of the core/shell fibers. For example, NF-PEG400/40
samples exhibited wide endothermic enthalpies of 38–59 J g−1, at
−16–10 °C, as well as sharper exothermic peaks that were as high as
35–55 J g−1, respectively, at −15 to −25 °C. The phase change char-
acteristics of NF-PEGMEs, shown Fig. 8, were primarily determined by
the core characteristics, e.g., phase change temperatures through cyclic
heating-cooling process. The samples produced with 30 wt% PEGMEs
yielded enthalpies up to 60 J g−1 and the samples produced with 20 wt
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Thermochimica Acta 662 (2018) 135–148
% PEGMEs yielded enthalpies up to 41 J g−1 in the 10th heating cycle at
their specific temperature intervals.
These phase change enthalpies of NF-PEG and NF-PEGME samples
were found remarkable regarding both the pertinent core concentra-
tions used in coaxial electrospinning and the measured enthalpies of the
core PCMs, as the evidence of successful fabrication of PAN based core/
shell nanofibers. The values of ΔHexpected (J g−1), given in Table 6, re-
present the theoretical maximums for heating enthalpies of the samples,
expected based on the multiplication between the calculated weight
ratios of the cores in the core/shell compositions (RWcore), say 0.870 for
NF-PEGs produced with 40 wt% core solutions and 0.833 for NF-
PEGMEs produced with 30 wt% core solutions, and the corresponding
enthalpy value of the core PCM given Table 5. The last column in
Table 6 demonstrates the electrospinning efficiencies in terms of per-
centages of the proportions between measured (ΔH) and expected
(ΔHexpected) heating enthalpies of the produced NFs where E and Eh
indicate the average and the highest efficiencies, respectively, attained
for the replicates of the corresponding NF product. On the other hand,
the encapsulation efficiencies were achieved as 25–60% for NF-PEGs
produced with 30 wt% core solutions and as 27–29% for NF-PEGMEs
produced with 20 wt% core solutions.
The phase transitions of NF-PEGs and NF-PEGMEs shifted to lower
temperature intervals during cooling cycles because the development of
inter-chain physical interactions of the PEG molecules was delayed;
additionally, some impurities coming from the electrospinning process
might inevitably be involved in the nanoweb structures. Freezing point
E.C.B. Noyan et al. Thermochimica Acta 662 (2018) 135–148

Table 6
Summary of the DSC results measured for each of three repeated samples of NF-PEGs and NF-PEGMEs (10 °C min−1) and the corresponding electrospinning efficiencies.

Sample 10th Heating 10th Cooling ΔHexpecteda(J g−1) Efficiencyb (%)

Phase transition temperatures Enthalpy ΔH (J g−1) Phase transition temperatures Enthalpy ΔH (J g−1)
(°C) (°C)

NF-PEG400/40 Tonset −16 to −9 x 49 Tonset −15 x 45 70 E 70

Tpeak 0–5 s 15 Tpeak −18 to −19 s 14 Eh 85
T end 9–10 R 38–59 T end −25 R 35–55

NF-PEG600/40 Tonset 5–8 x 78 Tonset 12–11 x 71 116 E 67

Tpeak 21–22 s 15 Tpeak 8 s 13 Eh 76
T end 26–27 R 67–88 T end 4–3 R 61–80

NF-PEG1000/40 Tonset 28–35 x 91 Tonset 31–18 x 90 137 E 66

Tpeak 36–40 s 39 Tpeak 28–14 s 39 Eh 95
T end 39–41 R 52–130 T end 24–10 R 53–131

NF-PEG1500/40 Tonset 44–46 x 105 Tonset 33– 28 x 105 150 E 70

Tpeak 50–51 s 32 Tpeak 29–24 s 36 Eh 86
T end 52–53 R 69–129 T end 25–20 R 64–131

NF-PEG2000/40 Tonset 50–52 x 75 Tonset 37–33 x 74 144 E 52

Tpeak 54–57 s 41 Tpeak 34–29 s 40 Eh 92
T end 56–59 R 42–133 T end 31–24 R 44–131

NF-PEGME550/30 Tonset −15 to −14 x 37 Tonset 3–2 x 34 120 E 30

Tpeak -1–0 s 5 Tpeak −5 s 6 Eh 33
T end 13–16 R 33–40 T end −16 to −17 R 30–38

NF-PEGME750/30 Tonset 12–18 x 45 Tonset 23–19 x 43 113 E 39

Tpeak 25–29 s 22 Tpeak 21–15 s 18 Eh 53
T end 31 R 29–60 T end 17–11 R 30–55

NF-PEGME5000/30 Tonset 53–55 x 45 Tonset 41–37 x 44 153 E 29

Tpeak 57–60 s 4 Tpeak 39–35 s 2 Eh 31
T end 59–62 R 42–47 T end 35–32 R 42–45

a
ΔH expected = RWcore X ΔH of PCM in Table 5; RWcore = 0.870 for NF-PEGs/40 & 0.833 for NF-PEGMEs/30.
b
Efficiency = (ΔH of NF sample/ΔH expected) x100; E = mean efficiency; Eh = highest efficiency attained among the replicates.

Table 7
Measured thermal parameters of the textile-based sandwich-like composite structures.

Composite Samplesa Thermal conductivity Thermal resistivity Thermal diffusivityb Specific heat capacity Thermal effusivityc Enthalpy change

−1 −1 2 −1 −1 −1 −2 −1
k (W m °C ) R = 1/k R/RA α (mm s ) c (J kg °C ) ϵ (J m °C ) ΔHheating(J g−1) ΔHcooling (J g−1)
(W−1 m °C)

A 0.1013 ± 0.0002 9.870 – 0.393 ± 0.006 257.9 ± 3.3 161.7 ± 0.9 – –

B 0.1006 ± 0.0002 9.940 1.00 0.223 ± 0.002 451.8 ± 3.9 213.2 ± 0.8 29 (2–20 °C) 22 (11–0 °C)
C 0.0991 ± 0.0002 10.089 1.02 0.149 ± 0.001 666.9 ± 3.6 257.1 ± 0.5 47 (33–43 °C) 42 (27–19 °C)
D 0.0966 ± 0.0001 10.349 1.05 0.248 ± 0.001 389.3 ± 2.0 194.0 ± 0.5 40 (45–52 °C) 38 (32–25 °C)

a
A:STS/L/NF-6PAN;B:STS/L/NF-PEGME550/30; C:STS/L/NF-PEG1000/40; D:STS/L/NF-PEG1500/40.
b k
∝= .
pc
c
ε= kρc ; ρ = material density (kg m−3).

depressions were observed as 13–27 °C and this behavior became more
apparent as the PEG or PEGME chain length increased. This super-
cooling effect remained the same from the 2nd to the 10th cycle for each
of the samples during the entire DSC analysis. Additionally, some losses
in the exothermic enthalpies with respect to the corresponding en-
dothermic enthalpies suggested a less ordered conformation in the core
chains during solidification (see Figs. 7 and 8).
The DSC results indicated that the implemented coaxial electro-
spinning method and the applied processing conditions were repeatable
and suitable to achieve heat storing PAN based nanofibers that were
promising for dynamic heat management applications at different
temperature intervals.
3.6. Results of PAN-PCM nanofiber applications into textiles
Table 7 shows the thermal parameters of the sandwich-like struc-
tures, A to D, measured on a Hot Disc TPS 2500S. All four structures
demonstrated almost the same thermal conductivity/resistance
behavior, dominated by the PAN based nanowebs as well as the textile
layers in the matrices. However, the composite samples, B, C and D,
containing NF-PEGME550/30, NF-PEG1000/40 and NF-PEG1500/40
nanowebs, respectively, yielded significantly high specific heat capa-
cities (452, 667, 389 J kg−1 °C−1), which were 1.75, 2.59 and 1.51
times greater than the specific heat capacity of 258 J kg−1 °C−1 ob-
tained for the composite sample A containing PAN hollow nanofibers
without PCM in their cores. Thus, much more enthalpies were needed
to change the temperatures of the samples B, C and D than that needed
to change the temperature of the sample A, and a buffering effect could
be achieved by incorporating PAN-PCM nanofibers into the composite
structures. Similarly, thermal effusivities were determined to be 213,
257 and 194 J m−2 °C−1 for B, C and D; all were higher than that
measured for A (162 J m−2 °C−1) as an indicator of the enhanced heat
exchange capabilities of the final products with their surroundings. The
thermal diffusivities were obtained lower for all samples, containing
PAN-PCM nanofibers, in accordance with the higher specific heat ca-
pacities of them. In addition to these, composite structures containing

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E.C.B. Noyan et al.
PAN-PCM nanofibers, say B, C and D, repeatedly absorbed and released
remarkable and constant heats at specific temperature intervals during
their thermal cycling DSC analyses (see Table 7), quite promising for
dynamic heat management applications of such textile-based advanced
structures.
4. Conclusions
In this study, new thermal energy storage materials, PAN-PCM bi-
component nanofibers, were developed using the method of coaxial
electrospinning. The shell material was a high molecular weight
(150,000 g mol−1) PAN copolymer, chosen due to its non-reactivity,
good thermal, chemical and fiber forming properties, as well as its
potential use in both energy and nanofiber applications. A number of
low molecular weight PEGs (400–2000 g mol−1) and PEGMEs
(550–5000 g mol−1) were chosen and used as core due to their high
latent heats of fusion in a wide range of low and moderate temperature
intervals as well as their thermal, chemical and environmentally
friendly properties. As a whole, sixteen different types of PAN-PCM
nanofibers were produced with pertinent shell/core concentrations, fi-
nely tuned solution parameters and the same process parameters ap-
plied in coaxial electrospinning, all allowing compound Taylor cone
formation, and continuous and beadless fiber fabrication.
SEM images of the NF samples revealed that distinct nanofibers with
smooth surfaces and cylindrical shapes along their lengths were pro-
duced mainly at the nanoscale. FTIR and TGA results confirmed the
formation of bicomponent structures without phase segregation as well
as the achievement of substantial chemical and thermal stabilities for
the PAN-PCM nanofibers. All samples repeatedly exhibited remarkable
enthalpies ranged from 38 to 133 J g−1 for PAN-PEGs and from 29 to
60 J g−1 for PAN-PEGMEs during heating cycles, and ranged from 30 to
131 J g−1 for PAN-PEGs and from 23 to 55 J g−1 for PAN-PEGMEs
during cooling cycles in DSC analyses at 10 °C min−1. Therefore, PAN-
PCM nanofibers providing repeatable heat storage and release capa-
cities at different temperatures (in a range of −16 to 62 °C during
heating and of 41 to −25 °C during cooling) were achieved in depen-
dence of the type and concentration of the core PCM. These results
show that a group of low molecular weight PEGs and PEGMEs could be
successfully encapsulated by a high molecular weight PAN shell under
the circumstances applied in coaxial electrospinning for the first time,
and the developed PAN-PCM nanofibers offered good thermal and
structural features, capable of meeting the requirements of many spe-
cific thermal management applications in cold and normal temperature
environments.
To seek the potential use of PAN-PCM nanofibers in textile-based
composites, four sandwich-like structures were developed and char-
acterized for their thermal properties. The composites, B, C, D, con-
taining three different types of PAN-PCM nanofiber webs, say NF-
PEGME550/30, NF-PEG1000/40 and NF-PEG1500/40, respectively,
exhibited higher specific heat capacities and thermal effusivities, de-
creased thermal diffusivities than their counterpart of A containing PAN
hollow nanofibers without PCM in their cores. In addition, composites
designed with PAN-PCM nanofibers performed repeated heat absorp-
tions and releases in their DSC analyses associated with the type and
weight of the NF web used in the matrix. All these results indicate that a
modified thermal behavior together with the ability to maintain the
continuity of the microclimate of the system despite fluctuations in the
temperature of the surrounding medium is possible with such design
alternatives.
In conclusion, the PAN-PCM nanofibers developed in this study are
promising for further manufacturing practices in the area of sensitive
thermal management across various industries, such as temperature-
controlled packaging for foods and medicines, biomedical materials for
thermal therapy, thermal sensors, thermoelectric systems, textiles and
apparel for cold and hot environments, and solar energy systems.
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Thermochimica Acta 662 (2018) 135–148
Acknowledgments
This work was supported by the Scientific & Technological Research
Council of Turkey [TUBITAK213M281], Istanbul Technical University
and Istanbul Kültür University. We wish to thank Arçelik A.Ş for their
thermal conductivity measurements.
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