Applied Energy 247 (2019) 615–629

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Facile flexible reversible thermochromic membranes based on micro/ T

nanoencapsulated phase change materials for wearable temperature sensor
Yayue He, Wei Li , Na Han, Jianping Wang, Xingxiang Zhang
⁎

State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Key Laboratory of Advanced Fibers and Energy Storage, School of Material Science and
Engineering, Tianjin Polytechnic University, Tianjin 300387, China

HIGHLIGHTS GRAPHICAL ABSTRACT

• Thermochromic membrane has tem-

perature indication and energy storage
performance.
• The thermochromic response of the
hydrophobic membrane is sensitive
and reversible.
• The thermochromic membrane ex-
hibits excellent reversible thermal cy-
cling property.
• Aheatfacile temperature colorimeter with
storage was designed and fabri-
cated.

ARTICLE INFO ABSTRACT

Keywords: A series of facile flexible reversible thermochromic membranes containing micro/nanoencapsulated phase change
Flexible reversible thermochromic membrane materials were fabricated, which presented excellent thermochromic performance and striking latent heat storage
Phase change materials property. In this composite membrane, the polyvinyl alcohol/water-soluble polyurethane composite was served as
Thermal storage polymer matrix material, and the reversible thermochromic micro/nanoencapsulated phase change materials (TC-M/
Temperature-sensitive
NPCMs) which energy storage efficiency reached 67.5%, were served as functional fillers. Moreover, trimesoyl
Microcapsule
chloride was used for modifying the water resistance of thermochromic membranes. The effects of TC-M/NPCMs
contents on the morphology, thermochromic performance, thermal property, thermal stability and thermal cyclic
durability of flexible thermochromic membranes were experimentally investigated using field-emission scanning
electron microscope (FE-SEM), atomic force microscope (AFM), digital camera, differential scanning calorimeter
(DSC) and thermogravimetric analyzer (TGA), et al. The results revealed that TC-M/NPCMs were distributed evenly
in matrix membranes. The color of these obtained flexible thermochromic membranes could change in response to
variation of external ambient temperature and thus presenting perfect thermochromic performance. As TC-M/NPCMs
content increased, the mechanical property and thermal stability of membranes declined, while the enthalpy raised.
In addition, the static water contact angles (WCAs) analysis indicated that the water resistance enhanced greatly after
surface modification. Furthermore, thermochromic membranes still exhibited worth mentioning thermal cyclic
durability undergoing 100 heating and cooling cycles. A facile temperature colorimeter was designed and fabricated,
by using the flexible thermochromic membrane with heat storage and temperature regulation property, which could
be served as a promising wearable temperature sensor. Hence, the application of the prepared thermochromic
membrane in thermal regulation, energy storage and wearable temperature sensor has great potential in the future.

⁎
Corresponding author.
E-mail addresses: [email protected], [email protected] (W. Li).

https://doi.org/10.1016/j.apenergy.2019.04.077
Received 14 November 2018; Received in revised form 2 April 2019; Accepted 15 April 2019
0306-2619/ © 2019 Elsevier Ltd. All rights reserved.
Y. He, et al. Applied Energy 247 (2019) 615–629

1. Introduction widely used membrane materials owing to their good film-forming

ability, low cost and easy physical and chemical modification. Suhas
Thermochromic materials have attracted extensive research interest et al. [24,25] provided in-depth analyses of novel type of membranes
owing to their potential applications in anti-counterfeiting mark [1], including cross-linking, grafting, blending and composite membranes
temperature indicators [2], wearable electric devices, medical diag- which were typically formed through an intimate and homogeneous
nosis [3], security materials [4], aerospace and other fields. Thermo- dispersion of filler particles in the polymer matrix. Nguyen et al. [26]
chromism refers to the color transition phenomenon that occurs when prepared thermoplastic polyurethane/functionalized graphene sheet
the substance is heated or cooled. Thermochromic materials are special nanocomposites by an in situ polymerization method. Kim et al. [27]
functional materials possessing a thermal memory function when the utilized the alumina-coated graphene as an additive to enhance the
color of compounds and mixtures emerging pronounced changes during thermal conductivity of the alumina sphere/thermoplastic poly-
heating or cooling [5]. urethane composite. Polyvinyl alcohol (PVA), due to its good bio-
Thermal energy storage plays a critical role in energy conservation compatibility, biodegradability, water-soluble and low biological toxi-
and emission reduction, exhibiting enormous potential in improving city, has been applied in numerous fields such as: filtration materials
thermal comfort [6,7] and energy availability [8], enabling efficient use [28], membranes, coatings [29], protective clothing [30], textile, drug
of energy [9]. Thermal energy storage works in different temperature release, et al. Suhas et al. [31] prepared mixed matrix membranes of
ranges. In terms of high temperature, it is applied for power generation, PVA loaded with zeolite particles having different silica alumina ratio
heat transfer fluid [10], and the like. While in low temperature, it is and used them in the pervaporation dehydration of ethanol and iso-
used for thermal comfort applications such as heating and cooling of propanol from their aqueous mixtures. A novel water-induced shape
buildings [11], thermal regulating textiles [12] and foams. The phase memory polymer based on PVA with graphene oxide (GO) was carried
change materials (PCMs) refer to materials that change the state of a out by Qi et al. [32], which provided an example for developing new
substance and provide latent heat under the condition of constant shape memory polymers. Water-soluble polyurethane (WPU) also has
temperature, which will hopefully become the optimal green environ- remarkable biocompatibility, low toxicity, good mechanical property,
mental protection carrier for energy conservation and environmental strength, flexibility, toughness and damping, so various WPU based
protection once widely applied in human life [13]. During the phase materials were widely used in the fields of coating, adhesive, fabric
change process, the PCMs absorb or release a large amount of latent coating [33], automobile, architecture and biomedical [34]. Sun et al.
heat [14]. However, there are emerging some defects in PCMs such as [35] performed experimental investigations on developing an en-
the low thermophysical properties during cycling [15], easy to leak vironmentally friendly method to fabricate multi-functional hybrid
from substrates [16] and poor thermal conductivity values [17], et al. A aerogels by chemical integration of WPU and GO. The prepared aero-
considerable amount of studies have primarily concentrated on the gels exhibited excellent insulation properties and had a broad appli-
encapsulation of PCMs with macro, micro and nanometer methods. cation prospect in various industries. Based on mentioned research
Microencapsulated PCMs have been extensively applied, which can above, PVA/WPU composite membrane was adopted as polymer matrix
guarantee controlled release, prevent corrosion PCM leakage, improve materials in this study. Therefore, the intention of the present study was
thermal and mechanical properties, and have poor environmental re- to developing a novel membrane based on PVA and WPU, which pos-
activity [18]. MicroPCMs have been extensively employed in the fab- sessed temperature indication and energy storage performance.
rication of building materials [19], thermal regulated fabrics [11], In this work, TC-M/NPCMs with excellent energy storage property
coatings, foams [20] and so on. A fabrication of novel micro/na- were prepared for fabricating flexible thermochromic membrane and
noencapsulated phase change material (M/N-EPCM) via emulsion then the membrane was modified by trimesoyl chloride (TMC) to en-
polymerization was investigated by Ahmet et al. [21]. They suggested hance its hydrophobicity. Properties of the prepared flexible thermo-
that the methylmethacrylate (MMA) monomer was used as shell and chromic membranes were determined, including morphology, me-
C19 as core material, and the prepared M/N-EPCM had good thermal chanical properties, melting crystallization properties, thermal
durability, thermal reliability, chemical stability, phase change rever- stability, thermal cyclic durability, color transition temperature and
sibility property and thermal conductivity. chromogenic properties. A small and portable temperature colorimeter
The research of thermochromic phase change materials with both was designed and manufactured to quickly and easily know the body
thermochromic function and energy storage is considered as a very surface temperature by comparing the color of thermochromic mem-
promising research topic with extensive and significant commercial brane with that of standard color card. Hence, the facile flexible ther-
value [22]. The thermochromic microcapsule is such a kind of material, mochromic membrane developed in this study exhibit conspicuous la-
which is sensitive to temperature response and can also store latent tent heat storage release property and surprising thermal cyclic
heat. It is micro/nanoencapsulated with dye including luminescent or durability, fast reversible thermochromic effect, and have widespread
leuco and phase change materials as the core materials. Geng et al. [23] application potential in thermal storage, functional clothing, wound
performed experimental investigations on thermochromic micro- dressing and wearable temperature sensor.
encapsulated phase change materials (TC-MPCMs) with crystal violet
lactone (CVL), bisphenol A and 1-tetradecanol as core material, which 2. Experimental
showed striking energy storage-release property and well micro-
structure. Thermochromic materials have also been studied extensively 2.1. Materials
in fabrics. Zhang et al. [3] fabricated a kind of reversible color changing
polyester fabrics via an approach of dyeing with thermochromic leuco PVA (1788, the polymerization degree of 1700 and polyvinyl
dye-loaded silica nanocapsules. In addition, some thermochromic fibers acetate hydrolysis degree of 88 mol%) was purchased from Shanghai
were obtained by spinning thermochromic pigments into melted poly- McLean Biochemical Technology co. LTD. (China). WPU with solids
mers. It appears from the aforementioned investigations that numerous content of 30% was a commercial product and purchased from
investigations have been conducted about the thermochromic PCMs Shenzhen Jitian Chemical Co. LTD. (China). The TC-M/NPCMs were
and reversible color changing fabrics. Nevertheless, no attempt is made fabricated according to our previous research [23]. TMC and n-hexane
to investigate the application of thermochromic phase change micro- were purchased from Shanghai Aladdin Biochemical Technology Co.
capsules in polymer membranes. LTD. (China). All solutions were prepared with deionized water, and all
Organic polymers have been considered as the most suitable and chemicals were used without further purification.

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2.2. Fabrication of PVA/WPU composite membranes the effect of the previous thermal history. The samples were cooled
afterwards to −20 °C at a rate of 10 °C·min−1 and then heated to 150 °C
The 10 wt% PVA solution was prepared by dissolving PVA in with the same rate.
deionized water under mechanical stirring at 80 °C until the PVA was The thermal stabilities of samples were characterized using TGA
completely dissolved. The transparent PVA solution and WPU solution (STA449F3, Netzsch, Germany) at a scanning rate of 10 °C·min−1 in the
were mixed in different weight ratios (10/0, 9/1, 8/2, 7/3, 6/4, 5/5, 4/ temperature range of 20 to 800 °C in a nitrogen atmosphere.
6, 3/7, 2/8, 1/9, 0/10) for 30 min to prepare PVA/WPU blend solu- The morphologies of samples were observed using FE-SEM (Gemini
tions. The obtained solutions were cast onto glass plates and then dried 500, Carl Zeiss, Germany) at an accelerating voltage of 10 KV after gold
for 12 h at 50 °C in vacuum to get the PVA/WPU composite membranes. coating, and the diameter of TC-M/NPCMs was measured using pro-
fessional software (Nano Measurer 1.2.5, Fudan University, Shanghai,
2.3. Fabrication of flexible thermochromic PVA/WPU/TC-M/NPCMs China). The morphology and surface roughness of membranes were
membranes characterized using AFM (S550, AGILENT, USA), and the scanning area
of membrane samples was 20 × 20 µm2.
TC-M/NPCMs were added to PVA/WPU blend solutions and dis- The microstructures of samples were observed by transmission
persed for 10 min under ultrasound to prepare TC-M/NPCMs disper- electron microscope (TEM) (HITACHI H-7650), and the accelerating
sions of 5 wt%, 10 wt%, 15 wt%, 20 wt% and 25 wt%. The dispersions voltage was 100 KV. One drop of TC-M/NPCMs dispersion washed with
were kept for 20 min under magnetic stirring. Put them in a vacuum to ethanol was dropped onto holey carbon support film and allowed to
remove the bubbles and then casted them onto glass plates. Flexible dry. A small amount of the PVA/WPU/TC-M/NPCMs casting membrane
thermochromic PVA/WPU/TC-M/NPCMs membranes were obtained at solution was diluted with deionized water and then one drop was de-
35 °C drying for 12 h in vacuum. posited on holey carbon support film and dried.
The static WCAs were tested by applying a drop sharp analysis
2.4. Surface modification of flexible thermochromic PVA/WPU/TC-M/ (DSA, DSA100, KRUSS, Germany). A droplet of deionized water (2 μL)
NPCMs membranes was dropped onto the surface of membranes at ambient temperature.
The elemental distribution was characterized by the energy dis-
TMC was used for surface modification of flexible thermochromic persive X-ray spectrometer (EDX) (OCTANE SUPER, EDAX, USA).
membranes. TMC (0.2 g) was dissolved in n-hexane (19.8 g) at ambient The surface chemical composition of membranes was analyzed with
temperature. The thermochromic membranes were immersed in TMC the X-ray photoelectron spectroscopy (XPS) (K-Ahpha, ThermoFisher,
solution for 1 min, 3 min and 5 min, respectively, and then taken out. UK).
After rinsing several times with deionized water, the samples were The thermal cycling studies of membranes were carried out using
dried by filter papers and dried in vacuum for 2 h to obtain the flexible heating and cooling microscope stage (Linkam THMS 600). The ex-
thermochromic surface modified membranes. As presented in Fig. 1, the periment was carried out in the temperature range of 18–60 °C at a rate
fabrication schematic diagram of flexible thermochromic PVA/WPU/ of 20 °C·min−1, and kept for 1 min at 18 °C and 60 °C during each
TC-M/NPCMs membrane was illustrated. thermal cycle processing, respectively. The samples were cycled for 0,
25, 50, 75, 100 times respectively.
2.5. Characterization
3. Results and discussion
The tensile properties of samples (length 40 mm × width
10 mm × thickness 40 μm) were measured with a GMT4000 testing 3.1. PVA/WPU composite membranes
machine from MTS Systems (China) Co. LTD. The tensile speed and
temperature were 50 mm·min−1 and 25 °C, respectively. The tensile strength and elongation at break of PVA/WPU composite
The fourier transform infrared spectroscope (FTIR) was used to membranes with different contents of WPU were shown in Fig. 2 (a).
measured chemical structures of samples through a NICOLET IS10 The single most striking observation to emerge from the data was that
spectrometer (Thermo Fisher Scientific, Shanghai, China) at ambient the elongation at break of the membranes showed a worth mentioning
temperature in the wave length range of 4000–500 cm−1. improvement that increased from around 10% to 700% with increasing
The thermal properties of samples were investigated using DSC WPU content, suggesting that the toughness and flexibility had a dra-
(NETZSCH 200F3). Samples were heated from ambient temperature to matically enhancement. It could be owing to the addition of the highly
150 °C at a rate of 30 °C·min−1 under nitrogen atmosphere to eliminate elastic WPU. Simultaneously, the tensile strength of membranes

Fig. 1. Fabrication schematic diagram of flexible thermochromic PVA/WPU/TC-M/NPCMs membrane.

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Fig. 2. (a) Mechanical properties of PVA/WPU composite membranes with various content of WPU, (b) tensile stress-strain curves of composite membranes (PVA/
WPU a: 10/0; b: 9/1; c: 8/2; d: 7/3; e: 6/4; f: 5/5; g: 4/6; h: 3/7; i: 2/8; j: 1/9; k: 0/10), (c) FTIR spectra and (d) TGA curves of the PVA, WPU and PVA/WPU (6/4)
composite membranes.

decreased via addition of WPU. There was a definite probability that since the OeH of PVA in the membrane formation process reacted with
intermolecular and intermolecular hydrogen bonds of PVA were da- the decomposed eNCO in the WPU molecule to form a carbamate
maged to a certain extent. group, its eC]O absorption intensity strengthened, which weakened
Fig. 2 (b) demonstrated the tensile stress-strain curves of various the influence of hydrogen bonding, so the eC]O absorption peak in-
membranes. It was obviously that the stress-strain behavior of mem- tensity change could be neglected.
branes varied greatly with different WPU contents. When the content of The thermal stabilities of the PVA, WPU and PVA/WPU (6/4)
WPU in the composite was less than 40 wt%, the stress-strain curve of composite membrane were measured by TGA, as shown in Fig. 2 (d).
the membranes showed clear yield which exhibited brittle fracture The TGA curve of the WPU could be roughly divided in two sections:
model. As the addition of WPU exceeded 40 wt%, curves presented 210–330 °C and 350–800 °C, which corresponded to the weight losses of
elastic deformation stress plateau and strain hardening behavior, which the hard and soft segment decomposition, respectively. The pure PVA
was also called as ductile fracture characteristics, implicating that the thermal degradation process was generally concentrated in 240–390 °C,
toughness of membranes improved [36]. mainly caused by the dehydration of PVA intermolecular and in-
As the content of WPU was 40 wt%, the elongation at break reached tramolecular; 400–800° C, which was primarily attributed by a break in
258.3% while the tensile strength of the composite membrane had a the covalent bond. The TGA data included the onset decomposition
less drop measured as 22.3 KPa, which was considered to have better temperature, the peak temperature and the weight loss, which were
comprehensive mechanical properties, so this ratio was selected for the summarized in Table 1. The thermal decomposition temperature of
next study. PVA/WPU composite membrane was measured between that of pure
The FTIR spectra of PVA, WPU and PVA/WPU (6/4) composite PVA and WPU, indicating that the thermal stability of the system was
membrane were given in Fig. 2 (c). For PVA, the characteristic ab- determined by the thermal stabilities of each component. In this
sorption peak at 3350 cm−1 represented the stretching vibrations of the polymer system, the thermal decomposition temperature of WPU was
hydroxyl group (OeH). Besides, the absorption peak at 1713 cm−1 lower than that of PVA, and the proportion of PVA was higher than that
assigned to the carbonyl group (eC]O), which was ascribed to the fact of WPU, so the weight loss temperature of the composite was shifted to
that the hydrolysis degree of PVA was 88%, as a result some ester low, closed to WPU but higher than that of WPU.
groups were also appeared in PVA. From the FTIR spectrum of WPU,
the characteristic absorption peak at 1540 cm−1 belonged to the 3.2. Flexible thermochromic PVA/WPU/TC-M/NPCMs membrane
bending vibration of NeH, and the peak of 1713 cm−1 related to the
stretching vibration of eC]O. The observed peak at 2930 and The surface morphology of TC-M/NPCMs was studied by FE-SEM,
2850 cm−1 could be assigned to the stretching vibration of methylene and the obtained micrographs were shown in Fig. 3 (a, b). It could be
(eCeH2e). The intensity of characteristic absorption peak at distinctly found in Fig. 3 (a) that the TC-M/NPCMs exhibited homo-
3350 cm−1 of composite membrane decreased. Among the plausible geneous sphere. The particle size of TC-M/NPCMs was measured in
explanations for this finding was that the OeH of PVA could form in- Fig. 3 (a), distributed ranging from 350 to 800 nm, and the average
termolecular hydrogen bonds with eC]O in WPU molecules. However, particle size was around 500 nm. In addition, there were some

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Table 1
Thermal stabilities of the PVA, WPU and PVA/WPU (6/4) composite mem-
branes.
Samples TGA data

T1,onset (°C) T1,max (°C) Mass1 T2,onset (°C) T2,max (°C) Mass2
(wt %) (wt %)

PVA 287.7 324.1 68.46 421.4 437.1 24.40

WPU 246.7 263.8 12.77 391.3 399.8 85.55
PVA/ 271.9 295.4 31.28 399.9 422.5 60.37
WPU
(6/4)

Note: T1, onset/T2, onset: the onset decomposition temperature of first/second

step on TGA curve; T1,max/T2,max, the peak temperature of first/second step on
TGA curve; Mass1/Mass2: weight loss of first/second step on TGA curve.

nanoparticles less than 100 nm adhered on the surface of TC-M/NPCMs,

which might be explained by the self-polymerization of the melamine-
Fig. 4. DSC curves of (a) 1-tetradecanol and (b) TC-M/NPCMs.
formaldehyde (MF) prepolymer. The microstructure of TC-M/NPCMs
could be remarkably observed in Fig. 3 (c). It could be apparently seen
that TC-M/NPCMs exhibited an obvious core-shell structure, with the Table 2
shell thickness of approximately 35 nm. Similarly, some nanoparticles Thermal properties of 1-tatradecanol and TC-M/NPCMs.
with a diameter of about 100 nm were also observed, which were Samples Melting Crystallization E%
considered to be the self-polymerized nanospheres of MF prepolymer. It
was of significance to observe that the TC-M/NPCMs all presented a Tm,0 (°C) Tm (°C) ΔHm (J/g) Tc,0 (°C) Tc (°C) ΔHc (J/g)
well-defined core-shell structure.
a 37.9 45.0 221.6 22.7 25.8 –222.8 –
As shown in Fig. 4, the melting and crystallization properties of 1- b 33.3 40.6 151.6 −3.7 3.1 −148.3 67.5
tetradecanol and TC-M/NPCMs were obtained from DSC analysis. The
data were listed in Table 2, including phase change temperature, Note: Tm,0: onset temperature on DSC melting curve; Tm: Peak temperature on
melting enthalpy (ΔHm), crystallization enthalpy (ΔHC) and energy DSC melting curve; ΔHm: Enthalpy on DSC heating curve; Tc,0: onset tem-
storage efficiency, which were important parameters to evaluate the perature on DSC cooling curve; Tc: Peak temperature on DSC cooling curve,
thermal storage capability of TC-M/NPCMs during the phase change ΔHc: Enthalpy on DSC cooling curve.
process. 1-Tetradecanol had a very high phase change enthalpy as could
be seen from the Fig. 4 and was considered to be able to store high
latent heat. Simultaneously, the ΔHm of TC-M/NPCMs reached a rela- flexible thermochromic membranes with various TC-M/NPCMs addi-
tively high value of 151.6 J/g, which could also store and release a tions. The macroscopic morphology of the thermochromic membranes
large amount of latent heat and was an excellent energy storage ma- at 25 °C was shown in Fig. 5 (a). It was apparent from the images that
terial. The enthalpy and phase change temperatures of TC-M/NPCMs the samples appeared blue at 25 °C, and as the elevation of TC-M/
had decreased, deriving from that the thermochromic dyes affected the NPCMs, the color of samples became significantly deeper. However,
crystallization of 1-tetradecanol, reduced the crystal perfection of 1- when the TC-M/NPCMs addition increased to more than 20 wt%, there
tetradecanol, and the 1-tetradecanol was difficult to crystallize when was no pronounced difference of samples color was detected. The FE-
the temperature reduced. The energy storage efficiency can be calcu- SEM images, two-dimensional and three-dimensional AFM images of
lated by the following formula: the flexible thermochromic membranes surface were displayed in Fig. 5
(b, c and d). From FE-SEM images, many small particles liking islands
E = [(HTC M / NPCMm + HTC M / NPCMc )/(HPCMm + HPCMc )] × 100% (1) with different sizes distributed randomly on the membranes surface.
where HTC-M/NPCMm and HTC-M/NPCMc were the latent heat of TC-M/ The most striking result to emerge from the data was that as the ad-
NPCMs during the melting and crystallization process, HPCMm and dition amount of TC-M/NPCMs ranging from 5 wt% to 25 wt%, the
HPCMs were the latent heat of PCM, that was 1-tetradecanol, during the surfaces of membranes were gradually covered by TC-M/NPCMs par-
melting and crystallization process, and E referred to the energy storage ticles. The AFM images highlighted the effect of TC-M/NPCMs contents
efficiency of TC-M/NPCMs [37]. Hence, according to Eq. (1), the energy on the roughness of samples. It could be identified that the average
storage efficiency (E%) of TC-M/NPCMs was 67.5%. roughness (Ra) increased from 55.3 nm to 308 nm as the addition
Fig. 5 revealed the macroscopic and microscopic morphology of amount ranging from 5 wt% to 25 wt%, which was justified by the

Fig. 3. (a, b) FE-SEM images and (c) TEM image of TC-M/NPCMs.

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Fig. 5. (a) Photographs, (b) FE-SEM images, (c, d) AFM images and average roughness of the flexible thermochromic PVA/WPU/TC-M/NPCMs membranes with
various contents of TC-M/NPCMs: (1) 5 wt%, (2) 10 wt%, (3) 15 wt%, (4) 20 wt% and (5) 25 wt%.

Fig. 6. TEM images of the flexible thermochromic PVA/WPU/TC-M/NPCMs membranes.

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increasing number of TC-M/NPCMs exposed on the membrane surface. temperature dropped below its phase transition temperature, bisphenol
Undoubtedly, when the TC-M/NPCMs content exceeded 20 wt%, the A released protons, that is, electrons were obtained, with the CVL ring
color of samples appeared bright blue, and the surfaces of samples were opened, molecules rearranged, conjugate double bonds connected and
almost covered by TC-M/NPCMs. combined with bisphenol A ions, thus developed color [38]. The phase
To provide even further insight into the structural and morpholo- change temperature of 1-tetradecanol was 37.9 °C, closed to human
gical characteristics, TEM analysis was also performed. The TEM body temperature, so when the temperature reached the body tem-
images of PVA/WPU/ TC-M/NPCMs membranes were shown in Fig. 6 perature, the thermochromic membranes changed from blue to color-
(a, b, c). The bright region corresponded to the polymer matrix and less. Besides, the melting process of organic PCM covered a wide tem-
dark region represented the TC-M/NPCMs. As seen from Fig. 6 (a), TC- perature range, that was, the melting range, in which temperature
M/NPCMs were almost uniformly distributed in the PVA/WPU matrix raised while melting [39]. Therefore, the color transformations of the
membrane. It could be seen from Fig. 6 (b) that although the contrast thermochromic membranes were gradually occur with the temperature
between the core materials and the shell materials was not very ob- gradient [40]. As we previously reported, TC-M/NPCMs showed note-
vious, while it could be clearly seen that the TC-M/NPCMs exhibited a worthy potential thermal storage and thermal regulation performance
core-shell structure in Fig. 3 (c). The boundary of the composite [23]. The thermochromic membranes produced by adding such func-
membrane could be observed in Fig. 6 (c). It was confirmed from the tional fillers to polymer membranes also had striking energy storage,
TEM images that the synthesized TC-M/NPCMs exhibited a uniform heat storage and thermal regulation properties, which could be pro-
spherical shape in the polymer matrix material without any visible vided with intuitive evidence by reversible thermochromic properties
damage or deformation. of membranes. Due to its reversibility, fast thermochromic effect, good
The flexible thermochromic PVA/WPU/TC-M/NPCMs membranes flexibility and biocompatibility, flexible thermochromic membranes
with different contents of TC-M/NPCMs presented thermochromic re- can widen their application in the field of wearable temperature sensor.
sponse to temperature change, which was sensitive, quick and re- The tensile strength and elongation at break of flexible thermo-
versible, as shown in Fig. 7. Thermochromism of thermochromic chromic PVA/WPU/TC-M/NPCMs membranes with different contents
membranes was caused by the TC-M/NPCMs, whose discoloration was of TC-M/NPCMs were exhibited in Fig. 8 (a). It could be distinctly seen
derived from the ternary compound core material. The core of TC-M/ that there was a reduction in the tensile strength and elongation at
NPCMs including color former (CVL), color developer (bisphenol A) break by addition of TC-M/NPCMs, which could be explained in the
and solvent (1-tetradecanol). In this thermochromic system, the CVL following aspects. Firstly, the matrix material was a dense membrane,
was served as an electron-donating part, the bisphenol A was conducted while adding TC-M/NPCMs was equivalent to introducing impurities
as an electro-attracting compound, and the 1-tetradecanol acted as the into the matrix material, which destroyed the density of the matrix
medium. 1-Tetradecan was considered as a common phase change material. During the stretching process, the defects first appeared
material, which could absorb or release energy in the process of tem- around TC-M/NPCMs nanoparticles, then contributing to the genera-
perature change. In the medium of 1-tetradecanol, when the tion of cavities between the matrix material and filler due to the peeling

Fig. 7. Photographs of the flexible thermochromic PVA/WPU/TC-M/NPCMs membranes with various contents of TC-M/NPCMs at different temperatures.

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Fig. 8. (a) Mechanical properties, (b) tensile stress-strain curves and (c) FTIR spectra of the TC-M/NPCMs and flexible thermochromic PVA/WPU/TC-M/NPCMs
membranes with various contents of TC-M/NPCMs. (d) TGA curves of the TC-M/NPCMs, PVA/WPU (6/4) composite membrane and flexible thermochromic PVA/
WPU/TC-M/NPCMs (20 wt%) membrane.

of the interface. In addition, as the increase of TC-M/NPCMs content, as (MF) as the shell material. The melamine resin shell contained a large
expected, the particles were closer to each other, the more and more amount of NeH group, which could probably form hydrogen bonds
weak points appeared in the material, and thus leading to the me- with eC]O groups in the matrix material [41,42]. The non/free hy-
chanical performance degradation. Typical tensile stress-strain curves drogen bonded NeH group showed broad bands at 3410 cm−1, whereas
of flexible thermochromic membranes with TC-M/NPCMs were illu- the hydrogen-bonded NeH group display stretching bands at
strated in Fig. 8 (b). There was no distinct distinction in the trend of 3280 cm−1 [43,44]. While the characteristic absorption peak of
each curve, and also no obvious yield could be observed. 1713 cm−1 assigned to the stretching vibration of eC]O. It could be
Considering both thermochromic and mechanical properties of seen from Fig. 8 (c) that as the content of TC-M/NPCMs increased, the
flexible thermochromic membranes, the membrane exhibited the op- N-H group peak at the 3410 cm−1 appeared hypsochromic shift, which
timal color and desirable thermochromic effect when the addition of might be result from the fact that hydrogen bonded NeH groups
TC-M/NPCMs was 20 wt%. The mechanical properties needed to be formed. When TC-M/NPCMs content increased, the interaction hy-
enhanced further; however, it could meet requirements of the material drogen bond (NeH···O]Ce) between the eC]O in the matrix material
used for the thermochromic membrane at present. Based on the analysis and the N-H of TC-M/NPCMs gradually strengthened, so that the
mentioned above, the flexible thermochromic membrane with TC-M/ amount of eC]O capable of stretching vibration was decreased. Al-
NPCMs content of 20 wt% was selected for further investigation. though hydrogen bonding was formed between the matrix and the
Fig. 8 (c) presented the FTIR spectra of TC-M/NPCMs, PVA/WPU filler, this force was weak relatively. The TC-M/NPCMs as weak points
(6/4) composite membrane and flexible thermochromic PVA/WPU/TC- in the material played a more important role than hydrogen bond
M/NPCMs membranes with various TC-M/NPCMs contents. In this during the stretching process. Therefore, mechanical properties of
study, TC-M/NPCMs were prepared by using melamine-formaldehyde flexible thermochromic membranes were declined after adding TC-M/

Table 3
Thermal stabilities of TC-M/NPCMs and various composite membranes.
Samples TGA data

T1,onset (°C) T1,max (°C) Mass1 (wt %) T2,onset (°C) T2,max (°C) Mass2 (wt %)

TC-M/NPCMs 159.3 192.1 19.62 386.0 392.0 68.93

PVA/WPU (6/4) 271.9 295.4 31.28 399.9 422.5 60.37
PVA/WPU/TC-M/NPCMs (20 wt%) 256.2 283.7 53.79 392.2 418.3 39.54

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NPCMs. Table 4
The thermal stabilities of TC-M/NPCMs, PVA/WPU (6/4) composite Thermal properties of various flexible thermochromic membranes and TC-M/
membrane and flexible thermochromic PVA/WPU/TC-M/NPCMs NPCMs.
membrane with 20 wt% TC-M/NPCMs were measured by TGA, and the Samples Melting Crystallization
curves were shown in Fig. 8 (d). The resultant TGA data were also listed
in Table 3. The weight loss curve of the TC-M/NPCMs could be roughly Tm,0 (°C) Tm (°C) ΔHm (J/g) Tc,0 (°C) Tc (°C) ΔHc (J/g)
divided in two stages, in which the first stage was mainly owing to the
A – – – – – –
weight loss of the core materials during 160–280 °C and the second B 33.5 38.2 9.8 −5.3 −1.5 −9.6
stage was probably caused by the decomposition of shell materials from C 33.1 37.4 17.7 −3.1 3.0 −15.5
300 to 800 °C. The TGA curve of the PVA/WPU composite membrane D 32.8 37.6 25.5 −2.3 3.5 –22.7
E 32.9 39.7 31.7 −2.9 4.0 −31.5
with 40 wt% WPU had two weight loss stages: 270–340 °C and
F 33.4 39.6 38.9 −2.5 3.2 −37.6
350–800 °C. We could observe that the thermal stability of the flexible G 33.3 40.6 151.6 −3.7 3.1 −148.3
thermochromic PVA/WPU/TC-M/NPCMs membrane declined, which
was likely ascribed to the low decomposition temperature of TC-M/
NPCMs. In this composite, the TC-M/NPCMs thermal decomposition NPCMs was 38.1 °C which was closed to the phase transition tem-
temperature was much lower than that of PVA/WPU composite mem- perature of 1-tetradecanol. The thermochromic membranes with TC-M/
brane. Nevertheless, the addition of TC-M/NPCMs was less, so the NPCMs possessed a melting peak at around 38.0 °C, and the enthalpies
weight loss temperature of the thermochromic membrane was shifted of melting curves gradually improved from 9.8 to 38.9 J/g with in-
to a low temperature slightly compared with PVA/WPU composite crease in added amount. TC-M/NPCMs were the only latent heat sto-
membrane. Besides, there were hydrogen bonds between TC-M/NPCMs rage material in these samples, so the magnitude of latent heat storage
and matrix materials; hence the weightlessness temperature was shifted capacity was linear with the mass fraction of TC-M/NPCMs, which can
towards higher temperature compared with TC-M/NPCMs. be expressed as the following formula:
Fig. 9 (a) and (b) underlined the DSC melting and crystallization
curves of PVA/WPU (6/4) composite membrane, flexible thermo- HM = HTC M / NPCMs (2)
chromic PVA/WPU/TC-M/NPCMs membranes and TC-M/NPCMs. The
melting and crystallization properties were presented in Table 3. There where ΔHM and ΔHTC-M/NPCMs represented the latent heat of thermo-
was no melting and crystallization peaks appeared on the DSC curves of chromic membranes and the latent heat of TC-M/NPCMs, respectively,
PVA/WPU composite membrane, indicating that there was no phase at melting or crystallization process, and η represented the mass frac-
transition occurred and no energy absorbed or released. Tm of TC-M/ tion of TC-M/NPCMs in the composites [45]. This relationship was
confirmed in Table 4. The latent heat increased with the increase in TC-

Fig. 9. DSC heating curves, (b) DSC cooling curves, (c) phase change temperatures and (d) phase change enthalpies of flexible thermochromic PVA/WPU/TC-M/
NPCMs membranes with various contents of TC-M/NPCMs and TC-M/NPCMs: (A) 0 wt%, (B) 5 wt%, (C) 10 wt%, (D) 15 wt%, (E) 20 wt%, (F) 25 wt%, and (G) TC-M/
NPCMs.

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M/NPCMs content of thermochromic membranes. It could be seen that In accord with the EDX mapping scanning, the chemical composi-
almost all experimental values were slightly larger than the corre- tions of flexible thermochromic membranes were determined. Fig. 12
sponding theoretical values. The possible reason was the measurement revealed the EDX spectra and data of weight and atomic percentages of
error within the allowable range. The 1-tetradecanol in the core of TC- samples, including the unmodified and modified membranes. Chlorine
M/NPCMs had latent heat capacity and could effectively store or re- (Cl) in TMC could be served as a characteristic element. By comparing
lease latent heat through its phase change at the required operating the elements atomic% of samples before and after surface modification,
temperature range, which suggessted that TC-M/NPCMs have broad it could be obviously seen that there was almost no Cl element in the
application prospects in latent heat storage systems. Therefore, the unmodified membrane, while the peak of Cl element emerged in the
flexible thermochromic membrane also had worth noting energy sto- spectrum of modified membrane, and the atomic% as shown in the
rage and release ability by adding such a thermochromic micro/na- table was 0.87%. Cl element was notably detected in the spectrum,
noencapsulated phase change material that having high latent heat which resulted from that the acyl chloride in TMC reacted with hy-
value to the flexible membrane. droxyl in the flexible thermochromic membrane, and then the resulting
trace hydrochloric acid infiltrates into the membrane.
3.3. Surface modification of the flexible thermochromic PVA/WPU/ TC-M/ XPS survey spectra (Fig. 13) were taken to further compare the
NPCMs membrane chemical compositions of the unmodified and modified flexible ther-
mochromic membranes. The XPS spectra of O 1s were divided into
Hydrophobic performance plays a significant part in the application three peaks by XPSPEAK4.1, which further proved the successful
of flexible thermochromic membrane especially for human skin wear- modification of TMC on the thermochromic membrane. The binding
able membrane; poor water resistance will also limit its applications in energy of 532.3 eV was deriving from CeO*eH bonds in the PVA and
many other aspects. Water contact angles were commonly used to es- the peak of 531.6 eV and 533.2 eV represented NeC]O*/OeC]O*
timate the relative hydrophilicity of membranes. The smaller the con- and O]CeO* respectively in the WPU [49]. The eOH in PVA could
tact angle, the higher the hydrophilicity, and vice versa [46,47]. In this react with acyl chloride group of TMC to form ester group (O]CeO)
study, thermochromic membranes were modified with TMC, and and traced hydrochloric acid. As indicated in Fig. 13, it could be seen
Fig. 10 showed the static WCAs at different modification periods. The that the intensity of two peaks of binding energy at 531.6 eV and
flexible thermochromic membrane with smaller value of contact angle 533.2 eV in the modified membrane clearly elevated compared to that
was more hydrophilic due to the fact that there were large amount of of the unmodified membrane, and the peak at 532.2 eV became smaller,
hydroxyl groups located in the PVA molecular side chain. As we in- indicating that O]CeO was generated. In summary, EDX and XPS
creased the surface modification period from 0 to 5 min, the WCAs analysis combined to show that the flexible thermochromic membrane
value improved from 64.8° to 94.9°. The two main factors that were was successfully modified by TMC.
responsible for higher WCAs were the surface hydrophilicity and Fig. 14 presented the DSC and TGA curves of flexible thermo-
roughness [48]. The surface hydrophilicity of the membrane declined chromic membranes of both unmodified and modified samples. The
after TMC modification and the average roughness of membrane was melting and crystallization properties and resultant TGA data were
decreased from 299 to 199 nm, which can be seen from the AFM image summarized in Table 5. In order to investigate that whether the surface
(Fig. 11 d). The results highlighted that the flexible thermochromic modification would damage the phase transition capability of the core
membrane changed from hydrophilic to hydrophobic after the surface material in the TC-M/NPCMs, we compared the melting and crystal-
modification, which was favorable for the water resistance of materials. lization data of unmodified and modified samples. It appeared from
As the modification period was longer than 1 min, the WAC of the Fig. 14 (a) that there were no pronounced differences in peak position
membrane did not confirm any significant differences, so the flexible and peak shape of crystallization and melting peak about DSC curves
thermochromic membranes modified for 1 min were served in sub- between the two samples. As displayed in Table 5, the Tm,0, Tm and ΔHm
sequent studies. of the modified membrane were also around 33 °C, 39 °C and 31 J/g,
Fig. 11 exhibited the macroscopic, microscopic morphology and respectively. No substantial distinction was highlighted between two
thermochromic response effect to temperature change of the modified samples, and the subtle difference was in the allowable range of error,
flexible thermochromic membrane. The photograph of flexible ther- so it could be considered that the modification has no effect on its latent
mochromic membrane at 25 °C was presented in Fig. 11 (a). Generally heat. The weight loss trend of the modified membrane was basically
speaking, its color was still showy blue under the room temperature of same as that of unmodified sample, which was still roughly divided into
25 °C, and there was almost no significant difference of color could be
found compared with the sample without surface modification. From
the FE-SEM image (Fig. 11 b), the membrane surface was still randomly
distributed with nanoparticles, and no substantial distinction could be
detected compared with the unmodified sample. The AFM character-
izations of the thermochromic membrane were conducted, the surface
roughness was quantified and the results were shown in Fig. 11 (c and
d). Sa of the sample decreased slightly, might be attributed to that the
TMC solution, as an organic phase, reacted with hydroxyl in the matrix
material, mainly acted on gullies of membrane surface, and played a
filling role. The flexible thermochromic membrane modified with TMC
still exhibited a dramatically response to a change of external tem-
perature, which was sensitive, quick and reversible, as shown in Fig. 11
(e). At low temperatures, the membrane appeared dark blue, and as the
temperature rose above 30 °C, the blue color gradually became lighter
and finally turned white. In conclusion, the macroscopic and micro-
scopic morphology and thermochromic property of the flexible ther-
mochromic modified membrane were hardly affected, the average
surface roughness was slightly reduced and the modified membrane
also possessed energy storage, heat storage and thermal regulation Fig. 10. Effects of modification period on the water contact angles of the
properties. flexible thermochromic PVA/WPU/TC-M/NPCMs membranes.

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Fig. 11. (a) Photographs, (b) FE-SEM images, (c, d) AFM images and average roughness, and (e) color change photo of the flexible thermochromic modified PVA/
WPU/TC-M/NPCMs membranes.

Fig. 12. EDX spectra of flexible thermochromic (a) unmodified and (b) modified PVA/WPU/TC-M/NPCMs membranes.

two stages, as shown in Fig. 14 (b). However, the weight loss tem- were not affected by the surface modification. Due to its desirable heat
perature in the first stage decreased slightly may be resulted from that storage capacity and good thermal reliabilities, we believe the modified
TMC reacted with eOH to produce a trace amount of hydrochloric acid, thermochromic membrane definitely can find its potential application,
which penetrated into the interior of membrane and destroyed hy- such as low temperature thermal energy storage, solar energy storage,
drogen bonds between the TC-M/NPCMs and matrix materials, re- smart textiles and thermal regulation.
sulting in a decrease of T1,onset in the first stage. It could be concluded
that the thermal stability was slightly reduced, however, the melting
and crystallization process of the flexible thermochromic membrane

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Fig. 13. XPS high-resolution spectra of O 1s peaks of flexible thermochromic (a) unmodified and (b) modified PVA/WPU/TC-M/NPCMs membranes.

3.4. Thermal cyclic durability of the flexible thermochromic PVA/WPU thermochromic membranes with different multiple thermal cyclic times
/TC-M/NPCMs membrane and its application were measured as shown in Fig. 16. The flexible thermochromic
membranes remained blue color at 25 °C below the melting point of TC-
To clarify the heat storage performance and durability of the flex- M/NPCMs, while the color turned white when samples were heated to
ible thermochromic PVA/WPU/TC-M/NPCMs membranes, DSC mea- 40 °C which was higher than the phase transition temperature of TC-M/
surements observations were performed on the samples subjected to NPCMs. Therefore, the thermochromic properties of the membrane
several heating and cooling cycles. From Fig. 15 (a), (b) and (d), we maintained stable, indicating that there was no effect on the thermo-
found that there was no obvious difference among the melting, crys- chromic materials, TC-M/NPCMs and the thermochromic composite
tallization behaviors and phase change enthalpies of flexible thermo- membrane even after 100 heating and cooling cycles. Furthermore, the
chromic membranes undergoing 25, 50, 75 and 100 cyclic times re- thermochromic response to external temperature change was still re-
spectively, compared with that of 0 times. Therefore, it was evident that versible, rapid and sensitive.
the membranes fully retain the heat storage and release properties even As a result, the flexible thermochromic membranes still possessed
after 100 thermal cycles. According to Fig. 15 (a), (b), (c) and dates of prominent latent heat storage and release property after 25, 50, 75, 100
Table 6, it could be observed that after undergoing 25, 50, 75 and 100 cyclic times, respectively. And the intuitive evidence could be provided
cycles, the Tm of the flexible thermochromic membranes shifted to the by reversible thermochromic properties of membranes after thermal
low temperature slightly, from 39.8 °C to 36.6 °C, and the Tc increased circulation.
toward the high temperature, from 4.3 °C to 9.7 °C. The primary cause A temperature colorimeter was prepared, of which middle was a
of the discrepancy was due to the decrease of crystal size in the core or membrane, and the two sides were standard color cards at different
migration into polymer shell materials porosity of TC-M/NPCMs as the temperatures, by using the flexible thermochromic membrane with heat
number of cycles increased [18]. The discrepancy of phase change storage and temperature regulation in this study, as shown in Fig. 17
temperature during repeated thermal cycling of flexible thermochromic (a). This temperature colorimeter was designed to be small and por-
membranes was within the acceptable range of thermal energy storage table. When it attached to various parts of human body, the color of
phase change material [50,51]. These results suggested that the flexible thermochromic membrane in the middle would change. By comparing
thermochromic membranes fabricated in this study presented sur- the color of membrane with the standard color cards, the temperature
prising cyclic durability, and thus they were able to repeated phase of a part of body could be known. Fig. 17 (b), (c), (d) and (e) were the
transition to store and release latent heat at almost steady tempera- measurement results of the temperature colorimeter on the forehead,
tures. opisthenar, wrist, palm at the ambient temperature of 26 °C, respec-
The reversible thermochromic properties of the flexible tively. The thermochromic membrane contained TC-M/NPCMs with

Fig. 14. (a) DSC curves and (b) TGA curves of flexible thermochromic (A): unmodified and (B): modified PVA/WPU/TC-M/NPCMs membranes.

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Table 5
Thermal properties of the flexible thermochromic PVA/WPU/TC-M/NPCMs membrane under different TMC modification period.
Samples Melting Crystallization TGA data

Tm,0 (°C) Tm (°C) ΔHm (J/g) Tc,0 (°C) Tc (°C) ΔHc (J/g) T1,onset (°C) T1,max (°C) Mass1 (wt %) T2,onset (°C) T2,max (°C) Mass2 (wt %)

A 32.9 39.7 31.7 −2.9 4.0 −31.5 256.2 283.7 53.79 392.2 418.3 39.54
B 33.2 39.5 31.1 −2.1 4.3 −31.0 226.2 244.1 44.58 385.1 407.9 46.06

functions of energy storage, thermal regulation and temperature in- Table 6

dication. When it was close to the skin, the PCMs undergone phase Thermal properties of flexible thermochromic membranes after various thermal
change and absorbed latent heat. At different temperatures, the latent cyclic times.
heat was absorbed by the core material and the phase change degrees Samples Melting Crystallization
were different, so the color of membrane varied at different tempera-
tures. The temperature colorimeter made by this principle could con- Tm,0 (°C) Tm (°C) ΔHm (J/g) Tc,0 (°C) Tc (°C) ΔHc (J/g)
veniently measure the temperature of various parts of human body
0th 33.2 39.5 31.1 −2.1 4.3 −31.0
surface, which was convenient to carry and of high accuracy and could 25th 32.1 39.5 31.2 −0.6 8.0 −31.1
be widely used in all aspects of life. Furthermore, the facile flexible 50th 32.7 38.2 32.1 0.2 8.9 –32.5
thermochromic membrane could be directly incorporated into fabrics 75th 32.4 38.0 31.8 0.6 8.6 −31.6
or applied to surfaces as a thermal management coating to manage 100th 31.9 36.6 31.6 0.5 9.7 −31.8

unwanted temperature variations and to regulate the body temperature

to keep it within a constant range. Due to the characteristics of thermal
4. Conclusion
energy storage capacity and temperature indication, the thermochromic
membrane could be also applied to some aspects: solar energy, textile
As discussed above, a facile flexible reversible thermochromic
industry, building materials, packaging materials, clothing materials
membrane with excellent thermochromic performance, latent heat
et al.
storage property and marked cyclic durability has been achieved in this
study. With the PVA/WPU composite membrane containing 40 wt%
WPU as the matrix material, we investigated the influence of the added

Fig. 15. (a) DSC heating curves, (b) DSC cooling curves, (c) phase change temperatures and (d) phase change enthalpies of flexible thermochromic membranes after
various thermal cyclic times.

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Fig. 16. Photographs of of flexible thermochromic membranes after various thermal cyclic times.

contents of TC-M/NPCMs on the properties of flexible thermochromic around 31.6 J/g even after 100th cycles, presenting excellent thermal
membranes. With TC-M/NPCMs increased from 5 wt% to 25 wt%, the cyclic durability. In the end, a facile temperature colorimeter was de-
surface of flexible thermochromic membranes was distributed uni- signed and fabricated, by using the flexible thermochromic membrane
formly by nanoparticles, the tensile strength decreased from 11.34 to with high energy storage efficient and temperature regulation property,
7.81 KPa, the phase transition enthalpies improved from 9.8 to 38.9 J/g which could be served as a promising wearable temperature sensor. The
and the blue color got deeper and deeper at 25 °C. The flexible ther- study had gone some way towards enhancing our understanding of the
mochromic membrane containing 20 wt% TC-M/NPCMs had the best application that TC-M/NPCMs used in polymer membranes. The facile
coloration, higher enthalpy, and better heat storage property and flexible thermochromic membranes developed in this study would have
thermochromic effect when met the requirements of mechanical prop- promising potential applications in thermal regulation clothing, in-
erties of materials. Furthermore, the water resistance of flexible ther- telligent textiles or fibers, wearable temperature sensor, reversible
mochromic membrane was modified successfully with trimesoyl thermochromic coating materials, food and medicine package and solar
chloride. The water contract angle increased from 64.6° to 94.9°, which energy storage due to its noteworthy latent heat storage release prop-
proved that the hydrophilicity was declined with increasing surface erty, excellent thermal cyclic durability and fast reversible thermo-
modification period from 0 to 5 min. The macroscopic and microscopic chromic effect.
morphology, thermochromic property and phase change enthalpy of
the flexible thermochromic membrane were hardly affected. The phase
change enthalpy of the flexible thermochromic membrane remained at

Fig. 17. (a) Temperature colorimeter; (b), (c), (d) and (e) applications of temperature colorimeter in different positions of body surface.

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Acknowledgements alginate nanocomposite membranes with enhanced isopropanol dehydration per-

formance via pervaporation technique. RSC Adv 2013;3:17120–30.
[25] Han SJ, Lee HI, Jeong HM, Kim BK, Raghu AV, Reddy KR. Graphene modified
The authors gratefully acknowledge the financial supports for this Lipophilically by stearic acid and its composite with low density polyethylene. J
research from the National Natural Science Foundation of China (No. Macromol Sci Part B Phys 2014;53:1193–204.
51573135 and No. 51203113), Tianjin Research Program of [26] Nguyen DA, Raghu AV, Choi JT, Jeong HM. Properties of thermoplastic poly-
urethane/functionalised graphene sheet nanocomposites prepared by the in situ
Application Foundation and Advanced Technology (No. polymerisation method. Polym Polym Compos 2010;18:351–8.
16JCYBJC17100), China Postdoctoral Science Foundation [27] Kim KT, Dao TD, Jeong HM, Anjanapura RV, Aminabhavi TM. Graphene coated
(2017M611167). with alumina and its utilization as a thermal conductivity enhancer for alumina
sphere/thermoplastic polyurethane composite. Mater Chem Phys
2015;153:291–300.
References [28] Xu CL, Zeng JB, Wang YZ. Sustainable waterborne polyurethane ionomer reinforced
poly(vinyl alcohol) composite films. Compos Sci Technol 2014;96:109–15.
[29] Haghju S, Bari MR, Khaled-Abad MA. Affecting parameters on fabrication of beta-D-
[1] Luo X, Li J, Li C, Heng L, Dong YQ, Liu Z, et al. Reversible switching of the emission
galactosidase immobilized chitosan/poly(vinyl alcohol) electrospun nanofibers.
of diphenyldibenzofulvenes by thermal and mechanical stimuli. Adv Mater
Carbohydr Polym 2018;200:137–43.
2011;23:3261–5.
[30] Liang J, Huang Y, Zhang L, Wang Y, Ma Y, Guo T, et al. Molecular-Level dispersion
[2] Davis DA, Hamilton A, Yang J, Cremar LD, Van Gough D, Potisek SL, et al. Force-
of graphene into poly(vinyl alcohol) and effective reinforcement of their nano-
induced activation of covalent bonds in mechanoresponsive polymeric materials.
composites. Adv Funct Mater 2009;19:2297–302.
Nature 2009;459:68–72.
[31] Suhas DP, Aminabhavi TM, Raghu AV. Mixed matrix membranes of H-ZSM5-loaded
[3] Zhang W, Ji X, Zeng C, Chen K, Yin Y, Wang C. A new approach for the preparation
poly(vinyl alcohol) used in pervaporation dehydration of alcohols: influence of si-
of durable and reversible color changing polyester fabrics using thermochromic
lica/alumina ratio. Polym Eng Sci 2014;54:1774–82.
leuco dye-loaded silica nanocapsules. J Mater Chem C 2017;5:8169–78.
[32] Qi X, Yao X, Deng S, Zhou T, Fu Q. Water-induced shape memory effect of graphene
[4] Kulcar R, Friskovec M, Hauptman N, Vesel A, Gunde MK. Colorimetric properties of
oxide reinforced polyvinyl alcohol nanocomposites. J Mater Chem A
reversible thermochromic printing inks. Dyes Pigm 2010;86:271–7.
2014;2:2240–9.
[5] Raditoiu A, Raditoiu V, Nicolae CA, Raduly MF, Amariutei V, Wagner LE. Optical
[33] Liang H, Feng Y, Lu J, Liu L, Yang Z, Luo Y, et al. Bio-based cationic waterborne
and structural dynamical behavior of Crystal Violet Lactone-Phenolphthalein binary
polyurethanes dispersions prepared from different vegetable oils. Ind Crops Prod
thermochromic systems. Dyes Pigm 2016;134:69–76.
2018;122:448–55.
[6] Li G, Zheng X. Thermal energy storage system integration forms for a sustainable
[34] Chattopadhyay DK, Raju KVSN. Structural engineering of polyurethane coatings for
future. Renew Sustain Energy Rev 2016;62:736–57.
high performance applications. Prog Polym Sci 2007;32:352–418.
[7] Tao YB, He YL. A review of phase change material and performance enhancement
[35] Sun F, Yang J, Zhang H, Yi L, Luo K, Zhao L, et al. Multi-functional composite
method for latent heat storage system. Renew Sustain Energy Rev 2018;93:245–59.
aerogels enabled by chemical integration of graphene oxide and waterborne poly-
[8] Nomura T, Sheng N, Zhu C, Saito G, Hanzaki D, Hiraki T, et al. Microencapsulated
urethane via a facile and green method. Compos Sci Technol 2018;165:175–82.
phase change materials with high heat capacity and high cyclic durability for high-
[36] Wang J, Ye L. Structure and properties of polyvinyl alcohol/polyurethane blends.
temperature thermal energy storage and transportation. Appl Energy
Compos Part B-Eng 2015;69:389–96.
2017;188:9–18.
[37] Lin Y, Zhu C, Alva G, Fang G. Microencapsulation and thermal properties of myristic
[9] Alva G, Huang X, Liu L, Fang G. Synthesis and characterization of micro-
acid with ethyl cellulose shell for thermal energy storage. Appl Energy
encapsulated myristic acid-palmitic acid eutectic mixture as phase change material
2018;231:494–501.
for thermal energy storage. Appl Energy 2017;203:677–85.
[38] Geng X, Li W, Yin Q, Wang Y, Han N, Wang N, et al. Design and fabrication of
[10] Tumirah K, Hussein MZ, Zulkarnain Z, Rafeadah R. Nano-encapsulated organic
reversible thermochromic microencapsulated phase change materials for thermal
phase change material based on copolymer nanocomposites for thermal energy
energy storage and its antibacterial activity. Energy 2018;159:857–69.
storage. Energy. 2014;66:881–90.
[39] Sun Q, Zhang H, Xue J, Yu X, Yuan Y, Cao X. Flexible phase change materials for
[11] Rodrigues SN, Martins IM, Fernandes IP, Gomes PB, Mata VG, Barreiro MF, et al.
thermal storage and temperature control. Chem Eng J 2018;353:920–9.
Scentfashion®: Microencapsulated perfumes for textile application. Chem Eng J
[40] Han P, Lu L, Qiu X, Tang Y, Wang J. Preparation and characterization of macro-
2009;149:463–72.
capsules containing microencapsulated PCMs (phase change materials) for thermal
[12] Chai L, Wang X, Wu D. Development of bifunctional microencapsulated phase
energy storage. Energy 2015;91:531–9.
change materials with crystalline titanium dioxide shell for latent-heat storage and
[41] Raghu AV, Anita G, Barigaddi YM, Gadaginamath GS, Aminabhavi TM. Synthesis
photocatalytic effectiveness. Appl Energy 2015;138:661–74.
and characterization of novel polyurethanes based on 2,6-bis(4-hydro-
[13] Ma Y, Zong J, Li W, Chen L, Tang X, Han N, et al. Synthesis and characterization of
xybenzylidene) cyclohexanone hard segments. J Appl Polym Sci 2007;104:81–8.
thermal energy storage microencapsulated n-dodecanol with acrylic polymer shell.
[42] Raghu AV, Gadaginamath GS, Mathew N, Halligudi SB, Aminabhavi TM. Synthesis,
Energy 2015;87:86–94.
characterization, and acoustic properties of new soluble polyurethanes based on
[14] Li F, Wang X, Wu D. Fabrication of multifunctional microcapsules containing n-
2,2′-[1,4- phenylenebis(nitrilomethylylidene)diphenol and 2,2′-[4,4′-methylene-di-
eicosane core and zinc oxide shell for low-temperature energy storage, photo-
2-methylphenylene-1,1′- bis(nitrilomethylylidene)] diphenol. J Appl Polym Sci
catalysis, and antibiosis. Energy Convers Manage 2015;106:873–85.
2007;106:299–308.
[15] Maruoka N, Akiyama T. Exergy recovery from steelmaking off-gas by latent heat
[43] Raghu AV, Gadaginamath GS, Mathew NT, Halligudi SB, Aminabhavi TM. Synthesis
storage for methanol production. Energy. 2006;31:1632–42.
and characterization of novel polyurethanes based on 4,4′- [1,4-phenylenedi-dia-
[16] Medina M, King J, Zhang M. On the heat transfer rate reduction of structural in-
zene-2,1-diyl] bis(2- carboxyphenol) and 4,4′-[1,4-phenylenedi-diazene-2,1-diyl]
sulated panels (SIPs) outfitted with phase change materials (PCMs). Energy
bis(2-chlorophenol) hard segments. React Funct Polym 2007;67:503–14.
2008;33:667–78.
[44] Suhas DP, Jeong HM, Aminabhavi TM, Raghu AV. Preparation and characterization
[17] Huang L, Petermann M, Doetsch C. Evaluation of paraffin/water emulsion as a
of novel polyurethanes containing 4,4′-{oxy-1,4-diphenyl bis(nitromethylidine)}
phase change slurry for cooling applications. Energy 2009;34:1145–55.
diphenol schiff base diol. Polym Eng Sci 2014;54:24–32.
[18] Wu CB, Wu G, Yang X, Liu YJ, Liang T, Fu WF, et al. Preparation of micro-
[45] Lin Y, Zhu C, Alva G, Fang G. Palmitic acid/polyvinyl butyral/expanded graphite
encapsulated medium temperature phase change material of Tris(hydroxymethyl)
composites as form-stable phase change materials for solar thermal energy storage.
methyl aminomethane@SiO 2 with excellent cycling performance. Appl Energy
Appl Energy 2018;228:1801–9.
2015;154:361–8.
[46] Suhas DP, Aminabhavi TM, Raghu AV. para-Toluene sulfonic acid treated clay
[19] Li D, Wu Y, Zhang G, Arici M, Liu C, Wang F. Influence of glazed roof containing
loaded sodium alginate membranes for enhanced pervaporative dehydration of
phase change material on indoor thermal environment and energy consumption.
isopropanol. Appl Clay Sci 2014;101:419–29.
Appl Energy 2018;222:343–50.
[47] Suhas DP, Raghu AV, Jeong HM, Aminabhavi TM. Functionalized graphene sheets
[20] Zhang H, Xing F, Cui HZ, Chen DZ, Ouyang X, Xu SZ, et al. A novel phase-change
embedded in chitosan nanocomposite membranes for ethanol and isopropanol de-
cement composite for thermal energy storage: Fabrication, thermal and mechanical
hydration via pervaporation. Ind Eng Chem Res 2014;53:14474–84.
properties. Appl Energy 2016;170:130–9.
[48] Suhas DP, Aminabhavi TM, Jeong HM, Raghu AV. Hydrogen peroxide treated
[21] Sari A, Alkan C, Bicer A, Altuntas A, Bilgin C. Micro/nanoencapsulated n-non-
graphene as an effective nanosheet filler for separation application. RSC Adv
adecane with poly(methyl methacrylate) shell for thermal energy storage. Energy
2015;5:100984–95.
Convers Manage 2014;86:614–21.
[49] Yan F, Chen H, Lu Y, Lu Z, Yu S, Liu M, et al. Improving the water permeability and
[22] Li W, Zhang XX, Wang XC, Tang GY, Shi HF. Fabrication and morphological
antifouling property of thin-film composite polyamide nanofiltration membrane by
characterization of microencapsulated phase change materials (MicroPCMs) and
modifying the active layer with triethanolamine. J Membr Sci 2016;513:108–16.
macrocapsules containing MicroPCMs for thermal energy storage. Energy
[50] Sharma A, Sharma SD, Buddhi D. Accelerated thermal cycle test of acetamide,
2012;38:249–54.
stearic acid and paraffin wax for solar thermal latent heat storage application.
[23] Geng X, Li W, Wang Y, Lu J, Wang J, Wang N, et al. Reversible thermochromic
Energy Convers Manage 2002;43:1923–30.
microencapsulated phase change materials for thermal energy storage application
[51] Shilei L, Neng Z, Guohui F. Eutectic mixtures of capric acid and lauric acid applied
in thermal protective clothing. Appl Energy 2018;217:281–94.
in building wallboards for heat energy storage. Energy Build 2006;38:708–11.
[24] Suhas DP, Raghu AV, Jeong HM, Aminabhavi TM. Graphene-loaded sodium

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