Journal of Energy Storage 56 (2022) 105973

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Journal of Energy Storage

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Research Papers

Concurrent magnetic and thermal energy storage using a novel

phase-change microencapsulated-nanoparticles fluid
Xinyi Liu a, b, Jifen Wang a, b, *, Huaqing Xie b, Zhixiong Guo c
a
School of Resources and Environmental Engineering, Shanghai Polytechnic University, China
b
Shanghai Engineering Research Center of Advanced Thermal Functional Materials, No.2360 Jinhai Rd., Shanghai 201209, China
c
Department of Mechanical and Aerospace Engineering, Rutgers, The State University of New Jersey, Piscataway, NJ 08854, USA

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

Keywords: A new class of magnetic phase-change microencapsulated-nanoparticles fluid (MPCMNF) was produced via
Magnetic nanoparticle dispersing magnetic capsules into deionized water with surfactant. The microcapsules were prepared by in-situ
Microencapsulate polymerization method to encase phase-change paraffin (PW) into CaCO3 shell with magnetic Fe3O4 nano­
Thermal property
particles. The microstructure, and the thermal and magnetic properties of the magnetic capsules were experi­
Phase-change material
mentally characterized. It is found that the PW@CaCO3/0.8%Fe3O4 (i.e., 0.8 % mass ratio of Fe3O4 to PW)
Energy storage
exhibits the highest thermal performance and encapsulation efficiency among the four mass fractions evaluated,
reaching enthalpy of 80.2 ± 2.6 J/g, thermal conductivity of 0.998 ± 0.017 W/(m⋅K), and encapsulation effi­
ciency of 56.2 ± 1.1 %. The saturation magnetization of the PW@CaCO3/0.8%Fe3O4 is 1.032 ± 0.021 emu/g,
indicating an excellent magnetic property. The thermal conductivity, magnetic property, viscosity and density of
the MPCMNF with different concentrations of PW@CaCO3/0.8%Fe3O4 have been measured. Results show that
the MPCMNF has a dual magnetic and thermal energy storage property, scouting particular applications in fluid
flow, heat transfer, and energy storage.

1. Introduction applications, such as building materials [7–9], textiles [10–12], food

Because phase-change materials (PCMs) absorb or release large
amounts of latent phase transition heat at a certain temperature, they
are able to utilize heat energy in an cost-effective manner [1]. During
phase change a solid PCM will transition into liquid state; and thus, PCM
must be encapsulated in a barrier layer in some applications to prevent
liquid leakage [2]. Microencapsulation techniques that use film forming
materials to wrap PCM into microparticles are rapidly evolving nowa­
days [3–5]. Phase-change microcapsules have many advantages. First,
they have the potential to enhance the processing properties of con­
ventional PCMs. For example, phase-change microcapsules can be
combined easily with a variety of polymer materials to create composite
polymer PCMs with improved performance [6]. Second, as a composite
material, the concerns such as volume change, leakage, and super­
cooling during the phase change process, may be avoided due to the
shell wall material’s cladding protection. Third, phase-change micro­
capsules have better stability and excellent utilization rate. They can
resist oxidation and reduce volatility of core materials. Hence, the
microcapsule technology has gained much attention in broad
packaging [13], and electronic devices [14], to name a few.
During the operation of electronic gadgets, a tremendous amount of
heat and electromagnetic radiation are generated, compromising the
performance and safety of users dramatically. Microcapsules can avoid
[15] such concerns due to their latent heat and electromagnetic
shielding. Phase-change microcapsules with magnetic functions can
meet the needs of military infrared electromagnetic double shielding
characteristics, greatly improving material operability. In recent years,
the study of magnetic nanoparticles has attracted widespread interest in
various disciplines, mainly in the fields of magnetic fluids [16],
biomedicine [17], and nuclear magnetic resonance imaging [18].
Magnetic nanoparticles have many special magnetic properties, such as
superparamagnetic and high coercivity [19]. Magnetic nanoparticles
can be suspended in a suitable carrier solution to form a magnetic liquid
in which the magnetic nanoparticles can be encapsulated by surfactant
molecules to prevent Van der Waals from interacting and coming
together [20].
Functionalization of the core and shell materials in microcapsules
appears to be critical. Numerous studies have been conducted to

* Corresponding author at: School of Resources and Environmental Engineering, Shanghai Polytechnic University, China.
E-mail address: wangjifen@sspu.edu.cn (J. Wang).

https://doi.org/10.1016/j.est.2022.105973
Received 13 July 2022; Received in revised form 5 October 2022; Accepted 24 October 2022
Available online 7 November 2022
2352-152X/© 2022 Elsevier Ltd. All rights reserved.
X. Liu et al.
optimize the utilization of phase-change microcapsules. Li et al. [21]
successfully prepared a type of screen-printed magnetic phase-change
microcapsules using paraffin as the core material and melamine form­
aldehyde resin as the shell material for magnetic field shielding by
coating the surface of the shell layer with a hydrophilic emulsifier and
dispersing the magnetic particles (Fe3O4, CrO2) into the shell layer. Gao
et al. [22] prepared a type of phase-change microcapsule with n-eico­
sane as the core material and cuprous oxide as the shell, and used it for
solar thermal energy storage and photocatalysis. Huang et al. [23]
improved the thermal properties of a conventional fluid via dispersing
magnetic phase-change microcapsules into the fluid such that the fluid
flow and heat transfer can be controlled by an applied magnetic field.
Liu et al. [24] used black phosphorous (BP) modified microcapsules with
n-docosane as core and CaCO3/Fe3O4 as shell with a phase change
enthalpy of >120 J/g and a thermal conductivity of >400 % higher than
pure PCM. The microcapsule system also achieved a photothermal
conversion efficiency of 95.08 %. By dispersing magnetic phase-change
microcapsules into multi-walled carbon nanotube nanofluids, Gao et al.
[25] prepared a novel magnetic phase change microcapsule slurry to
improve the photothermal conversion and thermal storage of direct
absorption solar collectors.
In this research, magnetic phase-change microcapsules
(PW@CaCO3/Fe3O4) with different Fe3O4 mass ratios are produced via
in-situ polymerization. The core material is paraffin wax (PW), a PCM
with high latent heat of transformation and good chemical stability. The
wall material is calcium carbonate (CaCO3), an inorganic material with
excellent thermal conductivity and chemical stability. The surface of the
prepared microcapsules is modified with magnetic Fe3O4 nanoparticles.
Fluids with magnetic Fe3O4 nanoparticles are known to have excellent
magnetic responsiveness [26,27]. The thermo-physical properties of the
prepared magnetic microcapsules are experimentally characterized. The
focus of this study is placed on quantifying the effects of Fe3O4 nano­
particles on the magnetic and thermal performance of the new type of
microcapsules. We first identify which Fe3O4 mass ratio produces the
best thermal performance as well as the highest encapsulation effi­
ciency; And then disperse such microcapsules into aqueous solution
containing Polyvinylpyrrolidone (PVP) surfactant (1:10 weight ratio
between PVP and water) to create a new class of magnetic phase-change
microencapsulated-nanoparticles fluid (MPCMNF). Finally, the thermal
property, magnetic property and viscosity of the MPCMNF with various
microcapsule concentrations are experimentally determined. The prep­
aration of magnetic phase change microcapsules with both phase change
and magnetic properties is expected to lead to a wide range of appli­
cations in areas such as military electronics. The MPCMNF obtained by
combining magnetic phase change microcapsules with fluids has
Fig. 1. Schematic synthetic strategy for preparing the magnetic phase-change microencapsulated-nanoparticles fluid.
2
Journal of Energy Storage 56 (2022) 105973
significant potential for applications in areas such as fluid heat transfer
and energy storage.
2. Experiment
2.1. Materials
The nanofluid containing magnetic Fe3O4 nanoparticles (particle
size: 10–12 nm, ρ = 1.15 g/cm3) was obtained from Wuhan University of
Technology. The paraffin wax (PW) (melting point: 52–54 ◦ C, RG), so­
dium dodecyl-benzenesulfonate (SDBS, AR), calcium chloride (CaCl2,
AR), sodium carbonate (Na2CO3, AR), ethanol (purity ≥99.7 wt%, AR),
petroleum ether (boiling range: 35–60 ◦ C, ACS), and poly­
vinylpyrrolidone K30 (PVP, GR) were acquired from Shanghai Titan
Scientific Co., Ltd.
2.2. Preparation of MPCMNF
The magnetic microcapsules were synthesized by in-situ polymeri­
zation. Fig. 1 shows the schematic diagram for preparing the MPCMNF.
The specific steps are as follows: (i) 1.50 g sodium dodecyl-
benzenesulfonate (SDBS) was dissolved in 100.0 ml water to obtain
solution. Added 10.0 g paraffin into a flask in a 65 ◦ C water bath for 15
min, put the solution to the flask and the mixed solution was heated at a
1000 rpm stirring rate for 30 min at 65 ◦ C. (ii) 10.0 g CaCl2 dissolved in
100.0 ml water was slowly added to the flask over a 3-hour period while
stirring at 1000 rpm. (iii) The solution of 9.50 g Na2CO3 dissolved in
100.0 ml water was slowly added to the flask over a 2-hour period while
stirring at 800 rpm. The ratio of CaCO3 shell to paraffin core in the
microcapsules is controlled to 1:1 by the amount added. (iv) Added
different masses of Fe3O4 nanoparticles (converted by the added mag­
netic fluid content to obtain desired mass ratio of Fe3O4 nanoparticles)
into the flask for 1 h. The mass fraction of the Fe3O4 nanoparticles to the
core paraffin was prepared in 0.3 %, 0.5 %, 0.8 %, and 1.0 %, respec­
tively. For comparison, a sample without addition of Fe3O4 nano­
particles (0 %) was also prepared. The specific dosage table was shown
in Table 1. (v) Magnetic phase-change microcapsules (PW@CaCO3/
Fe3O4) containing different mass fractions of Fe3O4 nanoparticles were
obtained. (vi) Different masses of PW@CaCO3/0.8%Fe3O4 and 1.50 g
polyvinylpyrrolidone K30 (dispersant) were combined in 15.0 ml water
and sonicated for 3 h. Dissolve 1.5 g PVP in 15.0 ml water and sonicate
for 3 h as a comparison base fluid. (vii) The final samples of magnetic
phase-change microencapsulated-nanoparticles fluid (MPCMNF) con­
taining different mass concentrations of PW@CaCO3/0.8%Fe3O4 in the
water/PVP base fluid were obtained. Five samples marked as
X. Liu et al. Journal of Energy Storage 56 (2022) 105973

Table 1 error (Us). The random error is obtained by repeating the test five times
Table of materials used for the preparation of magnetic phase change micro­ for the sample measured. The systematic error is the error of the in­
capsules with different mass fractions of Fe3O4.
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
strument itself. The overall uncertainty is Ur2 + Us2 . The magnetic
Samples PW Fe3O4 CaCl2 Na2CO3 SDBS properties were characterized by a vibrating sample magnetometer
(g) (g) (g) (g) (g)
(VSM, 7404). In VSM testing, the principle of electromagnetic induction
PW@CaCO3 10.00 0.00 10.00 9.60 1.50 was used, with the sample vibrating at a fixed frequency and amplitude
PW@CaCO3/0.3% 10.00 0.03 10.00 9.60 1.50 in the center of a set of probe coils. The signal generated by the vibration
Fe3O4
was measured with a lock-in amplifier. The dynamic viscosities of the
PW@CaCO3/0.5% 10.00 0.05 10.00 9.60 1.50
Fe3O4 prepared MPCMNFs at 25 ◦ C were measured with a rotational viscom­
PW@CaCO3/0.8% 10.00 0.08 10.00 9.60 1.50 eter (6rookfield DV-2 pro).
Fe3O4
PW@CaCO3/1.0% 10.00 0.10 10.00 9.60 1.50
3. Results and discussion
Fe3O4

3.1. Structure and chemical composition of the magnetic capsules

MPCMNF1, MPCMNF2, MPCMNF3, MPCMNF4 and MPCMNF5 were
prepared.
2.3. Characterization
The magnetic capsules’ crystal structure and chemical composition
were determined using an X-ray diffractometer (XRD, D8 Advance) and
a Fourier transform infrared spectroscopy (FTIR, Spectrum Two). The
XRD test results were obtained using the stepwise scanning method with
a 2θ scan range of 10◦ to 80◦ at 40 kV and 40 mA. The FTIR test results
were obtained by plotting 16 scans on a potassium bromide (KBr)
sample plate. The morphology and the elemental analysis of the mag­
netic capsules were observed using a scanning electron microscopy
(SEM, Hitachi S-4800) and an energy-dispersive X-ray spectroscopy
(EDS). For SEM and EDS measurements, took a small amount of sample
and sprinkled it directly onto the double-sided carbon conductive ad­
hesive of the specimen holder. The conductive adhesive was pressed
down with a glass plate and the poorly bonded particles were blown off
with an ear wash ball. After gold spraying them, the conductive speci­
mens were photographed using the SEM in high vacuum mode at an
accelerating voltage of 15 kv. Thermal characteristics were determined
using a differential scanning calorimeter (DSC, Perkin Elmer Diamond),
a thermogravimetric analyzer (TGA, STA-449c) and a thermal conduc­
tivity instrument (TCI, C-THERMAL). In the DSC instrument test, the
temperature range of the measured samples was set from 10 ◦ C to 80 ◦ C
at a heating rate of 5 ◦ C/min under a nitrogen atmosphere. In the TGA
test, the sample was heated from room temperature to 850 ◦ C in an
aluminum crucible at a heating rate of 10 ◦ C/min. For the TCI mea­
surements, the samples were tested at room temperature (25 ◦ C) and the
thermal conductivity values were obtained by taking 5 readings of each
sample and averaging them. The uncertainty in the measurement results
is made up of two components: the random error (Ur) and the systematic
The FTIR spectra of the PW, CaCO3, and PW@CaCO3/Fe3O4 are
shown in Fig. 2. The distinctive peaks at 2958 cm− 1, 2919 cm− 1, and
2853 cm− 1 in the PW spectrum indicate the C–H stretching vibration
peaks. The valleys at 1732 cm− 1, 1472 cm− 1 and 1150 cm− 1 correspond
to the C–– O stretching vibration peak, the C–C vibration peak, and the
C–O stretching vibration peak in the shell material, respectively. 575
cm− 1 is the peak vibration of Fe–O in Fe3O4 nanoparticles. All char­
acteristic absorption peaks could be found in the infrared spectra of the
PW, CaCO3, and the prepared capsules, indicating that the prepared
magnetic capsules do include PW, CaCO3 and Fe3O4 nanoparticles.
Fig. 3 shows the XRD spectra of the PW, CaCO3, Fe3O4 and
PW@CaCO3/Fe3O4. The X-ray diffraction peaks of PW at 21.8◦ and
23.8◦ can be attributed to its regular crystal structure, corresponding to
the diffraction peaks of the (011) and (100) crystal planes, respectively.
All the spectra exhibit characteristic diffraction peaks at 2θ = 24.95◦ ,
27.16◦ , 32.68◦ , 43.81◦ , and 49.05◦ , corresponding to the CaCO3’s planes
(110), (112), (114), (300), and (304), respectively [28]. Because of the
small amount of Fe3O4 nanoparticles added, the graph shows small
diffraction peaks for the Fe3O4 particles. A series of diffraction peaks in
the capsules are observed at 2θ = 35.6◦ , 43.4◦ , 63.1◦ , and 74.2◦ , which
are well assigned to the (311), (400), (440), and (533) planes of Fe3O4
nanoparticles, respectively. The Fe3O4 nanoparticles are successfully
presented in magnetic capsules with high characteristic peaks and
spikes. The results provide strong evidence for the successful synthesis of
magnetic capsules.
3.2. Morphology analysis of non-magnetic and magnetic capsules
The SEM images of the capsules are illuminated in Fig. 4 for non-
magnetic PW@CaCO3 without addition of Fe3O4 nanoparticles (see a,
a′ and d) and for the four magnetic capsules containing different masses

1
Fig. 2. (a) FTIR spectra of PW, CaCO3, and PW@CaCO3/Fe3O4, (b) FTIR spectra of Fe3O4 and PW@CaCO3/Fe3O4 (500 cm− - 650 cm− 1).

3
X. Liu et al.
Fig. 3. XRD patterns of PW, CaCO3, Fe3O4 and PW@CaCO3/Fe3O4.
of Fe3O4 nanoparticles (see b, c, e, and f). As shown in Fig. 4, all the
capsules possess a stable structure with a spherical shape. The
PW@CaCO3′ surface is smooth and dense. The Fe3O4 nanoparticles are
grouped in a granular pattern on the surface of the magnetic capsules.
With increase of the Fe3O4 mass fraction, more such nanoparticles are
adsorbed onto the surface of the microcapsules. The manufactured
Fig. 4. SEM images of PW@CaCO3/Fe3O4: (a, a′ and d) 0 % Fe3O4 (non-magnetic), (b) 0.3 % Fe3O4, (c) 0.5 % Fe3O4, (e, e′ and e′′ ) 0.8 % Fe3O4, and (f) 1.0 % Fe3O4.
4
Journal of Energy Storage 56 (2022) 105973
magnetic capsules are uniform in size. As can be seen in Fig. 4(a′ ) and
(e′′ ), there are numerous spherical microcapsules with good dispersion.
The size of the microcapsules increases after the addition of magnetic
nanoparticles. There is a small amount of agglomeration between the
microcapsules. This may be due to the strong attraction between the
magnetic nanoparticles, whose magnetic properties make it easy to carry
out enrichment [29]. A clear morphological difference exists between
the non-magnetic and magnetic capsules as shown in Fig. 4.
Fig. 5 shows the EDS spectrum of the PW@Ca2CO3/0.8%Fe3O4. As
observed, the capsule’s surface is mostly formed of C, O, Ca, and Fe
elements, indicating that the capsule’s shell material is composed of
CaCO3 and Fe3O4 nanoparticles. The elements are also evident in the
capsule’s element mapping picture.
3.3. Thermal properties of non-magnetic and magnetic capsules
The DSC curves of the PW, PW@CaCO3, and PW@CaCO3/Fe3O4 are
shown in Fig. 6. Based on Su et al.’s study [30] of calibration temper­
atures as well as methods for DSC testing, this study chose a measure­
ment temperature range between 10 ◦ C and 80 ◦ C and a heating rate of
5 ◦ C/min. It shows that the solid-liquid phase transition temperatures of
the prepared capsules are close to that of the core material PW. The
latent heats of all the capsules are much lower than that of the PW. The
results of the tests reveal that the phase change behavior of the micro­
capsules is comparable to that of the PW, with no significant difference
in the temperature range for phase shift.
The measured enthalpy, phase transition temperature, and coating
rate of the microcapsules are listed in Table 2 in detail. Tm and Tc denote
the phase change temperatures of the microcapsules during melting and
X. Liu et al. Journal of Energy Storage 56 (2022) 105973

Fig. 5. EDS spectrum of the PW@Ca2CO3/0.8%Fe3O4.

Table 2
Phase change properties of the PW, PW@CaCO3 and PW@CaCO3/Fe3O4.
Samples Melting process Crystallization Een (%)
process

Tm (◦ C) △Hm (J/ Tc (◦ C) △Hc (J/

g) g)

PW 51.9 ± 141.2 ± 48.0 ± 139.2 ± –

0.2 0.3 0.4 1.7
PW@CaCO3 53.4 ± 63.3 ± 50.8 ± 60.6 ± 44.2 ±
0.2 2.0 0.3 2.0 0.9
PW@CaCO3/0.3% 53.2 ± 74.7 ± 49.9 ± 71.8 ± 52.2 ±
Fe3O4 0.3 3.1 0.5 3.6 1.6
PW@CaCO3/0.5% 52.9 ± 77.4 ± 49.9 ± 75.5 ± 54.5 ±
Fe3O4 0.2 3.7 0.6 3.4 1.5
PW@CaCO3/0.8% 53.0 ± 80.2 ± 49.6 ± 77.4 ± 56.2 ±
Fe3O4 0.4 2.6 0.2 2.7 1.1
PW@CaCO3/1.0% 52.7 ± 79.1 ± 49.0 ± 76.3 ± 55.4 ±
Fe3O4 0.5 1.7 0.5 2.3 0.8

interfacial thermal resistance during the operation of the microcapsules,

Fig. 6. DSC curves of the PW, PW@CaCO3, and PW@CaCO3/Fe3O4.
crystallization, respectively. ΔHm and ΔHc denote the enthalpy of
melting and enthalpy of crystallization, respectively. The melt enthalpy
of the PW@CaCO3 is 63.3 ± 2.0 J/g and the crystallization enthalpy is
60.6 ± 2.0 J/g. The latent heat of magnetic phase change microcapsules
is greater than that of the non-magnetic phase change microcapsules.
This may be due to the large surface area of the Fe3O4 nanoparticles
allows them to bind closely to the CaCO3 shell. This increases the
thus increasing the latent heat of the phase change microcapsules. The
phase-change enthalpy first increases and subsequently falls as the mass
fraction of the Fe3O4 nanoparticles increases. At a mass fraction of 0.8 %,
the microcapsules reach a maximum enthalpy value of 80.2 ± 2.6 J/g
for melting and 77.4 ± 2.7 J/g for crystallization. At this point, the wrap
rate reaches the maximum (56.2 ± 1.1 %) as well. When the Fe3O4
nanoparticles increase to 1.0 %, both the enthalpy and the wrap rate
begin to decrease. This is because the excessive amount of magnetic
nanoparticles leads to agglomeration of particles, resulting in uneven
distribution of the Fe3O4 nanoparticles on the shell and poor adhesion to
the shell, thus reducing the latent heat of the microcapsules [21]. As a

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X. Liu et al. Journal of Energy Storage 56 (2022) 105973

compromise, only a reasonable amount of Fe3O4 nanoparticles can be

used to improve the enthalpy of the magnetic capsules. The present
results show that the melt enthalpy of the PW@CaCO3/0.8%Fe3O4 is
56.8 % of the melt enthalpy of PW and the crystallization enthalpy of the
PW@CaCO3/0.8%Fe3O4 is 55.6 % of the crystallization enthalpy of PW,
retaining most of the heat storage function of the PCM.

3.4. Thermal stability of non-magnetic and magnetic capsules

Thermal stability is critical to enable practical applications of phase-

change microcapsules. The thermogravimetric (TG) curves of the PW,
PW@CaCO3, and PW@CaCO3/Fe3O4 are displayed in Fig. 7, reflecting
the variation of sample mass loss with increasing temperature. The mass
loss of samples is mainly due to the decomposition and evaporation of
PW in microcapsules during temperature increase. As seen from the TG
curves in the figure, the PW is a typical one-step thermal degradation.
The starting decomposition temperature of paraffin is around 250 ◦ C,
and the maximum mass loss occurs around 360 ◦ C. The degradation of
the microcapsules may clearly be split into two sections: paraffin
decomposition and shell decomposition. The first step of mass loss
corresponds to the volatilization of paraffin in microcapsules [31]. The
Fig. 8. Thermal conductivities of PW, PW@CaCO3, and PW@CaCO3/Fe3O4.
presence of shell CaCO3 with adsorbed Fe3O4 nanoparticles produces a
physical protective barrier that reduces the disintegration and mass loss
of the PW at high temperatures, improving significantly the thermal thermal conductivity of the PW@CaCO3/0.8%Fe3O4 reaches 0.998 ±
stability of the microencapsulated phase transition material. 0.017 W/(m⋅K). It was evident that the thermal conductivity of magnetic
As seen from Fig. 7, the decomposition curves of the PW@CaCO3 and microcapsules increased with the addition of Fe3O4 nanoparticles. The
PW@CaCO3/Fe3O4 are quite similar. The PW@CaCO3 decomposes at magnetic capsules have a higher thermal conductivity to enable more
about 251 ◦ C. However, the decomposition temperature of the practical applications.
PW@CaCO3/Fe3O4 begins at around 260 ◦ C. The initial decomposition
temperature of phase change microcapsules gradually increases as the 3.6. Magnetic characteristics of magnetic capsules
amount of Fe3O4 nanoparticles added increases. This difference reveals
that the magnetic PW@CaCO3/Fe3O4 is more stable than the non- The saturated hysteresis lines of the PW@CaCO3 and PW@CaCO3/
magnetic PW@CaCO3. The Fe3O4 nanoparticles in the shell layer Fe3O4 are shown in Fig. 9. It is seen that the saturation magnetic in­
appear to have improved the microcapsules’ thermal stability. duction of the PW@CaCO3 is 0, indicating no magnetic response. When
the Fe3O4 mass fraction is 0.3 %, the saturation magnetic induction of
3.5. Thermal conductivity of non-magnetic and magnetic capsules the PW@CaCO3/0.3%Fe3O4 is 0.165 ± 0.015 emu/g. This indicates that
the magnetic properties of the prepared magnetic capsules come from
The measured thermal conductivities of the PW, PW@CaCO3, and the Fe3O4 nanoparticles. The saturation magnetic induction of the
PW@CaCO3/Fe3O4 are presented in Fig. 8. The low heat conductivity of magnetic microcapsules keeps increasing with the increase of the Fe3O4
pure PW is 0.243 ± 0.017 W/(m⋅K). However, the coating of the highly nanoparticles content. The saturation magnetic induction of the
thermally conductive shell resulted in a significant increase in the PW@CaCO3/0.8%Fe3O4 reaches 1.032 ± 0.021 emu/g. Thus, the
thermal conductivity of PW@CaCO3 to 0.825 ± 0.025 W/(m⋅K). With magnetic microcapsules have good magnetic properties.
the addition of the highly thermally conductive Fe3O4 nanoparticles When the magnetic substance is magnetized to saturation, due to the
[32], the thermal conductivity of the PW@CaCO3/Fe3O4 is further hysteresis phenomenon, if the magnetic induction in the magnetic me­
increased to be higher than that of the PW@CaCO3. For example, the dium is 0, a certain inverse magnetic field strength is required, which is

Fig. 7. TG curves of PW, PW@CaCO3, and PW@CaCO3/Fe3O4. Fig. 9. Hysteresis regression of the PW@CaCO3 and PW@CaCO3/Fe3O4.

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X. Liu et al. Journal of Energy Storage 56 (2022) 105973

called the coercive magnetic force (Hc) [33]. As seen from Fig. 9, all prepared microcapsules have great application potential as magnetic
magnetic microcapsules have a forced magnetic force of 0 Oe, indicating shielding materials that require repeated magnetization.
that these magnetic microcapsules are a soft magnetic material with a
high saturation magnetic induction strength and a low coercive force,
making them easy to magnetize and demagnetize. Therefore, the

Fig. 10. Pictures of MPCMNF samples with and without PVP at different times.

7
X. Liu et al.
3.7. Thermal energy storage of MPCMNF
Since the PW@CaCO3/0.8%Fe3O4 has the best thermal enthalpy and
excellent magnetic property, it is selected to synthesize the MPCMNF.
Polyvinylpyrrolidone K30 (PVP) as a polymeric surfactant can be used as
dispersant in order to make the microcapsules more dispersed in water.
Fig. 10 shows the images of MPCMNF samples with and without PVP at
different times after fabrication. Same amount of the PVP (1.5 g) was
added to 15 ml deionized water and sonicated for 3 h in preparing all the
MPCMNF samples with PVP. It is seen that PVP is an excellent disper­
sant, because the MPCMNF samples with PVP after 1 h fabrication are
more uniformly dispersed in water and the distribution of the micro­
capsules in the magnetic fluid is more stable. The microcapsules in the
MPCMNF samples without PVP tend to gather and precipitate in 1 h.
This difference is mainly due to the dispersant’s role in reducing the time
and energy required to complete the dispersion process, stabilizing the
dispersion, and adjusting the motility of the dispersion [34]. After 12 h,
sedimentation occurred even with PVP in the MPCMNF.
Fig. 11(a) displays the thermal conductivity of the base fluid (i.e.,
aqueous solution with 1:10 mass ratio between PVP and water) and the
prepared MPCMNF samples containing different volume concentrations
of PW@CaCO3/0.8%Fe3O4 measured at room temperature 25 ◦ C by the
TCI. The thermal conductivity of the base fluid was measured as 0.591
± 0.004 W/(m⋅K), a little bit higher than the thermal conductivity of
pure water which was measured as 0.582 ± 0.005 W/(m⋅K). The heat
conductivity of MPCMNF1 is 0.596 ± 0.004 W/(m⋅K) compared to the
base fluid, an increase of 0.85 %. When the PW@CaCO3/0.8%Fe3O4
reaches 7.56 ± 0.04 vol% for the MPCMNF5, a 10.49 % increase is
observed in thermal conductivity as compared to the base fluid.
According to the effective medium theory, the thermal conductivity
of a nanofluid can be predicted based on the following:
( )
KMPCMNF
= 1+
KPCM
− 1 × Cvol = 1 + 0.69Cvol . (1)
Kbase fluid Kbase fluid
In which, KMPCMNF, Kbase fluid, and KPCM are the thermal conductivity
of the MPCMNF, the base fluid, and the PW@CaCO3/0.8%Fe3O4 mi­
crocapsules, respectively, and Cvol is the volume concentration of the
PW@CaCO3/0.8%Fe3O4. Fig. 11(b) compares the theoretical prediction
(with values for Kbase fluid and KPCM from afore experimental measure­
ment) with the experimentally measured thermal conductivity of the
MPCMNFs. Although the measured value varies almost linearly with
micron capsules concentration, its slope is steeper than that of the
theoretical line. Hence, the real thermal conductivity of the prepared
MPCMNFs is greater than the effective medium theory because of
Fig. 11. (a) The measured thermal conductivity of the MPCMNF samples at 25 ◦ C; (b) comparison between the effective theory predictions and experimental
measurements.
8
Journal of Energy Storage 56 (2022) 105973
enhancement mechanisms such as Brownian motion, dispersion, inter­
face layer, etc. as summarized in a recent review [35].
3.8. Magnetic property of MPCMNF
In order to understand how the MPCMNFs respond to an applied
magnetic field, Fig. 12 shows the images of the MPCMNF1, MPCMNF2,
MPCMNF3 and MPCMNF4 samples in a breaker at different time instants
after applying an applied magnetic field outside the fluid. The magnet
used in the experiments has a magnetic strength of approximately 0.3 T
and a size of 20 × 10 × 6 mm. It is seen that almost all of the magnetic
capsules in the MPCMNFs are able to overcome the buoyancy force and
move rapidly to the side of the beaker towards the applied magnetic
field, indicating that the magnetic capsules can be controlled by the
external magnetic field. This could enhance convective heat transfer
[36].
3.9. Viscosity of MPCMNF
Viscosity is a main parameter affecting the flow pattern and resis­
tance of a fluid [37]. Fig. 13(a) plots the dynamic viscosity and density
of the MPCMNFs measured at room temperature 25 ◦ C with a constant
shear rate of 100 s− 1. Their values are also provided in Table 3. The
measured density and viscosity of the base fluid are 1.011 ± 0.0004 g/
cm3 and 5.01 ± 0.3 mPa⋅s, respectively. As seen from Fig. 13(a), the
viscosity of the MPCMNF jumps quickly with addition of the
PW@CaCO3/0.8%Fe3O4 capsules. For MPCMNF1 with 0.72 ± 0.04 vol
% of the PW@CaCO3/0.8%Fe3O4, its viscosity reaches 8.55 ± 0.3 mPa⋅s,
a huge increase by 70.7 %. Though the viscosity of the MPCMNF in­
creases with further increase of the capsule’s concentration, the
increasing magnitude is not appreciable. For example, the viscosity of
MPCMNF5 with 7.56 ± 0.04 vol% PW@CaCO3/0.8%Fe3O4 is 9.99
mPa⋅s, only a 16.8 % increase as compared with that of MPCMNF1 at a
very low concentration. The increase in the MPCMNF viscosity is due to
the increased shear actions within the microcapsules, which impede the
mutual movement between the fluid layers and result in an increase in
viscosity [38]. Fig. 13(b) compares the density variations between
experimental measurement and theoretical prediction. It is seen that the
density of the MPCMNF almost increases linearly with the concentra­
tion. The measured density of dry powder of PW@CaCO3/0.8%Fe3O4
microcapsules is 1.528 ± 0.003 g/cm3. The regression line for the
density ratio between the MPCMNF and its base fluid shows y = 1.0 +
0.47Cvol, in which y is the density ratio; while the theoretical one ac­
cording to effective medium theory is
X. Liu et al. Journal of Energy Storage 56 (2022) 105973

Fig. 12. Images of the MPCMNFs responding to an applied magnetic field.

Fig. 13. (a) Measured dynamic viscosity and density of the MPCMNF samples at 25 ◦ C; (b) comparison of the effective medium theory and experimental mea­
surement of the density of MPCMNFs.

Table 3
The prepared MPCMNF samples with different concentrations of PW@CaCO3/0.8%Fe3O4.
Sample name MPCMNF1 MPCMNF2 MPCMNF3 MPCMNF4 MPCMNF5

Mass concentration (wt%) 1.20 ± 0.01 2.94 ± 0.01 5.81 ± 0.01 8.33 ± 0.01 10.81 ± 0.01
Volume concentration (vol%) 0.72 ± 0.04 1.99 ± 0.01 3.96 ± 0.03 5.80 ± 0.03 7.56 ± 0.04
Density (g/cm3) 1.0161 ± 0.0004 1.0212 ± 0.0001 1.0310 ± 0.0003 1.0391 ± 0.0003 1.0483 ± 0.0004
Dynamic viscosity (mPa⋅s) 8.55 ± 0.30 9.31 ± 0.20 9.42 ± 0.40 9.66 ± 0.20 9.99 ± 0.30
Thermal conductivity (W/(m⋅K)) 0.596 ± 0.004 0.612 ± 0.004 0.621 ± 0.005 0.640 ± 0.005 0.653 ± 0.006

9
X. Liu et al.
( )
ρMPCMNF ρPCM
= 1+ − 1 × Cvol = 1 + 0.51Cvol . (2)
ρbase fluid ρbase fluid
In which, ρMPCMNF, ρbase fluid, and ρPCM are the density of the
MPCMNF, the base fluid, and the PW@CaCO3/0.8%Fe3O4 microcap­
sules, respectively. Thus, the measured density variation with capsules
concentration is very close to the theoretical prediction. The minor
difference can be attributed to the voids in dry PCM powders. The
effective medium theory could be corrected by the modification of a
porosity in the measured density of dry PCM powders as
( )
ρMPCMNF (1 − φ)ρPCM
= 1+ − 1 × Cvol = 1 + 0.47Cvol . (3)
ρbase fluid ρbase fluid
In which the porosity φ in the dry powder of PW@CaCO3/0.8%Fe3O4
microcapsules is estimated as 2.65 %.
4. Conclusion
In this comprehensive experimental study, we have produced inno­
vative dual-functional phase-change microcapsules with superior ther­
mal and magnetic performance via in-situ polymerization method to
encase phase-change PW into CaCO3 shell with magnetic Fe3O4 nano­
particles. The mass ratio of CaCO3 shell to PW core was controlled to 1:1.
The main findings of the study on magnetic phase change microcapsules
are as follows:
(1) Four different mass fractions of the Fe3O4 nanoparticles to the
core paraffin were prepared and compared. SEM images show
that the surface of the magnetic microcapsules is rougher than
that of the conventional capsules. Both spectrum analysis and
element mapping prove that the capsule’s surface is mostly
formed of C, O, Ca, and Fe elements, indicating that the capsule’s
shell material is composed of CaCO3 and Fe3O4 nanoparticles.
(2) With 0.8 % Fe3O4 mass fraction to the core PW, the magnetic
microcapsules (i.e., PW@CaCO3/0.8%Fe3O4) reach a maximum
enthalpy value of 80.2 ± 2.6 J/g for melting and 77.4 ± 2.7 J/g
for crystallization, indicating that the PW@CaCO3/0.8%Fe3O4
can store a large amount of heat with phase change temperature
similar to that of the paraffin. At this mass fraction, the encap­
sulation wrap rate also reaches the maximum at 56.2 ± 1.1 %.
The thermal conductivity of the PW@CaCO3/0.8%Fe3O4 is
measured as 0.998 ± 0.017 W/(m ⋅ K), more than four times of
that of the pure paraffin.
(3) The VSM images show that these magnetic microcapsules have a
large saturation magnetic induction strength and a small coercive
force, making them easy to magnetize and demagnetize.
A new class of magnetic phase-change microencapsulated-nano­
particles fluid is produced via dispersing the magnetic PW@CaCO3/
0.8%Fe3O4 microcapsules into a base fluid (i.e., aqueous solution with
1:10 weight ratio between PVP and water). Five MPCMNF samples with
different microcapsule volume concentrations are prepared and
compared. The main findings of the research on magnetic fluids are as
follows:
(4) The nanofluid samples with addition of surfactant PVP is more
uniformly dispersed and stable than the samples without PVP.
(5) The density, thermal conductivity, and viscosity increase with
increasing volume fraction of the microcapsules. For the
MPCMNF5 with 7.56 ± 0.04 vol% PW@CaCO3/0.8%Fe3O4, its
thermal conductivity is 0.653 ± 0.006 W/(m⋅K), 10.49 % greater
than that of the base fluid, indicating that it has excellent thermal
characteristic. In the meanwhile, MPCMNF5 has a dynamic vis­
cosity value of approximately 2 times that of the base fluid. The
density increase in the MPCMNF5 is not appreciable, only about
3.65 % heavier than the base fluid.
10
Journal of Energy Storage 56 (2022) 105973
(6) The MPCMNF density variation with concentration matches with
the prediction by the effective medium theory modified with a
powder porosity. However, the effective medium theory under­
predicts the variation of the MPCMNF thermal conductivity with
concentration.
(7) The magnetic microcapsules in the suspension are easily influ­
enced by the applied magnetic field, thus enabling local
convective heat transfer enhancement.
The prepared magnetic phase change microcapsules provide a new
avenue for the study of functionalized phase change materials. The
MPCMNFs have great potential for heat transfer and energy storage
applications.
CRediT authorship contribution statement
Xinyi Liu: Methodology, Software, Validation, Formal analysis,
Investigation, Data curation, Writing – original draft, Writing – review &
editing, Visualization, Project administration. Jifen Wang: Conceptu­
alization, Resources, Writing – review & editing, Supervision, Funding
acquisition. Huaqing Xie: Formal analysis. Zhixiong Guo: Conceptu­
alization, Writing – review & editing, Formal analysis, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
This work is supported by the National Natural Science Foundation
of China (Nos. 51776116, 52176081) and Shanghai Science and Tech­
nology Project (No. 22010500600). ZG has not been involved in the
afore-mentioned sponsored projects but has made substantial contri­
butions in advising the research direction, paper organization, result
analysis, and writing and editing.
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