materials

Article
Thermal and Mechanical Properties of Expanded
Graphite/Paraffin Gypsum-Based Composite Material
Reinforced by Carbon Fiber
Bo Zhang 1 , Yuanyuan Tian 1 , Xiaoyan Jin 1 , Tommy Y. Lo 2 and Hongzhi Cui 1, *
1 Guangdong Provincial Laboratory of Durability for Marine Civil Engineering, Shenzhen University,
Shenzhen 518060, China; 2172332351@email.szu.edu.cn (B.Z.); 2150150417@email.szu.edu.cn (Y.T.);
2172332306@email.szu.edu.cn (X.J.)
2 Department of Architectural and Civil Engineering, City University of Hong Kong, Hong Kong 518000,
China; lo.tommy@cityu.edu.hk
* Correspondence: h.z.cui@szu.edu.cn; Tel.: +86-755-8667-0364




Received: 5 October 2018; Accepted: 4 November 2018; Published: 7 November 2018


Abstract: Phase change material (PCM) is a kind of thermal energy storage material. Solid-liquid
PCM composite materials must overcome the issues of material leakage and low thermal conductivity
before they are suitable for widespread use in the fields of building and industry. In this study,
porous expanded graphite (EG) is used as a carrier, which absorbs the PCM to fabricate EG/paraffin
composites (EG/P) containing 90.6% paraffin, and a latent heat of up to 105.3 J/g was measured.
Because gypsum board is widely used in buildings, therefore, EG/P composites are suitable to be
integrated into gypsum to develop expanded graphite/paraffin gypsum-based composite material
(EGPG) for thermal energy storage. In order to optimize the performance of EGPG, carbon fiber
(CF) is used to reinforce their thermal and mechanical properties. The test results show that when
1 wt % CF is incorporated into the EGPG, the thermal conductivity increased 36.0%, and thus
EGPG shows superior thermal control through the significantly increased efficiency of heat transfer.
After 1 wt % CF was added, the flexural and compressive strength of EGPG were increased by 65.6%
and 6.4%, respectively. The improved thermal and mechanical performance of EGPG modified by
CF demonstrates that it is a structural-functional integrated building material suitable for building
envelope system.

Keywords: phase change material; expanded graphite; thermal energy storage; gypsum-based
composite material; carbon fiber; mechanical properties; thermal performances

1. Introduction
Energy consumption in the construction industry accounts for 40% of the total energy
consumption and 30% of the annual greenhouse gas emissions [1]. Global energy reserves are becoming
increasingly overwhelmed, thus energy-saving and environmentally friendly materials must be used
to reduce the consumption of energy. This has motivated research into the development of thermal
energy storage solutions, including sensible heat storage, latent heat storage, and electrochemical
energy storage [2–4]. Latent heat storage is widely used in various fields, such as solar thermal energy
storage and industrial waste heat recovery, due to its high energy storage density and isothermal phase
transition temperature [5,6]. Additionally, the use of air-conditioners has increased as the thermal
comfort index increases to meet the demand of higher living standards. Therefore, the use of latent heat
storage materials, such as phase change materials (PCMs), combined with air conditioning systems in
buildings may be used to significantly reduce energy consumption.

Materials 2018, 11, 2205; doi:10.3390/ma11112205 www.mdpi.com/journal/materials

Materials 2018, 11, 2205 2 of 17

PCMs include both organic and inorganic PCMs. So far, inorganic PCMs are restricted in practical
applications due to supercooling and phase segregation [7]. Organic PCMs are chemically inert
and have good stability and corrosion resistance [8,9]. Paraffin, a typical organic phase change
material, has been widely used because of its many advantages, including non-toxicity, stable chemical
properties, no phase separation, low volume change during the phase change process, high enthalpy,
and low cost [10]. However, the low thermal conductivity (about 0.24 W/m·K) of paraffin limits
its widespread application because of inefficient heat transfer when absorbing or releasing thermal
energy. In order to improve the thermal performance of paraffin as a PCM, its low conductivity should
be modified.
Carbon-based materials are widely used for their high thermal conductivity or excellent
mechanical properties. To improve the thermal management of insulated gate bipolar transistors
(IGBT), Chang et al. [11] investigated the effects of nano-graphite sheet loading on paraffin to the
thermal conductivity and shape-stability. They reported that the thermal conductivity of paraffin
mixed with 15 wt % nano-graphite sheets was improved by five times compared to that of pure paraffin,
and paraffin/nano-graphite sheets demonstrated greater shape stabilized properties. In addition,
expanded graphite (EG) has been recognized for its low density, high porosity, high thermal
conductivity, low price, and compatibility with organic phase change materials [12,13]. Hence,
incorporating EG into paraffin could significantly increase its thermal conductivity and improve
thermal transfer efficiency. Also, porous EG could be used as a carrier to absorb PCM to form a
stabilized-shape phase change material (SSPCM), which could then prevent leakage of the paraffin
during the process of melting. According to the research of Yang et al. [14], EG could absorb about 93.1%
paraffin and the latent heat of the EG/paraffin was up to 152.8 J/g, which has potential for thermal
energy storage applications. However, a cement paste containing 10 wt % EG/paraffin was found
to have a compressive strength of 14.6 MPa, a reduction in compressive strength of 77.9% compared
with pure cement paste. In practice, structural-functional integrated building materials are not only
required to meet energy storage performance, but also must have a higher mechanical performance.
Carbon fiber has been used to reinforce composite materials due to its high tensile strength
and thermal conductivity [15,16]. For example, Han et al. [17] proposed that after mixing 0.8 wt %
CF into cement, the flexural strength is increased by 14.6% relative to a control sample without
fiber. They explained that CF with high tensile strength could restrain the growth of cracks and it
bonds well with hydration products, and thus it could enhance the flexural strength of cement by
absorbing energy. However, they also mentioned that the addition of carbon fiber would cause a
decrease of compressive strength due to the generation of a larger air void inside the matrix. Similar to
Han et al. [17], Cui et al. [18] also found that CF helped to retrain crack pulling and thus improved the
mechanical strength of cement. They presented, in that study, that the flexural strength of cement paste
and alkali-activated slag mixed with 1 wt % CF was increased by 130.8% and 302.6%, respectively,
after 28 days, compared with a control. The above research both illustrate that CF can be used to
solve the matter of thermal energy storage building materials with low strengths. Apart from the
reinforcement of mechanical strengths, Jiang et al. [19] used carbon fiber to prepare carbon bonded
carbon fiber monoliths/PCM, and found that the in-plane thermal conductivity of the PCM composites
was improved by 57 times over pure PCM, while the out-of-plane thermal conductivity was increased
by 5.5 times. In addition, they showed that there was a linear relationship between the volume fractions
of CF in the PCM composite with the improvement of thermal conductivity. Further improvement
of thermal conductivity could achieve a higher heat transfer efficiency of PCM. In a word, CF is a
promising candidate for enhancing the thermal and mechanical properties of structural-functional
integrated building material.
Gypsum board usually was used as interior walls and ceiling board, while it does not
have an energy storage function. If PCM was successfully integrated with the gypsum matrix,
a structural-functional integrated gypsum board might be obtained and its application in building
can be very wide-ranging [20,21]. Therefore, in this study, EG is used as a carrier to contain paraffin
Materials 2018,
Materials 11, x2205
2018, 11, FOR PEER REVIEW 33of
of 17
17
Materials 2018, 11, x FOR PEER REVIEW 3 of 17
Besides, the morphology, thermal performance, and chemical structure of EG/P are characterized by
to fabricate EG/P with the aim of minimizing leakage and improving the thermal conductivity
Besides, the
scanning morphology,
electron microscopy thermal performance,
(SEM), differentialandscanning
chemicalcalorimeter
structure of(DSC),
EG/P are characterized by
thermogravimetric
of paraffin. Besides, the morphology, thermal performance, and chemical structure of EG/P are
scanning (TGA),
analysis electronand microscopy (SEM), differential
Fourier transform infrared scanning calorimeter (DSC),
(FT-IR) spectroscopy thermogravimetric
accordingly before it is
characterized by scanning electron microscopy (SEM), differential scanning calorimeter (DSC),
analysis (TGA),
incorporated into and Fourier matrix.
the gypsum transform infrared
Finally, (FT-IR) spectroscopy
the thermo-regulated accordingly
performance and before it is
mechanical
thermogravimetric analysis (TGA), and Fourier transform infrared (FT-IR) spectroscopy accordingly
incorporated into the gypsum matrix. Finally, the thermo-regulated performance
strengths of EGPG with or without CF was tested by means of a self-designed room model testing and mechanical
before it is incorporated into the gypsum matrix. Finally, the thermo-regulated performance and
strengths of EGPG with or without CF was tested by means of a self-designed room model testing
system.
mechanical strengths of EGPG with or without CF was tested by means of a self-designed room model
system.
testing
2. system.
Experimental
2. Experimental
2. Experimental
2.1. Materials
2.1. Materials
2.1. Materials
The paraffin used in the experiment, shown in Figure 1a, was purchased from Sinopec Group
Theaparaffin
and has
The paraffin
latent heatused
used ofinin theexperiment,
the experiment,
approximately 116.2shown
shown in
J/g.inThe Figure1a,1a,
melting
Figure was
and
was purchased
freezing
purchased from
temperatures
from Sinopec
Sinopec are Group
20.8
Group °C
and
and has
19.4 a latent
°C, heat of
respectively, approximately
which is 116.2
within J/g.
the The
human melting
comfort and freezing
level (16–26
has a latent heat of approximately 116.2 J/g. The melting and freezing temperatures are 20.8 C and temperatures
°C) [22]. The are 20.8
expanded
◦ °C
and ◦19.4
graphite
19.4 °C, respectively,
(EG), shown
C, respectively, which which
in Figure
is withinis within
1b, washuman
the the human
supplied comfort level◦ C)
by Teng-sheng-da
comfort level (16–26 (16–26
[22].°C)
Carbon [22].
Machinery
The The expanded
expanded Co., Ltd.
graphite
graphite
(Qingdao, (EG), shown
China), and inhasFigure
an 1b, was
expansion supplied
ratio of by
300. Teng-sheng-da Carbon
Polyacrylonitrile-based
(EG), shown in Figure 1b, was supplied by Teng-sheng-da Carbon Machinery Co., Ltd. (Qingdao, Machinery
short Co.,
carbon Ltd.
fibers
(Qingdao,
(PAN-CF, China),
700SC-12K), and has
shown an in expansion
Figure 1c,ratio
with of
an 300. Polyacrylonitrile-based
average diameter of
China), and has an expansion ratio of 300. Polyacrylonitrile-based short carbon fibers (PAN-CF, 7 μm short
and carbon
length of 3fibers
mm,
(PAN-CF,
were
700SC-12K), 700SC-12K),
purchased
shown from shown
Guangzhou
in Figure 1c,in Figure
with Kaben 1c,Composite
an averagewithdiameter
an average
Materialsdiameter
of 7 µm Co., of 7(Guangzhou,
Ltd.
and length μm
of 3 and
mm,length
were of 3 mm,
China). The
purchased
were
gypsum purchased
powder, from
shown Guangzhou
in Figure Kaben
1d, was Composite
super hard Materials
gypsum Co.,
with
from Guangzhou Kaben Composite Materials Co., Ltd. (Guangzhou, China). The gypsum powder, Ltd.
an (Guangzhou,
initial setting China).
time of The
8–10
gypsum
min
shownand powder,
inwas shown
purchased
Figure in Figure
from Guangzhou
1d, was super 1d,
hard gypsum was super
Bosheng hard
with anGypsum gypsum with
Products
initial setting time ofan
Co.,initial
Ltd.
8–10 setting
(Guangzhou,
min time of 8–10
China).
and was purchased
min and was purchased from Guangzhou Bosheng
from Guangzhou Bosheng Gypsum Products Co., Ltd. (Guangzhou, China). Gypsum Products Co., Ltd. (Guangzhou, China).
(a) (b) (c) 3mm (d)
(a) (b) (c) 3mm (d)

Figure 1. The morphology of the raw materials: (a) Paraffin; (b) EG (Expanded Graphite); (c) carbon
Figure 1. The morphology of the raw materials: (a) Paraffin; (b) EG (Expanded Graphite); (c) carbon
fiber;
Figure(d)1.gypsum.
The morphology of the raw materials: (a) Paraffin; (b) EG (Expanded Graphite); (c) carbon
fiber; (d) gypsum.
fiber; (d) gypsum.
2.2.
2.2. The
The Preparation
Preparation and
and Characterization
Characterization of of EG/P
EG/P
2.2. The Preparation and Characterization of EG/P
In
In this
this experiment,
experiment, EG EG is
is used
used asas aa carrier
carrier for
for the
the paraffin.
paraffin. Firstly, the vacuum
Firstly, the vacuum impregnation
impregnation
method
methodIn this
[23] experiment,
[23]waswasused
used EGpress
to
to press isliquid
used as a paraffin
liquid
paraffincarrier for
into the thethe
into paraffin.
mesopores Firstly,
mesopores
of EG, of the
then vacuum
EG,mixture
the ofimpregnation
then the mixture of
EG/paraffin
method
EG/paraffin [23] was
(EG/P)used to
compositepress andliquid
liquid paraffin
paraffin into
wasthe mesopores
filtered to of
remove EG,
(EG/P) composite and liquid paraffin was filtered to remove excess paraffin. After filtering the then
excess the mixture
paraffin. of
After
solution,
EG/paraffin
filtering the (EG/P)
solution, composite
EG/P was and
drainedliquid
on paraffin
high was
adsorptive filtered
paper, to
andremove
the excess
paper
EG/P was drained on high adsorptive paper, and the paper placed in the oven at 60 C. The paper was paraffin.
placed
◦ in the After
oven
filtering
at 60 °C. the
replaced The solution,
paper was
frequently EG/P
until thewas
replaced drained
excessfrequentlyon high
paraffin was adsorptive
until the excessand
removed paper,
paraffin
EG/P and
wasthe paper
removed
became placed
and EG/P
a constant in the
mass. oven
became
Then,
atconstant
athe60EG/P
°C. The paper
mass. was
Then, replaced
the EG/P frequently
(as shown in
(as shown in Figure 2a) could be collected. until
Figurethe excess
2a) couldparaffin
be was
collected.removed and EG/P became
a constant mass. Then, the EG/P (as shown in Figure 2a) could be collected.

(a) (b) (c)

(a) (b) (c)

Figure 2. The morphology of the prepared materials: (a) Appearance of the prepared EG/P; (b,c)
Figure 2. The morphology of the prepared materials: (a) Appearance of the prepared EG/P; (b,c)
prepared gypsum board.
prepared
Figure 2. gypsum board.
The morphology of the prepared materials: (a) Appearance of the prepared EG/P; (b,c)
prepared gypsum board.
Materials 2018, 11, 2205 4 of 17

To investigate fully the performance of the EG/P, many tests were conducted. DSC (Differential
Scanning Calorimeter, DSC-200F3, Selb, Germany) was used to measure the melting and freezing
temperature and enthalpy of the paraffin and EG/P. The temperature range of the measurement
process was 0 ◦ C to 60 ◦ C, with a heating/cooling rate of 1 ◦ C/min. A continuous nitrogen flow
passes though the measurement system at a rate of 50 mL/min. The thermal stability of EG/P was
determined by TGA (Thermal Analysis System, TGA Q50, New Castle, DE, USA). The sample was
tested in a nitrogen atmosphere in a temperature range of 0–600 ◦ C, using a heating rate of 10 ◦ C/min.
The chemical structure of paraffin and EG/P was detected by FT-IR (Fourier Transform Infrared
Spectrometer, Perkin Elmer Spectrum 100, Toronto, ON, Canada), and the test wavelength ranged
from 500 to 4000 cm−1 . The microstructure of EG and EG/P was observed by FESEM (Field emission
scanning electron microscope, SU-70, Tokyo, Japan) in the secondary electron mode.

2.3. The Preparation and Characterization of EGPG

2.3.1. The Sample Preparation of EGPG

The mix proportion of EGPG is shown in Table 1. The procedures of sample preparation are as
follows: Firstly, gypsum powder and EG/P were mixed and stirred for two minutes to ensure even
dispersion of EG/P before water and CF were added into the stirring pot. The mixture was then stirred
for 3 min at low-speed and a further 1 min at high-speed. After mixing, the EGPG was poured into
one of three steel molds measuring either 40 mm × 40 mm × 160 mm to test the mechanical strength,
40 mm × 200 mm × 200 mm to test the thermos-regulated performance (shown in Figure 2b,c),
or Φ30 mm × 40 mm to test the thermal conductivity. After 1 h, the samples were removed from the
mold and then were kept indoors in a temperature and humidity-controlled environment (20 ± 1 ◦ C
and 60% RH) for 7 days before testing.

Table 1. The mix proportions of EGPG (expanded graphite/paraffin gypsum-based composite materials).

No. Gypsum (g) Water (g) EG/P (g) CF (g)

GC 3600 1300 – –
GC-10%EG/P 3600 1300 360 –
GC-20%EG/P 3600 1300 720 –
GC-10%EG/P-1%CF 3600 1300 360 36
GC-20%EG/P-1%CF 3600 1300 720 36
Note: GC represents the gypsum control group; GC-10%EG/P represents gypsum mixed with 10%EG/P;
GC-10%EG/P-1%CF represents gypsum mixed with 10%EG/P and 1%CF.

2.3.2. Thermal Conductivity Test

Thermal conductivity is one of the most important parameters for any PCM because it determines
the heat transfer efficiency of the PCM. The thermal conductivity of EGPG were investigated using
a thermal conductivity tester (XIATECH, TC3000, Xian, China) based on the hot wire method [24].
Each reported value was the average of three samples, and the maximum standard deviation measured
was less than 0.002 W/(m·K). The measurement temperature ranged from 19 ◦ C to 21 ◦ C.

2.3.3. Thermo-Regulated Performance Test

The thermal-regulated performance of EGPG was measured through a self-designed room
model [25], as shown in Figure 3a. A foam environmental chamber, as shown in Figure 3b, with
internal dimensions of 1000 mm × 1000 mm × 1000 mm, was made to create a uniform temperature
environment surrounding the small test room during heating and cooling. A small test room 290 mm
× 290 mm × 285 mm in size was built. The test panel of EGPG with a size of 40 mm × 200 mm ×
200 mm was placed on the top, acting as a ceiling panel. All sidewalls were made of polystyrene
foam sheeting with a thickness of 45 mm. The internal dimension of the room was 200 mm × 200 mm
Materials 2018, 11, x FOR PEER REVIEW 5 of 17

Materials 2018, 11, 2205 5 of 17

mm, as shown in Figure 3c. The internal room temperature was recorded in real-time using a data-
logger and thermocouples (Type K, ±0.3 °C), which were placed in the center of the small test room.
× 200In mm,
this experiment,
as shown inaFigure
fan heater wasinternal
3c. The used forroom
heating, while cooling
temperature was controlled
was recorded by the
in real-time air
using
conditioning
a data-logger system programmed to(Type
and thermocouples maintain
K, ±an ◦
0.3ambient temperature
C), which at 17in
were placed °C.the
The top EGPG
center of thepanel
small
was heated
test room. for a period of 2.5 h and was then cooled down for another 3.5 h.

(a) (b) (c)

Airflow inlet

Airflow outlets

Schematicdiagrams
Figure3.3.Schematic
Figure diagramsofofthermal
thermalperformance
performancetesting:
testing:(a)
(a)Testing
Testingsystem;
system;(b)
(b)section
sectionofofthe
the
testingsystem;
testing system;(c)
(c)small
smallhouse
housemodel.
model.

In this experiment,
2.3.4. Temperature Cyclinga fan
Testheater was used for heating, while cooling was controlled by the air
conditioning system programmed to maintain an ambient temperature at 17 ◦ C. The top EGPG panel
wasTo test the
heated for aleakage
period behavior
of 2.5 h and of EG/P,
was thenthecooled
thermal cycling
down chamber3.5
for another wash. used to accelerate the
process of phase change. EG/P was enveloped between two filter paper sheets and compressed by 1
kPa static
2.3.4. load as mentioned
Temperature Cycling Testby Aydın et al. [26], and the samples then suffered different thermal
cycles from 0 °C to 40 °C with 2 °C/min heating/cooling rate.
To test the leakage behavior of EG/P, the thermal cycling chamber was used to accelerate the
In addition, to know the change of mechanical strength after thermal cycling, the flexural and
process of phase change. EG/P was enveloped between two filter paper sheets and compressed by
compressive strength of EGPG was evaluated again. After 7 days curing time in an indoor
1 kPa static load as mentioned by Aydın et al. [26], and the samples then suffered different thermal
environment, the samples with a size of 40 mm × 40 mm × 160 mm were placed in the thermal cycling
cycles from 0 ◦ C to 40 ◦ C with 2 ◦ C/min heating/cooling rate.
chamber for 500 thermal cycles from 10 °C to 40 °C with a 2 °C/min heating/cooling rate.
In addition, to know the change of mechanical strength after thermal cycling, the flexural and
compressive strength of EGPG was evaluated again. After 7 days curing time in an indoor environment,
2.3.5. Strength Tests
the samples with a size of 40 mm × 40 mm × 160 mm were placed in the thermal cycling chamber for
500 After
thermal7 days
cyclescuring
fromtime
10 ◦ Cand 500◦ Cthermal
to 40 with a cycles (from
2 ◦ C/min 10 °C to 40 °C),rate.
heating/cooling the 40 mm × 40 mm × 160
mm samples were tested according to the requirements of the China national standard of GB/T
2.3.5. Strength(test
176167.3-1999 Testsmethods of strength of gypsum). Mechanical loading rates for flexural strength
and compressive strength
After 7 days curing time tests and
were50050 ±thermal
10 N/s cycles
and 2.4(from
± 0.2 KN/s, respectively.
10 ◦ C to 40 ◦ C), the 40 mm × 40 mm ×
160 mm samples were tested according to the requirements of the China national standard of GB/T
2.3.6. Chemical Structure Tests
176167.3-1999 (test methods of strength of gypsum). Mechanical loading rates for flexural strength and
X-ray diffraction
compressive strength (XRD,
tests were 50 ±D8
Bruker 10 Advance, ± 0.2 KN/s,
Karlsruhe,
N/s and 2.4 Germany) was using an angle range
respectively.
from 5° to 80° was used to measure any change in the material phase of the gypsum after thermal
2.3.6. Chemical Structure Tests
cycling.
X-ray diffraction (XRD, Bruker D8 Advance, Karlsruhe, Germany) was using an angle range from
3.5◦Results and used
to 80◦ was Discussion
to measure any change in the material phase of the gypsum after thermal cycling.

3.1 Characterization
3. Results of EG/P
and Discussion

3.1. Characterization
3.1.1. of EG/P
The Microstructure of EG and EG/P
Figure
3.1.1. 4 shows the SEM
The Microstructure images
of EG and of
EG/PEG and EG/P at different magnifications. The pores observed
in the EG can be classified into one of three categories: (1) Interconnected and worm-like
Figure 4(2)
macrospores; shows the SEM
fractured images
pores on the ofsurface;
EG andandEG/P
(3)at different
internal magnifications.
mesopores. Figure The pores aobserved
4a shows worm-
like shape of EG and the pores on the surface are seen to be loose under a magnificationmacrospores;
in the EG can be classified into one of three categories: (1) Interconnected and worm-like of 285×. At
a(2) fractured pores
magnification on the
of 1000 surface;
times, and
a large (3) internal
number mesopores.
of pores Figure
can be seen 4a surface,
on the shows aasworm-like
in Figure shape
4b. Theof
EG and the pores on the surface are seen to be loose under a magnification of 285×. At a magnification
Materials 2018, 11, 2205 6 of 17

Materials 2018, 11, x FOR PEER REVIEW 6 of 17

of 1000 times, a large number of pores can be seen on the surface, as in Figure 4b. The network of
network ofin
mesopores mesopores
the EG areinmade
the EGbyare made by and
transparent transparent
lamellar and lamellar
graphite, andgraphite, and canat
can be observed be5000
observed
times
at 5000 times magnification,
magnification, as shown
as shown in Figure in Figure
4c. These large4c. Thesemesopores
volume large volume mesopores
are able area able
to absorb largetoquantity
absorb
a large
of quantity
paraffin, whichof paraffin,
does notwhich does not
leak when leak
in the whenphase
liquid in thebecause
liquid phase becauseaction
of capillary of capillary action
and surface
and surface
tension tension [9,27].
[9,27].

(a) (b)

300 μm 80 μm

(c) (d)

10 μm 300 μm

(e) (f)

80 μm 10 μm

images of
Figure 4. SEM images of EG
EG and
andEG/P:
EG/P: (a) 285
285×× magnification
magnification of EG; (b) 1000
1000××magnification
magnification of
of EG;
EG;
5000×
(c) 5000 × magnification
magnificationof of EG;
EG; (d) 280×magnification
(d) 280× magnificationofofEG/P;
EG/P;(e)(e)
1000× × magnification
1000magnification of of
EG/P; (f)
EG/P;
(f) 5000magnification
5000× × magnification of EG/P.
of EG/P.

Figure 4d shows the microstructure of EG/P magnified 280 times. From Figure 4d, it can be seen
that the surface of EG is more compacted and the EG is stuck together after it absorbs paraffin. This
may be due to residual paraffin on the surface of the EG, which acts as a binder to stick adjacent EG
Materials 2018, 11, x FOR PEER REVIEW 7 of 17

pieces together.
Materials Higher
2018, 11, 2205 resolution images of EG are shown in Figure 4e,f, with a magnification of
7 of 17
1000× and 5000×. Compared with Figure 4b,c, the larger scale mesopores disappear and the denser
microstructure is observed, indicating that the interior pores play a primary role on the absorption
Figure
capacity. 4d shows
These results the
weremicrostructure
consistent withofRenEG/P
et al.magnified 280 times.that
[28], who presented From Figure 4d,sizes
the mesopore it canof
be seen that the surface of EG is more compacted and the EG is stuck together
EG is typically in the range of 3–5 nm, which could generate high capillary force and tension force.after it absorbs
paraffin.
Thus, the This
PCMmaytends betodue to residual
adhere paraffin
to the internal on the surface
mesopore of the EG, which
of EG. Additionally, theyacts
also as a binder to
demonstrated
stick adjacent EG pieces together. Higher resolution images of EG are
that there was little change on the enthalpy of EG/Ca(NO3)2-NaNO3 after 500 thermal shown in Figure 4e,f, with
cycles,a
magnification of 1000 × and 5000 × . Compared with Figure 4b,c, the larger scale mesopores
indicating it has good thermal reliability for a long term period. It can be deducted that the leakage disappear
and the denser
of paraffin frommicrostructure
the interior of EGis observed,
would not indicating
occur. that the interior pores play a primary role on
the absorption capacity. These results were consistent with Ren et al. [28], who presented that the
mesopore
3.1.2. The sizes of EG
Thermal is typically
Properties of in
EG/Pthe range of 3–5 nm, which could generate high capillary force and
tension force. Thus, the PCM tends to adhere to the internal mesopore of EG. Additionally, they also
The thermo-physical properties of paraffin and EG/P were determined by DSC. As can be seen
demonstrated that there was little change on the enthalpy of EG/Ca(NO3 )2 -NaNO3 after 500 thermal
from Figure 5, the onset melting temperature of paraffin and EG/P are 20.8 °C and 22.3 °C, while its
cycles, indicating it has good thermal reliability for a long term period. It can be deducted that the
latent heat values are 110.7 J/g and 105.0 J/g, respectively. It can also see that the EG/P had a relatively
leakage of paraffin from the interior of EG would not occur.
higher onset melting temperature than that of pure paraffin. That may be explained by the
Clapeyron-Clausius
3.1.2. equation of
The Thermal Properties [29]:
EG/P
The thermo-physical properties of paraffin 𝑇2 ∆and 𝑉 EG/P were determined by DSC. As can be seen
ln = (𝑃2 − 𝑃1) (1)
from Figure 5, the onset melting temperature 𝑇1 of∆ paraffin
𝐻 and EG/P are 20.8 ◦ C and 22.3 ◦ C, while its
latent heat values are 110.7 J/g and 105.0 J/g, respectively. It can also see that the EG/P had a
where, T1higher
relatively and T2onset
represent thetemperature
melting phase change temperature;
than 𝑉 and That
that of pure∆paraffin. ∆ 𝐻 may arebetheexplained
volume change
by the
and enthalpy change during
Clapeyron-Clausius equation [29]: the phase change from α-phase (solid state) to β-phase (liquid state);
and P1 and P2 are the ambient pressures during the phase change. When the paraffin is melted, the
enthalpy (∆ 𝐻 ) and volume (∆ 𝑉 ) ofT2the paraffin ∆α Vm would increase and pressure (P2 > P1) also
β

increases [30], thus leading to an increase ln = ( P2 − P1) (1)

T1of the βmelting temperature.
∆α Hm
With respect to the cooling process, it can be found from Figure 5 that the enthalpy of paraffin
and EG/P
where, T1 andare 121.6 J/g and the
T2 represent 105.5 J/g, respectively.
phase Meanwhile,
change temperature; ∆α Vmthe
β
andonset
∆α Hfreezing
β temperature of EG/P
m are the volume change and
shifted upward
enthalpy changetoduring
19.9 °Cthe
compared with that
phase change fromofα-phase
pure paraffin
(solid by 19.4to°C.
state) This result
β-phase canstate);
(liquid be explained
and P1
by the crystallization-promoting effect that the network of inner EG performed
and P2 are the ambient pressures during the phase change. When the paraffin is melted, the enthalpyas a heterogeneous
nucleation
l center to promote
l the crystallization reaction of paraffin during the crystallization process,
(∆ s Hm ) and volume (∆s Vm ) of the paraffin would increase and pressure (P2 > P1) also increases [30],
resulting
thus in the
leading increase
to an increaseof of
onset
the crystallization [31].
melting temperature.

Figure 5. DSC
Figure 5. DSC (Differential
(Differential Scanning
Scanning Calorimeter)
Calorimeter) curves
curvesof
of paraffin
paraffinand
andexpanded
expandedgraphite/paraffin.
graphite/paraffin.

With respect to the cooling process, it can be found from Figure 5 that the enthalpy of paraffin and
In addition, according to the calculation method of Bao et al. [32], the encapsulation efficiency
EG/P are 121.6 J/g and 105.5 J/g, respectively. Meanwhile, the onset freezing temperature of EG/P
of EG was measured to be 90.6% by comparing the enthalpy of paraffin (116.2 J/g) and EG/P (105.3
shifted upward to 19.9 ◦ C compared with that of pure paraffin by 19.4 ◦ C. This result can be explained
J/g). In comparison to the works of Ramakrishnan et al. and Wen et al. [33,34], a higher value of latent
by the crystallization-promoting effect that the network of inner EG performed as a heterogeneous
Materials 2018, 11, 2205 8 of 17

nucleation center to promote the crystallization reaction of paraffin during the crystallization process,
resulting in the increase of onset crystallization [31].
In addition, according to the calculation method of Bao et al. [32], the encapsulation efficiency of
EG was2018,
Materials measured toPEER
11, x FOR be 90.6% by comparing the enthalpy of paraffin (116.2 J/g) and EG/P (105.38 J/g).
REVIEW of 17
In comparison to the works of Ramakrishnan et al. and Wen et al. [33,34], a higher value of latent
heat of
of EG/P
EG/Pwas was obtained
obtained from this
from research.
this In research
research. conducted
In research by Ramakrishnan
conducted by Ramakrishnan et al. et
[33],
al. they
[33],
prepared
they a form-stable
prepared phase phase
a form-stable changechange
materials expanded
materials perlite/paraffin
expanded and found
perlite/paraffin andthat its enthalpy
found that its
just had 80.1
enthalpy just J/g.
hadWen80.1 et al.Wen
J/g. [34] et
used diatomite
al. [34] as carrier as
used diatomite and capric-lauric
carrier acid as PCM
and capric-lauric acidtoasfabricate
PCM to
the diatomite/capric-lauric
fabricate acid. Although
the diatomite/capric-lauric the enthalpy
acid. Although of capric-lauric
the enthalpy acid
of capric-lauric acidwas
was141.5 J/g,
141.5 J/g,
diatomite/capric-lauric acid
diatomite/capric-lauric acidonly
onlyowned
owned87.3 87.3J/g. Therefore,
J/g. it could
Therefore, be summarised
it could be summarised that the
thathigh
the
value of enthalpy achieved here demonstrates the potential of EG/P materials
high value of enthalpy achieved here demonstrates the potential of EG/P materials in building in building energy
applications.
energy applications.
The thermal decomposition behavior of paraffin and and EG/P
EG/P were
were evaluated
evaluated using
using TGA
TGA analysis.
analysis.
shown in
As shown in Figure
Figure 6,
6, the
the weight-loss
weight-loss ratio
ratio of
of EG/P
EG/P is approximately 90.5%, which is roughly
equivalent to the mass ratio of paraffin calculated from DSC. This indirectly proves the homogeneity
of the samples and the accuracy of the measurement
measurement techniques.
techniques.

(a) (b)
Figure 6. TGA (Thermal Analysis System) and DTG (Derivative Thermogravimetric Analysis) curves
of (a) paraffin and (b)
(b) expanded
expanded graphite/paraffin.
graphite/paraffin.

It can be
be seen
seenthat
thatboth
bothparaffin
paraffin and EG/P started to decompose at approximately ◦ C.
180That
It can and EG/P started to decompose at approximately 180 °C.
That
impliesimplies the thermal
the thermal stability
stability of paraffin
of paraffin is not
is not changed
changed despite
despite beingincorporated
being incorporatedinto
intoEG, EG, and
and the
the
decomposition temperature was suitable for the engineering application.
decomposition temperature was suitable for the engineering application. However, a significant However, a significant
difference between paraffin
difference between paraffin and
and EG/P
EG/Pcan canalsoalsobebefound
found inin Figure
Figure 6. 6.
When When thethe EG/P
EG/P is heated
is heated to 274to
274 ◦ C, the paraffin inside the EG is completely decomposed, while pure paraffin must be heated to
°C, the paraffin inside the EG is completely decomposed, while pure paraffin must be heated to 306
306 ◦
°C. AC.similar
A similar result
result cancan be found
be found by by
thethe research
research ofof Zhangetetal.al.[31].
Zhang [31].InIntheir
theirstudy,
study,itit can
can bebe found
found
that ◦
that polyethylene
polyethylene glycol
glycol started
started to
to decompose
decompose at at 409
409 °C, C, while
while the
the decomposition
decomposition temperature
temperature of of
EG/polyethylene glycol occurred at 391 ◦ C. This phenomenon can be explained by the mechanism
EG/polyethylene glycol occurred at 391 °C. This phenomenon can be explained by the mechanism
that
that EGEGcould
couldprovide
provideananenhancement
enhancement in the thermal
in the thermal conductivity
conductivityof theofmaterial, resulting
the material, in a faster
resulting in a
response to applied
faster response heat and
to applied heata higher heat transfer
and a higher efficiency.
heat transfer Based on
efficiency. Basedthe on
above
the discussion, EP/G,
above discussion,
which has a suitable
EP/G, which phase change
has a suitable temperature,
phase change high enthalpy,
temperature, and good
high enthalpy, and thermal stability,stability,
good thermal can be usedcan
as
be an
used energy
as anstorage
energymaterial for buildings.
storage material for buildings.

3.1.3. The Thermal

3.1.3. The Thermal Reliability
Reliability of
of EG/P
EG/P
The thermal reliability
The thermal reliabilityofofEG/P
EG/Pwaswas evaluated
evaluated using
using DSCDSC analysis
analysis by comparing
by comparing before
before and
and after
after thermal
thermal cycles.cycles. As shown
As shown in Figure
in Figure 7 and7 Table
and Table
2, the2,average
the average enthalpy
enthalpy of EG/P
of EG/P with with 150, 350,
150, 250, 250,
350, and 450 thermal cycles are 105.1 J/g, 103.9 J/g, 103.2 J/g, and 103.0 J/g accordingly, which
and 450 thermal cycles are 105.1 J/g, 103.9 J/g, 103.2 J/g, and 103.0 J/g accordingly, which are roughly are
roughly equivalent to that enthalpy without any thermal cycles. Although the enthalpy
equivalent to that enthalpy without any thermal cycles. Although the enthalpy of EG/P has a few of EG/P
decreases under thermal cycles, these results can still confirm that the enthalpy of EG/P is guaranteed.
Besides, from Table 2, it is clear that the onset melting temperature drops and onset freezing
temperature rises after thermal cycles, but are not significant, indicating EG/P has stable melting and
freezing points. Therefore, it can be concluded that the newly developed EG/P has excellent thermal
reliability.
Materials 2018, 11, 2205 9 of 17

has a few decreases under thermal cycles, these results can still confirm that the enthalpy of EG/P
is guaranteed. Besides, from Table 2, it is clear that the onset melting temperature drops and onset
freezing temperature rises after thermal cycles, but are not significant, indicating EG/P has stable
melting and freezing points. Therefore, it can be concluded that the newly developed EG/P has
Materials 2018,
excellent 11, x FOR
thermal PEER REVIEW
reliability. 9 of 17

Figure 7. DSC
Figure 7. DSC curves
curves of
of expanded
expanded graphite/paraffin under different
graphite/paraffin under different thermal
thermal cycles.
cycles.

Table 2. The thermal properties of expanded graphite/paraffin under different thermal cycles.
Table 2. The thermal properties of expanded graphite/paraffin under different thermal cycles
Melting Melting Freezing Freezing
Cycles Melting Melting Freezing (◦ C)Freezing
Temperature (◦ C) Enthalpy (J/g) Temperature Enthalpy (J/g)
Cycles
Temperature Enthalpy Temperature Enthalpy
0 22.3 105.0 19.9 105.5
150 (°C)
22.0 (J/g)
104.9 (°C)
20.2 (J/g) 105.2
250 0 22.3
22.0 105.0
103.3 19.9
20.2 105.5 104.5
350 150 22.1
22.0 102.7
104.9 20.3
20.2 105.2 103.8
450 250 22.1
22.0 101.8
103.3 20.3
20.2 104.5 104.1
350 22.1 102.7 20.3 103.8
3.1.4. The Chemical 450
Structure of 22.1
EG/P 101.8 20.3 104.1
The FT-IR spectrum of paraffin, EG, and EG/P between 4000 cm−1 to 500 cm−1 are shown in
FigureThe
3.1.4. Chemical
8. The Structure
characteristic of EG/P
peak at 719 cm−1 that is observed for paraffin, EG, and EG/P is related
to theTherocking
FT-IRvibration
spectrumof of CH 2 [35].EG,
paraffin, TheandpeakEG/Pobserved
between at 4000
1380cmcm−1−to
1 for EG and
500 cm−1 areEG/Pshown samples
in Figureis
related to the symmetric deformation of CH , and the absorption peak at 1473 cm −1 is caused by
8. The characteristic peak at 719 cm that is 3observed for paraffin, EG, and EG/P is related to the
−1

the asymmetric
rocking vibrationstretching
of CH2 [35].vibration
The peak of the CH2 group
observed at 1380 [36].
cm−1Aforfurther
EG andtwoEG/P strong absorption
samples peaks
is related to
(2350 − 1
cm anddeformation −
2360 cm ) of1 areCHobserved in absorption
the EG andpeak EG/Patsamples,
the symmetric 3, and the 1473 cm−1which is due
is caused byto the
the stretching
asymmetric
vibration −1
stretchingof the C–Cofskeleton
vibration the CHin EG [37].
2 group [36].Figure 8 also
A further twoshows oscillating
strong absorption bands
peaksat 2849
(2350cm cm−1 and
2918
2360 cmcm−1−)1 are
thatobserved
are linkedin to
thethe
EGstretching
and EG/Pvibrations of CH2isand
samples, which dueCH 3 , respectively
to the [36]. However,
stretching vibration of the
there are no new
C–C skeleton characteristic
in EG [37]. Figure absorption
8 also shows bands in the EG/P
oscillating bands sample,
at 2849indicating
cm−1 andthat 2918the
cmabsorption
−1 that are

process
linked to of the
paraffin into EG
stretching is a physical
vibrations of CH interaction
2 and CHonly with no chemical
3, respectively reaction. there are no new
[36]. However,
characteristic absorption bands in the EG/P sample, indicating that the absorption process of paraffin
into EG is a physical interaction only with no chemical reaction.
Materials 2018, 11, 2205 10 of 17
Materials 2018, 11, x FOR PEER REVIEW 10 of 17

Figure8.8.FT-IR
Figure FT-IRspectrum
spectrumof
ofparaffin,
paraffin,EG,
EG,and
andexpanded
expandedgraphite/paraffin.
graphite/paraffin.
3.2. Thermal Conductivity of EGPG
3.2. Thermal Conductivity of EGPG
As shown in Table 3, it can be seen that the thermal conductivity of GC increases with an
As shown in Table 3, it can be seen that the thermal conductivity of GC increases with an
increasing concentration of EG/P. Compared with GC, when 10 wt % and 20 wt % of EG/P are added
increasing concentration of EG/P. Compared with GC, when 10 wt % and 20 wt % of EG/P are added
into GC, the thermal conductivity of GC-10%EG/P and GC-20%EG/P increases by 33.7% and 53.2%,
into GC, the thermal conductivity of GC-10%EG/P and GC-20%EG/P increases by 33.7% and 53.2%,
respectively. This improvement was attributed to the high thermal conductivity of EG/P (about
respectively. This improvement was attributed to the high thermal conductivity of EG/P (about 5
5 W/m·K) [35], and it could improve the thermal conductivity of EGPG. In addition, incorporating
W/m·K) [35], and it could improve the thermal conductivity of EGPG. In addition, incorporating CF
CF into the GC also improved thermal conductivity. The thermal conductivity of GC-10%EG/P and
into the GC also improved thermal conductivity. The thermal conductivity of GC-10%EG/P and GC-
GC-20%EG/P was increased by 36.0% and 28.6%, respectively, with the addition of 1 wt % of CF. It can
20%EG/P was increased by 36.0% and 28.6%, respectively, with the addition of 1 wt % of CF. It can
also be expected that the thermal exchange rate of GC-10%EG/P and GC-20%EG/P will also improve
also be expected that the thermal exchange rate of GC-10%EG/P and GC-20%EG/P will also improve
significantly with the inclusion of CF because of the high thermal conductivity that is achieved.
significantly with the inclusion of CF because of the high thermal conductivity that is achieved.
Table 3. The thermal conductivity of EGPG.
Table 3. The thermal conductivity of EGPG.
No. Thermal Conductivity (W/m·K) Energy Storage Capacity (J/g)
No. Thermal Conductivity (W/m·K) Energy Storage Capacity (J/g)
GC 0.742 0
GC
GC-10%EG/P 0.742
0.992 0
7.25
GC-10%EG/P
GC-20%EG/P 0.992
1.137 7.25
13.65
GC-20%EG/P
GC-10%EG/P-1%CF 1.137
1.350 13.65
7.20
GC-20%EG/P-1%CF
GC-10%EG/P-1%CF 1.462
1.350 13.57
7.20
GC-20%EG/P-1%CF 1.462 13.57
3.3. The Thermo-Regulated Performance of EGPG
3.3. The Thermo-Regulated Performance of EGPG
According to Equation (2), the energy storage capacity of EGPG can be calculated, and Table 3
showsAccording
the resultstofor each gypsum
Equation (2), theboard.
energy storage capacity of EGPG can be calculated, and Table 3
shows the results for each gypsum board.
∆HEG/P × m EG/P
∆HEGPG =
m gypsum ∆𝐻 / × 𝑚EG/P/ + mCF (2)
+ mwater +m
∆𝐻 = (2)
𝑚 + 𝑚 +𝑚 / +𝑚
where ∆HEGPG and ∆HEG/P represent the energy storage capacity of EGPG and EG/P, respectively;
where
and ΔHEGPG
mEG/P and ΔH
, mgypsum EG/P represent
, mwater , and mCF the energy
present thestorage
weight capacity
of EG/P,of EGPG and
gypsum, EG/P,
water, andrespectively; and
CF accordingly.
mEG/PThe
, mgypsum , mwater, and mCF
thermo-regulated performance
present the of EGPGofisEG/P,
weight evaluated through
gypsum, a self-designed
water, room model.
and CF accordingly.
As seen
Theinthermo-regulated
Figure 9, a similar trend of theof
performance temperature variationthrough
EGPG is evaluated with time is observed for
a self-designed all model.
room EGPG
groups. It also can observed that GC has a faster heating and cooling process compared
As seen in Figure 9, a similar trend of the temperature variation with time is observed for all EGPG with the
groups. It also can observed that GC has a faster heating and cooling process compared with the other
Materials 2018, 11,
Materials 2018, 11, 2205
x FOR PEER REVIEW 11 of
11 of 17
17

groups. This implies that the GC group had a poor energy storage capacity. However, the test panels
other groups. This implies that the GC group had a poor energy storage capacity. However, the test
containing EG/P show improved temperature regulation properties when compared to GC. That is
panels containing EG/P show improved temperature regulation properties when compared to GC.
due to the inclusion of EG/P, which has a high energy storage capacity and is able to absorb a
That is due to the inclusion of EG/P, which has a high energy storage capacity and is able to absorb
significant amount of heat during the heating phase (0 to 150 min). The heat stored by the EG/P is
a significant amount of heat during the heating phase (0 to 150 min). The heat stored by the EG/P
then released to slow the rate of decreasing temperatures during the cooling phase. Moreover, the
is then released to slow the rate of decreasing temperatures during the cooling phase. Moreover,
thermo-regulated performance of the EGPG was even more effective with an increase in EG/P
the thermo-regulated performance of the EGPG was even more effective with an increase in EG/P
content. For example, when the highest measured temperature of GC is reached at 26.7 °C (maximum
content. For example, when the highest measured temperature of GC is reached at 26.7 ◦ C (maximum
temperature, 159 min), the temperature of GC-10%EG/P and GC-20%EG/P were measured to be 25.4
temperature, 159 min), the temperature of GC-10%EG/P and GC-20%EG/P were measured to be
°C and 24.3 °C, respectively. This represents an improvement compared with the reference GC for a
25.4 ◦ C and 24.3 ◦ C, respectively. This represents an improvement compared with the reference GC
GC-10%EG/P and GC-20%EG/P of 1.3 °C and 2.4 °C, respectively. According to the research of
for a GC-10%EG/P and GC-20%EG/P of 1.3 ◦ C and 2.4 ◦ C, respectively. According to the research of
Mourid et al. [38], a PCM coating of 5.3 mm thickness on a standard wall could lead to a temperature
Mourid et al. [38], a PCM coating of 5.3 mm thickness on a standard wall could lead to a temperature
increase of about 6 °C during the night and reduce energy consumption by 20% compared to the
◦ C during the night and reduce energy consumption by 20% compared to the
increase
referenceofcase.
about
In 6addition to reducing the energy consumption, our previous research [39] shows
reference
that a 4 mm thick PCM panel reducing
case. In addition to the
integrated energy
into a wallconsumption,
could improveourthe
previous
energy research
efficiency[39]
rateshows that
by 65.3%,
aand
4 mm
it is thick PCM to
equivalent panel integrated
reducing into a wall gases
CO2 greenhouse couldemissions
improve bythe65.28%.
energy This
efficiency ratethat
indicates by 65.3%,
EGPG
and it is equivalent to reducing CO
materials are able to reduce temperature 2 greenhouse gases emissions by 65.28%. This indicates that
fluctuations, resulting in reduced electricity consumptionEGPG
materials
of heatingareandable to reduce
cooling temperature
systems, which hasfluctuations,
the effect ofresulting
improvingin the
reduced electricity
power consumption
generation management of
heating and cooling systems, which has the effect of improving the
and reducing environmental pollution to achieve an improved economic outcome. power generation management
and reducing environmental pollution to achieve an improved economic outcome.

GC
GC-10%EG/P
GC-10%EG/P-1%CF
GC-20%EG/P
GC-20%EG/P-1%CF

Figure 9. Temperature curves of center point of five small house models.

Figure 9. Temperature curves of center point of five small house models.
The effect of adding CF to EGPG can also be seen in Figure 9. GC-10%EG/P-1%CF and
The effect of adding
GC-20%EG/P-1%CF showCF an to EGPG can
improved also be seen inperformance
thermo-regulated Figure 9. GC-10%EG/P-1%CF and GC-
than that of GC-10%EG/P
20%EG/P-1%CF
and GC-20%EG/P. showBasedan improved thermo-regulated
on the results of Section 3.2, performance than thatthat
it can be deduced of GC-10%EG/P
CF increases and
the
GC-20%EG/P. Based on the results of Section 3.2, it can be deduced
thermal conductivity of GC-10%EG/P and GC-20%EG/P, and thus improves the heat transfer that CF increases the thermal
rate of
conductivity
EG/P within of
theGC-10%EG/P
EGPG matrix.and GC-20%EG/P,
Specifically, and thus temperature
the maximum improves theofheat transfer rate of EG/P
GC-10%EG/P-1%CF and
within the EGPG matrix.
GC-20%EG/P-1%CF decreasedSpecifically,
by 0.6 ◦ Cthe
andmaximum temperature
0.8 ◦ C compared of GC-10%EG/P-1%CF
with GC-10%EG/P and GC-
and GC-20%EG/P,
20%EG/P-1%CF
respectively. Hence,decreased
it can beby 0.6 °C and
concluded that 0.8
the °C compared
matrix with thewith GC-10%EG/P
highest and GC-20%EG/P,
thermal conductivity provides
respectively. Hence, it can be concluded that the matrix with the highest
the greatest increase in the heat transfer rate to the PCM, thus improving the thermo-regulated thermal conductivity
provides the of
performance greatest increase in theintegrated
structural-functional heat transfer
buildingrate materials.
to the PCM, thus improving the thermo-
regulated performance of structural-functional integrated building materials.
3.4. The Mechanical Properties of EGPG
3.4. The Mechanical Properties of EGPG
The mechanical properties of EGPG were tested after seven days curing time under ambient
conditions, and the results
The mechanical are shown
properties of EGPG in were
Figure 10. It
tested wasseven
after found thatcuring
days with an
timeincreasing EG/P
under ambient
content, a decreasing trend in the flexural and compressive strength was observed.
conditions, and the results are shown in Figure 10. It was found that with an increasing EG/P content, For example,
when 10 wt %trend
a decreasing and in
20the
wt flexural
% of EG/P and were mixed with
compressive GC, was
strength the flexural
observed.strength of GC-10%
For example, whenEG/P
10 wt
% and 20 wt % of EG/P were mixed with GC, the flexural strength of GC-10% EG/P and GC-20%
Materials 2018, 11, 2205 12 of 17
Materials 2018, 11, x FOR PEER REVIEW 12 of 17

and GC-20%
EG/P EG/Pbywas
was reduced reduced
36.0% by 36.0%
and 50.0% and 50.0%
compared with thecompared
referencewithGC the reference
material, GC material,
respectively. The
respectively. The compressive strength of GC-10%EG/P and GC-20%EG/P
compressive strength of GC-10%EG/P and GC-20%EG/P was found to decrease by 61.2% and 72.8%. was found to decrease
by 61.2%
This resultand
may72.8%.
be due This result
to the factmay
that be due tototal
a higher the fact that acan
porosity higher total porosity
be generated due tocanthebeaddition
generatedof
due towhich
EG/P, the addition
leads to oftheEG/P,
observedwhich leads tointhe
reduction observedstrength
mechanical reduction inIn
[40]. mechanical
the research strength [40].
conducted
In the
by research
Pilehvar et al.conducted by Pilehvarstrength
[41], the compressive et al. [41], the compressive
of cement had a large strength
reductionof cement
from 60had MPa a to
large
35
reduction
MPa at 28from
days60whenMPa 20%to 35 microencapsulted
MPa at 28 days when PCM20% wasmicroencapsulted
incorporated. They PCM was incorporated.
explained that this
They explained
pheromone that this
is because thepheromone is because
lower stiffness the lower
and strength stiffness
of EG/P andweaken
could strengththeof mechanical
EG/P couldstrength
weaken
theGC.
of mechanical
However, strength
1 wt % of
CFGC.hasHowever,
been found 1 wt
to % CF has the
improve been found to improve
mechanical strengththe of mechanical
EGPG. The strength
flexural
of EGPG.ofThe
strength flexural strength ofisGC-10%EG/P-1%CF
GC-10%EG/P-1%CF 12.4 MPa, which is 51.6% is 12.4higher
MPa, which is 51.6%
than that higher than that
of GC-10%EG/P, whileof
GC-10%EG/P, while no change in compressive strength was observed. These
no change in compressive strength was observed. These results were consistent with Zhu et al. [42], results were consistent
withreported
who Zhu et al.that
[42],
thewho reported
fibers thatbond
with high the fibers with
strength high bond
increase strength increase
the brittleness of plaster the brittleness of
gypsum-based
plaster gypsum-based
materials. In their study, materials. In their
the flexural study,ofthe
strength flexural
gypsum strengthby
increased of 91.5%
gypsum increased
from 2.1 MPa byto91.5%
4.04
from 2.1 MPa to 4.04 MPa as the addition of 1.2% polyvinyl
MPa as the addition of 1.2% polyvinyl alcohol fiber with the length of 12 mm. alcohol fiber with the length of 12 mm.

Figure 10.
Figure The mechanical
10. The mechanical strength
strength of
of EGPG
EGPG after
after seven
seven days
days curing
curing time.
time.

A temperature
A temperature cyclingcycling testtest was
was used
used to to measure
measure the the change
change in in mechanical
mechanical strength
strength of of EGPG
EGPG
materials under service conditions. Figure 11 shows the results of the mechanical strength afterafter
materials under service conditions. Figure 11 shows the results of the mechanical strength 500
500 heating/cooling cycles from 10 to 40 ◦ C. It is seen that the flexural and compressive strengths
heating/cooling cycles from 10 to 40 °C. It is seen that the flexural and compressive strengths of EGPG
of EGPG
are doubled are after
doubled after temperature
temperature cycling compared
cycling compared with samples with samples afterdays
after seven sevencuring
days curing
at room at
room temperature.
temperature. Based Based
on theon the results
results of SEM of SEM
and XRD,and XRD, dehydration
dehydration of theofgypsum
the gypsum is identified
is identified as
as the
the main cause of the higher mechanical strength. The morphology
main cause of the higher mechanical strength. The morphology of gypsum before temperature of gypsum before temperature
cycling, as
cycling, asshown
shownininFigureFigure12a, 12a, is calcium
is calcium sulfate
sulfate dihydrate
dihydrate (CaSO 4·2H42·O),
(CaSO 2H2which
O), which
has rodhasand
rodthick
and
thick plate-like
plate-like crystals
crystals measuring
measuring 6–156–15μm.µm. In comparison,
In comparison, irregular
irregular blockcrystals
block crystals(calcium
(calcium sulfate
sulfate
hemihydrate-CaSO
hemihydrate-CaSO44·0.5H2O, · 0.5H O, 2–10 µm) are observed after thermal cycling
2 2–10 μm) are observed after thermal cycling as shown in Figure 12b, as shown in Figure 12b,
which has a positive effect on improving the mechanical strength. Figure
which has a positive effect on improving the mechanical strength. Figure 13 shows that CF distributes 13 shows that CF distributes
in the
in the cracks
cracksand andonon thethe
surface
surface of EGPG,
of EGPG,which contributes
which to theto
contributes higher mechanical
the higher strength.strength.
mechanical Besides,
XRD results also have confirmed
Besides, XRD results also have confirmed that that CaSO 4 · 2H O
CaSO
2 transformed to CaSO
4·2H2O transformed 4to CaSO · 0.5H O after thermal
2 4·0.5H2O after
cycling, cycling,
thermal as shown as in Figure
shown in14. As shown
Figure 14. As fromshownthe sample
from before thermal
the sample cycling cycling
before thermal (black curve),
(black
the characteristic peaks are mainly generated at 11.7 ◦ , 20.6◦ , 23.6◦ , 29.2◦ , 31.1◦ , and 33.4◦ , which belong
curve), the characteristic peaks are mainly generated at 11.7°, 20.6°, 23.6°, 29.2°, 31.1°, and 33.4°, which
to CaSOto
belong 4 ·2H 2 O [43].
CaSO 4·2HHowever, in the sample
2O [43]. However, in after
the thermal
sample cycling (red curve),
after thermal the characteristic
cycling (red curve),peaks the
are identified at ◦
14.9 are
, 25.8 ◦ ◦
, 29.7 , and ◦
32.0 , 25.8°,
corresponding to the peak of CaSO4 ·0.5H
characteristic peaks identified at 14.9°, 29.7°, and 32.0°, corresponding to2 O.
the peak of
CaSO4·0.5H2O.
Materials 2018, 11, x FOR PEER REVIEW 13 of 17
Materials 2018, 11,
Materials 11, x
2205
FOR PEER REVIEW 13of
13 of 17
Materials 2018, 11, x FOR PEER REVIEW 13 of 17

Figure 11. The mechanical strength of EGPG after thermal cycling.

Figure 11. The mechanical strength of EGPG after thermal cycling.
Figure 11. The mechanical strength of EGPG
Figure 11. EGPG after
after thermal
thermal cycling.
cycling.

(a) (b)
(a) (b)
(a) (b)

10 μm 10 μm
10 μm 10 μm
10 μm 10 μm
Figure 12. The morphology of gypsum: (a) Before thermal cycling; (b) after thermal cycling.
Figure 12.
Figure The morphology
12. The morphology of
of gypsum:
gypsum: (a)
(a) Before
Before thermal
thermal cycling;
cycling; (b)
(b) after
after thermal
thermal cycling.
cycling.
Figure 12. The morphology of gypsum: (a) Before thermal cycling; (b) after thermal cycling.

(a) (b)
(a) (b)
(a) (b)

Carbon Fiber
Carbon Fiber
Carbon Fiber

500 μm 100 μm
500 μm 100 μm
Figure 13.
Figure The microstructure
13. The microstructure
500 μmof
of EGPG
EGPG with
with CF
CF (Carbon
(Carbon Fiber): (a) CF
Fiber): (a) CF in
in the
the100
cracks of EGPG;
μm of
cracks EGPG; (b)
(b) the
the
Figure
surface13.
surface of The microstructure
of EGPG
EGPG with
with CF after of
CF after EGPG with CF (Carbon Fiber): (a) CF in the cracks of EGPG; (b) the
fracture.
fracture.
Figure 13. The microstructure of EGPG with CF (Carbon Fiber): (a) CF in the cracks of EGPG; (b) the
surface of EGPG with CF after fracture.
surface of EGPG with CF after fracture.
Materials 2018, 11, 2205 14 of 17
Materials 2018, 11, x FOR PEER REVIEW 14 of 17

(a)

(b)

Figure 14. The XRD pattern of gypsum: (a) Before thermal cycling; (b) after thermal cycling.

4. Conclusions
4. Conclusions
In this study, EG/P was developed for use in a gypsum-based thermal energy storage material
In this study, EG/P was developed for use in a gypsum-based thermal energy storage material
for application as interior partitions or building envelope materials. Carbon fiber (CF) was used to
for application as interior partitions or building envelope materials. Carbon fiber (CF) was used to
improve the thermal conductivity and mechanical strength of the gypsum matrix to increase the rate
improve the thermal conductivity and mechanical strength of the gypsum matrix to increase the rate
of heat exchange of EG/P and allow its use in a wide range of building applications. The following
of heat exchange of EG/P and allow its use in a wide range of building applications. The following
conclusions can be drawn from the experimental findings:
conclusions can be drawn from the experimental findings:
1.
1. EG/Pwas
EG/P wasprepared
preparedsuccessfully
successfullyby bythe
thevacuum
vacuumimpregnation
impregnation method,
method, which
which produces
produces material
material
with a latent heat storage capacity of 105.3 J/g and phase change temperature of 22.28 ◦ C.
with a latent heat storage capacity of 105.3 J/g and phase change temperature of 22.28 °C. The
The results
results of FT-IRof FT-IR
reveal reveal
that thethat the components
components within
within EG/P areEG/P are chemically
chemically compatible, compatible,
and TGA
proves that EG/P can meet the requirements for thermal stability. As a result, aEG/P
and TGA proves that EG/P can meet the requirements for thermal stability. As result,
is
EG/P is demonstrated
demonstrated as a potential
as a potential candidate
candidate for buildings
for buildings as part
as part of ofoverall
overallefficient
efficient energy
energy
management scheme.
management scheme.
2.
2. BothEG/P
Both EG/Pand andCF CF improved
improved thethe thermal
thermal conductivity
conductivity of gypsum
of gypsum (GC).
(GC). Compared
Compared withwith
GC,GC,
the
the thermal conductivity of the GC-10%EG/P and GC-20%EG/P
thermal conductivity of the GC-10%EG/P and GC-20%EG/P was improved by 33.7% and 53.2%, was improved by 33.7% and
53.2%, respectively.
respectively. When 1When wt %1CF wt was
% CFadded,
was added, the thermal
the thermal conductivity
conductivity of GC-10%EG/P
of GC-10%EG/P and
and GC-
GC-20%EG/P
20%EG/P further
further increases
increases by 36.0%
by 36.0% and 28.6%,
and 28.6%, respectively.
respectively.
3. EG/P can significantly reduce temperature
EG/P can significantly reduce temperature fluctuations. The fluctuations. The maximum
maximum temperature
temperature of indoor
center position
position decreased by 2.4 °C ◦ C with the addition
center addition ofof 20
20 wt
wt %
% EG/P into GC.
EG/P into GC. CF
CF also has a role
inincreasing
in increasing thethe rate
rate of
of heat
heat transfer
transfer to EG/P
EG/Pwithin
withingypsum,
gypsum,and andthus
thusthe
thegreatest
greatest improvement
improvement
in temperature was 3.2 ◦ C, observed between GC-20%EG/P-1%CF and GC.
in temperature was 3.2 °C, observed between GC-20%EG/P-1%CF and GC.
4. With the
With the increase
increase of EG/P
EG/Pcontent,
content,thetheflexural
flexuraland andcompressive
compressive strengths
strengths of of EGPG
EGPG demonstrate
demonstrate
a dramatically decreasing trend.
a dramatically decreasing trend. However, However, the presence
presence of CF can improve the flexural strength
of GC-20%EG/P
of GC-20%EG/Pby by51.6%,
51.6%,withwithno nochange
changeinincompressive
compressivestrength.
strength.
5. After
After 500
500 heating/cooling
heating/coolingcycles, cycles,thethemechanical
mechanicalproperties
propertiesofofEGPG
EGPGincreased
increased by by about
about 100%,
100%,
which
which is is attributed
attributed to to the
the dehydration
dehydration of calcium sulfate dihydrate.
Author Contributions: B.Z. did the experiments and data analysis and wrote part of this paper. Y.T. did the
Author Contributions:
experiments B.Z. did
and data analysis thewrote
and experiments andpaper.
part of this data analysis
X.J. did and wrote
the data part of T.Y.L.
analysis. this paper.
wroteY.T.
partdid the
of this
experiments
paper. and datathe
H.C. provided analysis and
original wrote
ideas part
and didofthe
this paper. X.J. and
experiments did the
datadata analysis. T.Y.L. wrote part of this
analysis.
paper. H.C. provided the original ideas and did the experiments and data analysis.
Funding: This research received no external funding.
Funding: This research received no external funding.
Acknowledgments: The
Acknowledgments: The work
work described
described in
in this
this paper
paper was fully supported
was fully supported by grants from
by grants from Natural
Natural Science
Science
Foundation of China (51678367).
Foundation of China (51678367).
Conflicts of Interest: The authors declare no conflict of interest.
Materials 2018, 11, 2205 15 of 17

Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
PCMs Phase Change Materials
EG Expanded graphite
EG/P Expanded graphite/Paraffin composites
SSPCM Stabilized-shape Phase Change Material
EGPG Expanded graphite/paraffin gypsum-based composite material
CF Carbon Fiber

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