Journal of Energy Storage 83 (2024) 110543

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Journal of Energy Storage

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Research Papers

Preparation of diatomite paraffin composite phase change coating and its

simulation application in building wall
Zijie Geng a, Chen Shi a, *, Qing Zhao a, Liu Yang b
a
College of Materials Science and Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, Shaanxi, China
b
College of Architecture, Xi'an University of Architecture and Technology, Xi'an 710055, Shaanxi, China

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

Keywords: A new phase change heat storage coating is prepared in this study, which can regulate indoor temperature. The
Phase change coating composite phase change material (D/PCM) with modified diatomite and paraffin was prepared by the porous
Diatomite material adsorption method. D/PCM and coatings were characterized by differential scanning calorimetry (DSC),
Application simulation
scanning electron microscopy (SEM) and cycle leakage ratio. The SEM results showed that diatomite modified by
Cooling load
high-temperature expansion and acidification has a better adsorption capacity. D/PCM and C-D/PCM (heat
storage coatings with D/PCM) have nearly no leakage and still show good thermal stability after 500 thermal
cycles. In addition, the heat transfer process in a physical model of a reinforced concrete wall was simulated
based on hourly variations in summer temperatures in Xi'an, China. The results show that C-D/PCM with a phase
change temperature of 26–28 ◦ C and a thickness of 5 mm provides greater heat storage capacity, good tem­
perature regulation and energy savings within a reasonable thickness range in summer. The selected PCM
coatings have a small temperature fluctuation (2.54 ◦ C) and a high phase change utilization ratio (75 %), which
can reduce the wall cooling load by 18.67 % in summer and save energy.

1. Introduction application in the field of construction is limited [11–14]. The inorganic

In recent years, as people's requirements for indoor environmental
comfort continue to increase, the energy consumption of air-
conditioning, heating and other building equipment operations has
increased, and building energy consumption will continue to increase
[1,2]. Thermal energy storage (TES), is a technology that stores thermal
energy by heating or cooling a storage medium, allowing the stored
energy to be used later for heating and cooling applications and power
generation. Thermal energy storage (TES) technology is used in many
applications such as solar, geothermal, and construction [3–6]. Among
them, the incorporation of phase change materials (PCM) into the
building envelope [7–9], is an effective means to improve the energy
utilization ratio and alleviate energy problems.
PCMs are functional materials that store and release latent heat
through the melting and solidification process. Most of the PCM will leak
during the phase change process [10,11]. Researchers have developed
phase change microcapsule technology, which can alleviate the leakage
of phase change materials, but due to high cost, complex preparation
process, poor thermal conductivity and other problems, its widespread
porous material adsorption method [15] uses inorganic porous or
layered materials with large specific surface area as the adsorption
medium, and absorbs liquid PCM into the microporous structure or
layered structure through its capillary force and surface tension to play a
leak-preventing role, which has the advantages of the simple prepara­
tion process, low cost and good thermal conductivity [16]. In recent
years, studies have found that many different porous support materials
have good adsorption properties for paraffin, including diatomite,
bentonite, expanded perlite, expanded graphite, etc. [17–20]. Diatomite
is widely used because of its good pore structure, low price and good
absorption capacity. Li et al. [21] prepared LA-SA/Dm/EG with LA-SA
72.2 % and a phase change temperature of 31.17 ◦ C, whose melting
latent heat value was 117.30 J/g and freezing latent heat value was
114.50 J/g. Sari et al. [22] Adsorption of polyethylene glycol (PEG600)
with raw diatomite (RD)/carbon nanotubes (CNTs) pre-composites. The
DSC analysis showed that the S-SCPCMs had melting temperatures in the
range of about 7–8 ◦ C and latent heat capacity between 53.8 and 62.9 J/
g. Sari et al. [23] prepared the form-stable composite PCMs by incor­
porating galactitol hexa myristate (GHM) and galactitol hexa laurate

* Correspondent author.
E-mail address: shichen@xauat.edu.cn (C. Shi).

https://doi.org/10.1016/j.est.2024.110543
Received 5 September 2023; Received in revised form 15 December 2023; Accepted 8 January 2024
Available online 2 February 2024
2352-152X/© 2024 Elsevier Ltd. All rights reserved.
Z. Geng et al.
(GHL) into a porous of diatomite, perlite and vermiculite. The maximum
mass percentages of GHM adsorbed by perlite, diatomite and vermicu­
lite were determined as 67, 55 and 52 %. S. Benayache et al. [24]
researched the preparation of paraffin/calcined diatomite earth com­
posite PCM with a melting temperature of 28.44 ◦ C and latent heat of
about 56.40 J/g, and the composite has good thermal cycling perfor­
mance. Shi et al. [25] used the EV-DI mineral system as support material
and paraffin as PCM to prepare paraffin/expanded vermiculite-
diatomite composite phase change material. It has been verified that
phase change mortar can reduce indoor temperature fluctuation to
1.8 ◦ C in summer.
The phase change thermal storage materials are added to building
materials in different forms to form phase change envelope structure
[26–34], which is a hot topic. In recent years, research on roofs and
ceilings, windows, curtains, floors and wallboards with PCM has grad­
ually increased. Among them, building coatings as an important build­
ing material, usually used for decoration, protection and other
performance improvements, it is easy to use with another building en­
velope to save energy, and the coatings are in direct contact with the
indoor thermal environment, have a more direct effect on the indoor
thermal environment, may have a better energy-saving effect. Karlessi
et al. [35] prepared coatings of different colors, which contained
different melting points and different amounts of PCM, and tested their
surface temperatures. The results showed that the surface temperatures
of all PCM coatings were lower than those of infrared reflection coatings
and ordinary coatings, and they could save 5 % -12 % of cooling energy
per month. Zhu et al. [36] synthesized a microencapsulated phase
change material with octadecane as the core material and prepared it
into a composite coating. The results showed that the chamber coated
with MPCM could maintain a stable temperature for 64 min longer than
the heat storage chamber without MPCM, which had high application
potential in building heat storage, especially in the renovation of old
buildings. Baskar [37] prepared PCM together with other coatings
components into phase change coatings and coated it on the surface of
the mortar cube, tested the surface temperature, and found that the
surface temperature was 2.5 ◦ C lower than that of the conventional
mortar cube.
By summarizing and analyzing the above literature, although the
composite PCM can regulate indoor temperature, there are still several
problems at present. First, at present, research is only at the stage of
preparation and development of phase change coatings, and little
research has been done on the application of phase change coatings in
construction. Second, there is no research on the simulation application
model; In this study, diatomite is used as a porous adsorption material to
adsorb paraffin phase change material using the vacuum adsorption
method, and D/PCM is made to test its microscopic properties, leakage,
thermal properties, and thermal properties before and after cycles
resistance. Then, D/PCM is used as part of the multi-functional filler of
the coatings, and it was made into C-D/PCM with heat storage and
temperature regulation function with other coating components. C-D/
PCM are analyzed, and the wall panel model is established by COMSOL
Multiphysics to simulate its heat transfer in the summer thermal envi­
ronment of Xi'an city, the influence of phase change range, phase change
temperature and thickness on the thermal performance is studied.
Finally, through the comparative analysis of the inner surface temper­
ature, utilization, cooling load and energy-saving efficiency of the wall,
the optimal C-D/PCM design parameters and strategies are selected to
provide some reference for practical application.
2. Experiments and simulation
2.1. Materials
Paraffin phase change temperature 26–28 ◦ C purchased from
Aladdin Chemical Co. (Shanghai, China). Diatomite 325 mesh (Hebei
Jing hang Mineral Products Co.). Its properties are shown in Table 1. Re-
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Journal of Energy Storage 83 (2024) 110543
Table 1
Properties of diatomite (%).
Series SiO2 Al2O3 Fe2O3 CaO MgO LOI*
Diatomite ≥85 ≤3.0 ≤2.0 ≤2.27 ≤0.6 ≤2.0
LOI* = Loss on ignition.
dispersible powder (Langfang Laneng Chemical Co.). Calcium carbonate
(Sinopharm Group Chemical Reagent Co.). Calcium hydroxide (Sino­
pharm Group Chemical Reagent Co.).
2.2. Preparation of D/PCM and C-D/PCM
Fig. 1 shows the preparation process of D/PCM. First, the natural
diatomite is modified by “calcination and acidification”. Then, the
cleaned and dried diatomite was placed in a muffle furnace to calcine at
450 ◦ C for 2 h and cooled to room temperature naturally. Weigh a
certain amount of calcined modified diatomite, immerse it in hydro­
chloric acid solution at a liquid-solid ratio of 4:1, place it in a water bath
at 50 ◦ C, and stir for 4 h, wash, filter and dry after completion, to obtain
calcined and acidification modified diatomite.
In this experiment, the vacuum adsorption method was used to
adsorb liquid paraffin by the capillary force of porous diatomite, and the
diatomite/paraffin composite phase change thermal storage material
was prepared. The specific experimental scheme is as follows: Firstly,
put the paraffin into the oven at 100 ◦ C and dry it for 4 h. Weigh a
quantity of paraffin into a beaker, heat the water bath at 80 ◦ C and stir
until the paraffin is completely melted, weigh a certain amount of
modified diatomite earth into a filter flask, stir under vacuum adsorption
for 2 h to make it fully adsorbed, and then remove it and cool it down to
room temperature.
C-D/PCM was obtained by dispersing re-dispersible powder, other
makeup filler powder, and functional additives (such as defoamer, so­
dium tripolyphosphate dispersant, and hydroxyethyl cellulose thick­
ener) using a dispersing machine at 1000 rpm for 15 min, followed by
filtration and removal of foam for 20 min. Composition of basic mate­
rials of C-D/PCM is shown in Table 2 [36].The appearance of C-D/PCM
is shown in Fig. 2.
2.3. Performance testing
The microstructure of diatomite before and after modification was
observed by scanning electron microscope (SEM) (HitachiRegulus8100).
The temperature and latent heat of D/PCM and C-D/PCM were
measured by DSC (Micro DSCIIIA) at a heating rate of 5 ◦ C/min in a
nitrogen atmosphere from − 20 ◦ C to 80 ◦ C. The mean deviation values
for three repetitive measurements were calculated as ±0.23 ◦ C phase
change temperature and ± 2.55 J/g latent heat capacity. The sealing
performance of D/PCM and C-D/PCM was evaluated by measuring the
mass loss of samples subjected different thermal cycles (50, 100 and 200
cycles). This is done by using the thermocycling box (RK-TD-225), The
thermal cycle program is set as: Hold at 10 ◦ C for 2 h, then heat up at a
rate of 5 ◦ C/min to 60 ◦ C, and cool down at a rate of 5 ◦ C/min to 10 ◦ C
after holding for 2 h. The number of cycles is set to 500.
2.4. Simulation model analysis
2.4.1. Description of the simulated building
The application of prepared phase change heat storage coatings in
buildings was simulated by COMSOL in this study. Fig. 3 shows the
physical structure model of the established wall. The building materials
and physical parameters of this wall are shown in Table 3.
2.4.2. Model building
To simplify the model, the following hypotheses were proposed: (1)
The heat transfer process was one-dimensional along the wall thickness
Z. Geng et al. Journal of Energy Storage 83 (2024) 110543

Fig. 1. Preparation process of D/PCM.

The liquid fraction during a phase change is defined by the change in

Table 2
the temperature field, which is described by Eq. (2);
Basic compositions of C-D/PCM.
⎧
Component Weight(g) Component Weight(g) ⎨ 0 , T < TS
θ = (T − TS )/(TS − TL ), TS < T < TL (2)
Diatomite 9 Re-dispersible powder 13 ⎩
1 , T > TL
D/PCM 35 Other additives <0.1
Calcium carbonate 17 Water 90
Calcium hydroxide 26 where TS and TL are the melting temperature (◦ C) and freezing tem­
perature (◦ C), respectively, and θ is the liquid fraction (%).
The density, heat capacity and volume fraction are expressed by Eq.
(3)–(6);
ρ = ρS (3)

∂αm
CP = θ1 CPS + θ2 CPL + L⋅ (4)
∂T

1 θ2 − θ 1
αm = ⋅ (5)
2 θ2 + θ 1

θ1 + θ2 = 1 (6)

where, ρS is the solid phase density of the PCM (kg/m3), CPS and CPL are
the constant pressure heat capacities of the solid phase and liquid phase
(kJ/kg⋅◦ C); L is the latent heat of phase change (J/g); αm is the coeffi­
cient of volume expansion (1/◦ C).

2.4.3. Setting of boundary conditions and initial conditions

Fig. 2. Phase change heat storage coatings.
direction, and both the upper and lower surfaces were treated with heat
preservation; (2) The material is homogeneous and isotropic, and the
density is constant on the macro scale; (3) The expansion volume during
phase transformation can be ignored; (4) Liquid paraffin is Newton
incompressible fluid; (5) There is no macroscopic flow of liquid phase in
the composite material.
Based on the above hypothesis, the energy governing equation of the
composite wall surface is described by the equation method, as shown in
Eq. (1);
ρ⋅CP (∂T/∂t) + ∇⋅( − k∇T) = 0
where ρ is the material density (kg/m3), CP is the atmospheric pressure
heat capacity of the material (J/kg⋅◦ C), T is the time temperature (◦ C),
and k is the thermal conductivity (W/mK).
Set the initial temperature inside the envelope structure to 20 ◦ C. The
upper and lower parts of the envelope are thermally insulated. The
boundary conditions of the outer surface of the building envelope can be
obtained by the energy big data platform (provided by NASA), and
calculated according to Eq. (7)–(9).
The outdoor comprehensive temperature is composed of outdoor
temperature, direct solar radiation and scattered radiation. The calcu­
lated outdoor comprehensive temperature is shown in Fig. 4. In order to
simplify the model, the solar radiation model on sunny days is used to
calculate the amount of radiation received by the wall. According to the
Hay model, the scattered radiation is anisotropic, and the total solar
radiation received by the wall is I:
I = IDθ + IDV + IRV (7)
(1)
where IDθ is the intensity of direct solar radiation received by the vertical
wall, W/m2; IDV is the sky scattered radiation intensity received by the
vertical wall, W/m2; IRV is the intensity of ground reflected radiation
received by the vertical wall, W/m2.

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Z. Geng et al. Journal of Energy Storage 83 (2024) 110543

Fig. 3. Physical model of wall structure.

Table 3 where, Tout is the outdoor temperature, ◦ C; hout is the convective heat
Physical properties of materials. transfer coefficient of the outer surface, which is 19 W/(m2⋅K); α⋅I/hout is
the equivalent temperature of solar radiation, ◦ C; t1r is the external
Material layer d λ Cp ρ
[mm] [W/m • k] [J/kg • K]
[
kg/m3
] effective wavelength radiation temperature, which is 1.8 ◦ C.

Concrete 200 1.74 1050 2400

2.4.4. Validation of model
Cement mortar 20 0.9 1050 1700
C-D/PCM – 0.326 1435 1312 Based on experimental testing methods, establish a numerical model
of phase change coating walls to verify the accuracy of the model. The
temperature change curve of the external surface of the wall measured
by the experiment is used as the boundary heat source, and the part of
the wall contacting with the foam box is regarded as the thermal insu­
lation boundary. Fig. 5 is a schematic diagram of the heat transfer
model.
The average relative deviation AER is given by the following Eq.
(10):
{⃒ ⃒ }
⃒Xs − Xe ⃒
ARE = Average ⃒⃒ ⃒ × 100%
⃒ (10)
Xe

where xs is the instantaneous temperature in the simulation results (◦ C),

xe is the instantaneous temperature in the experimental results (◦ C).
Fig. 6 shows a comparison of the average temperature of the inner
surface of the wall between the experimental and simulation results.
From the Fig. 6, it can be seen that the numerical model of the phase
change coating wall established in this chapter has an average relative
deviation of no >5 % compared to the experimental test results. This
indicates that the results of COMSOL Multiphysics in solving solid heat
transfer and phase change heat transfer are relatively close to the actual
test values. Therefore, the numerical calculation model established
using phase change coating walls can obtain more accurate results.

Fig. 4. Temperature of a typical day.

3. Results and discussion

1 1
I = IDN × cosi + × IDH + × ISH × ρG (8) 3.1. Leakage of D/PCM and C-D/PCM
2 2
Lower cycle leakage ensures good performance and long service life
where IDN is the intensity of direct solar radiation received by the hor­
of composite phase change materials.
izontal plane, W/m2; i is the solar incidence Angle; IDH is the intensity of
scattered radiation in the horizontal sky, W/m2; ρG is the average
(1) The leakage ratio test of D/PCM
reflectance of the ground (0.2), ISH is the radiation intensity received at
the horizontal plane (W/m2).
The leakage performance test method of D/PCM is as follows: weigh
Outdoor comprehensive temperature Tse is calculated by the
a quantitative D/PCM and place it on a filter paper, evenly spread it out,
following formula:
with a thickness of 1–2 mm and a net weight of m1. After different cy­
Tse = Tout +
α⋅I
− t1r (9) cles, weigh the net weight of the composite PCM m2, and the leakage
hout ratio X is calculated by Eq. (11). [38,39].

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Z. Geng et al. Journal of Energy Storage 83 (2024) 110543

Fig. 5. Simulated verification experimental system.

X = (m2 − m1 )/m1 (11)

(2) The leakage ratio test of C-D/PCM

The performance test method for cyclic leakage ratio of C-D/PCM is

to use a silicone mold with ∅400 mm and a thickness of 150 mm to form
a sample, and place it on a filter paper. The weight before the cycle is m1,
and after different cold and hot cycles, the weight after the cycle is m2.
The calculation method for leakage ratio X is the same as the above Eq.
(11).

3.1.1. Leakage of D/PCM and C-D/PCM

Fig. 6. Verification curves of inner wall temperature.
In this study, the leakage of paraffin after 200 thermal cycles of D/
PCM was tested. The mass loss results are shown in Fig. 7(a). The
leakage ratio of D/PCM increases with increasing phase change material
content, D/PCM35% having the lowest leakage ratio (4.3 %). The
leakage ratio of 45 % D/PCM for 50 cycles (8.7 %) is much higher than
that for 40 % cycles (5 %), and most of the mass loss occurs in the first
50 cycles. This is because the continuous thermal cycling causes leakage
of phase change material from the unabsorbed D/PCM into the pores of
the porous material, leading to mass loss of the D/PCM, while the
remaining PCM is well packed and therefore has less mass loss.
As shown in Fig. 7(b), the loss ratio was lowest at D/PCM35% and
increased with increasing D/PCM, reaching a maximum value (0.8 %) at

Fig. 7. (a) mass loss of D/PCM before and after thermal cycling; (b) mass loss of C-D/PCM before and after thermal cycling.

5
Z. Geng et al.
D/PCM50%. Overall, however, the presence of the re-dispersible pow­
der component in the C-D/PCM made the PCM more effective in
encapsulating the porous material. The emulsion provides secondary
encapsulation of the PCM, resulting in better encapsulation with a mass
loss of no >1 % at 200 cycles.
3.1.2. SEM of D/PCM and C-D/PCM
The low leakage ratio is attributed to the excellent pore structure of
the modified diatomite, before and after the modification of the diato­
mite SEM Fig. 8(a) and(b) is shown below, and Fig. 8(a) is the SEM
image of the original diatomite. It can be seen that the diatomite is in the
shape of a disc with a large number of pores distributed on the surface. It
is a good inorganic porous material, but it suffers from the problems of
large pore size difference, uneven pore distribution and high surface
impurities, which will greatly affect the performance of diatomite. Fig. 8
(b) shows the SEM image of diatomite modified by the calcination and
acidification method. It can be seen that the surface structure of diato­
mite has been significantly improved, the number of micropores has
been significantly increased, the distribution is average and the surface
roughness is moderate. It can be seen that the modified diatomite ob­
tained by the calcination/acid leaching method has good structural
properties and practical application value.
Fig. 8(c) and(d) show the SEM morphology of D/PCM and C-D/PCM
after adsorption. Fig. 8(c) shows that almost no obvious pores are left in
the pores of diatomite after paraffin impregnation, indicating that
paraffin impregnation of diatomite has a good effect. As shown in Fig. 8
(d), it can be observed that many spherical particles are uniformly
distributed in C-D/PCM, and most of the PCM has the original
morphology.
3.2. Thermal properties of D/PCM and C-D/PCM
3.2.1. Thermal performance of D/PCM and C-D/PCM
To investigate the effect of paraffin and diatomite doping on the
relationship between heat storage/release capacity, melting/solidifica­
tion temperature of D/PCM, the DSC results of pure paraffin and D/PCM
doped with 35 %, 40 % and 45 % PA were analyzed as shown in Fig. 9,
Fig. 8. SEM morphology of diatomite (a) before and (b) after modification by “calcination and acidification”; SEM morphology of D/PCM (c) and C-D/PCM (d).
6
Journal of Energy Storage 83 (2024) 110543
and the corresponding results are shown in Table 4. The latent heat of
melting and solidification of paraffin is 238.4 J/g and 238.09 J/g,
respectively, whereas the melting latent heat of D/PCM with PA content
of 35 %, 40 %, and 45 % is 73.48 J/g, 92.38 J/g, and 103.56 J/g,
respectively. The latent heat of melting and solidification increases with
increasing PCM content because PA undergoes a phase change, whereas
diatomite does not undergo a phase change in the temperature range
measured by DSC [40]. In addition, the melting point of paraffin was
26.46 ◦ C, while the melting points of D/PCM with 35 %, 40 % and 45 %
PA content were 26.85 ◦ C, 26.47 ◦ C and 26.53 ◦ C, respectively. It can be
seen that the phase change temperature of D/PCM does not change with
the change of PCM content. Due to the hydrogen bonding interaction
between n-octadecane and diatomite, the phase change temperature of
D/PCM is almost unaffected [41].
In order to further investigate its performance, the latent heat of C-
D/PCM and the phase change temperature were tested, as shown in
Fig. 10. The melting/solidification temperatures of C-D/PCM were
(26.96 ◦ C and 25.81 ◦ C) and its latent heat of melting/solidification was
(32.05 J/g/30.16 J/g). The thermal properties of the prepared C-D/PCM
were compared with other composite coatings in the literature as shown
in Table 5. The C-D/PCM prepared in this study has better thermal
properties as obtained by comparison.
3.2.2. Thermal performance after thermal cycling
D/PCM should maintain stable thermal properties through multiple
melting and freezing cycles. Moreover, small changes in thermal per­
formance should also be observed after long-term use. According to
3.1.1, D/PCM with a good leakage ratio was selected for DSC analysis to
further determine whether its thermal performance was good. The DSC
after 200 and 500 thermal cycles is shown in Fig. 11. The melting
temperature of D/PCM in the 500 cycles (26.81 ◦ C) is almost unchanged
from that in the first cycle (26.47 ◦ C). The melting latent heat of the 500
cycles (86.60 J/g) was only 5.78 J/g less than after cycle (92.38 J/g). In
general, D/PCM exhibits excellent thermal stability, the phase change
temperature is almost the same and the phase change latent heat is
stable in the thermal cycle. As shown in Table 6, the latent heat loss of C-
D/PCM before and after 500 cycles does not exceed 0.5 %, and the phase
Z. Geng et al. Journal of Energy Storage 83 (2024) 110543

Fig. 9. DSC curves of samples: (a) paraffin endo; (b) paraffin ex; (c) D/PCM endo; (d) D/PCM ex.

Table 4
D/PCM latent heat value and phase change temperature.
Samples Melting latent heat (J/g) Melting point (◦ C) Solidification latent heat (J/g) Solidification point (◦ C)

PA 238.4 26.46 238.09 25.43

D/PCM35% 73.48 26.85 72.43 25.88
D/PCM40% 92.38 26.47 92.28 25.87
D/PCM45% 103.56 26.53 103.84 25.69

change temperature remains almost unchanged. It can be seen that the
coating has a good encapsulation effect and can be further applied.
3.3. Analysis of simulation result
Through the results of the previous experiments, C-D/PCM was
selected and simulated with the physical model of wall panels estab­
lished by COMSOL software. The effects of phase change range, phase
change temperature and phase change layer thickness on the thermo­
regulation performance of the wall panels were investigated, and the
design parameters were Table 7. The phase change time, phase change
utilization, inner surface temperature of the wall panels and cold
loading were used as indicators to determine the best parameters for the
optimal design of C-D/PCM.
3.3.1. Effect of phase change range on utilization and phase change time
Phase change range refers to the temperature range from the
beginning of the phase change (Tonset) to the ending of the phase change
(Tendset). Phase change range ΔT has an important impact on the change
of phase change coating in the heat transfer process of the wall, so four
different phase change ranges ΔT (2 k, 4 k, 6 k, 8 k) are set as the
research object, other parameters remain unchanged, to simulate the
heat transfer process of the wall in summer under climatic conditions in
Xi'an. The changes of wall internal surface temperature, liquid phase
fraction and phase change time of PCM were simulated, as shown in
Figs. 12 and 13.
Fig. 12(a) shows the effects of different phase change range on phase
change time and utilization ratio in typical summer meteorological days.
It can be seen from the figure that when the phase change range is 2 k,
the shortest phase change time is 13 h, and the phase change time in­
creases with the increase of the phase change range. It is one-sided to use
only phase change time to measure the thermal regulation effect, so the
phase change effect is characterized by the utilization ratio of the liquid
phase at the same time. As can be seen from the line point in Fig. 12(a),
the utilization ratio of phase change range 2 k with the shortest phase
change time is 0.785, but the utilization ratio is the highest compared to
0.585, 0.392 and 0.279, because the temperature of the inner wall itself
does not change much, and the phase change utilization ratio is not high
when the phase change range is too large.
Fig. 12(b) shows the change curve of the liquid phase ratio on a

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Z. Geng et al. Journal of Energy Storage 83 (2024) 110543

Fig. 14(b) shows that for 2 k, the liquid phase ratio at 26 ◦ C and 29 ◦ C
changes little, while the liquid phase ratio at 27 ◦ C and 28 ◦ C is higher
and has a larger amplitude, with fluctuations ranging from 0.215 to 1
and 0 to 0.885. This may be because 27 ◦ C and 28 ◦ C are closer to the
weather changes of the day, and the temperature spends more time near
their phase change temperature. The higher the melting and solidifica­
tion change time, the higher the utilization ratio. When ΔT=4 k, the
overall utilization ratio is lower than 2 k, and the liquid phase ratio
fluctuation from 0.335 to 0.94 at 27 ◦ C is more appropriate.
Phase change time and utilization ratio are important parameters to
characterize the temperature control effect of phase change materials.
Fig. 15(a) shows the typical daily phase change time and phase change
utilization ratio. When ΔT=2 k, the phase change temperature is
selected at 28 ◦ C, where the longest phase change time is 17 h and the

Fig. 10. DSC curves of melting and solidifying of C-D/PCM.

typical summer meteorological day. It can be seen from the figure that
the phase change range is closely related to the amplitude of the liquid
phase ratio. When the phase change range is 2 k, the amplitude is
maximum, and the larger the phase change range, the smaller the
amplitude. This is because if the phase change range is too large, the
material cannot fully melt to absorb heat and solidify to release heat.
A typical meteorological day is not globally representative. Fig. 13
shows the total time and utilization ratio of phase change in summer. For
the phase change range of 2 k, the total time and phase change utili­
zation ratio are 1147 h and 0.75 respectively; when the phase change
range increases to 4 k, the total time is 1867 h, and the phase change
utilization ratio is 0.61. The total phase change time increases while the
phase change utilization ratio decreases, which is the same as typical
meteorological daily law. Combined with the two parameters of phase Fig. 11. DSC curve of D/PCM before and after thermal cycling.
change time and utilization ratio, the phase change range of 2 k and 4 k
is more appropriate, although the phase change time is longer at 6 k and
Table 6
8 k, the phase change utilization ratio is not high, and the material
Latent heat and phase change temperature of C-D/PCM before and after cycling.
cannot fully melt and solidify.
Cycles Melting Melting Solidification Solidification
point (◦ C) latent heat point (◦ C) latent heat (J/g)
3.3.2. Effect of phase change temperature on utilization and phase change
(J/g)
time
0 26.96 32.05 25.81 30.16
To explore the effect of phase change temperature on the heat
200 26.94 31.95 25.66 30.10
transfer process of the wall, four phase change temperatures (26 ◦ C, 500 26.93 31.93 25.65 30.09
27 ◦ C, 28 ◦ C, 29 ◦ C) are selected when ΔT=2 k, and three phase change
temperature points (25 ◦ C, 27 ◦ C, 29 ◦ C) are selected when ΔT=4 k to
study the effect of phase change temperature on thermal regulation
Table 7
performance. Simulation parameter Settings of building wall.
The selection of the temperature point of the phase change has a
Sample 1 2 3 4
certain influence on the time at which the phase change begins. Fig. 14
(a) shows the time at which the phase change begins to occur. As the Phase change range [k] 2 4 6 8
temperature of the phase change increases, the time at which the phase 26 27 28 29
Phase change temperature [ C]◦
25 27 29
change begins to occur is gradually delayed. In contrast, 27 ◦ C, 28 ◦ C and Thickness [mm] 1 2 5
29 ◦ C are more suitable as the choice of phase change temperature.

Table 5
Comparison of thermal properties of the obtained C-D/PCM with that of some composite PCM coatings in the literature.
Samples Melting point (◦ C) Melting latent heat (J/g) Solidification point (◦ C) Solidification latent heat (J/g) Reference

MPCM coating (30 %) 27.29 45.5 25.39 45.55 [36]

MPCM/paint (15 %) 29.73 9.547 26.63 9.629 [13]
MPCM/paint (20 %) 30.01 12.78 26.63 12.25 [13]
C-D/PCM
26.96 32.05 25.81 30.16 Present study
(35 %)

8
Z. Geng et al. Journal of Energy Storage 83 (2024) 110543

Fig. 12. Effect of phase change range in a typical meteorological day (a) change of phase change time and utilization ratio; (b) change of liquid phase ratio.

highest utilization ratio reaches 0.885, 27 ◦ C followed, 26 ◦ C and 29 ◦ C

were the worst. Moreover, by comparing the diagrams of 2 k and 4 k, it
can be seen that the phase change time of 2 k is <4 k and the phase
change utilization ratio is higher than 4 k, which is the same as Fig. 13.
The thermal regulation effect of temperatures 26 ◦ C and 29 ◦ C is
poor, the phase change time is <1000 h, and the utilization ratio is
<0.45. For ΔT=4 k, when the temperature is 25 ◦ C and 29 ◦ C, the uti­
lization ratio is 0.296 and 0.411, which is shown in Fig. 15(b). For the
two parameters of comprehensive utilization ratio and phase change
time, 27 ◦ C is the most appropriate phase change temperature point
when ΔT=2 k.

3.3.3. Effect of PCM thickness on utilization and temperature

Thickness is an important parameter affecting the temperature
control effect of phase change materials, so set different phase change
layer thickness (1 mm, 2 mm, 5 mm) parameters, other parameters
remain unchanged, the application effect of different phase change
layers in June, July and August was simulated, and its effect law was
studied.
As can be seen from Fig. 16, with the increase in thickness, the
Fig. 13. Effect of summer phase change range on phase change time and adjustment effect on the temperature of the inner wall becomes more
utilization. obvious. When the coating thickness is 1 mm, the temperature fluctua­
tion is the largest and the temperature peak is relatively high; when the
coating thickness is 5 mm, the time delay of temperature peak appears is
2 h, and the maximum reduction can be 1.03 ◦ C. And the fluctuation is

Fig. 14. Effect of phase change temperature on the typical meteorological day: (a) phase change start time; (b) liquid fraction.

9
Z. Geng et al. Journal of Energy Storage 83 (2024) 110543

Fig. 15. Effect of phase change temperature on phase change time and utilization (a)in a typical meteorological day; (b) in summer.

process has a more obvious adjustment to the temperature.

30 From Fig. 17(a), it can be seen that the phase change utilization ratio
June July August
of 5 mm is lower than that of 1 mm and 2 mm, but the phase change time
1mm
29 Tmax=28.76℃ 2mm
is longer than that of the other two groups. Especially in August, the
Tmax=28.74℃
Tmax=28.60℃ Tmax=28.57℃ 5mm phase change utilization ratio of the day is 0.925, and the phase change
time is 2 h longer than the other two groups, so the temperature
Temperature (℃)

Tmax=28.76℃
28 adjustment effect on the day is more obvious. As can be seen in Fig. 17
Tmax=27.73℃ (b), the temperature fluctuation decreases significantly with the increase
of thickness, which decreases by 0.23 ◦ C, 0.2 ◦ C and 1.03 ◦ C in June,
27
July and August, respectively. The maximum daily temperature de­
creases with the increase in thickness, while the minimum temperature
26 increases accordingly. But the temperature difference is greatest on
typical weather days in August. This may be because the phase change
temperature range is 26–28 ◦ C, and the temperature fluctuation range in
25
August is relatively closer to this scale, so the effect of phase change
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20 materials is more obvious and the utilization ratio is higher.
Time (h) Fig. 18 shows the temperature curve of the full-size inner wall tem­
perature for the whole summer. With the increase of the thickness of the
Fig. 16. Effect of thickness on inner surface temperature in typical meteoro­ PCM layer, the maximum temperature decreases to a certain extent. The
logical day. maximum temperature of the 5 mm phase change layer decreases by
0.317 ◦ C on average, while the temperature of 1 mm and 2 mm de­
significantly reduced, the temperature difference is only 2.862 ◦ C, which creases slightly, 0.152 ◦ C and 0.18 ◦ C. It shows that it has a certain
is reduced by 0.407 ◦ C. This is because the latent heat of the phase temperature control effect.
change is certain, the heat capacity of the material increases with the
increase of the thickness of the phase change, and the heat absorbed by
melting and the heat released by solidification during the phase change

Fig. 17. Effect of thickness on building wall: (a) phase change time and utilization; (b) temperature fluctuation of the inner surface.

10
Z. Geng et al.
Fig. 18. Full-size temperature curve of building wall.
3.4. Analysis of heating and cooling load
In order to evaluate the energy-saving effect, the instantaneous
cooling of external walls with PCM and without PCM is calculated
respectively, as shown in Fig. 19. The indoor and outdoor temperature is
low from 0:00 to 8:00 in the morning, and the heat release of paraffin
makes the indoor temperature rise. Since 8:00, the outdoor temperature
begins to rise, and phase change begins to occur inside the wall with
PCM, and the paraffin melts and absorbs heat to reduce the temperature.
Therefore, the cooling load required by the wall with PCM is lower than
without PCM. The temperature reaches its peak from 12:00 to 14:00,
and the cooling load required is also the highest. In general, the addition
of a PCM layer has a certain reduction effect on the cooling load, which
can reduce the cooling load by 19.37 % in a day.
As can be seen from Fig. 20, with the harmonic fluctuation of outdoor
temperature, the cooling load keeps changing, and the higher the tem­
perature, the cooling load required increases. In summer, the maximum
cooling load of 1440.7 W is lower than that of 1769.7 W without a PCM
wall, and the total load of 74,581 W is lower than that of 91,705 W
without a PCM wall, reducing the cooling load by 18.67 %. In general,
PCM can effectively reduce heat dissipation and cooling load.
4. Conclusion
In this study, C-D/PCM with 35 %D/PCM was prepared, and a wall
model was constructed to analyze its heat transfer process in the
Fig. 19. Hourly loading change of building wall.
11
Journal of Energy Storage 83 (2024) 110543
building and the energy-saving effects. The main findings of this study
can be summarized as follows:
(1) Modified diatomite was combined with paraffin to prepare D/
PCM with phase change temperature of 26.47 ◦ C and latent heat
of 92.38 J/g. Moreover, it has good cycle resistance. After 500
thermal cycles, the latent heat of phase change is only reduced by
5.78 J/g, and the phase change temperature remains unchanged.
C-D/PCM with 35 % D/PCM was prepared, which has a latent
heat of 31.11 J/g and heat loss ratio of <1 % after 500 thermal
cycles, and has good encapsulation performance.
(2) The simulation results show that the phase change temperature of
26–28 ◦ C has 75 % phase change utilization and 1175 h phase
change time. The peak temperature of the 5 mm phase change
layer is 1.03 ◦ C lower than that of the 1 mm, and the temperature
difference is 2.862 ◦ C, which reflects the effect of reducing the
temperature peak of PCM to reduce the temperature fluctuation.
According to COMSOL simulation calculation, the optimal phase
change temperature of C-D/PCM on the south wall of Xi ‘an in
summer is 26–28 ◦ C, and the latent heat is 31.11 J/g, the ideal
thickness is 5 mm.
(3) By comparing the hourly cooling load and the whole summer
cooling load of the external wall, compared with the wall without
PCM, the wall with C-D/PCM can effectively reduce the cooling
and heating load by 19.37 % on a typical meteorological day and
18.67 % in the whole summer, which has a better energy-saving
effect.
(4) For further work, the following aspects are worth noting: some
thermal conductivity enhancing materials can be added to
enhance thermal conductivity, and the effects of different ther­
mal conductivity properties in building applications can be
studied; How to make the coating contain more PCM to improve
its temperature regulation effect is also worth further research;
And for better practical applications, the preparation cost of PCM
materials is worth considering.
Author statement
No conflict of interest exists in the submission of this manuscript, and
manuscript is approved by all authors for publication. All the authors
listed below have approved the manuscript that is enclosed.
CRediT authorship contribution statement
Zijie Geng: Writing – original draft, Software. Chen Shi: Method­
ology, Conceptualization. Qing Zhao: Resources, Formal analysis. Liu
Z. Geng et al.
Fig. 20. Variation of cooling load of building wall in summer.
Yang: Supervision.
Declaration of competing interest
The authors declared that they have no conflicts of interest to this
work. We declare that we do not have any commercial or associative
interest that represents a conflict of interest in connection with the work
submitted.
Data availability
Data will be made available on request.
Acknowledgments
This study was supported by “the 14th Five-Year” National Science
and Technology Major Project of China (No. 2022YFC3802700) and Key
research and development project in Shaanxi Province (2024SF-YBXM-
634).
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