3.2 5.

Article

Novel Passive Radiation Cooling

Materials with High Emissivity
Discovered by FDTD Method

Jiangbo Wu, Tao Ma, Xiaoze Du, Shujun Liu, Ziyi Sui and Xinzhen Xia

https://doi.org/10.3390/en16041832
 energies
Article
Novel Passive Radiation Cooling Materials with High
Emissivity Discovered by FDTD Method
Jiangbo Wu , Tao Ma, Xiaoze Du * , Shujun Liu, Ziyi Sui and Xinzhen Xia
Citation: Wu, J.; Ma, T.; Du, X.; Liu,
S.; Sui, Z.; Xia, X. Novel Passive
Radiation Cooling Materials with
High Emissivity Discovered by
FDTD Method. Energies 2023, 16,
1832. https://doi.org/10.3390/
en16041832
Academic Editor: Jae-Weon Jeong
Received: 12 January 2023
Revised: 4 February 2023
Accepted: 9 February 2023
Published: 12 February 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Energies 2023, 16, 1832. https://doi.org/10.3390/en16041832
School of Energy and Power Engineering, Lanzhou University of Technology, Lanzhou 730050, China
* Correspondence: duxz@ncepu.edu.cn; Tel.: +86-(10)-61773923
Abstract: The cooling with the traditional condensation method leads to huge energy consumption,
while increasing attention has been paid to radiant cooling because of its characteristics of no
additional energy consumption and no pollution. In order to obtain materials with higher infrared
emissivity and better performance for daytime passive radiation cooling materials, the infrared
emissivity of different materials was studied based on the finite-difference time-domain method.
A new composite material with high emissivity has been found. The results show that the highest
emissivity can reach 99.1% by adding Si3 N4 , Al2 O3 and Fe2 O3 particles with volume fractions of 6%
and diameters of 50 nm into polydimethylsiloxane. This is the most excellent emissivity ever found.
By combining the emitting layer made of polydimethylsiloxane mixed with nanoparticles with the
reflecting layer made of Ag foil, the new film material can reach a solar transmissivity of 96.4% and a
“sky window” mean emissivity of 94.2%. A new composite material with high emissivity and high
reflectivity has been realized. The new composite material can be used as a radiation cooling material
with good performance and help to solve the cooling problem caused by energy consumption.
Keywords: radiation cooling; atmospheric transparent window; FDTD method; high emissivity; zero
energy consumption
1. Introduction
The global average surface temperature increased by about 0.3 ◦ C again in the last
decade [1]. The problem of global temperature warming due to human activities has become
increasingly serious [2]. In the face of rising temperatures, the need for cooling will increase
in the coming decades [3]. However, obtaining cold energy through traditional methods
will lead to greater energy consumption, which will lead to more serious environmental
problems [4,5]. At present, some novel cooling methods are realized through the passive
cooling of phase change materials (PCM) [6–8] and passive daytime radiation cooling
(PDRC) [9,10]. However, the special feature of PDRC is that the material itself can radiate
heat in the form of an electromagnetic wave in the low temperature space (3K) through
the atmospheric window (8–13 µm), so as to achieve effective cooling [11–13]. Therefore,
zero energy consumption and environment-friendly cooling can be realized by PDRC. At
present, PDRC is a promising technology in many fields such as building facades (window,
roof and wall), solar cell cooling, electricity generation and clothing [14–17]. Therefore,
PDRC technology, as a renewable energy technique with no pollution and zero energy
consumption, is of great significance for the field that needs to use fossil fuels for cooling.
In addition to atmospheric radiation, heat conduction and convection between mate-
rials and the environment, there are two main factors for improving the PDRC efficiency.
The first is to reduce the amount of radiation absorbed by the sun during the day, which
radiates between 0.3–2.5 µm at the surface [18]. The high reflectivity of solar radiation in
this band is the first characteristic of good radiative cooling materials. In this regard, Zhong
et al. obtained a composite with a high reflectance of 98% by adding an Ag deposit layer
and expanded polytetrafluoroethylene (PTFE) to a glass substrate, which has a temperature
https://www.mdpi.com/journal/energies
Energies 2023, 16, 1832 2 of 14

drop of 2.7 ◦ C in cloudy humid areas [19]. Dong et al. used the spectral band complemen-
tarity method to find a new PDRC coating. The coating, which contains BaSO4 , CaCO3 and
SiO2 particles, has a reflectivity of up to 97.6%. At the same time, the coating can reduce the
temperature of the covering by 8.3 [20]. In addition, the reflectivity of pure metal materials
is found to be more than 96% only for metallic Ag. Although there are other metals with
high reflectivity (e.g., Al), they are much less reflective than Ag. Thus, Ag foil is often used
in the study of materials with high reflectivity. Some studies have found that the reflectivity
of Ag combined with polyester material will produce unexpected effects [21]. For the study
on adding Ag to the reflector layer, Yang et al. studied a composite film composed of PTFE
and Ag. The thickness of the composite film is 0.24–1 mm, and it can have extremely high
reflectance in the band 0.28–4 µm; the reflectance can reach 0.99, which means it is the
material with the highest reflectance reported at present [22]. These are some of the ways
to reduce the amount of radiation absorbed by the sun during the day. Secondly, if the
radiation cooling has a high cooling ability during the day, the emissivity of the material at
the atmospheric window (8–13 µm) should be improved [23,24]. Currently, the materials
with high emissivity mainly include aerogel, nanoparticle, nanofiber and polymer. Li et al.
developed a silica-alumina nanofiber aerogel. Based on the scattered reflection and selective
emission of the optical fiber network in the aerogel, the emissivity of the material can reach
93%. The aerogel also has a high reflectivity, of up to 95% [25]. Chae et al. took sapphire as
the substrate and attached Al2 O3 and Si3 N4 thin films on it; they found that the reflectivity
of the composed material could reach 96%, the emissivity could reach more than 90% and
a temperature drop of 10 ◦ C was observed in the experiment [26]. Zhou et al. studied a
thin film thermal emitter combined with polydimethylsiloxane (PDMS) and metal. The
thickness of the thin film was more than 100 µm, and the emissivity reached 94.6% in the
experiment. It was also measured that after the directionality of the thermal emitter was
enhanced, the emitter could reach a temperature drop of 11 ◦ C and a cooling power of up
to 120 W/m2 in the open air. Since PDMS materials are cheap, the project can be used on
a large scale [27]. Although there are many directions in the research on materials with
high emissivity, the research on synthetic materials of polymers and nanoparticles is also
increasingly favored by many researchers.
However, in the current research on nanoparticle materials, researchers prepare com-
posite materials by testing the optical characterization of ordinary materials and then by
verifying complementary or mutually reinforcing properties. Therefore, many mixtures
of materials involving particles need to be simulated in advance using the corresponding
software to predict whether the model will work. Li modeled and simulated the radiant
cooling film with the finite-difference time-domain (FDTD) method. The final simulation
results show that when the volume fraction of SiO2 and SiC is 8% and 1%, respectively,
and the thickness of the radiant cooling film is between 60 and 90 µm, the emissivity of the
radiant cooling film is more than 90%. Then, experiments were carried out on the basis of
the simulation, and the experimental values were basically consistent with the simulated
values [28]. Wang prepared a composite material with high emissivity and reflectivity by
taking Al as the reflection substrate and PDMS film containing Si3 N4 as the emission layer.
The emissivity simulated by FDTD is basically consistent with the experimental values.
Moreover, it is found that the temperature of the material decreases by 10 ◦ C at most when
it is outdoors [29].
In this paper, we design a new composite material. The emission layer of the material
is prepared in the form of a mixture of nanoparticles and polymers. Ag foil with high
reflectivity, which is easy to obtain and process, is selected as the reflective layer. The
new material has the excellent characteristics of high emissivity and high reflectivity. The
emission layer materials are selected and combined by Al2 O3 , Si3 N4 , SiC, SiO2 , Fe2 O3 and
PDMS with high emissivity in the atmospheric window band (8–13 µm). The emissivity
of the composite was simulated by adding different particle diameters, volume fractions
and mixtures of different particles into the transparent PDMS film. Three kinds of particles,
Si3 N4 , Al2 O3 and Fe2 O3 , are obtained by simulation and have a good complementary effect
Energies 2023, 16, 1832 3 of 14

on the low emissivity band of PDMS materials. The results show that the highest emissivity
can reach 99.1% by adding Si3 N4 , Al2 O3 and Fe2 O3 particles with a volume fraction of 6%
and a diameter of 50 nm into PDMS. This is the most excellent emissivity ever found. By
combining the emitting layer made of PDMS mixed with nanoparticles with the reflecting
layer made of Ag foil, the new film material can reach a solar transmissivity of 96.4% and a
“sky window” mean emissivity of 94.2%. A new composite material with high emissivity
and high reflectivity has been realized. The completion of this research can provide some
help to the energy consumption problem of traditional cooling and refrigeration.

2. Accuracy Verification of FDTD Simulation

2.1. Mechanisms of the FDTD Method
FDTD is a discrete method that samples the E and H components of the electromagnetic
field in space and time. By using this discrete method, Maxwell rotation equations with
time variables are transformed into a set of difference equations, and the electromagnetic
field in space is solved step by step along the time axis. The mathematical model of FDTD
is as follows.
First, the generalized Maxwell equation can be expressed as:

∂B
∇×E = −M (1)
∂t
∂D
∇×H = J+ (2)
∂t
∇• D = ρ (3)
∇• B = 0 (4)
where M = σm H, J = σe E, σm and σe are the permeability and electrical conductivity respec-
tively, corresponding to the magnetic loss and electrical loss of the medium respectively.
With respect to an isotropic, uniform, lossy medium, there is a constitutive relation:
D = εE, B = µH, ε = ε r ε 0 , µ = µr µ0 .
In the passive medium space of no charge source and current source, the wave equation
of an electromagnetic wave can be derived by applying Maxwell’s equations and a simple
vector operation as follows:
∂2 E
∇2 E − µ ε 2 = 0 (5)
∂t
∂2 H
∇2 H − µ ε =0 (6)
∂t2
According to the above equations and constitutive relations, two component forms of
curl equations can be obtained:

∂Hy
 
∂Ex 1 ∂Hz
= − − σe Ex (7)
∂t ε ∂y ∂z

∂Ey
 
1 ∂Hx ∂Hz
= − − σe Ey (8)
∂t ε ∂z ∂x
1 ∂Hy
 
∂Ez ∂Hx
= − − σe Ez (9)
∂t ε ∂x ∂y
1 ∂Ey
 
∂Hx ∂Ez
= − − σm Hx (10)
∂t µ ∂z ∂y
∂Hy
 
1 ∂Ez ∂Ex
= − − σm Hy (11)
∂t µ ∂x ∂z
∂Ey
 
∂Hz 1 ∂Ex
= − − σm Hz (12)
∂t µ ∂y ∂x
  
∂ ∂ ∂ 
=  -σ 
∂ μ  ∂ ∂ 
Energies 2023, 16, 1832 ∂ ∂ ∂  4 of 14
=  -σ 
∂ μ  ∂ ∂ 

The above six differential equations constitute the basis of numerical algorithms for
the interaction between electromagnetic waves and three-dimensional object structures.
FDTD divides the simulation model into discrete time and space grid-constructed
cells, as shown in the Figure 1a. This method can deal with the electromagnetic scattering
and radiation of objects with complex shapes and materials with an uneven medium. It
has a wide range of applications in the simulation of micro- and nano-optical materials.
The FDTD running flow is shown in Figure 1b.

Building geometric
Other material Data
models
Z
Define material Material data text
parameters file

Ez Hx Simulated locale Boundary condition

setting setting

Hy
Ey Y Radiation source
Division of grid
setting
Hz
Ex
Check preview
Monitor Settings
memory
X “ ” represents direction
Export data and Simulation of
graph analysis operation
(a) (b)
Figure 1. (a) Schematic diagram of FDTD method; (b) FDTD running flowchart.
Figure 1. (a) Schematic diagram of FDTD method; (b) FDTD running flowchart.

2.2. Validation of Accuracy of FDTD Method

In order to verify the accuracy of FDTD simulation, we first simulated and verified
the emissivity of PDMS materials in the experiment of Zhou et al. The experimental data in
this paper show that the emissivity of PDMS materials in the 8–13 µm band can reach as
high as 94.6%.
The ratio of the main agent A and curing agent B of PDMS material is 10:1. Therefore,
when selecting the type of PDMS material in the database, the data of refractive index n
and extinction coefficient k of the material should be selected according to this ratio, as
shown in Figure 2.
In the actual model, the PDMS film is 5 cm long, 5 cm wide and only 150 µm thick. Due
to the uneven scale of graphics caused by the modeling of this data, the length and width
of the PDMS model were set as 10 µm and the thickness as 150 µm, and the simulation
area of the XY plane of its boundary could be set with periodic boundary conditions. This
will not only make the graphics more coordinated, but also reduce the number of grids.
Figure 3 shows the model of PDMS film.
Energies 2023, 16, 1832 5 of 14

2.0
Extinction coefficient
Refractive index

1.5

Value 1.0 （ µ ）

0.5

0.0

0 5 10 15 20

Wavelength（ µm）

Figure 2. Refractive index n and extinction coefficient k of PDMS material.

Reflectivity monitor
Plane wave light source

Region of simulation

PDMS film

Transmission rate monitor

(a) (b)
Figure 3. Model of PDMS film. (a) 3D modeling diagram for PDMS materials; (b) XZ interface
coordination scale with “zoom extent”.

Under the above boundary conditions, the band of the plane wave light source is
8–13 µm. The emissivity of the model was calculated according to Kirchhoff’s radiation
law, and compared with the figures and data in the paper, as shown in Figure 4. Through
comparison, it can be seen that in the band of 8–8.5 µm, the simulated trend is completely
inconsistent with the experimental value, but it is very close to the theoretical trend of the
other side. This is because there will be a drop in the initial part of the iterative calculation,
and only the extinction coefficient of PDMS material at the 8–13 µm band was selected
in the simulation process. However, in the 8.5–13 µm band, the simulated emissivity is
almost the same as the experimental trend of Zhou, and the simulated emissivity is up to
96.5%, which is only 1.9 percentage points less than the data in the paper 94.6%. This is
because compared with the simulation, the influence of clear sky weather conditions and
atmospheric dust during the actual test may lead to the lower emissivity measured.
In addition, the peak emissivity of PDMS can be seen near the wavelength of 8.7 µm
and 12 µm, while the effect is not optimal near the wavelength of 10.7 µm. However, on
the whole, the simulation results are consistent and reliable.
Energies 2023, 16, 1832 6 of 14

1.0

0.9

0.8

Emissivity
0.7
Experimental value of the paper
0.6 Theoretical value of the paper
Simulation value
0.5

0.4 Zhou L. Zhou, L. et al., 2019

8 9 10 11 12 13
Wavelength（ µm）

Figure 4. The experimental value and theoretical value in Zhou’s paper [29] compared with the
simulated emissivity value of the FDTD method.

3. Simulation Methods and Conclusions

3.1. Selection of Materials
In order to make the composite material have high emissivity, some coupling or
innovation is required depending on the properties of the single material. Here, SiO2 ,
SiC, Si3 N4 , Al2 O3 and Fe2 O3 were selected to simulate the emissivity. Finally, the selected
particles were integrated into PDMS film, and then the highest emissivity composites were
selected by comparing the ratio of materials through simulation. In addition, the reflectance
of Ag foil was also simulated.
Therefore, first of all, the emissivity of a single material was compared for the above
five particles with the same thickness, and the results are shown in Figure 5b. For the
reflectance simulation of Ag foil, Ag with a thickness of 200 nm is selected, because if
the increase in the thickness of Ag exceeds 130 nm, it will no longer affect the reflectance.
However, considering the difficulty of manufacturing 130 nm Ag foil in the actual process,
Ag with a thickness of 200 nm is selected based on the consideration of the material
manufacturing process and cost. Its reflectivity is shown in Figure 5c.
After the extinction coefficient of the material is obtained, as shown in Figure 5a, the
optical properties of the material can be further simulated, and the emissivity of various
materials in the atmospheric window band can be obtained, as shown in Figure 5b. It is
clear that in the atmospheric window band, each material has a different peak. Among
them, Si3 N4 has a peak emissivity of 90.8% near the wavelength of 9 µm, Al2 O3 has a peak
emissivity of 92.1% near the wavelength of 10.6 µm, SiO2 has a peak emissivity of 91.8%
and 92% near the wavelength of 8 µm and 11.6 µm, Fe2 O3 has a peak emissivity of 93.6%
near the wavelength of 13 µm, and SiC has an average effect. The reflectance of Ag foil
to the surface solar radiation in the band 0.3–2.5 µm is shown, and it can be seen that the
reflectance is basically stable at 96.4%, as show in Figure 5c.
Compared with the emissivity of PDMS material in Figure 5, Al2 O3 can be selected
to supplement the emissivity of PDMS material near 10.5 µm, and Fe2 O3 can be selected
to supplement the emissivity of PDMS material near 13 µm. In addition, it is also shown
in the figure that Si3 N4 has a good overall emissivity in the band 8–9.3 µm, and there
is a peak emissivity near 9 µm. Therefore, Si3 N4 is used to supplement the emissivity
of PDMS material near 8 µm. The combination of PDMS and Si3 N4 was simulated con-
sidering the comprehensiveness of the simulation, although the experimental values in
Zhou’s paper [29] have shown that the emissivity of the PDMS material is better at 8 µm.
 μ
μ
μ
μ
μ
Energies 2023, 16, 1832 7 of 14
μ

2.5 1.0
Fe2O3
SiO2 SiO2

Extinction coefficient values k

2.0 0.8
Si3N4
SiC

Emissivity
1.5 Al2O3 0.6 Si3N4
Fe2O3
1.0 SiC 0.4

0.5 0.2
Al2O3

0.0 0.0

‐2 0 2 4 6 8 10 12 14 16 8 9 10 11 12 13 14
Wavelength (m) Wavelength (m)

(a) (b)
1.0

0.8 Ag foil

0.6
Reflective

0.4

0.2

0.0

0.0 0.5 1.0 1.5 2.0 2.5

Wavelength (m)

(c)
Figure 5. Properties of different materials. (a) Extinction coefficients of different materials; (b) emis-
sivity of different materials at atmospheric window bands; (c) reflectance of Ag foil in the band
0.3–2.5 µm.
μ
3.2. Optimization of Material Parameters
In the previous analysis, it was found that Si3 N4 , Al2 O3 and Fe2 O3 could complement
the low emissivity band of PDMS materials in the 8–13 µm band. Here, we designed the
simulation of the influence of different volume fractions μ and diameter sizes of particles on
emissivity when the three materials of Si3 N4 , Al2 O3 and Fe2 O3 were mixed in PDMS mate-
rials. After selecting the best working condition, the three materials were mixed in PDMS
materials at the same time, and then the optimal mixing ratio of particles was observed.

3.2.1. Optimization of Volume Fraction

Here, the influence of different volume fractions of the above three material particles
on emissivity in PDMS was determined. According to the control variable method, the
diameter of the three materials is 50 nm, the thickness of the PDMS material is 150 µm, and
the volume fraction of the three materials is 1%, 5% and 8%, respectively. Then, the single
particles with different volume fractions are mixed with the PDMS material, and a total of
nine groups of simulation conditions are shown in Table 1.
Energies 2023, 16, 1832 8 of 14

Table 1. Different volume fractions of different particles are added to PDMS.

Number VSi3N4 /vol% VAl2O3 /vol% VFe2O3 /vol% Thickness of PDMS (µm)
1 1% 1% 1% 150
2 5% 5% 5% 150
3 8% 8% 8% 150

The influence of the volume fraction of the three materials on the emissivity of PDMS
was obtained through simulation, and the results are shown in Figure 6.

1.0

0.9

0.8

Emissivity
0.7 PDMS
PDMS+1% Si3N4
0.6 PDMS+5% Si3N4
PDMS+8% Si3N4
0.5

0.4

8 9 10 11 12 13

Wavelength（µm）

(a) (b)
1.0 1.0

0.9 0.9
Emissivity

0.8 0.8
Emissivity

PDMS PDMS
0.7 0.7
PDMS+1% Al2O3 PDMS+1% Fe2O3
PDMS+5% Al2O3 PDMS+5% Fe2O3
0.6 0.6
PDMS+8% Al2O3 PDMS+8% Fe2O3
0.5 0.5

0.4 0.4

8 9 10 11 12 13 8 9 10 11 12 13
Wavelength(µm) Wavelength（ µm）

(c) (d)

Figure 6. Emissivity of PDMS after adding particles with different volume fractions: (a) Schematic
diagram of radiant cooling process of composite materials; (b) emissivity of PDMS materials mixed
with different volume fractions of Si3 N4 ; (c) emissivity of PDMS materials mixed with different
volume fractions of Al2 O3 ; (d) emissivity of PDMS materials mixed with different volume fractions
of Fe2 O3 .

The model of PDMS film mixed with a single kind of micro- and nano-particle is shown
in Figure 6a. Then, the influence of the volume fraction on the emissivity of the mixture
was explored by adding different volume fractions of a single particle to the PDMS film. It
can be seen that after the addition of 1%, 5% and 8% Si3 N4 particles to PDMS materials,
the emissivity of the mixed materials increases to a certain extent in the 8–9 µm band. It
is worth noting that the emissivity of the composites does not increase with the grow of
the volume fraction of the particles. Under the control of the three groups of working
conditions, the emissivity of the material is the highest when the particle volume fraction is
5%, followed by 8% and 1%. When the particle volume fraction is 5%, the emissivity of the
mixture reaches 99.1% at 8.7 µm. Compared with the pure PDMS material, the emissivity
Energies 2023, 16, 1832 9 of 14

of the material in this band is improved by about 2% after the addition of Si3 N4 particles,
which is a significant change, as shown in Figure 6b. At the same time, it can be seen in
Figure 6c,d that after adding Al2 O3 and Fe2 O3 of different volume fractions into PDMS, the
emissivity of the original PDMS material in the band of 10.5–11 µm will also be improved.
Importantly, after adding Al2 O3 , the emissivity of the original PDMS material in the band
of 10.5–11 µm will be significantly improved, and the emissivity will be increased by a
surprising 9.9%. The highest emissivity in this band is 97.7%. The addition of Fe2 O3 also
improves the emittance of PDMS film at the 12.3–13 µm band, and the emittance of PDMS
film at this band is increased by 5% compared with that of pure PDMS film. It is worth
noting that the optimum volume fraction of the three materials is 5%, but the emissivity
will decrease when the added particles exceed a certain volume fraction. This is because,
compared with the mixed material, the pure particle material will have a lower emissivity
than the PDMS material. It is only because of the mixing that the emissivity of the band
is increased. However, with the increase in particles, the emissivity of particles in the
mixed material will account for a larger proportion, but the overall emissivity of the mixed
material will decline.

3.2.2. Optimization of Particle Diameter

In this section, the influence of different particle diameters on emissivity of each
material particle in PDMS film is discussed. According to the conclusion of the previous
section, the particle volume fractions are set as 5% in this section, the diameter of the three
materials is 20 nm, 50 nm and 80 nm, respectively, and the thickness of the PDMS material
is 150 µm. There are nine working conditions in total. The simulation scheme is shown in
Table 2.

Table 2. Different diameter of different particles are added to PDMS.

Number Si3 N4 /(nm) Al2 O3 /r (nm) Fe2 O3 /r (nm) Thickness of PDM (µm)
1 20 20 20 150
2 50 50 50 150
3 80 80 80 150

Adding different particles of different diameter with a volume fraction of 5% into

PDMS thin films, the influence of the diameter of micro-nanoparticles on the emissivity
was obtained, and the results are shown in Figure 7.
The thickness of PDMS film is 150 µm, in which the volume fraction of each micro-
nanoparticle is 5%. When Si3 N4 nanoparticles with diameters of 20 nm, 50 nm and 80 nm
were added to PDMS thin films, it was found that the emissivity of the materials was very
similar, and the maximum difference was only 2%. It can be seen that the influence of
particle diameter on emissivity is not obvious at a certain volume fraction. However, it
is worth noting that when the diameter is 50 nm, the emissivity of the mixed material is
the largest, up to 99.1%, followed by 80 nm particles, and the worst effect is the diameter
of 20 nm, as shown in Figure 7a. It can also be seen in Figure 7b,c that the diameter of
micro-nanoparticles does not significantly improve the emissivity of the mixed material,
but only weakly changes with the change of diameter. However, it can be determined from
the simulation data that the emissivity of the mixed material can reach the maximum when
the particle diameter is 50 nm.
Energies 2023, 16, 1832 10 of 14

1.0 1.0

0.9 0.9

0.8 0.8

Emissivity
Emissivity
PDMS PDMS
0.7 PDMS+20nm Si3N4 0.7 PDMS+20nm Al2O3
PDMS+50nm Si3N4 PDMS+50nm Al2O3
0.6 0.6
PDMS+80nm Si3N4 PDMS+80nm Al2O3
0.5 0.5

0.4 0.4

8 9 10 11 12 13 8 9 10 11 12 13
Wavelength（ µm） Wavelength（ µm）

(a) (b)
1.0

0.9

0.8
Emissivity

PDMS
0.7
PDMS+20nmFe2O3
0.6 PDMS+50nmFe2O3
PDMS+80nmFe2O3
0.5

0.4

8 9 10 11 12 13
Wavelength（ µm）

(c)
Figure 7. Effect of different diameter particles on emissivity of PDMS films: (a) influence of Si3 N4
particle diameter on emissivity; (b) influence of Al2 O3 particle diameter on emissivity; (c) influence
of Fe2 O3 particle diameter on emissivity.

Combined with the above situation, we discovered that the working parameters that
significantly improved the emissivity after adding particles to PDMS were the volume
fraction of 5% and the particle diameter of 50 nm.

3.2.3. Optimization of Mixed Particles

In the above simulation, we obtained the influence of particle volume fraction and
diameter on the emissivity of PDMS materials when a single type of particle is added to
the material. However, a single kind of particles can only improve the emissivity of PDMS
in a specific band. If three kinds of particles are added to PDMS materials at the same
time, the low-band emissivity of PDMS materials can be theoretically supplemented, and
the emissivity of mixed materials can be improved on the whole. In this section, three
kinds of micro- and nanoparticles with diameter of 50 nm were mixed into PDMS film with
thickness of 150 µm in different proportions to observe the influence of particle ratio on
emissivity. It should be noted that the bottom of the PDMS is covered with 200 nm thick
Ag foil, which is used to reflect the surface solar radiation of the 0.3–2.5 µm band, thus
achieving a greater degree of radiative cooling.
Here, according to previous studies, it is found that the optimal volume fraction of a
single particle is 5%, and with the increase in volume fraction, the emissivity of the material
will decrease. Therefore, the volume fraction of mixed particles should not be too large,
otherwise it will affect the emissivity of the whole material. In order to distribute particles
more evenly, the overall integral number of the three particles is 3% and 6%; namely, the
volume fraction of a single particle is 1% and 2%. Such a distribution can make the ratio
Energies 2023, 16, 1832 11 of 14

of particles more uniform. Although the overall integral number of the second scheme
exceeds 5%, it is close to 5% on the whole and is more uniform. Therefore, the distribution
scheme shown in Table 3 is designed.

Table 3. The design of mixing particles in proportion.

Thickness of PDMS
Number VSi3N4 /vol% VAl2O3 /vol% VFe2O3 /vol%
(µm)/Ag foil (nm)
1 1 1 1 150/200
2 2 2 2 150/200

The result shown in Figure 8 can be obtained by mixing the same proportion of
particles into the PDMS film.

1.0

0.9

PDMS film with three 0.8

Emissivity
nanoparticles
0.7

PDMS
0.6
PDMS+2% Si3N4+2% Al2O3+2% Fe2O3
0.5 PDMS+1% Si3N4+1% Al2O3+1% Fe2O3

Ag foil 0.4

8 9 10 11 12 13
Wavelength（ µm）

(a) (b)
Figure 8. Mixed particles of different proportions were added to PDMS films. (a) Schematic diagram
of PDMS material with three particles added on Ag foil base; (b) influence of different proportions of
mixed particles on emissivity.

Figure 8a shows the model diagram of the mixed material with 200 nm thick Ag
foil as the reflection layer and 150 µm thick PDMS film with Al2 O3 , Fe2 O3 and Si3 N4
nanoparticles as the emission layer. The diameter of the three micro-nanoparticles is 50 nm.
The total volume fraction of the particles is 3% and 6%, corresponding to the two cases
where the volume of the three particles is 1% and 2% respectively. Figure 8b shows the
comparison between the emissivity of the material after adding the mixed particles with
3% and 6% volume fraction respectively and that of the original PDMS material. It can be
seen in Figure 8b that when three kinds of particles are added, the emissivity of the mixed
material increases significantly at the 8–9 µm band, 10.5–11.7 µm band and 12.3–13 µm
band. The emissivity at the 8.7 µm wavelength increased by 2.4% from 96.3% to 99.1%. At
the wavelength of 10.6 µm, the emissivity increases the most, from 81.4% to 90.4%, reaching
a maximum increase of 9%; at the wavelength of 11 µm and 11.4 µm, the emissivity peaks
reach 96.7% and 97.7%. For the 12.3–13 µm band, the emissivity increases from 87.3% to
91.7% at 12.5 µm, achieving the greatest improvement. On the whole, the addition of three
kinds of particles makes the overall emissivity of PDMS material experience a surprising
improvement, and the average emissivity of the emission layer is 94.2%.

4. Discussion
In summary, a new daytime radiation cooling material based on Ag foil as the reflection
layer and mixed with Si3 N4 , Al2 O3 and Fe2 O3 nanoparticles as the emission layer of PDMS
thin film is proposed. The composite material can effectively reflect the solar radiation
Energies 2023, 16, 1832 12 of 14

in the band of 0.3–2.5 µm near the ground surface, and can have surprising emission in
the band of the atmospheric window of 8–13 µm. The highest emissivity of the material
can reach 99.1%, which is a very impressive emissivity at present. The overall emissivity
of the material in the specific band is clearly improved, and its average emissivity is
maintained at 94.2%. This will also allow the material to use its properties to reduce the
temperature of the covering in direct sunlight, resulting in truly energy-free, green and
energy-saving work. Although this work is only carried out by using simulation software,
it has a positive reference. In the later stage, the research on this material will be put
into actual experimental demonstration. For the research on daytime passive radiation
cooling, it is still important to explore the research and development of more materials
and innovation. In the future, the study of materials with extremely high emissivity and
reflectivity will be of great significance to the research of daytime radiation cooling.

5. Conclusions
In conclusion, a new kind of PDRC material is obtained by combining the emission
layer made of PDMS mixed with nanoparticles with the reflection layer made of Ag foil.
The new material achieves excellent performance with high emissivity and high reflectivity,
and it can reach a solar transmissivity of 96.4% and a “sky window” mean emissivity of
94.2%. Through simulation, the following conclusions are obtained.
(1) The study on different conditions of adding single nanoparticles in PDMS films
shows that compared with the diameter conditions, the change of the volume fraction of
micro-nanoparticles has a more significant effect on the material emissivity, and the optimal
particle diameter is 50 nm and the optimal particle volume fraction is 5%.
(2) The emissivity of PDMS film at 8~9 µm, 10.5~11.7 µm and 12.3~13 µm can be
improved by adding Si3 N4 , Al2 O3 and Fe2 O3 into PDMS film, and the emissivity of the
composites is higher and more uniform.
(3) The emissivity of the new material with Ag substrate and PDMS film mixed with
three kinds of particles as the emission layer will reach 94.2% in the atmospheric window
band, and the maximum emissivity can reach 99.1%. The reflectance of the composite
material to solar radiation is also very considerable, and overall can reach about 96%, and
up to 96.4%.
Despite the amazing achievements made in the recent years in PDRC, substantial
challenges remain for the broad application of this technology. First of all, climatic factors
play an important role in the cooling performance of PDRC. The transparency of the
atmospheric window will be weakened by clouds and high humidity, which will reduce
the cooling performance of the PDRC. Therefore, there will be some difficulty and space to
explore the wide application of this technology in cities with high humidity and coastal
areas. Secondly, sufficient physical, optical and chemical stability is a must for cooling
materials. PDRC materials are mostly used in outdoor environments. Materials need to be
blown through the wind, direct sun and rain while maintaining their cooling properties.
This is a considerable challenge and requires further exploration. In addition, the cooling
material and cooling system of PDRC also face an important problem. After a period of
outdoor work, the surface will be covered by dust and dirt, which will seriously affect the
performance of the cooling material. Therefore, it is necessary to develop self-cleaning or
anti-pollution properties for new PDRC materials in the future. Overall, although PDRC has
developed significantly in recent years, it will be necessary to address the above challenges
in the coming years to meet practical applications and expand the scope of PDRC.

Author Contributions: Investigation, X.D. and J.W; data curation, T.M. and J.W.; visualization and
writing original draft preparation, T.M.; project administration, X.D.; funding acquisition, J.W. and
X.D.; resources, X.D.; supervision, S.L., Z.S. and X.X. All authors have read and agreed to the
published version of the manuscript.
Energies 2023, 16, 1832 13 of 14

Funding: This research was funded by the Key Program of the National Natural Science Foundation
of China, grant number 52130607, the Science and Technology Program of Gansu Province, grant
number 21JR7RA262, the Double First-Class Key Program of Gansu Provincial Department of Edu-
cation, grant number GCJ2022-38 and the 2022 Gansu Provincial University Industry Support Plan
Project, grant number 2022CYZC-21.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Wang, Y.-R.; Hessen, D.O.; Samset, B.H.; Stordal, F. Evaluating global and regional land warming trends in the past decades with
both MODIS and ERA5-Land land surface temperature data. Remote Sens. Environ. 2022, 280, 113181. [CrossRef]
2. Matthews, H.D.; Wynes, S. Current global efforts are insufficient to limit warming to 1.5 ◦ C. Science 2022, 376, 1404–1409.
[CrossRef]
3. Goldstein, E.A.; Raman, A.P.; Fan, S. Sub-ambient non-evaporative fluid cooling with the sky. Nat. Energy 2017, 2, 17143.
[CrossRef]
4. Chen, G.; Wang, Y.; Qiu, J.; Cao, J.; Zou, Y.; Wang, S.; Jia, D.; Zhou, Y. A facile bioinspired strategy for accelerating water collection
enabled by passive radiative cooling and wettability engineering. Mater. Des. 2021, 206, 109829. [CrossRef]
5. Zeng, S.; Pian, S.; Su, M.; Wang, Z.; Wu, M.; Liu, X.; Chen, M.; Xiang, Y.; Wu, J.; Zhang, M.; et al. Hierarchical-morphology
metafabric for scalable passive daytime radiative cooling. Science 2021, 373, 692–696. [CrossRef] [PubMed]
6. Qureshi, Z.A.; Al-Omari, S.A.B.; Elnajjar, E.; Al-Ketan, O.; Al-Rub, R.A. Architected lattices embedded with phase change
materials for thermal management of high-power electronics: A numerical study. Appl. Therm. Eng. 2023, 219, 119420. [CrossRef]
7. Al-Omari, S.A.B.; Qureshi, Z.A.; Elnajjar, E.; Mahmoud, F. A heat sink integrating fins within high thermal conductivity phase
change material to cool high heat-flux heat sources. Int. J. Therm. Sci. 2022, 172, 107190. [CrossRef]
8. Al-Omari, S.A.B.; Qureshi, Z.A.; Mahmoud, F.; Elnajjar, E. Thermal management characteristics of a counter-intuitive finned heat
sink incorporating detached fins impregnated with a high thermal conductivity-low melting point PCM. Int. J. Therm. Sci. 2022,
175, 107396. [CrossRef]
9. Zhang, Q.; Wang, S.; Wang, X.; Jiang, Y.; Li, J.; Xu, W.; Zhu, B.; Zhu, J. Recent progress in daytime radiative cooling: Advanced
material designs and applications. Small Methods 2022, 6, 2101379. [CrossRef]
10. Chan, Y.H.; Zhang, Y.; Tennakoon, T.; Fu, S.C.; Chan, K.C.; Tso, C.Y.; Yu, K.M.; Wan, M.P.; Huang, B.L.; Yao, S.; et al. Potential
passive cooling methods based on radiation controls in buildings. Energy Convers. Manag. 2022, 272, 116342. [CrossRef]
11. Cheng, Z.; Wang, F.; Wang, H.; Liang, H.; Ma, L. Effect of embedded polydisperse glass microspheres on radiative cooling of a
coating. Int. J. Therm. Sci. 2019, 140, 358–367. [CrossRef]
12. Sun, J.; Wang, J.; Guo, T.; Bao, H.; Bai, S. Daytime passive radiative cooling materials based on disordered media: A review.
Sol. Energy Mater. Sol. Cells 2022, 236, 111492. [CrossRef]
13. Chen, M.; Pang, D.; Chen, X.; Yan, H.; Yang, Y. Passive daytime radiative cooling: Fundamentals, material designs, and
applications. EcoMat 2022, 4, e12153. [CrossRef]
14. Chen, J.; Lu, L. Development of radiative cooling and its integration with buildings: A comprehensive review. Sol. Energy 2020,
212, 125–151. [CrossRef]
15. Wang, Z.; Kortge, D.; Zhu, J.; Zhou, Z.; Torsina, H.; Lee, C.; Bermel, P. Lightweight, passive radiative cooling to enhance
concentrating photovoltaics. Joule 2020, 4, 2702–2717. [CrossRef]
16. Ishii, S.; Dao, T.D.; Nagao, T. Radiative cooling for continuous thermoelectric power generation in day and night. Appl. Phys. Lett.
2020, 117, 013901. [CrossRef]
17. Zhang, X.A.; Yu, S.; Xu, B.; Li, M.; Peng, Z.; Wang, Y.; Deng, S.; Wu, X.; Wu, Z.; Ouyang, M.; et al. Dynamic gating of infrared
radiation in a textile. Science 2019, 363, 619–623. [CrossRef]
18. Cheng, Z.; Han, H.; Wang, F.; Yan, Y.; Shi, X.; Liang, H.; Zhang, X.; Shuai, Y. Efficient radiative cooling coating with biomimetic
human skin wrinkle structure. Nano Energy 2021, 89, 106377. [CrossRef]
19. Zhong, H.; Zhang, P.; Li, Y.; Yang, X.; Zhao, Y.; Wang, Z. Highly solar-reflective structures for daytime radiative cooling under
high humidity. ACS Appl. Mater. Interfaces 2020, 12, 51409–51417. [CrossRef] [PubMed]
20. Dong, Y.; Han, H.; Wang, F.; Zhang, Y.; Cheng, Z.; Shi, X.; Yan, Y. A low-cost sustainable coating: Improving passive daytime
radiative cooling performance using the spectral band complementarity method. Renew. Energy 2022, 192, 606–616. [CrossRef]
21. Gentle, A.R.; Smith, G.B. A subambient open roof surface under the Mid-Summer sun. Adv. Sci. 2015, 2, 1500119. [CrossRef]
22. Yang, P.; Chen, C.; Zhang, Z.M. A dual-layer structure with record-high solar reflectance for daytime radiative cooling. Sol. Energy
2018, 169, 316–324. [CrossRef]
23. Zou, W.; Luo, H.; Yang, M.; Xu, J.; Zhao, N. Biomimetic Robust All-Polymer Porous Coatings for Passive Daytime Radiative
Cooling. Macromol. Rapid Commun. 2022, 2200695. [CrossRef]
24. Hu, L.-C.; Xue, C.-H.; Liu, B.-Y.; Guo, X.-J.; Wang, J.-H.; Deng, F.-Q. Scalable superhydrophobic flexible nanofiber film for passive
daytime radiative cooling. ACS Appl. Polym. Mater. 2022, 4, 3343–3351. [CrossRef]
25. Li, T.; Sun, H.; Yang, M.; Zhang, C.; Lv, S.; Li, B.; Chen, L.; Sun, D. All-Ceramic, compressible and scalable nanofibrous aerogels
for subambient daytime radiative cooling. Chem. Eng. J. 2023, 452, 139518. [CrossRef]
Energies 2023, 16, 1832 14 of 14

26. Chae, D.; Son, S.; Liu, Y.; Lim, H.; Lee, H. High-Performance Daytime Radiative Cooler and Near-Ideal Selective Emitter Enabled
by Transparent Sapphire Substrate. Adv. Sci. 2020, 7, 2001577. [CrossRef] [PubMed]
27. Zhou, L.; Song, H.; Liang, J.; Singer, M.; Zhou, M.; Stegenburgs, E.; Zhang, N.; Xu, C.; Ng, T.; Yu, Z.; et al. A polydimethylsiloxane-
coated metal structure for all-day radiative cooling. Nat. Sustain. 2019, 2, 718–724. [CrossRef]
28. Li, P. Preparation and Properties of SiO2 /SiC Composite Film by Radiation Refrigeration; Beijing University of Chemical Industry:
Beijing, China, 2020. [CrossRef]
29. Wang, Y. Numerical Simulation of Thermal Radiation Characteristics of SiO2 Ceramic Fiber Fabric Based on FDTD Method; Harbin
University of Science and Technology: Harbin, China, 2022. [CrossRef]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.