Materials & Design 233 (2023) 112281

Contents lists available at ScienceDirect

Materials & Design

journal homepage: www.elsevier.com/locate/matdes

Numerical simulation of the effective thermal conductivity of cement-based

composites: Microscopic insights into diatomite/silica aerogel
Zhiyong Liu a, b, Xi Jin a, Yunsheng Zhang a, Jinyang Jiang a, *
a
Jiangsu Key Laboratory for Construction Materials, Southeast University, Nanjing 211189, China
b
School of Materials Science and Engineering, Southeast University, Nanjing 211189, China

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

Keywords: Silica aerogel used in cement composites to prepare novel thermal superinsulation material has been gradually
Silica aerogel applied in buildings and can effectively reduce building energy consumption. In this paper, the geometric voxel
Diatomite construction method is used to heterogeneity model the thermal conductivity of a cement-based diatomite/silica
Composite materials
aerogel composite (DSAC), and thermal conductivity simulations are carried out using a heat conduction model
Thermal conductivity
Simulations
framework analogous to an electrical resistance model framework. The simulation results show that the simu­
lated thermal conductivities of cementitious DSAC materials with different DSAC composite contents agree well
with the corresponding experimental values. The saturated thermal conductivity of the cementitious DSAC
material is 2.5 times the dry thermal conductivity at 28 d. This shows that the thermal conductivity model
proposed in this paper can effectively predict the effective thermal conductivity of cementitious DSAC materials
and can provide strong support for the material design and performance prediction of cementitious DSAC
materials.

1. Introduction the thermal conductivity of silica aerogel, established a mathematical

For a long time, building insulation accounts for more than 2/3 of the
entire thermal insulation industry market. Aerogel materials have the
advantages of environmental friendliness, easy preparation, flame
retardant, excellent and thermal insulation performance, which are used
increasing yearly. Silica aerogel is a special three-dimensional network
structure, the pore size is less than the average free path of air molecules.
Silica aerogel can block heat conduction, heat convection, heat radia­
tion, which thermal conductivity as low as 0.017–0.040 W/(m⋅K). In
addition, it also has the advantages of low density (0.1–0.5 g/cm3), high
specific surface area, high adsorption, excellent hydrophobicity (water
contact angle greater than 145 ), close fitting with the substrate, easy to
◦
relationship between the density of silica aerogel and the heat transfer of
gas, solid or radiation [1], and considered the overall thermal conduc­
tivity of silica aerogel as the sum of three-phase thermal conductivity.
Lee et al. [2] further developed a calculation method of the gas phase
thermal conductivity of silica aerogels on this basis. Zeng et al. [3]
deduced the mean free path of gas molecules in aerogel materials. Ac­
cording to the mean free path, the relationship between the thermal
conductivity of aerogel materials and the gas viscosity can be derived
from molecular dynamics theory. The expression of this method for
calculating the overall thermal conductivity of silica aerogels is simple,
but its disadvantage is that there are many empirical constants without
specific physical significance.

compound with other materials, can effectively eliminate CUI (corrosion
under the insulation layer), meet the RoHS standard limit and other
advantages, becoming a popular functional filler.
To realize the intelligent design of silica aerogel composites, scholars
have conducted a considerable amount of research on the heat transfer
model of silica aerogel. Previous research aimed to establish models of
various heat transfer modes (gas, solid or radiation heat transfer) in
silica aerogel materials. Fricke first established a calculation model for
To further explore the thermal conductivity mechanism of silica
aerogels, Zeng et al. [4] proposed three kinds of cubic arrays, namely,
orthogonal square rods, orthogonal cylindrical rods and orthogonal
spherical arrays, to characterize the structure of silica aerogels and
deduced a thermal conductivity model of silica aerogels using the
equivalent circuit method, which was an important breakthrough for
research on the thermal conductivity of silica aerogels. Zhao et al. [5]
developed an improved analytical model for the total thermal

* Corresponding author.
E-mail address: jiangjinyang16@163.com (J. Jiang).

https://doi.org/10.1016/j.matdes.2023.112281
Received 3 March 2023; Received in revised form 10 August 2023; Accepted 27 August 2023
Available online 28 August 2023
0264-1275/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
Z. Liu et al.
conductivity of silica aerogels and proposed a three-dimensional cluster
aggregation structure with random diffusion to calculate the thermal
conductivity of silica aerogels at different temperatures. This model is a
pure prediction model that can analyse the thermal conductivity and
high-temperature characteristics of silica aerogels only by taking the
microstructure measured by experiments and analysis as input param­
eters. Yu et al. [6] used the equivalent circuit method to establish a
semiempirical model to derive the effective thermal conductivity of
composite aerogel materials, and this model involves the nanoscale heat
transfer effect and the microscale influence of additives such as emul­
sifiers and reinforcement fibres, which can better predict the effective
thermal conductivity. Feng et al. [7] built a model to describe the scale
heat transfer mechanism of fumed silica-based thermal insulation
composites (including fibre additives) and studied the thermal conduc­
tivity of composites at different temperatures, including the proportion
of gas thermal conductivity, solid thermal conductivity and radiation
heat transfer. Fatemeh et al. [8] modified the classical unit cell model of
nanocomposite aerogels by considering the influence of phonon scat­
tering and the existence of secondary porosity. The deviation between
the modified classical unit cell model (MCUM) results and the test results
was less than 10%, which is very consistent. Zhang et al. [9], using the
law of conservation of energy and the principle of heat transfer, devel­
oped a heat conduction model for cement-based materials containing
aerogels using the Jacobi iteration method. The results showed that the
numerical and experimental results were consistent. Wei [10] and Lu
[11] also used orthogonal spherical arrays to characterize the repre­
sentative basic structure of nanoporous aerogel materials, extracted
typical structural unit models to represent the microstructure of the
composite materials, and then used the equivalent circuit method to
obtain an analytical model of the effective thermal conductivity of
aerogel materials. These studies were based on the orthogonal sphere
model proposed by Zeng. The advantage of the conventional structure is
that it simplifies the heat transfer analysis inside the material, but it also
ignores the complex microstructure of the aerogel material.
To further study the microstructure of nano-porous aerogels, Xie
et al. assumed that aerogel materials have fractal characteristics in a
certain scale range, proposed a fractal orthogonal sphere model to
describe the microstructure of nano-porous silica aerogel materials [12],
and deduced the corresponding analytical model of effective thermal
conductivity using the equivalent circuit method. Wang et al. [13]
proposed a random growth method to generate the micromorphology of
porous media and used the lattice Boltzmann method to conduct a nu­
merical study on the effective thermal conductivity of a material. Pang
et al. [14,15] established a model for the effective thermal conductivity
of hollow SiO2 spherical microparticle silica aerogels with different core
shell ratios and measured the temperature response of the hot surface
using the steady-state method to obtain the core/shell ratio with the best
thermal conductivity. Based on this, they proposed a thermal conduc­
tivity model for the heat conduction and radiation of emulsifier fibre-
doped silica aerogels. Xie et al. [16] proposed a structural reconstruc­
tion algorithm for particle-type multiphase materials and fibre-type
multiphase materials based on the random growth method. On this
basis, they proposed a numerical calculation method for the combined
heat transfer due to heat conduction and heat radiation in aerogel
composite insulation materials. The random growth method is based on
a grid system of structural reconstruction, in which each pixel represents
a segment of multiphase material. By using the random growth method,
the value of each pixel is set to a number, which represents its phase
according to certain rules. The final result of structural reconstruction is
a two-dimensional matrix, in which different pixel values represent
different phases. He et al. [17] proposed a thermal conductivity model
for aerogel-filled granular materials. According to the dispersion of
aerogel particles, the microstructures of thermal insulation composites
were divided into clusters, network chains and pores. A corresponding
model was established, and the thermal conductivity equation based on
the heat transfer analysis of the composites was derived. Fu et al. [18]
2
Materials & Design 233 (2023) 112281
used a random generation-growth method that follows the solid-phase
growth principle to reconstruct the two-dimensional open-cell meso­
scopic structure. The pore size of aerogels was controlled preliminarily,
and the similarity between reconstructed and real structures was
enhanced with this generation method. The results agreed well with
published data, which demonstrates that this method can accurately
describe the stochastic character of an aerogel structure and is reliable
for practical applications.
In previous studies, the thermal conductivity of silica aerogel ther­
mal insulation materials was studied by empirical methods or analytical
methods (Mie scattering theory, Rossland approximation, Maxwell
model, lattice Boltzmann method, etc.). Although these theoretical
models can be used to estimate the heat transfer of aerogel materials,
they focus on the nanoscale, and there are some assumptions among
them, which will inevitably lead to calculation errors. For example, it is
assumed that all particles are distributed ideally, such as in a random
distribution in space, random distribution on the plane, and unidirec­
tional distribution in a specific direction. The influence of the properties
of the raw materials used to prepare composite materials, such as the
fibre length and diameter, on the heat transfer characteristics of com­
posite materials is ignored. At the microscale, the overall heat transfer
effect of aerogel composite insulation materials in cementitious material
systems and the influence of doping concentration and particle type on
the heat transfer of composite materials have not been fully studied.
The heat transfer effect of aerogel composite insulation materials in
cementitious material systems and the influence of dosage as well as
particle type on the heat transfer of composite materials have not been
systemically studied. To better explore the design of cement-based
diatomite/silica aerogel thermal insulation composites and to study
the influence of the diatomite/silica aerogel composite (DSAC) content
and the diatomite/silica aerogel mass ratio in the DSAC on the thermal
conductivity of these cement-based materials, this study establishes a
framework to predict its effective thermal conductivity. In current work,
the geometric voxel construction method is used to heterogeneously
model the thermal conductivity of DSAC, which can investigate the ef­
fect of different dosages of silica aerogel on the thermal conductivity of
the sample. Meanwhile, the thermal conductivity of cement-based
diatomite/silica aerogel thermal insulation composites is verified by
using a method analogous to that used to determine electrical resistance
and the finite difference method (FDM). Finally, the thermal conduc­
tivity of cement-based diatomite/silica aerogel thermal insulation
composites will be verified by using the measured results and the esti­
mated results from analytical models.
2. Establishment of the thermal conductivity model
In this section, a microstructure model of cement-based diatomite/
silica aerogel thermal insulation composites with different DSAC con­
tents and mass ratios of diatomite to silica aerogel is established on the
microscale by taking into account structural characteristics. The
detailed experimental process of sample preparation can be found from
previous study [19].
2.1. Basic assumptions of the model
Diatomite is a white powdery solid with a density of 2.3 g/cm3 and a
specific surface area of 50 m2/g. It has strong water absorption, with a
water absorption rate four times its own volume, a melting point of 165-
175℃, and pH value of 6.5–7.5. The chemical compositions of raw
materials are shown in Table 1. Table 2 lists pore structure character­
istics of silica aerogel samples.
According to the characterization analysis, schematic diagrams and
images of cement-based composites are shown in Fig. 1. On the micro­
scale, the cement paste matrix and DSAC composites are inhomoge­
neous. The C-S-H matrix and unhydrated cement clinker (C3S, C2S, C3A,
C4AF), capillary pores, and hydration products (calcium hydroxide,
Z. Liu et al. Materials & Design 233 (2023) 112281

Table 1
Chemical compositions of raw materials (wt%).
Series SiO2 Al2O3 Na2O Fe2O3 K2O MgO CaO TiO2 MnO P2O5 SO3

Diatomite 89.14 7.2 2.67 1.26 0.47 0.34 0.31 0.16 0.05 0.03 0.02
Cement 20.00 4.78 0.19 2.98 0.61 1.95 62.90 0.21 – – –

thermal conductivity is constant, so the cement-based diatomite/silica

Table 2
aerogel thermal insulation composite is considered a two-phase com­
Pore structure characteristics of silica aerogel samples.
posite, in which DSAC particles are embedded in the cement paste ma­
Bulk density (g/ Specific surface area Average pore size Pore volume trix. At this scale, the structure is influenced by the size, morphology and
cm3) (m2/g) (nm) (cm3/g)
volume content of the DSAC composite particles.
0.085 809.923 10 2.61

2.2. Porosity test

ettringite) constitute the matrix of the hardened cement paste.
As shown in Fig. 1, the structure of DSAC composite materials is very
complex, and it is very difficult to directly model them for heat transfer
analysis and calculation, so it is necessary to adopt several assumptions
to further simplify the model. The main method of heat transfer is
conduction, convection and radiation, and the heat transfer effects of
radiation and convection are ignored to simplify the model. DSAC
composites are assumed homogeneous and isotropic in the simulation.
Because the study scale is the microscale and the pore size of silica
aerogel is 7–80 nm, with a difference of 103 orders of magnitude, the
pore size of silica aerogel is ignored in this heat transfer analysis, and it
is considered that silica aerogel completely fills the pore space of diat­
omite in DSAC composites.
Based on the above assumptions, the DSAC composites prepared in
this work can be regarded as having a complex self-similar microstruc­
ture, and the microstructure of the phase change composites can be
regarded as regular spherical particles. To simplify the calculation, it is
assumed that the cement paste matrix is homogeneous and that its
The cement-based DSAC composites are characterized by vacuum
saturation [20] and the gravity method [21]. The gravity method forms
samples with dimensions of 50 mm × 50 mm × 20 mm, and three slices
are considered for each mass ratio. The volumes of these slices are
measured by the drainage method according to Archimedes’ principle,
and then these slice samples are put into a vacuum kettle, which is
vacuumized to negative pressure so that the samples absorb water for 24
h to reach the saturation state, and the quality ms of the saturation state
is measured. After that, the water-saturated paste slices are dried in a
vacuum drying oven at 105 ◦ C until they reach a constant weight. The
porosity (ϕ) can be calculated by using the dry weight (mdried ), water
absorption saturation mass (ms ) and volume (Vvol ) of the sample:
ms − mdried
ϕ= (1)
ρw Vvol
where ρw is the density of water. For Table 3, with a fix ratio of diatomite
to silica aerogel (2), the porosity of samples are numbered and listed by

Fig. 1. Schematic diagrams and images of the cement-based composites: (a) diatomite scanning electron microscopy (SEM) photograph, (b) diatomite schematic
diagram, (c) DSAC composite SEM photograph, and (d) DSAC composite schematic diagram.

3
Z. Liu et al. Materials & Design 233 (2023) 112281

mass ratio of DSAC composite to cement (d/c), and this table lists the 1) According to the results of particle size distribution analysis of
porosity of cement-based DSAC materials with different DSAC com­ DSAC composites, the number and volume fraction of each particle size
posite contents. For Table 4, with a fix ratio of DSAC composite to in the microstructure can be input, and simulated DSAC composites can
cement (0.2), the porosity of samples are numbered and listed by be simplified as a composite of spherical particles.
different mass ratios of diatomite to silica aerogel, and this table lists the 2) The simulated spherical particles are randomly placed into cubic
porosity of cement-based DSAC materials with different diatomite/silica cement paste boxes in the order from large particles to small particles. In
aerogel mass ratios. The experimental studies concern a total of 8 types the process of placement, the particles cannot overlap each other.
of samples in two groups presented in two tables. 3) According to the measured value of porosity by the water satu­
ration method, pores are formed in the cubic cement paste box by the
random erosion method.
2.3. Obtaining the voxel number of DSAC composites 4) Periodic boundary conditions are used, which means that if a
particle is placed across the boundary of the box, the excess part of the
Different from the continuous basis model, the model constructed by particle will be manually moved to the other side of the box.
the geometric voxel construction method is composed of cubic voxels. According to the four DSAC doses used in this study, the particle
Because the DSAC composite material is assumed to be spherical parti­ diameter and voxel number of the DSAC in the final cement-based ma­
cles, in the process of forming spherical particles, a voxel point is set as terials are shown in Table 5.
the centre of the sphere, a fixed length is given for the corresponding According to the number of particles corresponding to the diameter
radius, and all neighbouring voxel points within the sphere are defined of each DSAC particle and periodic boundary conditions in the four
as the DSAC particle phase. Then, the diameter of the sphere is set to different cement-based DSAC materials, the microstructure results are
2r +1 voxels. Fig. 2 is a schematic diagram of spheres with different shown in Fig. 4. Fig. 4 is microstructures of cement-based DSAC mate­
diameters composed of voxels. rials corresponding to different DSAC composite contents and cement
Because of the cubic regularity of a single voxel shape, the number of mass ratios. Fig. 4(a)~(d) are the microstructure diagrams of the
voxels contained in spherical particles in the voxel construction method cement-based DSAC materials corresponding to DSAC composite and
is irregular. Ranging from small to large in diameter, the number of cement mass ratios of 0.1, 0.15, 0.2 and 0.25, respectively. The left side
voxels contained in a sphere with a diameter of 2r + 1 voxels varies with is an arbitrary section of the microstructure, and the right side is a three-
the initial radius of the sphere. For the convenience of calculation, a dimensional microstructure diagram. In the figure, the black part is the
resolution of 1 µm/voxel is adopted; that is, the space is dispersed into cement paste matrix, the white part is the pore, and the yellow part is the
voxels with a side length of 1 µm. DSAC composite. It can be seen from the figure that with the increase in
According to the particle size distribution curve of the DSAC com­ the mass ratio of DSAC composites to cement, the distribution of DSAC
posite material measured by a laser particle size analyser [22,23], the composites in the microstructure is obviously dense, and the relative
size of the component microstructure is determined, and the side length cement paste matrix content is reduced.
of the microstructure is 3–4 times the maximum particle size. The test The particle diameter and voxel number of DSAC particles in the
results are shown in Fig. 3 (taking md : msa = 2 as an example). The final cement-based materials corresponding to four different diatomite/
maximum particle size of the DSAC composites is approximately 60 µm, silica aerogel mass ratios in the DSAC composites used in this study are
so the component microstructure of the cement-based DSAC materials is shown in Table 6.
set to 200 × 200 × 200 µm3. The microstructure results generated according to the diameter of
According to the content of DSAC in the microstructure of the three- each DSAC particle corresponding to the number of particles and peri­
dimensional cement-based DSAC material, the diatomite/silica aerogel odic boundary conditions are shown in Table 6. Fig. 5 is microstructure
mass ratio (md : msa ) in the DSAC composite, and the porosity (ϕ), the of cement-based DSAC materials corresponding to different diatomite/
number of DSAC voxels and the number of pore voxels needed in the silica aerogel mass ratios in DSAC composites. Fig. 5(a)~(d) are the
system can be obtained from the following formula: microstructure diagrams of cement-based DSAC materials when the
⎧
⎨ X + Y + Z = 8 × 10
6 diatomite/silica aerogel mass ratio in the DSAC composites is 1, 2, 3 and
X × ρD (2) 4, respectively, in which the left side is an arbitrary section of the
⎩
Y ×ρ
= d/c microstructure and the right side is a three-dimensional microstructure
schematic diagram. In the figure, the black part is the cement paste
where X represents the pixel number corresponding to the DSAC com­ matrix, the white part is the pore space, and the yellow part is the DSAC
posite material, Y represents the pixel number corresponding to the composite.
cement paste particles, Z represents the pixel number corresponding to
pores, ρd represents the density of the DSAC composite material, ρ 2.4. Heat conduction theory
represents the density of cement and d/c is the mass ratio of DSAC
composite materials to cement. Hasselman [25] and others proposed a method of calculating thermal
The two-phase structure of cement-based DSAC was established resistivity in a way that is analogous to the calculation of electrical re­
using a digital image-based model program [24]. The modelling process sistivity and decomposed a model into corresponding conductor net­
is as follows: works. This approach was used to transform the problem of thermal
conductivity into the problem of conductivity of corresponding grids.
Table 3 The method of adopting the electrical resistance analogy for simulating
Porosity of cement-based DSAC materials with different DSAC composite the heat conduction of the established geometric voxel model is intro­
content. duced in detail below.
In the two-dimensional cement-based DSAC materials, arbitrary
Mass ratio of Mass of water absorption Dry weight mdried (g) Porosity
DSAC saturation state ms (g) (%) sections are taken as research units. First, it is necessary to establish a
composite to square network composed of diffusion units for heat transfer, taking the
cement (d/c) centre point of each pixel in the network as the transmission node,
d/c = 0. 1 53.9 48.33 47.24 38.08 34.36 33.08 29.30 connecting four adjacent nodes on the same side with connecting lines,
d/c = 0. 15 47.08 51.47 48.6 33.77 37.15 34.7 27.69 and taking the connecting lines as the heat transfer channels between
d/c = 0. 2 47.21 47.97 46.71 34.07 35.75 33.13 25.96 nodes, that is, as the “wires”. Fig. 6(a) shows a simple two-dimensional
d/c = 0. 25 40.59 42.59 42.48 27.96 29.83 29.4 25.65
transmission network with a size of 4 × 5 voxels. In Fig. 6(a), orange is

4
Z. Liu et al. Materials & Design 233 (2023) 112281

Table 4
Porosity of cement-based DSAC materials with different diatomite/silica aerogel mass ratios.
Different mass ratios of diatomite/silica aerogel (md : msa ) Mass of water absorption saturation state ms (g) Dry weight mdried (g) Porosity (%)

md : msa = 1 39.91 35.6 39.62 26.01 23.1 25.36 27.11

md : msa = 2 47.21 47.97 46.71 34.07 35.75 33.13 25.96
md : msa = 3 49.82 50.97 51.9 38.07 38.3 39.54 24.52
md : msa = 4 52.29 52.72 52.74 40.14 40.06 39.17 23.59

Fig. 2. Schematic diagram of voxel particles corresponding to particles with diameter 3 and diameter 5.

Table 5
Number of DSAC particles corresponding to each diameter in the cement
microstructure with different DSAC contents.
Particle Number of Number of Number of Number of
diameter particles (d/c particles (d/c particles (d/c particles (d/c
= 0.1) = 0.15) = 0. 2) = 0.25)

3 7596 9958 11,791 13,254

5 1682 2205 2611 2935
7 697 913 1081 1215
9 410 537 636 715
11 269 352 417 469
15 130 171 202 227
21 53 70 83 93
25 17 22 26 29
29 11 14 16 18
33 7 9 11 12
39 4 5 6 7
45 2 3 4 4
Fig. 3. Particle size distribution curve of DSAC composites. 51 1 2 2 2

the cement paste matrix, and white is the DSAC composite material. The
where the sums λi and λj are the thermal conductivities of pixel points i
phase thermal conductivity of each pixel is assigned to the corre­
sponding node, high- and low-temperature fields (Thigh and Tlow) are and j, respectively. After calculating the thermal conductivity of each
applied on both sides of the heat transfer direction set by the micro­ node, the heat conduction between the two nodes satisfies the Fourier
structure, and the other boundaries are sealed to obtain an equivalent law:
heat transfer network, as shown in Fig. 6(b). dTij
The thermal conductivity between two adjacent nodes depends on qijl = − λij (4)
dx
the phase thermal conductivity at the node. When the thermal con­
ductivity of one of the two pixel points i and j is 0, the thermal con­ where qijl is the heat flux through pixels i and j; dTij is the temperature
ductivity between two nodes in the heat transfer network cannot be gradient between pixels i and j; and dx is the distance between two pixels
effectively transmitted; that is, the thermal conductivity between two i and j. When the heat conduction reaches a steady state, the tempera­
nodes in the heat transfer network λij is 0. When two pixel points i and j ture value at each point will not change again; that is, at any moment,
are of different phases, the specific calculation formula of λij is: the amount of heat entering and outflow at each node will reach a dy­
( ) namic balance. The relationship is as follows:
1 1
λij = 2/ + (3) ∑k=6 ∑k=6 dTij
λi λj qijl = − λijk =0 (5)
k=1 k=1 dx

5
Z. Liu et al. Materials & Design 233 (2023) 112281

Fig. 4. Microstructures of cement-based DSAC materials corresponding to different DSAC composite contents and cement mass ratios (200 × 200 × 200 µm3).

⎧
Table 6 ⎪
⎪
T(1, j) = Tlow j = {1, 2, ..., N}
Voxel number of DSAC particles in cement-based DSAC composites with
⎪
⎪
⎪
⎨∑k=4 k
different particle diameters md : msa . T(i, j) − T(i, j)
λijk = 0 i, j = {2, 3, ..., N − 1} (6)
⎪
⎪ △l
Particle Number of Number of Number of Number of ⎪
⎪ k=1
⎪
⎩
diameter particles particles particles particles
T(N, j) = Thigh j = {1, 2, ..., N}
(voxels) (md : msa = 1) (md : msa = 2) (md : msa = 3) (md : msa = 4)

3 13,515 11,791 10,797 10,110

where l is the length of the whole network; and T(i, j)l − T(i, j) is the
5 2993 2611 2391 2239
7 1239 1081 990 927
temperature difference. Further expanding Formula 7 (taking N = 4 as
9 729 636 582 545 an example) gives:
11 478 417 382 358 ⎡ ⎤⎡ ⎤
15 232 202 185 173 − S21 V21 0 0 λ21 0 0 0 T21
21 95 83 76 71 ⎢ V21 − S21 V22 0 0 λ22 0 0 ⎥ ⎢ ⎥
⎢ ⎥⎢ T22 ⎥
25 30 26 24 22 ⎢ ⎥⎢ ⎥
⎢ 0 V22 − S23 V23 0 0 λ23 0 ⎥⎢ T23 ⎥
29 19 16 15 14 ⎢ ⎥⎢ ⎥
⎢ 0 λ24 ⎥ ⎢ ⎥
33 12 11 10 9 ⎢ 0 V23 − S24 0 0 0 ⎥⎢ T24 ⎥
39 7 6 6 5
⎢ ⎥⎢ ⎥
⎢ λ21 0 0 0 − S 31 V 31 0 0 ⎥ ⎢ T25 ⎥
45 4 4 3 3 ⎢ ⎥⎢ ⎥
⎢ 0 λ 0 0 V − S V 0 ⎥⎢ T26 ⎥
51 2 2 2 2 ⎢
⎢
22 31 32 32 ⎥⎢
⎥⎢
⎥
⎥
⎣ 0 0 λ23 0 0 V32 − S33 V32 ⎦⎣ T27 ⎦
0 0 0 λ24 0 0 V32 − S34 T28
In the formula, k represents the number of nodes adjacent to the ⎛ ⎞
central node. In the two-dimensional model, k is 4, representing the four ⎜ ⎟
adjacent nodes on the top, bottom, left and right of the central node. In ⎡ ⎤ ⎡ ⎤⎜
⎜ S21 = λ + V + λ
⎟
⎟
− λ11 0 ⎜ ⎟
the three-dimensional model, the k value is 6, representing six adjacent
11 21 21
⎢− ⎜ ⎟
λ12 ⎥ ⎢ 0 ⎥ ⎜ S = λ + V + λ + V 21 ⎟
points of the central node. ⎢
⎢
⎥
⎥
⎢
⎢
⎥⎜
⎥⎜
22 12 22 22 ⎟
When the relationship between the thermal conductivity of the heat ⎢− λ13 ⎥ ⎢ 0 ⎥⎜ S23 = λ13 + V23 + λ23 + V22 ⎟ ⎟
⎢ ⎥ ⎢ ⎥⎜ ⎟
⎢− ⎥ ⎢ 0 ⎥
conduction network and the pixels of adjacent nodes is determined, ⎢ λ14 ⎥ ⎢ ⎥⎜
⎜
S24 = λ14 + V24 + λ23 ⎟
⎟
= Thigh⎢ ⎥ + Tlow⎢ ⎥⎜
periodic boundary conditions are added to the inner and outer surfaces ⎢
⎢ 0 ⎥ ⎥
⎢−
⎢ λ11 ⎥
⎥⎜
S31 = λ21 + V31 + λ31 ⎟ ⎟
⎜ ⎟
of the network. The high and low temperature gradients in the two ⎢
⎢ 0 ⎥ ⎥
⎢−
⎢ λ32 ⎥
⎥⎜ S32 = λ22 + V32 + λ32 + V31 ⎟
⎜ ⎟
conduction directions, Tlow = 0 ℃ and Thigh = 1.0 ℃, are based on the ⎢
⎣ 0 ⎦
⎥ ⎢
⎣−
⎥⎜
λ33 ⎦⎜ S33 = λ23 + V33 + λ33 + V32 ⎟ ⎟
concept of relative thermal conductivity. Tlow and Thigh have no effect on ⎜ ⎟
0 − λ34 ⎜ S = λ + V + λ ⎟
the heat conduction behaviour in cement-based DSAC materials. ⎜ 34 24 34 33 ⎟
⎝ ⎠
Based on heat conduction equations, the temperature of each node
can be obtained by solving the whole matrix equation in the three-
(7)
dimensional transmission grid. In this study, the FDM is used to solve
the matrix equation. In a two-dimensional transmission network, com­ where Vij is the distance between two nodes i and j; The matrix is a five-
bined with boundary conditions, we can obtain: diagonal symmetric matrix, the thermal conductivity on the grid
transmission unit corresponds to the subdiagonal value of the matrix,
and the sum of the thermal conductivities of each transmission unit

6
Z. Liu et al. Materials & Design 233 (2023) 112281

Fig. 5. Microstructure of cement-based DSAC materials corresponding to different diatomite/silica aerogel mass ratios in DSAC composites.

Fig. 6. Simple two-dimensional heat transfer network schematic diagram of 4 × 5 voxels.

connected with the node is the diagonal value. results of the three-dimensional model in three directions and takes their
When the temperature of each node satisfies: average value as the final thermal conductivity.
⃒ (n+1) ⃒
∑⃒T − Tn ⃒
<β (8) 3. Analysis of simulation results
i
T (n+1)

the system is in a steady state. In Formula 8, n is the number of it­ 3.1. Effective thermal conductivity of the cement paste matrix and DSAC
erations during the solution, i is the number of nodes, and β is the preset composite
tolerance (β = 10− 3 ) that defines whether the interior of the heat con­
To carry out simulations, it is necessary to measure and reasonably
duction network has reached a steady state. The heat flux through the
assume the thermal conductivity input parameters. First, to determine
outer surface at this time satisfies the following formula:
the effective thermal conductivity of the cement paste matrix, it is
∑i=N ∑j=N ∑i=N ∑j=N l
necessary to determine the thermal conductivity of each phase in the
qijl λijl T(i,j)Δl− T(i,j)
(9)
i=1 j=1 i=1 j=1
Qk =
l
=
l cement paste matrix. The measured thermal conductivity of the cement
paste matrix in the saturated and dry states (1.03 W/m⋅K and 0.78 W/
Accordingly, the thermal conductivity λk of the whole grid system is: m⋅K, respectively) is similar to the calculated thermal conductivity
Qk ⋅l (1.08 W/m⋅K and 0.77 W/m⋅K) of the cement paste matrix by Liu Cheng
λk = (10) et al. [26] using the prediction of C-S-H thermal conductivity at the
A⋅(Thigh - Tlow )
nanoscale. The thermal conductivities of tricalcium silicate hydrated
where Qk represents the total heat passing through the surface in the (C3S) and dicalcium silicate hydrated (C2S) are 3.45 W/m⋅K and 3.35
steady state. It can be predicted that different heat conduction directions W/m⋅K, respectively [27]. Therefore, the average thermal conductivity
in the grid may correspond to different thermal conductivity values. of the cement clinker is 3.4 W/m⋅K. The thermal conductivities of DSAC
Therefore, this paper statistically evaluates the thermal conductivity composites with different diatomite/silica aerogel mass ratios measured

7
Z. Liu et al. Materials & Design 233 (2023) 112281

by experiments are detailed in Table 7.

To study the effect of water saturation on the thermal conductivity of
cement paste, water saturation is defined as the ratio of the pore content
of the current water-filled capillaries to the pore content of the saturated
capillaries. To simulate cement paste with different water saturations,
air-filled capillary pores were randomly divided into water-filled capil­
lary pores according to the known water–air ratio. The thermal con­
ductivity prediction model described in the previous section is applied to
different cement-based diatomite/silica aerogel thermal insulation
composites.

3.2. Effective thermal conductivity of cement-based diatomite/silica

aerogel thermal insulation composites

After the thermal conductivity of a cement paste matrix and DSAC

composite is obtained, it can be input into the model to predict the
overall thermal conductivity of the cement-based DSAC composite. To
predict the thermal conductivity of cement-based DSAC composites
under saturated and completely dry conditions, the two conditions Fig. 7. Relationship between the thermal conductivity of cement-based DSAC
should be assumed separately. For saturated cement-based DSAC ma­ materials and the diatomite/silica aerogel ratio in the DSAC.
terials, it is considered that all pores are filled with water, and the
thermal conductivity of water-filled pores is input for calculation. For
dry cement-based DSAC materials, it is considered that all pores are
filled with air, so the thermal conductivity of air-filled pores is input for
prediction.
Fig. 7 shows the simulation results of the relationship between the
thermal conductivity of cement-based DSAC materials and the dose of
DSAC composite. The simulated values of thermal conductivity in
saturated and dried materials are determined in the X, Y and Z directions
of the respective three-dimensional model. It can be observed that with
the increase in DSAC dose, that is, the increase in the d/c value, the
thermal conductivity of the cement-based DSAC materials decreases,
reaching the lowest thermal conductivity when d/c = 0.25; the thermal
conductivity of the saturated materials decreases more obviously, which
is consistent with the experimental trend.
To further verify the model, Fig. 8 shows the prediction diagram of
the influence of the mass ratio of diatomite and silica aerogel in DSAC
composites on the thermal conductivity of cement-based DSAC mate­
rials. The predicted values of thermal conductivity in saturated and
dried materials are determined in the X, Y and Z directions of the
respective three-dimensional model. It can be observed that with the
increase in diatomite content in the DSAC composite, that is, the in­ Fig. 8. Relationship between the thermal conductivity of cement-based DSAC
crease in the md : msa value, the thermal conductivity of the cement- materials and the diatomite/silica aerogel ratio in the DSAC.
based DSAC material increases; the thermal insulation performance
becomes worse, which is consistent with the experimental trend. the comparison of the thermal conductivity under completely saturated
conditions.
3.3. Fitting simulation results with experimental values It can be seen from Fig. 9 that when the mass ratio of the DSAC
composite to cement is 0.1, 0.15 and 0.2 in the saturated and dry states,
To verify the consistency between the simulation results and the the simulated thermal conductivity of the cement-based DSAC materials
experimental results, the experimental results are compared with the with different DSAC composite contents is basically consistent with the
simulation results. The comparison of the predicted and measured experimental values. However, when the mass ratio of the DSAC com­
thermal conductivities of cement-based DSAC materials with different posite to cement is 0.25, the predicted thermal conductivity of the
DSAC composite contents and diatomite/silica aerogel ratios is shown in cement-based DSAC material is slightly larger than the measured ther­
Fig. 9 and Fig. 10, respectively [19]. In both figures, (a) shows the mal conductivity. This is because the cement-based DSAC materials are
comparison of the predicted thermal conductivity with the measured dried to a constant weight in an oven at 60 ◦ C, but the traditional drying
thermal conductivity under completely dry conditions, and (b) shows method cannot fully evaporate the moisture in the test block. When a
large number of DSAC composites are added, the internal porosity of the
Table 7 cement-based DSAC material is high due to the characteristics of the
Thermal conductivities of some compounds. high specific surface area and high porosity of the DSAC composites, and
the measured porosity is lower than the real value, which leads to the
Compound Air-filled Water- DSAC DSAC DSAC DSAC
pore filled pore (md: (md: (md: (md: relative reduction of pores in the microstructure and high thermal
msa = msa = msa = msa = conductivity in the simulation calculation.
1) 2) 3) 4) As shown in Fig. 10, the simulation results of cement-based DSAC
Lambda 0.026[28] 0.607[29] 0.0357 0.0433 0.0486 0.0524 materials with different diatomite/silica aerogel mass ratios (i.e., diat­
(W/m⋅K) omite/silica aerogel mass ratios of 1, 2, 3 and 4) are in good agreement

8
Z. Liu et al.
Fig. 9. Comparison of the predicted and measured thermal conductivities of cement-based DSAC materials with different DSAC composite contents [19].
Fig. 10. Comparison of the predicted and measured thermal conductivities of cement-based DSAC materials with different diatomite/silica aerogel mass ratios [19].
with the measured results, whether in a saturated or dried state. How­
ever, Fig. 10(b) shows that the measured thermal conductivity of
cement-based DSAC materials with a diatomite/silica aerogel mass ratio
of 4 in water-saturated DSAC composites is slightly larger than the
corresponding simulated predicted thermal conductivity, which is an
inevitable result because this model assumes that in the DSAC com­
posite, diatomite pores are considered to be completely filled by silica
aerogels, and when the diatomite/silica aerogel mass ratio is 4, it is
obvious that the amount of diatomite is significantly greater than that of
silica aerogels, silica aerogels can no longer completely fill their pores,
and the predicted thermal conductivity after water saturation is natu­
rally small.
The consistency between the predicted thermal conductivity and the
measured thermal conductivity of cement-based DSAC materials shows
that the proposed thermal conductivity model can provide strong sup­
port for the design of the effective thermal conductivity of cement-based
DSAC materials.
4. Conclusions
To realize the intelligent design of cement-based DSAC materials, a
microscale heat conduction model framework analogous to an electrical
resistance model framework was developed based on reasonable
9
Materials & Design 233 (2023) 112281
assumptions to predict the effective thermal conductivity of cement-
based DSAC materials. The conclusions are as follows:
1) The benchmark test results show that although the thermal con­
ductivity of DSAC composites is quite different from that of the cement
paste matrix, the results based on combining the proposed heat con­
duction method with the FDM are still in good agreement. The heat
conduction model proposed in this work can estimate the effective
thermal conductivity of cement-based DSAC materials well.
2) The thermal conductivity of cement-based DSAC materials is
closely related to the water saturation. When d/c = 0.1 and md:msa = 2,
the saturated thermal conductivity of the cement-based DSAC is almost
2.5 times the dry thermal conductivity at 28 d.
3) The addition of the DSAC composite reduces the overall thermal
conductivity of cement-based DSAC materials. The increase in the
diatomite/silica aerogel mass ratio of the DSAC composite will reduce
the overall thermal conductivity of cement-based DSAC materials. The
simulated thermal conductivity of cement-based DSAC materials is in
good agreement with the measured values.
4) In the follow-up research, the heat transfer model formula based
on pore size distribution will be emphatically studied. This is of great
significance for more accurate prediction of thermal conductivity and
better preparation of silica aerogel with high quality performance.
5) When silica aerogel is doped in the cement-based system, it is easy
Z. Liu et al.
to appear phase stratification and lead to the decline of the performance
of thermal insulation materials. Therefore, to improve the dispersion
uniformity and stability of aerogel in the composite is one of the key
problems to be solved in its application.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
The authors gratefully acknowledge the financial support from the
National Key Research and Development Program of China
(2021YFB2601200), the National Natural Science Foundation of China
(52078125, U21A20150, 52293431), the Science Foundation for
Distinguished Young Scholars of Jiangsu Province (BK20220071), and
the Fundamental Research Funds for the Central Universities
(RF1028623199).
References
[1] J. Fricke, X. Lu, P. Wang, D. Büttner, U. Heinemann, Optimization of monolithic
silica aerogel insulants, Int. J. Heat Mass Transf. 35 (9) (1992) 2305–2309.
[2] O.-J. Lee, K.-H. Lee, T. Jin Yim, S. Young Kim, K.-P. Yoo, Determination of
mesopore size of aerogels from thermal conductivity measurements, J. Non Cryst.
Solids 298 (2-3) (2002) 287–292.
[3] S.Q. Zeng, A. Hunt, R. Greif, Transport-properties of gas in silica aerogel, J. Non
Cryst. Solids 186 (1995) 264–270.
[4] S.Q. Zeng, A. Hunt, R. Greif, Geometric structure and thermal conductivity of
porous medium silica aerogel, J. Heat Transfer-Trans. ASME 117 (4) (1995)
1055–1058.
[5] J.-J. Zhao, Y.-Y. Duan, X.-D. Wang, B.-X. Wang, Experimental and analytical
analyses of the thermal conductivities and high-temperature characteristics of
silica aerogels based on microstructures, J. Phys. D-Appl. Phys. 46 (1) (2013)
015304.
[6] Y. Chen, D. Li, X.-Q. Xie, Y. Gao, Y.-L. He, Theoretical modeling and experimental
validation for the effective thermal conductivity of moist silica aerogel, Int. J. Heat
Mass Transf. 147 (2020) 118842.
[7] J. Feng, M. Liu, S. Ma, J. Yang, W. Mo, X. Su, Micro-nano scale heat transfer
mechanisms for fumed silica based thermal insulating composite, Int. Commun.
Heat Mass Transfer 110 (2020) 104392.
[8] F.P. Soorbaghi, M. Kokabi, A.R. Bahramian, Predicting the effective thermal
conductivity of silica/clay mineral nanocomposite aerogels, Int. J. Heat Mass
Transf. 136 (2019) 899–910.
10
Materials & Design 233 (2023) 112281
[9] H. Zhang, Y. Tan, G. Wang, Y. Nan, L. Wang, Development of a numerical model to
calculate heat transfer in a cement-based material incorporated with expanded
perlite filled with aerogel, Int. J. Thermophys. 41 (10) (2020).
[10] G.S. Wei, X.X. Zhang, F. Yu, Effective thermal conductivity analysis of xonotlite-
aerogel composite insulation material, J. Therm. Sci. 18 (2) (2009) 142–149.
[11] G. Lu, X.-D. Wang, Y.-Y. Duan, X.-W. Li, Effects of non-ideal structures and high
temperatures on the insulation properties of aerogel-based composite materials,
J. Non Cryst. Solids 357 (22-23) (2011) 3822–3829.
[12] T. Xie, Y.L. He, Heat transfer characteristics of silica aerogel composite materials:
Structure reconstruction and numerical modeling, Int. J. Heat Mass Transf. 95
(2016) 621–635.
[13] M. Wang, N. Pan, Predictions of effective physical properties of complex
multiphase materials, Mater. Sci. Eng. R-Reports 63 (1) (2008) 1–30.
[14] H.-Q. Pang, T.-H. Fan, C.-Y. Zhu, T.-Y. Liu, Y.-F. Gao, Representation of the
characteristic temperature of correlative thermal conductivity of Opacifier-fiber
doped silica aerogel by steady-state method at large temperature differences, Int. J.
Thermophys. 43 (10) (2022).
[15] J. Czyzewski, A. Rybak, K. Gaska, R. Sekula, C. Kapusta, Modelling of effective
thermal conductivity of composites filled with core-shell fillers, Materials 13 (23)
(2020) 5480.
[16] T. Xie, Y. He, M. Wu, et al., Study on theoretical model for the effective thermal
conductivity of silica aerogel composite insulating materials, J. Eng. Thermophys.
35 (2) (2014) 299–304.
[17] F. He, Y. Wang, W. Zheng, J.-Y. Wu, Y.-H. Huang, Effective thermal conductivity
model of aerogel thermal insulation composite, Int. J. Therm. Sci. 179 (2022)
107654.
[18] Y. Fu, Z. Qu, L. Zhou, Prediction of the effective thermal conductivity of aerogel
nano-porous materials, Energy Procedia 105 (2017) 4769–4775.
[19] Z. Liu, Z. Zhang, S. Zhang, Y. Zhang, Z. Yuan, H. Li, J. Jiang, Microstructure and
performance characterization of thermal-insulating and water-resistive aerogel
incorporated cement-based materials, Cem. Concr. Compos. 130 (2022) 104535.
[20] Q. Gui, M.F. Qin, K.F. Li, Gas permeability and electrical conductivity of structural
concretes: impact of pore structure and pore saturation, Cem. Concr. Res. 89
(2016) 109–119.
[21] T. Yoshida, M. Kurimoto, Y. Manabe, et al., Particle porosity and relative
permittivity of epoxy/hollow silica nanocomposites, in: IEEE Conference on
Electrical Insulation and Dielectric Phenomenon (CEIDP), 2017, pp. 441–444.
[22] M.S. Meddah, S. Zitouni, S. Belaabes, Effect of content and particle size distribution
of coarse aggregate on the compressive strength of concrete, Constr. Build. Mater.
24 (4) (2010) 505–512.
[23] H.S. Yang, Y.J. Che, Influence of particle size distribution of fine and micro-
aggregate on the microstructure of cement mortar and paste, Mater. Res. Innov. 19
(2015) S130–S133.
[24] S. Liu, K. Zhu, S. Cui, X. Shen, G. Tan, A novel building material with low thermal
conductivity: Rapid synthesis of foam concrete reinforced silica aerogel and energy
performance simulation, Energ. Buildings 177 (2018) 385–393.
[25] D.P.H. Hasselman, L.F. Johnson, Effective thermal-conductivity of composites with
interfacial thermal barrier resistance, J. Compos. Mater. 21 (6) (1987) 508–515.
[26] C. Liu, R. Qian, Z. Liu, G. Liu, Y. Zhang, Multi-scale modelling of thermal
conductivity of phase change material/recycled cement paste incorporated
cement-based composite material, Mater. Des. 191 (2020) 108646.
[27] M.J.A. Qomi, F.J. Ulm, R.J.M. Pellenq, Physical origins of thermal properties of
cement paste, Phys. Rev. Appl 3 (6) (2015).
[28] J.K. Carson, S.J. Lovatt, D.J. Tanner, A.C. Cleland, Experimental measurements of
the effective thermal conductivity of a pseudo-porous food analogue over a range
of porosities and mean pore sizes, J. Food Eng. 63 (1) (2004) 87–95.
[29] F.M. Etzler, D.M. Fagundus, The extent of vicinal water - implications from the
density of water in silica pores, J. Colloid Interface Sci. 115 (2) (1987) 513–519.