Journal of Non-Crystalline Solids 552 (2021) 120457

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Journal of Non-Crystalline Solids

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

Domain structure, microscopic segregation and dynamics heterogeneity in T

alumina-silicate liquid
To Ba Vana,b, P.K. Hunga,b, L.T. Vinha,b, , N.V. Yenc, N.T.T. Had, L.T. Sand
⁎

a
Simulation in Materials Science Research Group, Advanced Institute of Materials Science, Ton Duc Thang University, Ho Chi Minh City, Viet Nam
b
Faculty of Electrical and Electronics Engineering, Ton Duc Thang University, Ho Chi Minh City, Viet Nam
c
Institute of Theoretical and Applied Research, Duy Tan University, Hanoi, 100000, Viet Nam
d
Department of Computational Physics, Hanoi University of Science and Technology, Viet Nam

ARTICLE INFO ABSTRACT

Keywords: We report molecular dynamics simulation for SiO2.Al2O3 liquid. The result shows that the system contains small
microscopic segregation TO-subnets (T is Si or Al) and two large ones consisting of 18 - 35% of total atoms. The average size of SiO-
domain structure subnets is larger than AlO-subnets, and T-O-T angle distribution is quite different for three O types. The mi-
dynamics heterogeneity croscopic segregation occurs with formation of three distinct domains, whose number density is 57, 67 and 69
alumina-silicate liquid
atom/nm3. Diffusion proceeds by collective movements without and with exchange of coordinated atoms. The
molecular dynamics
exchange of coordinated atoms gives the major contribution. During 300 ps, there are Si-rich and Al-rich regions,
where immobile and mobile O resides respectively. By examining atom's flow through a fixed cubic lattice we
find that the system contains immobile and mobile regions where the atom flow significantly differs from each
other. The dynamic heterogeneity is related to non-uniform spatial distribution of bond breaking-reforming.

1. INTRODUCTION
Amorphous and liquid silicates, a mixture of SiO2 with other oxides
such as Al2O3, CaO, MgO, Na2O, are of fundamental importance for
theoretical understanding of the glass transition and physical phe-
nomena that one encounters in multi-component melts [1,2,3]. For
instance, the motion of sodium through specific channels is thought to
cause very fast sodium mobility, and the existence of those channels is
reflected by a pre-peak around 0,95−1 Å−1 in static structure factor [4].
According to Angell's classification, silicate liquid is the strong type in
opposite to fragile liquids which depart from Arrhenius viscosity-tem-
perature relation [5]. Silicate in both liquid and glassy states comprises
a network of SiO4 tetrahedrons that are de-polymerized by forming
non-bridging oxygen (NBO) as the modifier oxides are added. The de-
gree of polymerization quantified via Qn species, where Q represents
SiO4 and n is the number of bridging oxygen (BO), dictates the viscosity
and transport property. It is shown that the viscosity of de-polymerized
melt increases with pressure, while the isothermal viscosity of poly-
merized melts shows anomalous pressure dependence [6,7].
Alumina-silicates have been intensively studied by both experi-
ments [8,9,10,11] and simulations [12,13,14,15,16,17,18]. Experi-
ments using different techniques such as NMR, IR and Raman spec-
troscopy, and X-ray scattering indicate that the chemical ordering of
aluminum is very complicated when built into the tetrahedral network
[19,20,21,22,23]. At low alumina concentrations, Al atoms are four-
fold coordinated, but these AlO4 are accompanied with oxygen tri-
clusters, the structural units where an oxygen is bonded with three T (T
is Si or Al). The existence of tri-clusters is confirmed by ab-initio mo-
lecular orbital calculation [12,13]. In contrast, the five-fold and six-fold
coordinated Al atoms are dominant in the system with high alumina
concentrations. It is suggested that AlO5 species dominated in high-
temperature liquids, transform into AlO4 and AlO6 species in glassy
state [21,23]. The study for silicate glasses up to 110 GPa [22] showed
that below 16 GPa the average T-O coordination number rapidly in-
creases from 4 to 6, and then at higher pressures the structural change
in Al-O coordination from 6 to larger than 6 occurs, where Al atoms
play an important role in densification process. Molecular dynamics
(MD) simulation has found the evidence for tri-clusters, micro-phase
separation and Al-rich network structure percolation through the tet-
rahedral Si-O network [17]. A strong correlation between the mean
square displacement and the exchange of coordinated atoms is found,
and the T-O bond breaking-reforming takes place non-uniformly in
network structure [18]. In accordance to previous studies, the local
environment around Al differs strongly from the one around Si. They
also show a strong distortion of SiO4 and the breakdown of inter-
mediate range order with increasing alumina concentration. However,

⁎
Corresponding author: Phone: 0084985554433
E-mail addresses: tobavan@tdtu.edu.vn (T.B. Van), lethevinh@tdtu.edu.vn (L.T. Vinh).

https://doi.org/10.1016/j.jnoncrysol.2020.120457
Received 19 March 2020; Received in revised form 22 September 2020; Accepted 24 September 2020
0022-3093/ © 2020 Elsevier B.V. All rights reserved.
T.B. Van, et al.
the relatively large scale fractures like the low-density, high-density
phase and microscopic segregation are not identified from those stu-
dies, although this has a specific meaning in the material science. Such
issue is one among the aims of present simulation which is performed
for the silicate liquid with high network modifier concentration.
Dynamics heterogeneity (DH) could be extracted from multi-point
and multi-time correlation functions, which allow to finding the spatial
correlation between particle displacements for a finite time interval
[24,25,26,27]. Unlike phenomenological approaches, the atomic si-
mulation provides full access to trajectory of atoms, and one can get
more details about the interplay between dynamics and local environ-
ment at atomic level in both space and time. The relationship between
DH and structure heterogeneity for silicate liquids, as far as we know,
remain poorly understood. These issues therefore stand in a focus of the
present work as well. Our calculation consists of several stages. Firstly,
we build a large SiO2.Al2O3 model. Then we map out T-O subnets and
three O types. Next, structural and dynamics characteristics such as the
Voronoi volume, T-O-T angle distribution and number of visited co-
ordinated atoms are calculated. Finally, the distribution of atoms
around nodes of a fixed cubic lattice and atom's flow through them are
determined. Our calculation is generic one and may be employed for
other silicate structures.
2. COMPUTATIONAL METHOD
MD simulation is done in a cubic box containing 1000 Si, 3500 O
and 1000 Al under periodic boundary conditions. We use our self-de-
veloped codes. The inter-atomic potentials of Born–Mayer type which
were successfully employed to simulate alumina silicate system (see e.g.
refs. [15,18,28,29]), are given as follows:
e2 r termine the number of atoms around each node. The atom is located
Uij (r ) = Zi Zj + Bij exp
r R (1)
with i, j = Al, Si, O. Here r is the interatomic distance and Zi, Zj are the
charges of ions: ZAl=3, ZSi=4 and ZO=-2. Other parameters of po-
tentials are: BAlAl=0 eV, BAlO=1779.86 eV, BOO=1500 eV, BSiSi=0 eV,
BSiO=1729.5 eV and R=29 nm. The Verlet algorithm is employed to
calculate the atom motion with time step of 0.5 fs. The Coulomb in-
teraction is taken into account using Ewald-Hansen method. Initially,
we have prepared a well annealed sample at 5000 K, and then cooled
down it to 3000 K at constant volume. The sample is additionally re-
laxed for 5 ns in the canonical ensemble (NVT). After that we performed
a long relaxation of about 30 ns in the micro-canonical ensemble (NVE)
at temperature and pressure close to 3000 K and zero GPa, respectively.
The obtained sample describes well the structure and dynamics of
alumina-silicate liquid. More details about procedure to make the
model of alumina silicate liquid can be found elsewhere [14,15]. To
collect the structural and dynamical data additional runs have been
done to produce 100 consecutive configurations separated by 10 ps.
In order to calculate structural units (TOx and OTy) the cutoff dis-
tance rcutoff is taken from the position of first minimum of partial pair-
correlation function, rcutoff = 2.6 Å for Si-O and Al-O pair. The T-O bond
is formed by T and O which stand from each other at the distance less
than rcutoff. All O are assorted into three types: OSA is connected with
both Si and Al by T-O bonds; OSS and OAA are connected respectively
with Si and Al atoms. Two types of TO-subnets are considered: i) SiO-
subnet consists of Si and OSS which are bonded with each other by Si-O
bonds, and ii) AlO-subnet comprises Al and OAA connected by Al-O
bonds. The size of TO-subnet is defined as the number of atoms be-
longing to it. Different types of O and TO-subnets are illustrated in
Fig. 1a. The smallest TO-subnet contains one T with coordinated atoms
OSA. Thus, the structure consists of separate TO-subnets and OSA located
in the boundaries between them.
Voronoi polyhedron has been calculated for every G atom (G-
polyhedron). Here G is either of Si, Al or O. To calculate polyhedron's
volume, a simple cubic lattice with m × m × m nodes and length lSB is
2
Journal of Non-Crystalline Solids 552 (2021) 120457
inserted in the simulation box, where lSB equals the size of simulation
box. The volume of G-polyhedron is given as VGP = mGVSB/m3, where
mG is the number of nodes which are closer to G than other nodes; VSB is
the volume of simulation box; VSB = lSB3. m is set to 220 and therefore
provides the high calculation accuracy. The volume of TO-subnet is
given as the sum of polyhedron's volumes for all atoms of this subnet.
Diffusion is mainly realized via T-O bond breaking-reforming
TOx TOx+ 1 and OTy OTy + 1 (2)
As the transformation (2) occurs, TOx and OTy exchange the co-
ordinated atoms. To evaluate the atom's mobility, we calculate the
number of visited coordinated atoms nvca during the observation time
tobs. As an example, Fig. 1b illustrates how to calculate nvca through four
consecutive configurations. Here the list of coordinated atoms changes
for different configurations. The configurations obtained from the si-
mulation are separated by 10 ps. The nvca characterizes the mobility of
given atom. To give more details about the dynamics, we specify two
sets of mobile and immobile O, and denote them to SMO and SIMO,
respectively. Each set contains 10% of total O, i.e. 350 O, and the time
tobs is set to 300 ps. SMO and SIMO consist of atoms which have re-
spectively smaller and larger nvca than the one of the rest O. We also
specify the third set of O (SRO) whose atoms are taken randomly from
the system. As we show below, because the rate of transformation (2)
for AlOx and OAly is significantly larger than that for SiOx and OSiy,
SIMO atoms are immobile and the majority of them are OSS and OSA. In
contrast, SMO atoms are mobile, and most of them are OAA and OSA.
The number <nvca> obtained by averaging nvca over all atoms of
SIMO, SMO and SRO equals 3.1, 73.38 and 37.29, respectively.
To give a view about spatial distribution of atoms, we insert another
cubic lattice with 10 × 10 × 10 nodes and length lSB. Then we de-
around a node if this node is closer to the given atom than other nodes.
Each node may be occupied or empty depending whether the atom is
located around it or not. Two nodes form a mutual linkage if they are
separated at the distance equal to the lattice constant. The node-cluster
consists of occupied nodes connected with each other by mutual lin-
kages as illustrated schematically in Fig. 2. The spatial distribution of
atoms is identified by the distributions of atoms around node and size of
node-cluster.
DH can be evaluated by examining the atom flow through nodes of a
fixed cubic lattice. To do this we insert a lattice with 12 × 12 × 12
nodes and length lSB, and then determine the list of atoms located
around each node during tobs. After that, we specify sets of immobile,
mobile and random nodes which are denoted to SIMN, SMN and SRN,
respectively. Each set contains 8% of total nodes. SMN, SIMN comprises
nodes whose navn is respectively larger and smaller than the one of the
rest nodes. Here navn is the number of atoms visiting the given node
during tobs. SRN nodes are taken randomly from the lattice.
3. RESULTS
3.1. Structure of SiO2.Al2O3 liquid and microscopic segregation
Firstly, we examine the ability of potentials (1) to reproduce the
structural data of experiment and ab-initio simulation
[29,30,31,32,33,34,35]. In general, the structural result obtained in our
simulation is close to the one from MD simulation [15] which, as shown
from studies [15,20], reproduces well the structure of alumina-silicate
liquid. Fig. 3 displays the partial and total pair-correlation functions.
For Si-O pair, the position of first peak takes the value of 1.58 Ǻ which
is well consistent with experimental value of 1.58–1.6 Ǻ [32], but un-
derestimates when compared to the result of ab-initio simulation [30].
The function gSiO(r) remains essentially zero between 2.2-2.46 Ǻ in-
dicating the strong covalent Si-O bond. For pairs Al-O and O-O the
position of first peak is located respectively at 1.66 and 2.64 Ǻ that
T.B. Van, et al.
Fig. 1. a) OSS, OSA, OAA, SiO-subnet and AlO-subnet; b) Coordinated atoms for O labeled 11 in four consecutive configurations. Here the list of visited coordinated
atoms includes 2 Si and 4 Al; nvca = 6.
slightly underestimate the data of ab-initio simulation [30]. The gAlO(r)
is lower and broader with non-zero values between first and second
peaks indicating that the covalent Al-O bond is weaker than Si-O one.
The total pair-correlation function is shown in Fig. 3b. Here the com-
parison of our result is made with MD simulation [29] and previously
measured liquid at similar compositions [20]. The function g(r) re-
produces well the shape and position of peaks, but its height over-
estimate. The adding of dipolar expansion in potentials (1) could give
better agreement with experimental g(r). We also compare the bond
angle distribution of our simulation. The peaks of O-Si-O, O-Al-O and
Si-O-Si angle distribution at 105o, 105o and 160o, respectively, are in
reasonable agreement with the data of ab-initio simulation (109° for O-
Si-O angle, 107.6° for O-Al-O angle) and experiment (106.7° for O-Al-O
angle, 151.4° for Si-O-Si angle). Overall, the chosen potential provides a
small inconsistence for the pair-correlation function and bond angles,
however this does not affect our major simulation results and conclu-
sions
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Journal of Non-Crystalline Solids 552 (2021) 120457
The fraction of structural units and three O types are listed in
Table 1. Among the range of coordinated atoms, SiO4 and AlO4 are
dominant (about 96% of total Si and 59% of total Al, respectively). The
fact that the fraction of OT2 remains relatively large but is markedly less
than the unit indicating the modified tetrahedral structure of liquid. We
also find a number of tri-clusters, and the fraction Cx = nOX/nO de-
creases in the order: SA → SS → AA. Probably, this trend takes place
due to much stronger Si-O bond compared to Al-O bond, and implies
that SiO2 do not fully mix with Al2O3. The T-O-T angle distributions
shown in Fig. 4 are characteristic of the link between TOx units. The
graph is quite different for three O types. In particular, the graph for OSS
has a sharp peak at 160o indicating that Si forms the corner-sharing
tetrahedral network. Meanwhile, the distribution for OSA and OAA is
more complex, for instance, the distribution for OSA possesses a
shoulder around 91o and a pronounced peak at 1530. According to
previous studies [3,36,37], the oxygen tri-clusters occupying con-
siderable quantities are mainly composed of O (Al, Al, Al) and O (Al, Al,
T.B. Van, et al. Journal of Non-Crystalline Solids 552 (2021) 120457

Fig. 2. Two-dimension lattice schematically illustrating the

spatial distribution of atoms. Here the total number of atoms
and nodes is 20 and 64, respectively, and the number of oc-
cupied and empty nodes is 12 and 52, respectively. There are
five single-node clusters and two large clusters including one
3-node and one 4-node cluster. The number of atoms around
node varies from 0 to 5.

Table 1
Fraction of structural units and three O types. Here CSiOx = nSiOx/nSi;
CAlOx = nAlOx/nAl; COTy = nOTy/nO; x and y are the number of coordinated O
and cation, respectively; CX = nOX/nO; nSiOx, nAlOx, nOTy and nOX are the number
of SiOx, AlOx, OTy and OX, respectively; nSi, nAl and nO are the total number of
Si, Al and O, respectively; OX is either OSS, OSA or OAA.
X CSiOx CAlOx y COTy X CX

3 0.0013 0.3076 2 0.7707 SA 0.4800

4 0.9642 0.5921 3 0.2216 SS 0.3283
5 0.0338 0.0949 4 0.0076 AA 0.1917
6 0 0.0046 - - - -

Fig. 4. T-O-T angle distribution for three O types.

Si). The tri-clusters can be treated as a corner shared by three tetra-

hedrons, two of which, mostly both AlOx have a certain probability to
share an edge (O-O). These results are consistent with the fact that the
shoulder, and the pre-peak at 91o (see Fig. 4) are related to the dis-
tortion of tetrahedrons and other structure features such as the edge-
Fig. 3. a) Partial pair-correlation function; b) Total pair-correlation function.
sharing tetrahedrons and tri-clusters composed of O (Al, Al, Si).
The result of present study is compared with experimental data of Wilding et al
Characteristic of TO-subnets in Table 2 are obtained by averaging
[20] and MD simulation of Bouhadja et al [29].
over 31 consecutive configurations separated by 10 ps. The system
contains small TO-subnets having less than 158 atoms and two very

4
T.B. Van, et al. Journal of Non-Crystalline Solids 552 (2021) 120457

Table 2 densities and chemical compositions: the high-density domains include

Characteristics of TO-subnets. Here sSS is the size's range of SiO-subnet; <nSS> the silica and alumina domain, while the low-density domain is the
is the average number of SiO-subnets; CSiz = nSiz/nTSLS; z is the number of O; mixed domain. The existence of high-density domains indicates that
nSiz is the number of Si bonded with z O atoms, and nTSLS is the total number of SiO2 and Al2O3 do not mix fully to forming the homogeneous structure.
Si in largest SiO-subnet; CAz = nAlz/nTALS; in the same notation manner the
Fig. 6 presents the volume distribution for G-polyhedrons, and also
corresponding quantities for AlO-subnet are sAS, <nAS>, nAlz and nTALS.
the distribution of atoms around node of a fixed lattice with 1000
sSS <nSS> sAS <nAS> z CSiz CAlz nodes. As seen, the volume distribution for O-polyhedrons is much
broader in comparison with other type polyhedrons, and their volume
1-10 68.82 1-10 170.37 1 0.1639 0.2710
11-17 1.73 11-20 4.36 2 0.3380 0.3945
in average is significantly larger than the one of Si-polyhedrons and Al-
1975-2046 1 21-100 2.73 3 0.3456 0.2463 polyhedrons. This turns out that the silica, alumina domain containing
- - 101-158 0.82 4 0.1526 0.0763 respectively a large number of Si and Al might occupy the dense region.
- - 880-1366 1 5 0 0.0116 In contrast, the mixed domain, most atoms of which are OSA, resides in
- - - - 6 0 0.0003
the loose region. The number of LSS and LAS atoms around a node
varies up to 11 (see Fig. 6b), and the number of nodes, around which
not any atoms of those subnets are found, represents respectively about
large ones: the size of AlO-subnet and SiO-subnet is about 18 and 35%
32 and 60% of total nodes. So the alumina and silica domains do not
of total number of atoms, respectively. Moreover, Si and Al atoms are
distribute uniformly through the simulation box, instead they spread
very differently embedded into the network structure. Namely, total
over the relatively small sub-volume of simulation box. On the other
number of SiO-subnets is significantly smaller than AlO-subnets. The
hands, the distribution for LSS also differs strongly from the one for LAS
average size of the largest SiO-subnet (LSS) is about two times larger
indicating that the number density as well as local atom's arrangement
than that of largest AlO-subnet (LAS). About 68% of Si atoms in LSS are
is different for alumina and silica domains. Overall, we can conclude
bonded with 2 or 3 OSS, while Al atoms bonded with 1 or 2 OAA are
that the structure of the liquid is strongly heterogeneous with separate
dominant in LAS (CAlz = 0.2710 and 0.3945). Because the polyhedrons
silica and alumina domains which have different local atom's arrange-
for atoms of LSS as well as LAS occupy a percolated region, the system
ment and reside in dense regions. Meanwhile the mixed domain occu-
possesses three separate domains: the alumina domain consists of G-
pies the loose region.
polyhedrons of LAS, the silica domain consists of G-polyhedrons of LSS
and the mixed domain comprises G-polyhedrons of small TO-subnets
and OSA-polyhedrons. 3.2. Diffusion mechanism and dynamics heterogeneity
Fig. 5 shows the time dependence of volume's fraction and number
density of domains which equals the ratio between the number of atoms As the transformation (2) occurs, one T-O bond is broken and a new
in the domain and volume of the domain. The volume's fraction for one is formed. Consequently, the coordinated atoms are exchanged
silica domain varies slightly around 0.34, while the same for the alu- between structural units. Thus, the number of unbroken T-O bonds and
mina domain changes strongly around 0.17. This trend is related with number of visited coordinated atoms nvca are important characteristics
the fact that the chemical composition and size of LAS fluctuate largely for dynamics in the liquid. As seen in Fig. 7, a much faster decrease of
with time due to much larger rate of AlOx ↔ AlOx+1 compared to SiOx unbroken Al-O bonds compared to Si-O bonds indicates the relative
↔ SiOx+1. The average number density in the silica, alumina domains strong Si-O bond versus the weak Al-O bond. Also the rate of Al-O bond
is found to be respectively 69 and 67 atom/nm3, and the one for mixed breaking-reforming is significantly higher than the one of Si-O bond.
domain equals 57.5 atom/nm3 that is slightly smaller than the average The mean square displacement (MSD) per atom monotonously in-
number density of the system (62 atom/nm3). We note that the che- creases against the number of visited coordinated atoms nvca. This
mical composition of the mixed domain is close to the one of the means that the exchange of coordinated atoms accompanied with the
system. Therefore, the microscopic segregation occurs in the liquid transformation (2) gives the major contribution for diffusion.
reflecting in coexistence of three separate domains with different Table 3 summarizes MSD for different type atoms. All atoms are

Fig. 5. The number density (a) and volume fraction VD/VSB (b) as a function of time. Here VD and VSB are the volume of domain and total volume of simulation box,
respectively.

5
T.B. Van, et al.
Fig. 6. a) The volume distribution for Si-polyhedrons, O-polyhedrons and Al-
polyhedrons; b) The fraction of nodes versus the number of atoms around node.
Fig. 7. Fraction of unbroken T-O bonds (left) and MSD per atom versus nvca (right) as a function of time. Here MSD and nvca are determined for 300 ps.
6
Journal of Non-Crystalline Solids 552 (2021) 120457
Table 3
MSD per atom for 10 ps. Here nI and nT are the number of first type atoms and
total atoms, respectively; <xI2> and <xII2> are the MSD for the first and the
second type atoms, respectively; <xT2> is the MSD for all atoms.
nI/nT <xI2> <xII2> <xT2>
Si 0.7143 1.5713 5.2326 2.6174
O 0.5134 1.9835 11.0094 6.3756
Al 0.1101 1.7880 11.1036 10.0776
sorted into two types. The number of visited coordinated atoms for the
first type is unchanged after 10 ps, while the one for the second type
increases. We observe that MSD for the second type atoms is sig-
nificantly larger than the one for the first type atoms, and MSD of the
first type atoms for Si, O and Al is close to each other. This again
confirms the fact that the transformation (2) gives the major con-
tribution to the diffusion. On the other hand, as <xT2> increases in the
order Si → O → Al, the diffusivity of Si is chiefly smaller than the one of
O and Al. The slowest diffusivity for Si is due to two factors: the fraction
nI/nT is larger and <xII2> is significantly smaller than those for O and
Al. This result follows that the diffusion is realized by two parallel
processes. On the one hand, the atoms move collectively without ex-
change of coordinated atoms and make small displacements. On the
other hand, they exchange the coordinated atoms via T-O bond
breaking-reforming and displace by large distances.
Fig. 8a presents the distribution of O around nodes for SMO, SIMO
and SRO. In general, the graph for SMO, SIMO strongly differs from that
for SRO. The number of SRO atoms around node is less than 4, while the
number of SMO, SIMO atoms around node varies in the range up to 6.
This result indicates that unlike SRO atoms which are uniformly dis-
tributed through the lattice, SMO and SIMO atoms tend to gather
around smaller number of nodes. Since all O atoms move from one to
other nodes, the atoms of specified sets will visit more nodes as the time
proceeds (see Fig. 9). The fraction of occupied nodes nON/nTN is shown
in Fig. 8b. SRO atoms spreads over whole lattice so fast that nON/nTN
practically reaches 1.0 after 500 ps. In contrast, nON/nTN for SIMO and
SMO approaches respectively to 0.347 and 0.735 indicating that the
atoms of those sets move not through whole volume, but only a sub-
volume of the model. In Fig. 8b we also plot nON/nTN for SIMO-SMO
nodes. The nON/nTN for SIMO-SMO nodes increases up to 0.15 which is
significantly smaller than the one for SIMO and SMO nodes. Therefore,
during the time tobs the system contains separate micro-regions where
T.B. Van, et al.
Fig. 8. a) Fraction of nodes versus number of atoms around node; b) Fraction of
occupied nodes nON/nTN as a function of time. Here nON is the number of nodes
which the specified atoms visit during the given time; nTN is the total number of
nodes; SIMO, SMO and SRO node denotes the one around which the atoms of
corresponding set reside; SIMO-SMO node denotes to the one around which
both SIMO and SMO atoms reside.
either SIMO or SMO atoms reside. The spatial distribution for SIMO and
SMO atoms can be described as illustrated in Fig. 9. The picture shows
separate node-clusters consisting of SIMO-SMO, SIMO* and SMO*
nodes for short and long time. We note that SIMO atoms mostly are OSS
and OSA. Therefore, the region containing SIMO* nodes, represents the
Si-rich region. Meanwhile, the majority of SMO atoms are OAA and OSA,
and the region containing SMO* nodes, represents the Al-rich region.
Thus, the system consists of separate Si-rich and Al-rich regions where
either immobile or mobile O atoms gather during the time tobs. The
transformation (2) happens in Al-rich region more frequently than in Si-
rich regions, i.e. the T-O bond breaking-reforming happen non-uni-
formly in the space. The liquid therefore exhibits the dynamics and
chemical heterogeneity.
The characteristics and size distribution of node-clusters for SMN,
SIMN and SRN are shown in Table 4. Obviously, the larger the number
of atoms visiting the node navn, the larger the atom's flow through the
given node is. This means that the node-clusters for SIMN and SMN
occupy the immobile and mobile region, respectively. As seen from
Table 4, SRN nodes form 105 node-clusters with the size less than 11,
7
Journal of Non-Crystalline Solids 552 (2021) 120457
while the majority of SIMN and SMN nodes gather in a node-cluster
with the size from 96 to 106. Consequently, SMN and SIMN nodes are
not uniformly distributed through the lattice, instead they tend to
gather into large node-clusters. We note that the size of the largest
node-cluster for SMN and SIMN is 5.5 and 6.1% of total nodes, re-
spectively, and the average number of atoms visiting SMN nodes is by 7
times larger than the ones visiting SIMN nodes. Therefore, the dynamics
is remarkably cooperative and heterogeneous so that the system con-
tains two separate regions, where the average atom flow is quite dif-
ferent for those regions during the time tobs.
4. CONCLUSION
Our simulation indicates that at 3000 K and ambient pressure the
SiO2.Al2O3 liquid possesses a modified network structure comprising
small TO-subnets and two large ones which contain 18 and 35% of the
total number of atoms. The volume of O-polyhedron in average is sig-
nificantly larger than the one of Al-polyhedron and Si-polyhedron. Si
and Al are very differently built in the network structure, namely: i) The
average size of SiO-subnets and fraction of OSS is significantly larger
than the one of AlO-subnets and OAA, respectively; and ii) T-O-T angle
distribution is quite different for OSS, OSA and OAA. The simulation re-
veals the microscopic segregation with formation of two high-density
domains (the silica and alumina domain) and a low-density domain (the
mixed domains). The silica domain consists of G-polyhedrons of the
largest SiO-subnet, and the alumina domain consists of G-polyhedrons
of the largest AlO-subnet. The mixed domain comprises OSA-poly-
hedrons and G-polyhedrons of small TO-subnets. The volume fraction
for silica, alumina and mixed domains equals 0.34, 0.17 and 0.49, re-
spectively, and the number density in those domains is found to be 69,
67 and 57.5 atom/nm3, respectively. Moreover, the number density and
chemical composition of the mixed domain is close to those of whole
system.
Diffusion is found to proceed by two parallel processes. On the one
hand, the atoms move collectively without exchange of coordinated
atoms. On the other hand, they exchange coordinated atoms via T-O
bond breaking-reforming and displace over large distances. The second
process gives the essential contribution to the diffusion. The rate of Al-O
bond breaking-reforming is significantly larger than that of Si-O bond,
and the breaking-reforming events are distributed non-uniformly
through the network structure. Further insight into dynamics is gained
by calculating the distribution of immobile and mobile O around nodes
of a fixed lattice. We find that the mobile and immobile O atoms are
non-uniformly distributed in the space. They reside respectively in se-
parate Al-rich and Si-rich regions. By calculating the flow of atoms
through nodes of the fixed lattice during 300 ps, the simulation reveals
that the system contains two separate large regions where the average
flow of atoms in immobile region is about 7 times smaller than the one
in mobile region. We also find that the liquid exhibits the chemical and
dynamics heterogeneity which is directly related to non-uniform spatial
distribution of T-O bond breaking-reforming.
5. CRediT author statement
P. K. Hung and N.V.Yen conducted the models; To Ba Van,
P.K.Hung, L.T.Vinh, N.T.T.Ha, L.T. San analyzed data. P.K.Hung, To Ba
Van and L.T.Vinh writing- reviewing and editing the manuscript. All
authors discussed the results and contributed to the final manuscript.
Declaration of Competing Interest
I, the Corresponding Author, confirm that there are no known
conflicts of interest associated with this publication and there has been
no significant financial support for this work that could have influenced
its outcome.
T.B. Van, et al. Journal of Non-Crystalline Solids 552 (2021) 120457

Fig. 9. Two-dimensional lattice illus-

trating the distribution of SIMO and
SMO atoms around nodes of the lattice
for short time (a) and long time (b).
Here SIMO* and SMO* node denote the
node where only SIMO or SMO atoms
reside respectively, SIMO-SMO node is
the node around which both SIMO and
SMO atoms reside. For short time a
number of nodes are not visited by
SIMO as well as SMO atoms (non-oc-
cupied node). In the case of long time
the number of non-occupied nodes de-
creases, while in contrast the number
of SIMO-SMO nodes increases. For the
long time the system still contains se-
parate node-clusters of SIMO* or SMO*
nodes, i.e. micro-regions containing
only the SIMO* nodes (Si-rich regions)
or the SMO* nodes (Al-rich regions).

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