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Viscosity and structure of CaO–Al2O3–TiO2-based

mold fluxes with various CaO/Al2O3 mass ratios

Zhanlong Piao, Kai Zeng, Yan Wang, Caijun Zhang, Ming Gao & Yang Liu

To cite this article: Zhanlong Piao, Kai Zeng, Yan Wang, Caijun Zhang, Ming Gao & Yang Liu
(2023) Viscosity and structure of CaO–Al2O3–TiO2-based mold fluxes with various CaO/Al2O3
mass ratios, Ironmaking & Steelmaking, 50:7, 828-836, DOI: 10.1080/03019233.2023.2214404

To link to this article: https://doi.org/10.1080/03019233.2023.2214404

Published online: 23 May 2023.

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IRONMAKING & STEELMAKING
2023, VOL. 50, NO. 7, 828–836
https://doi.org/10.1080/03019233.2023.2214404

RESEARCH ARTICLE

Viscosity and structure of CaO–Al2O3–TiO2-based mold fluxes with various

CaO/Al2O3 mass ratios
Zhanlong Piaoa, Kai Zenga, Yan Wanga, Caijun Zhanga, Ming Gaob and Yang Liuc
a
Hebei High Quality Steel Continuous Casting Engineering Technology Research Center, College of Metallurgy and Energy, North China
University of Science and Technology, Tangshan, People’s Republic of China; bState Key Laboratory of Advanced Technology for Iron and Steel
Metallurgy, University of Science and Technology Beijing, Beijing, People’s Republic of China; cPeople’s Republic of China Metallurgical Testing
Certification Co., Ltd., Beijing, People’s Republic of China

ABSTRACT ARTICLE HISTORY

The effects of CaO/Al2O3 mass ratio on the viscosity and structure of new CaO–Al2O3–TiO2-based Received 27 February 2023
fluorine-free mold fluxes for high titanium steel are investigated by viscometer, molecular Revised 9 May 2023
dynamics (MD) simulations and Raman spectroscopy. When the CaO/Al2O3 mass ratio increased Accepted 10 May 2023
from 0.6 to 1.4, the viscosities and activation energies reduced from 0.43 to 0.10 Pa·s and 127.8–
KEYWORDS
74.2 kJ·mol−1, respectively. While the break temperatures raised from 1385 to 1507 K. Moreover, Fluorine-free mold fluxes;
according to MD simulation results, the concentration of high coordination of Al–O and Ti–O high titanium steel; CaO/
bonds decreased, and the complex structure units of Q3, Q4 and Q5 turned to the simple structure Al2O3; molecular dynamics;
units of Q0, Q1 and Q2. Raman spectra suggested that the concentrations of Ti–O–Ti(Al) linkage viscosity; structure; break
and Q2(Si-O−) decreased significantly, but the concentration of Q1(Si–O−) increased. Therefore, temperature; activation
CaO/Al2O3 could simplify the network structure and decrease the viscosity of new CaO–Al2O3– energy
TiO2-based fluorine-free mold fluxes for high titanium steel.

Introduction deteriorates the lubrication of mold flux [10]. Meanwhile, vis-

cosity is a very important physicochemical property related
Recently, high titanium steel has received increasing atten-
to the fluidity of mold flux. If the viscosity is sharply increased,
tion in the fields of automobiles, ships, bridge and building
the infiltration of liquid slag is hindered; the low level of lubri-
engineering because of its corrosion resistance, abrasive
cation and heat transfer results in quality degradation of the
resistance, oxidation resistance, and nitrogen fixation [1–4].
casting blank surface [11]. The improvement in the above
However, the slag-metal reaction in the casting process, [Ti]
macroscopic properties are usually achieved by controlling
+ (SiO2) = [Si] + (TiO2), consumes SiO2 and increases the con-
the melt structure of the mold flux.
centration of TiO2 in the mold flux. Such composition
There have been several studies in recent years. Wang et al.
changes modify the physicochemical properties of the mold
suggested that CaO/Al2O3 decreased the viscosity of CaO–
flux, such as melting temperature, viscosity and crystallization
Al2O3-based mold flux, leading to a depolymerised structure
properties, and limit the lubrication and heat transfer. The
[12]. Moreover, a similar trend was found in CaO–BaO–
quality of the casting blank deteriorated, eventually leading
Al2O3–CaF2–Li2O slags, CaO–Al2O3–B2O3-based slags and
to breakout phenomena [5, 6]. The slag-metal reaction is an
Al2O3–Cr2O3–CaO–CaF2 slags [13–15]. However, Wang et al.
important restrictive step in the smelting process, which
reported that the viscosity of CaO–Al2O3-based fluoride-free
reduces the production efficiency of high titanium steel.
mold flux was decreased and then increased with the increas-
Therefore, how to inhibit the slag-metal reaction is particu-
ing CaO/Al2O3 ratio [16]. And Zhang et al. found a similar trend
larly important. Obviously, the traditional CaO–SiO2 slag
in CaO–Al2O3–MgO slag. Clearly, CaO/Al2O3 mass ratio has
system does not meet this requirement, and CaO–Al2O3
different impacts in various slag systems [17]. Thus, it is
slag system, aiming at high Al steel, can effectively reduce
urgent to clarify the role of CaO/Al2O3 in CaO–Al2O3–TiO2-
the extent of the slag-metal reaction [7, 8]. However, the
based mold flux about the viscosity and structure.
slag-metal reaction obviously happens in the casting
In the present work, the rheology properties of mold fluxes
process of high titanium steel, because the content of the
were tested by viscometer, the structural role of CaO/Al2O3
resultant TiO2 is zero in CaO–Al2O3 slag system.
was analysed by the MD simulations (SCIGRESS software)
The new CaO–Al2O3–TiO2-based fluorine-free mold flux has
and Raman spectroscopy. This paper provide a research foun-
been proposed for the first time to inhibit the slag-metal reac-
dation for developing a new CaO–Al2O3–TiO2-based fluorine-
tion by adding the resultant TiO2 and reducing the reactant
free mold flux.
SiO2. The slag-metal reaction is successfully inhibited, stabilis-
ing the physicochemical properties of mold flux in the casting
process [5]. However, the CaO–Al2O3-based mold flux has Materials and methods
some unfavourable properties, such as strong crystallization
Sample preparation
and poor lubrication [9]. Besides, TiO2 is added to the
fluorine-free CaO–Al2O3–TiO2-based mold flux as amphoteric The chemical compositions of samples were analysed by an
oxide, which further increases the crystallization and X-ray fluoroscope(XRF) and the results are listed in Table 1.

CONTACT Caijun Zhang zhangcaijun@ncst.edu.cn Hebei High Quality Steel Continuous Casting Engineering Technology Research Center, College of
Metallurgy and Energy, North China University of Science and Technology, Tangshan 063000, People’s Republic of China
© 2023 Institute of Materials, Minerals and Mining
 IRONMAKING & STEELMAKING 829

Table 1. The chemical composition of mold fluxes.

Wt(%)
Sample CaO/Al2O3 CaO Al2O3 TiO2 BaO SiO2 MgO B2O3 Li2O Na2O
A 0.6 17.2 28.8 11.5 10.6 5.7 2.1 9.8 4 10.3
B 1.0 23.4 23.1 11.7 10.3 6.1 1.8 10 4 9.5
C 1.4 26.9 19.1 12.2 9.6 6.1 1.9 10.3 4 9.9

The samples were composed of reagent grade chemicals Table 2. Parameters of BMH potentials.
CaO, SiO2, TiO2, MgO, Al2O3, Li2CO3, Na2CO3, BaO and B2O3, Atom1 Atom2 Aij Bij
and Li2O and Na2O were come from Li2CO3 and Na2CO3, O O 2.40e-20 5.88
respectively. These mixtures were mechanically blended in O Al 1.38e-21 6.06
O Ti 3.89e-21 6.06
a ball crusher for 2 h, followed by heating in an induction O Ba 1.35e-19 6.06
furnace (heating rate: 25°C/min), when the temperature O Ca 1.15e-20 6.06
reached at 1400°C, and maintained for 10 min in order to Al Al 6.64e-23 6.25
Al Ti 1.93e-22 6.25
be homogenise. Subsequently, the fully glassy phase of Al Ca 5.92e-22 6.25
mold fluxes were from the molten samples which were Al Ba 7.48e-21 6.25
poured into water. Finally, they were crushed and ground Ti Ti 5.63e-22 6.25
Ti Ca 1.72e-21 6.25
into powders. The X-ray diffraction(XRD) was used to identify Ti Ba 2.18e-20 6.25
the mineralogical phase of samples, and, the experiments Ca Ca 5.27e-21 6.25
were measured for three times to guarantee its reproducibil- Ca Ba 6.67e-20 6.25
Ba Ba 8.44e-19 6.25
ity. There are no characteristic diffraction peaks in Figure 1,
suggesting their fully amorphous structure. These quenched
samples were used for further structural analysis.
Poland) [18]. The choice of potential function is a key, two-
body Born–Mayer-Huggins (BMH) is widely applied in the
Viscosity measurements MD simulation process for melt [19–21]. The BMH potential
function is shown in Equation (1) [22].
qi qj
The viscosity of mold fluxes were measured by viscometer, where the Uij (r) is the interatomic pair potential; is the
and the rotational speed was 12 rpm. The MoSi2 furnace rij
long-range Coulomb potential, qi and qj are the selected
was heated to 1400°C at 10°C/min, meanwhile, the graphite
charges of atoms i and j, respectively; rij is the distance
crucible with a 300 g mold flux was placed into the furnace,
whose size is w 56 mm × 80 mm. In order to obtain the homo- between atoms i and ions j; Aij exp (−Bij r) is the short-range
Cij
geneous liquid slag, the holding time was 10 min when the repulsion interactions; 6 is the van der Waals forces, which
temperature was 1400°C. And when the MoSi2 furnace was rij
cooled to 1300°C at 5°C/min, the viscosity was tested for is insignificant effect without consideration. The relevant par-
three times, which is the average value. Subsequently, the vis- ameters are listed in Table 2.
cosity was always tested when the MoSi2 furnace was still In the condition of BMH potential functions, the melts
cooled at the same cooling rate. Thus, the relationship of vis- must be the liquid phase in the calculation process. NVT
cosity and temperature was achieved. ensemble was employed in this system, and the number of
particles (N), sample volume (V), and temperature (T) was
constants. The leapfrog algorithm was applied in the calcu-
Molecular dynamic simulation lation process of atoms motion, wherein the time step was
set to 1 fs (10−15 s). The number of atoms was 6000 in this
The role of CaO/Al2O3 in the CaO–Al2O3–TiO2 slag system is
system, which was randomly put into the ‘box’ with the per-
analysed by Scigress software (FQS Poland Sp.z.o.o, Kraków,
iodic boundary conditions. Basides, the volume could be

Figure 1. XRD results of the samples. Figure 2. Temperature control programme.

830 Z. PIAO ET AL.

Table 3. Composition, atomic numbers, density and length of samples at 1673 K.

Content(wt-%) Atomic number
Sample CaO Al2O3 TiO2 BaO Ca Al Ti Ba O Total Length (Å) Density (g/cm3)
A 29 49 12 10 761 1412 220 96 3511 6000 42.496 3.213
B 39 39 12 10 1058 1161 228 99 3454 6000 42.995 3.225
C 36.5 36.5 12 10 1278 976 233 102 3411 6000 43.378 3.2

calculated by the atomic number and the density. Figure 2
shows the temperature control programme in the simulation
process, and the parameters information of composition,
atomic numbers, etc are listed in Table 3.
Raman spectroscopy measurements
The role of CaO/Al2O3 in the structure of this system was ana-
lysed by the micro-Raman spectrometer (LabRAM HR Evol-
ution, HORIBA Jobin Yvon, France) at room temperature.
The as-quenched samples were tested in the frequency
band range of 200–1600 cm−1 with the excitation wave-
length was 532 nm. The PeakFit v4 software with Gaussian
function was applied to fit the Raman spectra.
Results and discussion
The viscosity
The measured viscosities of the CaO–Al2O3–TiO2 slag system
with different CaO/Al2O3 mass ratios were listed in Table 4. It
is obviously that the viscosity decreased from 0.43 to 0.10 Pa·s
with CaO/Al2O3 mass ratio increased, which suggested that
CaO/Al2O3 contributed to abate the viscosity of CaO–Al2O3–
TiO2 slag system.
as shown in Equation (3).
Ea
ln h = ln h0 + (3)
RT
Ea can be obtained by the slope of Equation (3), and
the functions were fitted with the least square
method. These results were shown in Figure 3 and
Table 4.
Figure 3 showed that ln h had a linear relationship with 1/T
in all three samples, indicating their Newtonian flow beha-
viours at high temperatures [24]. In addition, when the
CaO/Al2O3 mass ratio increased, the slopes of relational
expression decreased, i.e. the activation energies decreased
(Table 4), demonstrating that the minimum energy barrier
was reduced with the increasing CaO/Al2O3 mass ratio and
sample viscosity.
The break temperature (Tbr) corresponds to the tempera-
ture that the viscosity increases abruptly in the cooling
process. Moreover, Tbr could reflect the flow situation of the
liquid slag film where in the gaps between the shell and
mold wall [25], and evaluate the lubrication effect of mold
flux. As shown in Figure 4 and Table 4, the Tbr of sample C
is 1507 K, which is the highest among samples. It is obviously
that Tbr increased with CaO/Al2O3 mass ratio, implying that
CaO/Al2O3 contributed to improve the precipitation of
crystallization.

The activation energy and break temperature Partial radial-distribution functions (RDFs) and
coordination numbers (CNs)
Once the frictional resistance between each flow unit was
overcome, the liquid slag will stream. The minimum resist- The effect of CaO/Al2O3 mass ratios on the structure of CaO–
ance is the energy barrier of one equilibrium position Al2O3–TiO2 slag system was analysed by the Scigress soft-
moved to another equilibrium position, namely the activation ware. The partial RDFs was obtained in the simulation
energy. The activation energy could reflect the degree of process, which could provide some structural information,
difficult and easy of the fluid flow, which was closely such as average bond length, the existence probability and
related to the viscosity. Ordinarily, the activation energy stability of the atoms, etc. The equation of partial RDFs is
could be calculated by the Arrhenius equation [23], as
shown in Equation (2).


Eh
h = Aexp (2)
RT
Where η, A, T, R and Eη represent the viscosity(Pa·s), the pre-
exponent factor, the absolute temperature (K), the gas con-
stant (8.314 J·mol−1·K−1), and the activation energy
(J·mol−1), respectively. The Equation (2) was taken logarithmic

Table 4. Viscosity, functions, activation energies and break temperature of

samples.
Viscosity Ea Tbr
Sample (Pa·s) Function R2 (kJ·mol−1) (K)
A 0.43 Lnη = −10.57 + 0.99 127.8 1385
15373/T
B 0.28 Lnη = −8.68 + 0.99 97.8 1437
11762/T
C 0.10 Lnη = −7.84 + 8929/ 0.99 74.2 1507
T
Figure 3. Relationship between ln η and 1/T.
 IRONMAKING & STEELMAKING 831

 
Dr Dr
nij r − , r + is the number of atom j surrounding
2 2
 
Dr Dr
atom i within the specified distance r − , r + .
2 2
The average CNs could describe the coordination numbers
of structural units, which is achieved by numerical integration
of the partial RDFs within the cutoff radius, and the cutoff
radius is the first valley corresponding to the abscissa
values in the RDFs curves, the equation of CNs is expressed
as followed [28].

4pNj r 2
Nij (r) = r gij (r)dr (5)
V
0

The Al–O, Ti–O, Ba–O, and Ca–O in melts with different

CaO/Al2O3 mass ratios (0.6–1.4) of RDFs curves are shown
Figure 4. Viscosity-temperature curves for different CaO/Al2O3 mass ratios.
in Figure 5. The average bond length of atomic pairs is
the first peak corresponding to the abscissa values in the
expressed as followed [26, 27]. RDFs curves, and the ordinate values with the first peak is
the existence probability of the atom in the RDFs curves,
  namely, gij (r). If the gij (r) is bigger, the existence probability
Dr Dr
, nij r− ,r+ .
V  2 2 of atom j is greater within the range where the distance
gij (r) = (4) from the atom i is r. The average bond length of Al–O
Ni Nj j 4pr2 Dr
and Ca–O are 1.75 and 2.25 Å, respectively, which is consist-
ent with the findings of others [29, 30]. The gAl−O (r) and
wherein, V is the volume of simulated box; Ni and Nj are the gCa−O (r) increase with increasing CaO/Al2O3 mass ratio,
numbers of atoms i and j, respectively, and suggesting that the existence probability of atom O

Figure 5. RDFs of (a) Al–O, (b) Ti–O, (c) Ba–O, and (d) Ca–O in melts with different CaO/Al2O3 mass ratios.
832 Z. PIAO ET AL.
Figure 6. CNs of (a) Al–O, (b) Ti–O, (c) Ba–O, and (d) Ca–O in melts with different CaO/Al2O3 mass ratios.
around Al and Ca is improved. The average bond length
between Ti–O and Ba–O are 1.95 and 2.65 Å, which
agrees with the results in previous studies [31, 32]. The
gTi−O (r) and gBa−O (r) increase when the CaO/Al2O3 mass
ratio increases from 0.6 to 1.0, and suddenly decrease
when the mass ratio changes from 1.0 to 1.4. It suggests
that the existence probability of atom O around Ti and Ba
increase first then decrease. In addition, the order of the
Figure 7. CNs distributions of (a) Al–O and (b) Ti–O in the melts.
average bond length is Ba–O > Ca–O > Ti–O > Al–O,
suggesting that Ba–O is the most unstable, and Al–O is
the most stable. Moreover, the order of gi−O (r)(i = Al, Ti,
Ba, Ca) values is Al–O > Ti-O > Ca-O > Ba-O at a constant
CaO/Al2O3 mass ratio, implying that the existence prob-
ability of atom O around Al is the biggest. The existence
probability of atom O around Ba is the least and the
average bond length of Ba–O is the largest, suggesting
 IRONMAKING & STEELMAKING 833

that Ba–O is easy to depolymerise to Ba and O, provider the Raman spectroscopy analysis
free oxygen in the melt.
The Raman spectra was deconvoluted with Gaussian fitting
The Al–O, Ti–O, Ba–O, and Ca–O in melts with different
method [33] and the correlation coefficient R2⍰99.5%, the
CaO/Al2O3 mass ratios (0.6–1.4) of CNs curves are shown
fitting curves are shown in Figure 9. The CaO–Al2O3–TiO2
in Figure 6. There is a platform in the CN curves, which is
slag system is made up of multiple components, resulting
wider and smoother, the stability of atomic pairs is higher.
in appearing many fitting peaks. The band focuses on the
Besides, the platform corresponding to the ordinate values
558 and 582 cm−1 is the Al–O–Al linkages, which is
is the coordination number of atomic pairs. The platform
caused by the transverse motions of BO. The fitting peak,
appears in Al–O CNs curves, corresponding to the ordinate
locating between 686 and 705 cm−1, is related to Al–O
value is approximately 4, which means that the average CN
stretching vibrations in the AlO− 2 units with zero BO (QAl,
0
of Al–O is mainly 4. And the slope of the platform abates
NBO/Al = 4), wherein the NBO is the abbreviation of non-
with CaO/Al2O3 mass ratio augmented, suggesting that
bridge oxygen [34–36]. The fitting peak, assigning
the high coordination number of Al–O structural units
between 761 and 772 cm−1, is corresponded to Al–O
gradually change to the low coordination number, In
stretching vibrations in the AlO− 2 units with two BOs (QAl,
2
other words, CaO/Al2O3 can simplify the Al–O structural
NBO/Al = 2) [37, 38]. The fitting peak, centreing between
units. There is a platform in the Ti–O CNs curves, and its
830 and 843 cm−1, is ascribed to the vibrations of Ti–O–Ti
ordinate value is approximately 5. It is obviously that the
(Al) linkages or both [39, 40]. The fitting peak, assigning
slope of the platform also abates with CaO/Al2O3 mass
between 920 and 926 cm−1, is considered to symmetric
ratio, and the high coordination number of Ti–O structural
stretching of Si–O− from [Si2O7]6− units (Q1Si, NBO/Si = 3).
units transfer to low coordination number, illustrating that
The fitting peak, centreing between 978 and 1001 cm−1, is
the Ti–O structural units become simple with CaO/Al2O3
attributed to the symmetric stretching of Si–O− from
mass ratio. It is clear that no platform is found in the Ba–
[SiO3]2− units (Q2Si, NBO/Si = 2) [41]. The fitting peak, locating
O and Ca–O CNs curves, illustrating that the stability of
between 1200 and 1201 cm−1, is corresponded to the
Ba–O and Ca–O are poor, and they are difficult to form
stretching vibration of the [BO3] units or the asymmetric
the network structure, which agrees with the RDFs results.
stretching of Si–O− from SiO− 4
2 units (QSi, NBO/Si = 0) [42,
Besides, the atom O, from Ba–O and Ca–O, contributes to
43]. The fitting peak, assigning between 1327 and
simplify the melt structure.
1344 cm−1, is related to the symmetric vibrations of BO3
The CNs distributions of Al–O and Ti–O with different CaO/
bonded with BO4 units [44, 45].
Al2O3 mass ratios are shown in Figure 7. The CNs of Al–O are
The concentration of the structural unit is the ratio of
mainly AlIII, AlIV, AlV and AlVI in Figure 7(a), and the AlVI is the
the structural unit area to the overall structural units and
main coordination mode among Al–O bond. Besides, the con-
can be acquired using the Gaussian function of the
centrations of AlIII and AlIV increase with CaO/Al2O3 mass
Raman spectra. Besides, the area of the individual fitted
ratio, but the concentrations of AlV and AlVI decrease at the
peak is a semi-quantitative computation. The correlation
same time, indicating that the complex structure of AlV and
between the concentration of structural units and CaO/
AlVI changes to the simple structure of AlIII and AlIV as CaO/
Al2O3 mass ratio is shown in Figure 10. Depending on
Al2O3 mass ratio increases. The CNs of Ti–O are mainly TiIV,
the proportion of the structural units in melt, the main
TiV and TiVI in Figure 7(b), and the concentration of TiV is
structural units are Ti–O–Ti (Al) linkages, AlO− 2 units in
the highest among the Ti–O bonds. Moreover, as the CaO/
the Q2Al species, Si–O− from [Si2O7]6− in the Q1Si species
Al2O3 mass ratio increases, the concentrations of TiIV, TiV
and AlO− 0
2 units in the QAl species. Furthermore, as CaO/
increase, while the concentration of TiVI decreases,
Al2O3 mass ratio increases, the concentration of the Ti–
suggesting that the complex structure of TiVI turns to the
O–Ti (Al) linkages and Q2(Si–O−) decrease significantly;
simple structure of TiIV and TiV. In summary, the high coordi-
the concentrations of Q0(Al–O−) and Q2(Al−O–) remain
nation number of the Al–O and Ti–O structural units turn to
the low coordination number structural units when the
CaO/Al2O3 mass ratio increases, which simplifies the structure
of the melt.

Distributions of Qi
The Qi species is an important index when analysing the
structural feature of melt, and i represents the number of
bridge oxygen (BO). The Al–O structure is the main investi-
gated subject to reflect the changes in the melt structure
because it is the major component in the aluminate system.
The distribution of Qi species of Al–O structure is shown in
Figure 8. Obviously, the concentrations of Q0, Q1 and Q2
increase with CaO/Al2O3 mass ratio, while the concentrations
of Q3, Q4 and Q5 decrease. It suggests that the complex struc-
ture units of Q3, Q4 and Q5 transfer to simple structure units of
Q0, Q1 and Q2 as CaO/Al2O3 mass ratio increases. The chan-
ging trend of Qi species in Al–O is consistent with that of
the CNs. Figure 8. Distribution of Qi species in the melts.
834 Z. PIAO ET AL.
Figure 9. Deconvoluted Raman spectra of the melts.
almost unchanged, and the concentration of Q1(Si–O−)
increases. The other structure units are not described in
detail because their concentrations are smaller and less
variable. In summary, with increase in CaO/Al2O3 mass
ratio, the concentrations of simple structural units
increase, and the concentrations of complex structural
units decrease. The melt structure is simplified and the
Figure 10. Changing trends of the structural units in melts.
viscosity of the melt decrease. These results successfully
verify the MD simulation results.
Conclusions
The effects of CaO/Al2O3 mass ratio on the viscosity and
structure of CaO–Al2O3–TiO2-based fluorine-free mold
fluxes were investigated by employing the viscometer, Sci-
gress software, and Raman spectroscopy. The conclusions
are as follows:
(1) With the CaO/Al2O3 mass ratio increased from 0.6–1.4,
the viscosity decreased from 0.43–0.10 Pa·s and the acti-
vation energy also decreased from 127.8–74.2 kJ·mol−1. It
suggested that CaO/Al2O3 could reduce the minimum
energy barrier and then decrease the viscosity. Besides,
the break temperature increased from 1385 to 1507 K
with CaO/Al2O3 mass ratio increased, enhancing the crys-
tallization ability of mold fluxes.
(2) The average bond lengths of Al–O, Ti–O, Ca–O and Ba–O
were 1.75, 1.95, 2.25 and 2.65 Å, respectively. The Ca–O
and Ba–O were unstable and dissociated into Ba, Ca,
and O. These atoms, especially the free oxygen could sim-
plify the slag structure. Moreover, the high coordination
number of Al–O and Ti–O transferred to a low coordi-
nation structure and the complex structure units of Q3,
Q4 and Q5 also turned to simple structure units of Q0,

Q1 and Q2 with increasing CaO/Al2O3 mass ratio,
suggesting that the complexity of the network structure
was reduced.
(3) The results of Raman spectra showed that the main struc-
tural units were Ti–O–Ti (Al) linkages, AlO−
2 units in the Q
2
6− 1 −
species, [Si2O7] in the Q species and AlO2 units in the
Q0 species in the melts. With the increasing CaO/Al2O3
mass ratio, the concentrations of the Ti–O–Ti (Al) linkages
and Q2(Si−O−) decreased significantly, while the concen-
tration of Q1(Si–O−) increased. This concentration change
trend agreed with the MD simulation results. Through the
MD simulation and Raman analysis, the CaO/Al2O3 struc-
ture could simplify the network and decrease the vis-
cosity of the CaO–Al2O3–TiO2-based fluorine-free mold
fluxes for high titanium steel.
Acknowledgments
We would like to thank Editage (www.editage.cn) for English language
editing.
Disclosure statement
No potential conflict of interest was reported by the author(s).
Funding
This work was supported by National Natural Science Foundation of
China: [Grant Number 52174313]; Natural Science Foundation of Hebei
Province of China: [Grant Number E2021209037]; Basic scientific research
expenses of provincial universities: [Grant Number JST2022002]; Doctoral
Innovation program of Hebei Province: [Grant Number CXZZBS2021096].
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