Received: 20 December 2018 

|  Revised: 25 March 2019 

|
  Accepted: 23 April 2019

DOI: 10.1111/jace.16526

ORIGINAL ARTICLE

Effect of CaF2, B2O3 and the CaO/SiO2 mass ratio on the

viscosity and structure of B2O3‐containing calcium‐silicate‐based
melts

Gi Hyun Kim   | Il Sohn

Department of Materials Science and

Engineering, Yonsei University, Seoul,
Korea
Correspondence
Il Sohn, Department of Materials Science
and Engineering, Yonsei University, 50
Yonsei‐ro, Seodaemun‐gu, Seoul, Korea,
03722.
Email: ilsohn@yonsei.ac.kr
Funding information
Graduate School of YONSEI University
Research Scholarship Grants; National
Research Foundation of Korea, Grant/
Award Number: NRF-2018R1A2B2006609
Abstract
The relationship between the viscosity and structure of B2O3‐containing calcium‐
silicate‐based mold fluxes and the effects of fluidizers including CaF2, CaO, and
B2O3 on the viscosity and their correlation with the structural aspects were studied
using a rheometer with Fourier transformation infrared and Raman spectroscopy.
The viscosity decreased with increasing CaF2 addition up to 28 wt% at a fixed CaO/
SiO2 ratio of 0.3, which was related to depolymerization. Furthermore, CaF2 addi-
tion also affected the apparent activation energy for viscous flow, which decreased
with increasing CaF2 content to 105.1 from 151.1 kJ/mol. At higher C/S ratios, the
viscosity decreased in the presence of greater Ca2+ and O2− supplied from CaO,
which subsequently increased the activation energy to 149.7 from 122.0  kJ/mol.
With regard to the B2O3‐melt, polymerization of the network structure was observed
by comparing the B2O3‐free to 4.4 wt% B2O3 content. However, the viscosity was
relatively constant with increasing B2O3 addition. However, the viscosity decreased
due to greater simplification of the network structure above 4.4 wt% B2O3. The break
temperature decreased with greater B2O3 addition as the crystallization was inhib-
ited. Furthermore, the apparent activation energy decreased as depolymerization of
the network structures occurred above 4.4 wt% B2O3.

KEYWORDS
B2O3, CaF2, CaO/SiO2 mass ratio, mold flux, network structure, viscosity

1  |   IN T RO D U C T ION for application in high‐Al‐content steels exhibiting transfor-

The development of continuous casting mold fluxes has been
an active topic of research aiming for greater productivity
and improved quality in steel products. Optimized fluxes
ensure sufficient and uniform lubrication between the par-
tially solidified shell and water‐cooled copper mold, uniform
heat transfer across the solidified flux film, and insulation
from excessive radiative heat loss above the top surface of
the flux film.1‒13 In particular, the wider use of B2O3 fluid-
izers in the constituents that compose calcium‐silicate and
calcium‐aluminate‐based mold fluxes has been implemented
mation induced plasticity and twinning induced plasticity
steels.14,15 The use of B2O3 is often employed to lower both
the liquidus and solidus temperatures of the melt and expand
the solid‐liquid co‐existing region of the flux to enhance
lubrication.1,7,13,16,17
To ensure uniform heat transfer across the copper mold,
optimal use of B2O3 in continuous casting mold flux requires
a uniform distribution of amorphous and crystalline phases
dispersed within the flux layer. Often known for its glass‐
forming ability in the glass industry, B2O3 in mold fluxes has
been known to inhibit crystallization by forming complex

J Am Ceram Soc. 2019;00:1–16. wileyonlinelibrary.com/journal/jace © 2019 The American Ceramic Society     1 |

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2      KIM and SOHN
boro‐silicate structural units, which may not be optimal for
steel grades requiring lower heat removal.4‒6,8,14,16
In general, fluoride‐containing compounds such as CaF2
and NaF have been widely used as fluidizers in commercial
continuous casting mold powders. In the typical silicate‐based
mold fluxes, CaF2 and NaF can depolymerize the silicate
structural units, leading to a lower viscosity.18‒20 According to
Sakamaki et al,21 additional NaF interacts with Si‐O to form
Si‐F bonds, and bridged oxygen anions (O0) become non‐
bridged oxygen anions (O−) in the Na2O‐NaF‐SiO2 system.
According to Hayashi et al,22 CaF2 addition was found to affect
the silicate network structures through Ca2+, as Ca‐F+ pairs
indirectly link to the silicate network structures, which can re-
duce the resistance for shearing, and the viscosity is decreased
in CaO‐CaF2‐SiO2(‐FeOx) systems with higher CaF2 content.
In addition, according to Takeda et al23 and Sasaki et al,24,25
Na‐F and Ca‐F+ complexes are formed, and F− anions are not
directly linked to the silicate network structures and do not
directly depolymerize the silicate network structures in Na2O‐
NaF‐SiO2 and CaO‐CaF2‐SiO2 since F− anions tend to move to
higher‐field‐strength alkali and alkali earth cations. However,
it can be speculated that the bonding preference of F− anions
towards the alkali and alkali earth cations tends to better release
the O2− to interact with the O0 in the silicate structural units.
In the case of B2O3‐containing melts, Kim and Morita26
and Park and Sohn27 characterized the network‐forming abil-
ities of B2O3 in high‐temperature melts by forming 4‐coordi-
nated boron structural units. According to Kim and Morita,28
B2O3 could be incorporated into the silicate network at low
C/S ratios forming complex boro‐silicate structures, but at
higher basicities of 1.15, a higher B2O3 content increased the
amount of complex independent meta‐borate structures in the
CaO‐SiO2‐B2O3 ternary system. According to Zhou et al1 and
Zhou and Wang,2 B2O3 in F‐free mold fluxes resulted in a de-
crease in the viscosity and the crystallization temperature to
form the calcium‐boro‐silicate (Ca11Si4B2O22) phase that re-
placed the cuspidine (Ca4O7Si2F2) phase, as also observed by
Yang et al3 Similar results were also observed by Yan et al14
and Fox et al,17 who reported that the addition of network‐
forming B2O3 resulted in prolonged incubation times and
lower crystallization temperature in CaO‐Al2O3‐based melts.
The effect of B2O3 additions to the structure of Ti‐bearing
molten fluxes was studied by Li et al29 using a combination
of Fourier transform infrared (FTIR), Raman spectroscopy,
nuclear magnetic resonance (NMR), and X‐ray photoelectron
spectroscopy. The results showed a tendency of the non‐ring
[BO3] to convert into the [BO4]‐tetrahedral, which promoted
polymerization of the structural units and subsequently in-
hibited crystallization. However, the pronounced amount of
two‐dimensional ring [BO3] structures resulted in decreased
strength between the structural units and tended lower the
flux viscosity with B2O3 addition even with the existence of
complex [BO4]‐tetrahedral structural units.
Thus, to ensure that a flux can retain the cuspidine
(Ca4Si2O7F2) primary crystal phase during crystallization,
while having a lower melting temperature and optimal vis-
cosity, a fundamental understanding of the CaF2, C/S ratio,
and B2O3 effects on the thermo‐physical properties and struc-
ture is necessary but has not yet been obtained in the contin-
uous casting for high‐carbon steels with a high casting speed
between 3.0 and 3.5 m/min to diminish the defects and cracks
on the surface of the slabs relative to the results of using a
commercial mold flux.9
In this study, the viscosity of B2O3‐containing calcium‐
silicate commercial melts was studied and correlated with the
structure for temperatures up to 1673 K (1400°C). The effect
of CaF2, C/S ratio, and B2O3 on the viscosity was observed in
detail considering the post‐experimental compositional vari-
ation. Structural analysis of as‐quenched fluxes from 1673 K
(1400°C) was carried out with FTIR and Raman spectroscopy.
2  |   EXPERIM ENTAL M ETHOD
AND PROCEDURES
2.1  |  Materials preparation
Commercial mold fluxes (Flux 1, 4, 5, and 6) and reagent
grade chemicals (Flux 2, 3, 7, and 8) were used in the prepara-
tion and comparison of the calcium‐silicate containing B2O3
multi‐component fluxes. The post‐experimental composition
was the average of three separate measurements using X‐ray
fluorescence (S4 Explorer, Bruker AXS GmbH, Germany)
and inductively coupled plasma‐optical emission spectros-
copy (700 Series, Agilent, USA) as presented in Table 1.
In the post‐experimental composition, the volatilization of
fluoride was observed within 1 wt%. Flux 1, 4, 5, and 6 are
commercial mold fluxes used for high‐carbon steels, and the
others in the present work are synthesized fluxes using rea-
gent grade chemicals that mimic the major components of
commercial fluxes. CaCO3, Na2CO3, and Li2CO3 were fully
calcined and mixed with the other constituents. The mixed
powders were pre‐melted at 1673  K (1400°C) and crushed
for the actual experiments, following similar procedures de-
scribed previously.9,18,30‒33
2.2  |  Viscosity measurements
Pulverized pre‐melted flux (100  g) was placed in a
Pt‐10%Rh crucible (OD: 42 mm, ID: 46 mm, H: 65 mm),
which was inserted into a tight‐fitting Al2O3 crucible (OD:
52 mm, ID: 46 mm, H: 70 mm). UHP Ar (99.9999%) gas
of 300 sccm was injected into the reaction tube of a verti-
cal resistance furnace, as shown in Figure 1A. Figure 1B
shows the viscosity measurements of Flux 2 taken during
the cooling cycle with respect to time. Sequential measure-
ments were taken during the holding period of the target
KIM and SOHN
|
     3

temperature during cooling. Using the rotating spindle

CaO/SiO2
method, the torque of the Pt‐10%Rh bob was measured with
a Brookfield rheometer (LV‐II+; Brookfield Engineering

0.8
0.8
1.0
0.8
0.4
0.3
0.3
0.3
Laboratories, Middleboro, MA) which was calibrated by
standard silicon oils (9.5, 47.8, and 96.7 mPa/s) at a rota-
tion speed of 100  rpm. A reference B‐type thermocouple

2.6 (±0.016)
2.5 (±0.010)
2.3 (±0.031)

2.7 (±0.14)
2.5 (±0.13)
2.6 (±0.02)
2.8 (±0.19)
2.4 (±0.11) (Pt‐30%Rh: Pt‐6%Rh) was used to calibrate the furnace
temperature control thermocouple connected to a propor-
Li2O

tional integral derivative controller to within ±3 K of the

target temperature of 1673  K (1400°C). The temperature
T A B L E 1   Chemical composition of the flux samples after experiments using X‐ray fluorescence and inductively coupled plasma‐optical emission spectroscopy

4.4 (±0.0014) was lowered in 25 K intervals for 10 minutes and held for

7.2 (±0.08)
4.2 (±0.22)
4.6 (±0.26)
2.4 (±0.05)
2.4 (±0.03)
2.7 (±0.04)

30 minutes to obtain thermal equilibrium within the molten

flux. The temperature was subsequently lowered below
B2O3

the break temperature of the flux until a high volumetric

0

ratio of the solid particle region was achieved. The viscos-

ity measurements are expressed as the average of the col-
13.4 (±0.46)
12.9 (±0.49)

14.3 (±1.2)
13.6 (±1.2)
12.5 (±2.9)
14.0 (±1.3)
28.0 (±1.4)

lected data for 5 minutes; thermal equilibrium was reached

after 25  minutes. Typical standard errors were less than
CaF2

±0.007 Pa/s, as is typical for this method.30

0

2.3  |  Structural analysis using FTIR and

14.3 (±0.19)
16.2 (±0.19)
16.4 (±0.19)
17.2 (±0.20)
15.5 (±0.19)
14.6 (±0.19)
16.7 (±0.19)

15.3 (±0.2)

Raman spectroscopy
Na2O

Sufficient B2O3 additions result in the formation of independ-

ent and incorporated borate structural units within the domi-
nant silicate structural units found in calcium‐silicate‐based
0.7 (±0.0095)
0.7 (±0.0096)

2.6 (±0.018)
2.2 (±0.015)
2.2 (±0.015)
2.4 (±0.016)
4.6 (±0.014)
0.6 (±0.009)

fluxes. The schematic of the various borate structural units

adapted from previous reports is depicted in Figure 232,34
and the structural change from silicate network structures
FeO

to boro‐silicate network structures by B2O3 additions is de-

picted in Figure 3.35 The borate structures can be classified
3.3 (±0.069)
3.3 (±0.045)
3.2 (±0.044)
3.1 (±0.044)
3.1 (±0.044)
3.6 (±0.072)
3.7 (±0.073)
3.9 (±0.049)

broadly into three‐dimensional and two‐dimensional struc-

tural units, where the three‐dimensional structural units are
MgO

more complex. Within the present study, structural analysis

of as‐quenched glassy fluxes from 1673  K (1400°C) was
conducted using a combination of FTIR and Raman spectros-
1.7 (±0.057)
2.1 (±0.057)
2.1 (±0.056)
1.9 (±0.057)
3.3 (±0.126)
3.3 (±0.079)

copy. The reference data to identify the IR‐ and Raman‐active

2.2 (±0.12)
3.4 (±0.14)

structural units was obtained from the literature.9,27,28,32,35‒37

Al2O3

The structural analyses were performed at least three times

to estimate the standard errors; the standard errors of the de-
convoluted area of Raman spectroscopy are the differences
30.5 (±0.42)
33.0 (±0.21)
27.9 (±0.19)
31.2 (±0.20)
37.5 (±0.22)
54.6 (±0.51)
45.4 (±0.49)
31.9 (±0.21)

between the observed spectra and the fitted spectra by Peakfit

v4 program (AISN software Inc., United Kingdom).30
SiO2

3  |  RESULTS AND DISCUSSIO N

10.4 (±0.012)

23.9 (±0.16)
26.6 (±0.13)
27.8 (±0.13)
24.5 (±0.13)
16.0 (±0.11)
17.6 (±0.12)
14.6 (±0.14)

3.1  |  Effect of CaF2 on the viscosity

The effect of CaF2 on the viscosity in the CaO‐SiO2‐Al2O3‐
CaO

MgO‐FeO‐Na2O‐CaF2‐Li2O‐B2O3 multi‐component flux at a

C/S ratio of 0.3 and various temperatures is shown in Figure
4A,B. Higher concentrations of CaF2 lowered the viscosity of
Flux

the flux. Relative to the CaF2‐free flux, the flux with CaF2 had
8
7
6
5
4
3
2
1
 |
4      KIM and SOHN

F I G U R E 1   (A) A schematic of the experimental apparatus and (B) a relation between viscosity and temperature cycle for viscosity
measurements in the present study

F I G U R E 2   A schematic of borate structural units

a significantly lowered viscosity, which can be correlated with
the depolymerization of the silicate structures with higher
CaF2 addition, which has been previously elucidated,9,18,20
where CaF2 can react with the complex silicate network struc-
tures resulting in the depolymerization of silicate rings and
chains to form simple silicate network structures such as di-
mers and monomers. Figure 4B shows that a 28 wt% CaF2‐
containing flux exhibited a slower increase in viscosity during
cooling and a break temperature of 1223 K (950°C). Below
the break temperature, the viscosity calculated by FactSage®
significantly increased by the precipitated crystal phase; the
estimated viscosities for Flux 1 in the fully liquid state (below
the break temperature, the viscosity is not affected by the pre-
cipitated crystals because the crystals occupy a smaller volu-
metric fraction) were determined using an Arrhenius‐type
equation. The Einstein‐Roscoe equation considers the solid
phase volumetric fraction within the liquid phase below the
crystallization temperature estimated by FactSage®.38
The Einstein‐Roscoe equation assumes that solid crystals
are insoluble spherical particles according to the following
Equation (1), where the constants a and n are 1.35 and 2.5,
respectively39‒43:
KIM and SOHN
|
     5

𝜂 = 𝜂0 × (1 − a × f )−n
where η is the dynamic viscosity of the solid‐liquid phase
containing spherical solid particles (Pa·s), η0 is the dynamic
(1) viscosity of the fully liquid phase (Pa·s), and f is the volumetric
fraction of the spherical solid particles.
Numerous works39‒43 have examined the effect of solid
particles on the viscosity under solid‐liquid co‐existing mix-
tures by stirring the fluid with a spindle at various rotation
speeds. The present approach assumed a crystalline solid
dispersed in a Newtonian fluid when the volume fraction of
solid particles was lower than 0.1.

3.2  |  Effect of the CaO/SiO2 mass ratio

on the viscosity
Figure 5A,B show the effect of the C/S ratio on the viscos-
ity at comparable contents of other constituents in the flux.
Increasing the C/S ratio from 0.4 to 0.8 had a significant ef-
fect in lowering the viscosity. The addition of CaO provides
free oxygen ions (O2−) in the flux at various temperatures,
which can be used to modify the complex silicate and boro‐
silicate network structures connected by the bridged oxygen
atoms (O0) resulting in higher amounts of O−, as suggested
by Waseda and Toguri44. This modification of the network
structures is clearly evident for acidic fluxes (Flux 4), where
the C/S ratio is 0.4. At a higher C/S ratio above 0.8, the addi-
tional O2− has a smaller effect on the viscosity. The combined
effects of the higher C/S ratio and pre‐existing fluidizers in-
cluding Li2O, Na2O, and CaF2 limited the change in viscos-
ity above a C/S ratio of 0.8. This trend correlated well with
the modification of the structural units comprising the flux,
which is discussed later in detail.
In terms of the crystallization behavior and its correlation
with the structure, the excess O2− from CaO can modify the
complex network flux structures and simplify the structural
F I G U R E 3   A schematic of effect of B2O3 addition in the silicate
units comprising the melt. A more simplified unit structure
network structures
requires less driving forces for atom re‐organization and

F I G U R E 4   Viscosity of the CaO‐SiO2‐(3.3‐3.4)Al2O3‐(3.6‐3.9)MgO‐(0.6‐0.7)FeO‐(14.6‐16.7)Na2O‐(2.4‐2.7)B2O3‐(2.3‐2.5)Li2O multi

component fluxes (wt%) with respect to (A) CaF2 content and (B) temperature at a fixed CaO/SiO2 ratio of 0.3
 |
6      KIM and SOHN

F I G U R E 5   Viscosity of the CaO‐SiO2‐(1.9‐2.1)Al2O3‐(3.1‐3.2)MgO‐(2.2‐4.6)FeO‐(15.5‐17.2)Na2O‐(12.5‐14.0)CaF2‐(4.2‐4.6)B2O3‐

(2.5‐2.8)Li2O multi‐component fluxes (wt%) with respect to (A) CaO/SiO2 ratio and (B) temperature

crystallization. In addition, the lower viscosity enhances
ionic mass transport in the molten oxide system increasing
the mass transfer coefficient and the kinetics.1‒5,8,10,11 The
flux for a C/S ratio of 1.0 (Flux 6) has a relatively high
break temperature, which is discussed later in detail.
3.3  |  Effect of B2O3 on the viscosity
Figure 6A and C show the effect of B2O3 on the viscosity at
comparable contents of other constituents in the fluxes at a
fixed C/S ratio of 0.8. Comparison of the B2O3‐free (Flux 7)
and 4.4 wt% B2O3 (Flux 5) fluxes showed negligible effects
on the viscosity within the temperature range of this work.
By comparing the viscosity measurements of the B2O3‐con-
taining and B2O3‐free fluxes as a function of temperature
in Figure 6B, the addition of B2O3 is found to significantly
extend the minimum temperature at which stable viscosity
measurements can be made. This extension corresponds to a
decrease in the break temperature of the melt with B2O3 ad-
ditions and subsequent extension of the solid‐liquid region.
Above the break temperature of the melt, the addition of B2O3
up to 4.4 wt% had a negligible influence on the viscosity,
which is attributed to the existence of other highly basic flu-
idizers of Li2O and Na2O composing the flux in excess of 17
wt%. In the present compositional range of this work, B2O3
enhanced the formation of boro‐silicate network structures29
but did not increase the viscosity due to the competitive ef-
fects between the degree of polymerization (DOP, Q3/Q2) of
the network structures and the presence of [BO3]‐trigonal and
[BO4]‐tetrahedral structural units.35 With greater B2O3 con-
tent of 8.8 wt% (Flux 8), the viscosity in the fully liquid re-
gion was lower than that of other fluxes. The lower viscosity
observed with B2O3 addition of 8.8 wt% can be explained by
the greater proportion of independent borate structural units
compared to the silicate structural units relative to the flux
with 4.4 wt% B2O3, which is discussed later in detail.
3.4  |  Effect of CaF2 on the structural
units of high‐temperature melts
Using FTIR and Raman spectroscopy, the silicate structural
units between 1200 and 800  cm in terms of wavenumber

F I G U R E 6   Viscosity of the CaO‐SiO2‐(1.7‐2.2)Al2O3‐(3.1‐3.3)MgO‐(2.2‐2.6)FeO‐(14.3‐17.2)Na2O‐(2.6‐2.7)Li2O multi‐component fluxes

(wt%) with respect to (A) B2O3 contents and (B) temperature at a fixed CaO/SiO2 ratio of 0.8 and (c) comparisons of other work1
KIM and SOHN
and Raman shift can be observed. The non‐bridged oxy-
gen per tetrahedral cation (NBO/T) and in particular the
ratio of Q3/Q2 can be correlated with the DOP, as described
previously.45‒51 From the FTIR analysis, the existence and
estimated depth of the trough at specific wavenumbers can
be assigned to the silicate and borate structural units. From
the Raman analysis, a more quantitative analysis through
deconvolution of the spectra and subsequent area fraction
analysis can reveal the amount of structural units present
in the fluxes.45
Figure 7 shows the change in structural units with CaF2 ad-
ditions according to the FTIR analysis at comparable amounts
of the other constituents. The flux containing 28 wt% CaF2
(Flux 1) had a deeper trough at NBO/T = 4 with respect to
the other silicate structural units in comparison to the flux
containing 14 wt% CaF2 (Flux 2) and CaF2‐free flux (Flux
3). With CaF2 addition, the bands between 1200 and 800 cm,
which are assigned to Si‐O stretching vibrations became nar-
rower, which indicates that the larger silicate structural units
gradually disappeared. Specifically, the peaks of NBO/T = 3
and 1 became weaker, but the peaks of NBO/T  =  4 and 2
become stronger with increasing CaF2. At 28 wt% CaF2, the
peak of NBO/T = 0 at approximately 1150 cm is compara-
tively less pronounced and the peaks of the stretching vibra-
tion in [BO3]‐trigonal structural units are stronger than for the
14 wt% CaF2 and CaF2‐free fluxes. The FTIR results suggests
changes of the NBO/T = 4, 3, 2, 1 and [BO3] structural units
with CaF2 addition. To supplement the qualitative structural
analysis of the FTIR spectra, semi‐quantitative Raman spectra
for structural analysis were also obtained
The typical Raman spectra for flux 6, shown in Figure 8,
can be deconvoluted and analyzed by integrating the area. The
corresponding Raman analysis, shown in Figure 9A, shows
F I G U R E 7   Fourier transform infrared results of as‐quenched
samples from 1673 K (1400°C) with respect to CaF2 contents from 0 to
28 wt% at a fixed CaO/SiO2 ratio of 0.3
     7
|
similar trends to the FTIR. The effect of CaF2 on the fraction
of structural units is shown in Figure 9A. The average NBO/T
and the DOP (Q3/Q2) are represented in Figure 9B.
Major structural unit changes could be identified for the
NBO/T = 4 and 3, the Q3/Q2, bending vibration in boro‐sil-
icate structural units and metaborate and BO2O− linked to
[BO4]‐tetrahedral structures in borate structural units.
With CaF2 addition up to 14 wt%, the NBO/T = 3, DOP,
and bending vibrations of the Si‐O‐Si bonds decreased, but
the BO2O− linked to [BO3]‐trigonal structural units increased
due to excess Ca2+ from CaF2 addition at low C/S ratios.34,52
Thus, the modification of the relatively larger silicate struc-
tural units and generation of the simple borate structural units
decreased the viscosity.
With greater CaF2 addition up to 28 wt%, the DOP slightly
decreased, and the simpler structural units of NBO/T = 4 in-
creased. In addition, the borate structural units were further
transformed from BO2O− linked to [BO3]‐trigonal structural
units to BO2O− linked to [BO4]‐tetrahedral structural units with
[BO3] resulting in the incorporation of [BO4]‐tetrahedral units
into the [SiO4]‐tetrahedral structures linked with BO2O−‐trigo-
nal structures having O− similar to alkali cations since Ca2+
could compensate the B4+ in [BO4]‐tetrahedral units at higher
CaF2 contents, producing BO2O− structural units.34,52‒55 This
finding is consistent with the 11B NMR findings of Park et al9
that non‐ring type [BO3]‐trigonal and [BO4]‐tetrahedral struc-
tural units were more prevalent at greater CaF2 content.
According to Umesaki et al,56 the average NBO/T can be
calculated using the mole fraction (Xi) of tetrahedral struc-
tural units with non‐bridging oxygen per cation (T). The aver-
age NBO/T values are 1.30, 0.95, and 0.92 at 0 wt%, 14 wt%,
and 28 wt% CaF2, respectively, which are corresponded with
the DOP as shown in Figure 9B.
F I G U R E 8   Observed Raman spectra and the deconvoluted
spectra for Flux 6
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8      KIM and SOHN

F I G U R E 9   (A), The structural fractions and (B) the average non‐bridged oxygen per tetrahedral cation (NBO/T) and the degree of
polymerization from the integration of the deconvoluted Raman spectra with respect to CaF2 contents for Flux 1, 2, and 3 at a fixed CaO/SiO2 ratio
of 0.3

Thus, CaF2 affected both the silicate and borate structures

in B2O3 containing multi‐component calcium‐silicate‐based
fluxes, which is consistent with the aforementioned viscosity
trends.

3.5  |  Effect of the CaO/SiO2 mass

ratio on the structural units of high‐
temperature melts
Using FTIR and Raman spectroscopy, the effect of the
C/S ratio on the structural units of the flux was analyzed
as shown in Figures 10 and 11, respectively. Considering
the dominant chemical composition in the fluxes, the pro-
nounced structural units are the silicate structural units,
where SiO2 comprises approximately 30‐40 wt% with B2O3
addition not exceeding 5 wt%. According to Kim et al,57
the ratio of Na2O/B2O3 could affect the formation of bo-
rate structural units, which could be transformed to ring and
non‐ring [BO3] and [BO4]‐tetrahedral structures, as previ-
ously illustrated within Figure 2. In the boro‐silicate flux
system of the present work, borate structural units could
be incorporated into the silicate structures, resulting in a
complex boro‐silicate structural unit. With higher C/S ra-
tios, the trough corresponding to NBO/Si  =  0 disappears,
while a greater depth can be observed for the NBO/Si = 4
trough, as shown in Figure 10. The O2− mainly supplied by
the CaO depolymerizes the complex silicate structural units
to simpler silicate structural units (NBO/=4), subsequently
decreasing the DOP. The silicate stretching band also shifts
towards lower wavenumbers with the relative disappearance
of NBO/T = 1 and 0 at higher C/S ratios, as the NBO/T = 0
structural units are modified with the interaction of O2−.
For the borate stretching bands observed between 1600
and 1200  cm, the prominent peak at 1350  cm, which is
F I G U R E 1 0   Fourier transform infrared results of as‐quenched
samples from 1673 K (1400°C) with respect to CaO/SiO2 ratio from
0.4 to 1.0
typically assigned to the stretching vibrations of the B‐O
in [BO3]‐trigonal structural units, is diminished with an in-
creasing C/S ratio. This finding is consistent with the results
of Zhang et al,13 who found that excess O2− transformed
the [BO3]‐trigonal structural units to BO2O− having O− and
[BO4]‐tetrahedral structural units.58,59
Figure 11A,B shows the effect of the C/S ratio on the
structural units after deconvolution and subsequent area inte-
gration of the Raman spectra. In the silicate structural units,
NBO/T = 4 increased and the DOP decreased, correspond-
ing to a depolymerization with higher C/S ratios. The aver-
age NBO/T values are 2.47, 2.26, and 1.74 at 0.4, 0.8, and
1.0 of C/S ratios, respectively, which are corresponded with
the DOP in Figure 11A. With respect to the borate structural
KIM and SOHN
|
     9

F I G U R E 1 1   (A), The structural fractions and (B) the average non‐bridged oxygen per tetrahedral cation (NBO/T) and the degree of
polymerization from the integration of the deconvoluted Raman spectra with respect to CaO/SiO2 ratio for Flux 4, 5, and 6

units, the fraction of BO2O− vibration linked to [BO4]‐tetra- [BO3]‐trigonal structural units can be converted into [BO4]‐
hedral structural units gradually increased with higher C/S tetrahedral structural units by reaction with O2− supplied
ratios as the excess O2− interacted with the O0 and trans- from alkali and alkali‐earth oxides including Na2O, Li2O, and
formed the [BO3]‐trigonal to [BO4]‐tetrahedral structures in- CaO. Ring and non‐ring type [BO3] structural units are two‐
corporated into silicate structures. As a result, the fraction of dimensional trigonal structures and [BO4] structural units are
BO2O− vibration linked to [BO3]‐trigonal structures slightly three‐dimensional tetrahedral structures.
decreased. According to the 11B magic angle spin‐NMR re- Figure 12 shows the effect of B2O3 on the structural units
sults of Park et al9 and Raman results of Kim et al,57 the of the melt analyzed by FTIR between the wavenumbers of
borate structural units can transform to either the non‐ring 1600 and 600 cm. The wavenumber region between 1600 and
[BO3], ring [BO3], or [BO4]. With an increasing C/S ratio, 1200 cm can be assigned to the stretching vibrations of the B‐O
the majority of non‐ring [BO3] and [BO4] (1B, 3Si and 0B, bonding in [BO3]‐trigonal related structures. The stretching vi-
4Si) increased. According to Park et al,9 there are 2 types brations of Si‐O bonding in [SiO4]‐tetrahedral related structures
of [BO4]‐tetrahedral structural units: (1B, 3Si) and (0B, appear within the wavenumbers between 1200 and 800 cm.
4Si). The [BO4] (1B, 3Si) unit corresponds to [BO4] bonded With B2O3 addition to 4.4 wt%, the stretching vibration
around one [BO4] and three [SiO4] and the [BO4] (0B, 4Si) bands between 1150 and 750 cm became narrower due to the
unit corresponds to [BO4] bonded around four [SiO4]. As
previously mentioned, the [BO4]‐tetrahedral structural units
are incorporated into the silicate structures according to the
11
B NMR results. In the Raman analysis of the present com-
positional range, the variation of BO2O− vibrations linked
to [BO4]‐tetrahedral structural units was consistent with the
results of Kim et al28 with a higher C/S ratio. As mentioned
by Park et al9 and in other reports,28,57 borate structures can
be incorporated into silicate structures depending on the
number of O−. Therefore, the variation of BO2O− vibrations
linked to [BO4]‐tetrahedral structural units increased at the
expense of [BO3]‐trigonal structural units according to the
present Raman results.

3.6  |  Effect of B2O3 on the structural

units of high‐temperature melts
As previously illustrated, molten B2O3 can form 3 types F I G U R E 1 2   Fourier transform infrared results of as‐quenched
of structural units, namely, ring [BO3], non‐ring [BO3], samples from 1673 K (1400°C) with respect to B2O3 contents from 0
and [BO4] tetrahedral structural units. B2O3 comprising of to 8.8 wt% at a fixed CaO/SiO2 ratio of 0.8
 |
10      KIM and SOHN
presence of borate structural units relative to the B2O3‐free
flux. In addition, the bending vibrations of Si‐O‐Si and the
stretching vibration in NBO/T = 3 and 2 became less promi-
nent, but that at NBO/T = 4 and 1 became more pronounced,
and the stretching vibrations of [BO3] appeared at the wave-
numbers of 1450, 1370, and 1230 cm.
With additional B2O3 from 4.4 to 8.8 wt%, the band between
1150 and 750  cm became narrower and the stretching vibra-
tions of [BO3] became more pronounced at the wavenumbers
of 1450, 1370, and 1230 cm, which led to higher depolymer-
ization and subsequently lower viscosity. This result correlates
well with that of Zhang et al,13 who found that higher B2O3
addition resulted in greater propensity toward the dissociated
simple network structures from more complex structures.
From the Raman analysis of Figure 13A,B, a similar trend to
the FTIR results can be observed. From 0 to 4.4 wt% B2O3 ad-
dition, the DOP was increased and the [BO4]‐tetrahedral struc-
tural units could be observed, but the Si‐O‐Si bending vibration
decreased. The lower amount of Si‐O‐Si bending vibrations
suggests that some of the borate structural units were incorpo-
rated into the silicate structures, breaking the Si‐O‐Si bonding
forming boro‐silicate structural units. In addition, NBO/T = 4
and [BO3] and [BO4] structural units with BO2O− increased
even though the DOP‐related Q3/Q2 ratio increased. Therefore,
the viscosity was unchanged by the competition between the
increased DOP by incorporated borate structural units and the
modification of the network structures by O− in BO2O− with
[BO3] and [BO4] structural units. In the boro‐silicate system,
the effect of B2O3 on the structural aspect was elucidated using
FTIR, Raman, and NMR spectroscopy.35,47 It was concluded
that additional B2O3 was incorporated into the silicate network
structures by connecting the 4Si atoms (0B, 4Si) to the [BO4]‐
tetrahedral structures, inhibiting the formation of independent
[BO4]‐tetrahedral structures and resulting in higher DOPs for
F I G U R E 1 3   (A), The structural fractions and (B) the average non‐bridged oxygen per tetrahedral cation (NBO/T) and the degree of
polymerization from the integration of the deconvoluted Raman spectra with respect B2O3 contents for Flux 5, 7, and 8 at a fixed CaO/SiO2 ratio of
0.8
the boro‐silicates with initial B2O3 addition, which is depicted
in Figure 3. The average NBO/T values are 2.18, 2.26, and 2.04
at 0 wt%, 4.4 wt%, and 8.8 wt% B2O3, respectively, which are
corresponded with the DOP in Figure 13B. With greater addi-
tion of B2O3 from 4.4 to 8.8 wt%, the DOP decreased, but the
amount of O− in BO2O− linked to the [BO3] and [BO4] struc-
tural units increased, which led to a modification of the network
structures and a lowered viscosity.
Therefore, complex structural changes were observed
from the addition of 4.4 wt% B2O3 relative to the B2O3‐free
state by linking between Si and B but the viscosity was al-
most constant. As more B2O3 is added, the network structures
become slightly depolymerized with greater amounts of the
O− in borate structures resulting in lower viscosity.
3.7  |  Activation energy for viscous
flow and the break temperature
Figure 14 shows the temperature dependence of Flux 4, 5,
and 6 with the natural logarithm of the viscosity as a function
of the reciprocal temperature following Equation (2)
( )
Ea
𝜂 = 𝜂0 × exp
RT (2)
where η is the viscosity, Ea is the activation energy for the vis-
cous flow, R is the ideal gas constant (8.314 kJ/mol/K), and T
is the temperature.
The shaded symbols are the measured viscosities, the open
symbols are the calculated viscosities using FactSage® consid-
ering the fraction of solid crystalline particles co‐existing in the
liquid according to the Einstein‐Roscoe Equation (1), and the
half‐shaded symbols are the break temperature of the fluxes.
KIM and SOHN
|
     11

the open‐times symbols, which corresponds to the high solid

F I G U R E 1 4   Temperature dependence and estimated break
temperature of Flux 4, 5, and 6 according to the Arrhenius type
relationship for viscous flow
In the open symbols, the dynamic viscosity of the fully liquid
phase and the volumetric fraction of the precipitated crystal-
line phases can be calculated using viscosity calculation and
equilibrium calculation in FactSage®. The linear regression of
fraction, intersects at the break temperature. The obtained acti-
vation energies for viscous flow within the fully liquid region
and below the break temperature are provided in Table 2, and
the break temperatures of fluxes are provided in Table 3.
The break temperature determines the lubrication ability
of flux below the meniscus within the solid‐liquid co‐existing
temperature region. During continuous casting, the infiltrated
liquid flux layer between the partially solidified steel shell and
the water‐cooled copper mold solidifies. If a lower break tem-
perature can be achieved, complete solidification of the flux
can be extended within the mold and improve the lubrication
ability of the flux traversing the mold.8,9,13 Mills et al8 and
Fox et al17 suggested that the break temperature is similar to
the crystallization temperature; however, the break tempera-
ture more closely correlates with the bulk crystallization and
not the initial crystallization temperature of the flux often ob-
served in situ using high‐temperature confocal laser scanning
microscopy.9 Thus, the trend of the break temperature typi-
cally follows the bulk crystallization temperature of the fluxes.
A higher CaF2 lowered the activation energy for the vis-
cous flow for Flux 1, 2, and 3. Flux 2 and 3 had the higher
viscosity than Flux 1 and they exhibited a large increase in

T A B L E 2   Activation energy (kJ/mol)

Activation energy
for viscous flow of various silicate base
Flux (kJ/mol) Remark Reference
mold fluxes
1 105.1 (±3.5) High CaF2  
2 122.5 (±1.5)    
3 151.1 (±0.9) CaF2‐free  
4 122.0 (±3.0) C/S = 0.4  
5 149.7 (±2.9) C/S = 0.8  
6 132.5 (±7.0) C/S = 1.0  
7 151.8 (±3.8) B2O3‐free  
8 121.2 (±10.5) High B2O3  
CaO‐SiO2‐4.2%‐4.5% Al2O3‐Na2O‐(B2O3)‐Li2O‐(F)
7.4Na2O‐1.0Li2O‐7.3F, 193.6 (±12.0) B2O3‐free Zhou L et
C/S = 1.25 al1
10.9Na2O‐10.0B2O3‐2.0Li2O, 152.7 (±2.4) F‐free  
C/S = 1.25
11.9Na2O‐10.0B2O3‐2.9Li2O, 160.7 (±2.4) F‐free  
C/S = 1.25
9.9Na2O‐8.0B2O3‐2.0Li2O, 154.9 (±3.5) F‐free  
C/S = 1.15
7.9Na2O‐6.0B2O3‐2.0Li2O, 228.6 (±4.6) F‐free  
C/S = 1.15
CaO‐SiO2‐8.0% Na2O‐B2O3‐2.0% Li2O, C/S = 1.15
3.9B2O3 382.3 (±34.4) F‐free Lu B et al5
5.8B2O3 183.0 (±8.9) F‐free  
7.9B2O3 173.8 (±16.3) F‐free  
The bold texts indicate which compositions are changing below.
 |
12      KIM and SOHN

T A B L E 3   Break and crystallization

Break temperature
temperatures (K) of various silicate base
Flux (K) Remark Reference
mold fluxes
1 1223 High CaF2  
2 No crystallization    
3 No crystallization CaF2‐free  
4 1323 C/S = 0.4  
5 1248 C/S = 0.8  
6 1383 C/S = 1.0  
7 1373 B2O3‐free  
8 1248 High B2O3  
20% CaO‐40% SiO2‐10% Al2O3‐10% MgO‐20% Na2O‐1% Li2O‐B2O3
1.5, 4, 8B2O3 1405, 1301, 1123 F‐free Fox AB et
al17
CaO‐SiO2‐4.2%‐4.5% Al2O3‐Na2O‐(B2O3)‐Li2O‐(F)
7.4Na2O‐1.0Li2O‐7.3F, 1531 B2O3‐free Zhou L et
C/S = 1.25 al1
10.9Na2O‐10.0B2O3‐2.0Li2O, 1480 F‐free  
C/S = 1.25
11.9Na2O‐10.0B2O3‐2.9Li2O, 1462 F‐free  
C/S = 1.25
9.9Na2O‐8.0B2O3‐2.0Li2O, 1495 F‐free  
C/S = 1.15
7.9Na2O‐6.0B2O3‐2.0Li2O, 1507 F‐free  
C/S = 1.15
CaO‐SiO2‐8.0% Na2O‐B2O3‐2.0% Li2O, C/S = 1.15
3.9, 5.8, 7.9B2O3 1464, 1505, 1456 F‐free Lu B et al5
The bold texts indicate which compositions are changing below.

viscosity with decreasing temperature, as shown in Figure
4. Flux 1 had smaller network structures due to higher CaF2
content, which led to a slight increase in the viscosity with
decreasing temperature.
As the C/S ratio increased from 0.4 (Flux 4) to 0.8 (Flux
5), the activation energy increased, but the viscosity de-
creased. In the FactSage® calculation, Flux 4 and 5 were
expected to form cuspidine (Ca4Si2O7F2) as the precipi-
tated crystalline phase during cooling. In addition, Flux
5 with greater CaO concentrations had a higher thermo-
dynamic driving force for forming cuspidine (Ca4Si2O7F2)
than Flux 4 according to Park et al.9 During cooling, Flux
5 had a higher activation energy for viscous flow by higher
crystallization tendency than Flux 4 because of increased
ionic mass transfer and kinetics associated with the lower
viscosity. It was also observed that the viscosity in solid‐
liquid region below the break temperature was signifi-
cantly increased by the precipitated crystals, as shown in
Figure 5B.
With a higher C/S ratio from 0.8 (Flux 5) to 1.0 (Flux
6), the activation energy decreased. The depolymerized
network structures by higher C/S ratio led to the lower
viscosity, which also decreased the activation energy be-
cause the smaller network structures had lower resistance
for viscous flow. However, the break temperature increased.
In the CaO‐SiO2‐MgO ternary phase diagrams containing
2 wt% Al2O3, 16 wt% Na2O, and 14 wt% CaF2 which cal-
culated using FactSage® and presented in Figure 15. In
the phase diagram, higher C/S ratio increased a liquidus
temperature of the system at above a region having lower
liquidus temperature. It is speculated that the liquidus tem-
perature increased by the precipitated crystals from cus-
pidine (Ca4Si2O7F2) to merwinite (Ca3MgSi2O8) having
higher crystallization temperature with higher C/S ratio.
Therefore, the break temperature increases with increasing
C/S ratio.
According to Lee et al,60 the activation energy for vis-
cous flow was dominated by the equilibrium of the silicate
anion structural units as shown in Figure 16 which also rep-
resented the effect of the precipitated crystalline phases on
determining the activation energy for viscous flow in this
study using the FactsSage® calculation as shown in Figure
15. The C/S ratio led to change the activation energy for vis-
cous flow by the precipitated crystalline phase which altered
KIM and SOHN
F I G U R E 1 5   CaO‐SiO2‐MgO ternary phase diagram containing 2 wt% Al2O3, 16 wt% Na2O, and 14 wt% CaF2 calculated by FactSage®
F I G U R E 1 6   Activation energy (kJ/mol) for viscous flow and
the C/S ratio
with the C/S ratio according to the phase diagram as shown
in Figure 15. When the precipitated crystalline phase was not
changed, the activation energy for viscous flow increased by
the higher thermodynamic driving force for forming the cus-
pidine (Ca4Si2O7F2) with higher CaO contents. With higher
C/S ratio, the precipitated crystalline phase the precipitate
     13
|
crystalline phase changed from cuspidine (Ca4Si2O7F2) to
merwinite (Ca3MgSi2O8), which decreased the activation
energy for viscous flow by higher CaO contents. Therefore,
the precipitate crystalline phase changed from cuspidine
(Ca4Si2O7F2) to merwinite (Ca3MgSi2O8) with the higher
C/S ratio in this system, which also altered the activation en-
ergy for viscous flow.
From the results of Flux 5 and 7, no appreciable effect
with B2O3 up to 4.4 wt% on the activation energy could be
observed, but B2O3 did lower the break temperature, which
lowered the crystallization temperature and extended the
solid‐liquid co‐existing region. As the B2O3 content in-
creased up to 8.8 wt%, the activation energy decreased due
to the depolymerized network structures by the O− in bo-
rate structural units. The break temperature also decreased
because the increased B2O3 content (with its low melting
temperature) inhibited the crystallization tendency.2,16,61,62
4  |  CONCLUSIONS
The influence of CaF2, CaO/SiO2 mass ratio, and B2O3 on
the viscous behaviors, structures, break temperatures, and
activation energy for the viscous flow was investigated and
 |
14      KIM and SOHN
correlated using a rheometer, FTIR and Raman spectros-
copy, and FactSage® calculations. The limited modifications
of the viscosities and structures of the fluxes were achieved
with 14 wt% CaF2, CaO/SiO2 ratio of 0.8, and 4.4 wt% B2O3,
respectively. According to the structural analyses, the net-
work structures were highly depolymerized at above 14 wt%
CaF2 and 4.4 wt% B2O3, otherwise, the structures occasion-
ally depolymerized above a CaO/SiO2 ratio of 0.8. Unlike
other fluidizers such as CaO, Na2O, Li2O, and CaF2, B2O3
transformed from [BO3] to [BO4] by alkali and alkali earth
cations and free oxygen ions (O2−), which randomly con-
nected to [SiO4]‐tetrahedral structures and produced BO2O−
structural units containing non‐bridging oxygen (O−) and
[BO4]‐tetrahedral units. The process corrupts the uniform-
ity of structures and influences the viscous behaviors, break
temperature, and activation energy for the viscous flow. The
break temperature and the activation energy for the viscous
flow were related to not only the network structures but also
the primary crystalline phases, as elucidated by the Einstein‐
Roscoe equation and FactSage® calculations. Generally,
CaF2 and B2O3 additions decreased the viscosity, the break
temperatures, and the activation energy for the viscous flow
if the crystallization phases were the same in the solid‐liquid
co‐existing region. With a higher CaO/SiO2 ratio, the vis-
cosity decreased, and the break temperature and the activa-
tion energy influenced the crystallization behavior. Finally,
the addition of B2O3 extended the solid‐liquid co‐existing
region by inhibiting the precipitation of the primary crystal
phases.
ACKNOWLEDGMENTS
This research was supported by the Graduate School of
YONSEI University Research Scholarship Grants in 2017
and National Research Foundation of Korea, Project No.
NRF‐2018R1A2B2006609.
ORCID
Gi Hyun Kim  https://orcid.org/0000-0002-7101-9353
Il Sohn  https://orcid.org/0000-0002-8571-9182
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