A Further Evaluation of the Coupling Relationship between Dephosphorization and Desulfurization Abilities or Potentials for CaO-based Slags : Influence of Slag Chemical Composition

Xue Min Yang 1,*, Jin Yan Li 2, Meng Zhang 2, Fang Jia Yan 1, Dong Ping Duan 1 and Jian Zhang 3 1 CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China; yanfangjia@gmail.com (F.J.Y.); douglass@ipe.ac.cn (D.P.D.) 2 Department of Metallurgy and Raw Materials, China Metallurgical Industry Planning and Research Institute, Beijing 100711, China; lijinyan@mpi1972.com (J.Y.L.); zhangmeng@mpi1972.com (M.Z.) 3 School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China; zhangjian_27@126.com * Correspondence: yangxm71@ipe.ac.cn; Tel.: +86-10-82544930


Introduction
For the purpose of refining low or ultra-low phosphorus and sulfur steel products with high mechanical properties, simultaneous dephosphorization and desulfurization of iron-based melts has been widely applied as a routine sub-process during hot metal pretreatment operation and the secondary refining process of molten steel in most metallurgical companies.It is well known that the greater oxygen potential of slags or iron-based melts, higher content of basic oxides in slags, and lower temperature at dephosphorization zone are three preferred operation conditions for promoting dephosphorization reactions under a fixed mass ratio of slags to iron-based melts from the viewpoint of dephosphorization thermodynamics.However, the corresponding three preferred operation conditions for promoting desulfurization reactions can be summarized as smaller oxygen potential of slags or iron-based melts, higher content of basic oxides in slags, and higher temperature at the desulfurization zone.Evidently, conditions for promoting dephosphorization reactions are to some degree opposite to those for enhancing desulfurization reactions for an assigned slag system.Moreover, a larger amount of slags or fluxes is also beneficial for promoting dephosphorization as well as desulfurization from the viewpoint of kinetics.However, a reasonable mass ratio of slags to iron-based melts should be controlled in order to decrease production cost in industrial plants.It can be concluded that besides the easily controlled temperature and content of basic oxides in slags or fluxes, controlling the optimal range of slag oxidization ability is a challenging task to successfully maintain ideal dephosphorization ability and acceptable desulfurization ability during simultaneous dephosphorization and desulfurization processes of iron-based melts.
CaO-Fe t O-Al 2 O 3 slag system was recommended by Ban-ya et al. [1] for simultaneous dephosphorization and desulfurization during the secondary refining process of molten steel.The recommended CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags by Ban-ya et al. [1] exhibited a large variation range of slag oxidization ability with the mass percentage of Fe t O varying from 1.88 to 55.50.Nevertheless, no conclusions or results on the linkage between dephosphorization and desulfurization abilities or potentials of the slags were provided by Ban-ya et al. [1].The coupling relationships between dephosphorization and desulfurization abilities or potentials for CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags [1] over a large range of slag oxidization ability during the secondary refining process of molten steel have been recently proposed by Yang et al. [2] as log L P + 5 log L S or log C  [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18].The proposed coupling relationships [2] for the CaO-based slags have been verified to be independent of slag oxidization ability as expected.
It should be specially mentioned that the linkage between phosphate capacity C PO 3−   4   and sulfide capacity C S 2− for slags was first correlated by Sano et al. [19] in 1990 as log C which is also derived in details by Yang et al. [2] However, Ban-ya et al. [20,21] clearly proved and argued that the ratio of the activity coefficient to the standard equilibrium constant, i.e., f %, i /K Θ i or γ i /K Θ i , of dephosphorization and desulfurization products cannot hold constant in multi-components solutions like molten slags, fluxes and salts.Thus, the assumption of the term on the right-hand side of the relationship between C PO 3−   4   and C S 2− by Sano et al. [19] being constant is not a theoretically correct conclusion.Furthermore, the intrinsic relationship between the phosphorus distribution ratio L P = (% P 2 O 5 )/[% P] 2 and sulfur distribution ratio L S = (% S)/[% S] for slags with fixed chemical compositions has scarcely been investigated.
Under these circumstances, the proposed coupling relationships for the CaO-based slags should be further verified and evaluated from the viewpoint of whether or not they are also independent of slag chemical composition.The slag chemical composition was described in this contribution by Metals 2018, 8, 1083 3 of 27 three group parameters including the reaction abilities of components described by the mass action concentrations N i , activity a R, i relative to pure liquid or solid matters as standard state, slag basicity containing simplified complex basicity (% CaO)/[(% P 2 O 5 ) + (% Al 2 O 3 )] or optical basicity Λ, and the comprehensive influence of iron oxides Fe t O and basic oxide CaO.
The ultimate objectives of this study can be summarized as (1) to further verify the linkage between dephosphorization and desulfurization abilities or potentials for a fixed flux or slags not only regardless of slag oxidization ability as expected but also independent of slag chemical composition; (2) to provide fundamental information for optimizing the chemical composition of slags or fluxes with the aim of enhancing simultaneous dephosphorization and desulfurization abilities or potentials of iron-based melts by a fixed flux or slags; (3) to enrich the foundations of the reaction mechanism during the simultaneous dephosphorization and desulfurization process of iron-based melts by a fixed flux or slags over a large variation range of slag oxidization ability; (4) moreover, to open new application fields of the IMCT [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] for metallurgical slags.

Influence of Slag Chemical Composition on Proposed Coupling Relationships between Dephosphorization and Desulfurization Abilities and Potentials for CaO-based Slags
The chemical compositions of CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags equilibrated with liquid iron by Ban-ya et al. [1] and three parameters for representing slag oxidization ability as the mass percentage of Fe t O through (% Fe t O) = (% FeO) + 0.9(% Fe 2 O 3 ); calculated [3] comprehensive mass action concentration N Fe t O of Fe t O and oxygen potential p O 2 of the CaO-based slags over a temperature range from 1811 to 1927 K (1538 to 1654 • C) are summarized in Table 1.In addition, the determined [2] and calculated [2] coupling relationship terms as log L P + 5 log L S or log C  [1], predicted log L IMCT P, calculated [3] or log L IMCT S, calculated [4] by the IMCT models, determined log C PO 3− 4 , determined [3] or determined log C S 2− , determined [5] after Ban-ya et al. [1], and predicted log C IMCT PO 3− 4 , calculated [3] or log C IMCT S 2− , calculated [5] by the IMCT models are also tabulated in Table 2 for comparison.Thus, the effects of chemical composition of slags described by three group parameters including the reaction abilities of components represented by the mass action concentrations N i , two kinds of slag basicity as simplified complex basicity (% CaO)/[(% P 2 O 5 ) + (% Al 2 O 3 )] and optical basicity Λ, and the comprehensive effect of iron oxides Fe t O and basic oxide CaO on proposed coupling relationships [2] for the CaO-based slags are further evaluated in the next section.
Table 1.Chemical compositions of CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags over a large range of slag oxidization ability equilibrated with liquid iron after Ban-ya et al. [1] and three parameters for representing slag oxidization ability as the mass percentage of Fe t O, calculated [3] comprehensive mass action concentration N Fe t O of Fe t O, and oxygen potential [3] p O 2 of the slags over a temperature range from 1811 to 1927 K (1538 to 1654 • C).

New Test
No. [ [3] or log L IMCT S, calculated [4] by the IMCT models, determined log C PO 3− 4 , determined [3] or determined log C S 2− , determined [5] after Ban-ya et al. [1], and predicted log C IMCT PO 3− 4 , calculated [3] or log C IMCT S 2− , calculated [5] by the IMCT models over a temperature range from 1811 to 1927 K (1538 to 1654 It was verified [3] that good corresponding relationships between mass percentages of components and calculated [3] mass action concentrations N i of CaO, FeO, Fe 2 O 3 , and Al 2 O 3 as components are established for the CaO-based slags.Thus, the calculated [3] mass action concentrations N i of components based on the IMCT [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] can be applied to the representation of the chemical composition of the CaO-based slags, like the mass percentage (% i) of components.As a newly-formed structural unit FeO • Fe 2 O 3 , according to the IMCT [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18], the calculated [3][4][5] mass action concentration N FeO•Fe 2 O 3 of FeO • Fe 2 O 3 can be used to describe the reaction ability of FeO•Fe 2 O 3 .In addition, the calculated [3][4][5] comprehensive mass action concentration N Fe t O of iron oxides Fe t O can also be applied to the description of reaction ability of Fe t O. Thus, the calculated [3][4][5] [3] phosphorus distribution ratio log L IMCT P, calculated using the IMCT-L P model for the CaO-based slags equilibrated with liquid iron are shown in the first layers of Figure 1.Likewise, the relationships of the N i of six components against the calculated [4] sulfur distribution ratio log L IMCT S, calculated using the IMCT-L S model for the CaO-based slags are also illustrated in the second layers of Figure 1.Meanwhile, the relationship of the aforementioned N i of the six components against determined log L P, measured + 5 log L S, measured or log L P, measured + log L S, measured − 5 log N Fe t O after original data from Ban-ya et al. [1], or calculated log L IMCT P, calculated + 5 log L IMCT S, calculated or log L IMCT P, calculated + log L IMCT S, calculated − 5 log N Fe t O based on results by Yang et al. [3,4] for the CaO-based slags is displayed in the first and second layers of Figure 2, respectively.The average values of term log L P + 5 log L S or log L P + log L S − 5 log N Fe t O after original data from Ban-ya et al. [1] or based on results from Yang et al. [3,4] over three sub-divided temperature ranges are also exhibited in Figure 2 by lines.The distinguishing lines between CaS and FeS for representing the reducing and oxidizing zones are added on the horizontal ordinates in the sub-figures of Figure 1 and other figures in the following text if necessary.To improve the display resolution, the horizontal ordinates in the sub-figures of Figure 1 and other figures in the following text, if necessary, are also split into two zones through adding break symbols for describing the reducing and oxidizing zones.It should be emphasized that the exponential growing tendency of the phosphorus distribution ratio log L P = log (% P 2 O 5 )/[% P] 2 against the slag oxidization ability expressed by N Fe t O of iron oxides in Figure 1(f1) as well as the backward tick-shaped or asymmetrical relationship of the sulfur distribution ratio log L S = log{(% S)/[% S]} against N Fe t O of iron oxides in Figure 1(f2) based on the normal scale of the horizontal ordinates cannot normally be displayed.However, the intrinsic relationships of the mass action concentrations N i of six components against log L P or log L S cannot be changed by adding break symbols on the horizontal ordinates in the sub-figures of Figure 1.It can be observed in Figures 1 and 2  With regard to the dephosphorization ability of the CaO-based slags, it can be observed in the first layers of Figure 1 that increasing N CaO or N Al 2 O 3 can result in a significantly decreasing tendency of log L P as shown in Figure 1(a1,d1); however, increasing N FeO , N Fe 2 O 3 or N FeO•Fe 2 O 3 can lead to an increasing trend of log L P as shown in Figure 1(b1,c1,e1).Certainly, the result in Figure 1 3(b,c,e); however, increasing N Fe t O can lead to a decreasing trend of N CaO or N Al 2 O 3 as illustrated in Figure 3(a,d).The promotive effect of increasing N Fe t O on log L P can be counteracted by the decrease of N CaO for the CaO-based slags.There are some extreme proofs to support this finding as the CaO-based slags with high CaO but very low Fe t O, which are widely applied at reduction stage during electric arc furnace (EAF) steelmaking process or used during the blast furnace (BF) ironmaking process, can only extract sulphur, rather than phosphorus, from iron-based melts.Thus, not only the independent effect of iron oxides Fe t O and basic oxide CaO, but also the comprehensive effect of iron oxides Fe t O and basic oxide CaO plays a decisive role in log L P between the CaO-based slags and liquid iron.This finding is in good agreement with the well-known conclusion that the CaO-based slags with middle Fe t O and high CaO, which are commonly used in a top-bottom combined oxygen blowing converter for the steelmaking process or dephosphorization pretreatment of hot metal, indicates a greater dephosphorization ability coupling with limited desulfurization ability for iron-based melts.This result can be applied to the explanation of reason that the promotive effect of increasing N FeO or N Fe 2 O 3 or N FeO•Fe 2 O 3 or N Fe t O on log L P can be counteracted by a decrease of N CaO for the CaO-based slags as shown in Figure 1 With respect to the desulfurization ability of the CaO-based slags, it can be obtained from the second layers of Figure 1 , and Fe t O (f) against determined term log L P, measured + 5 log L S, measured or log L P, measured + log L S, measured − 5 log N Fe t O after Ban-ya et al. [1] in the first layer or calculated term log L IMCT P, calculated + 5 log L IMCT S, calculated or log L IMCT P, calculated + log L IMCT S, calculated − 5 log N Fe t O based on the results from Yang et al. [3,4] in the second layer for CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags equilibrated with liquid iron over a temperature range of 1811 to 1927 K (1538 to 1654 • C), respectively.f1) and 1(f2) but is also irrelevant to the mass action concentrations i N of six components over a narrow temperature range.

Influences of Reaction Abilities of Components on Coupling Relationships between Dephosphorization and Desulfurization Potentials for CaO-based Slags
The relationship of calculated [3][4][5] mass action concentrations i N of six components as CaO, FeO, Fe2O3, Al2O3, FeO•Fe2O3, and FetO against the calculated [3] phosphate capacity With respect to the desulfurization ability of the CaO-based slags, it can be obtained from the second layers of Figure 1 that increasing N CaO or N Al 2 O 3 accompanied with a decrease in N FeO or N Fe 2 O 3 or N FeO•Fe 2 O 3 or N Fe t O can result in an obviously increasing tendency of the sulfur distribution ratio log L S of the CaO-based slags in the reducing zone.This result can be reasonably explained by the IMCT-L S model [4] for the CaO-based slags in the reducing zone that basic oxide CaO expressed by N CaO shows a promoting effect on desulfurization ability, while iron oxides Fe t O expressed by N Fe t O exhibit a decaying influence on the desulfurization ability of the CaO-based slags in the reducing zone.However, increasing slag oxidization ability, i.e., increasing N FeO or N Fe 2 O 3 or N FeO•Fe 2 O 3 or N Fe t O , can lead to a slightly increasing trend of log L S of the CaO-based slags in the oxidizing zone.This result can be explained by the IMCT-L S model [4] for the CaO-based slags in the oxidizing zone that only ferrous oxide FeO expressed by N FeO influences log L S of the CaO-based slags in the oxidizing zone.
On the proposed coupling relationships [2] between L P and L S for the CaO-based slags, it can be observed in Figure 2 that the proposed terms log L P + 5 log L S in the reducing zone and log L P + log L S − 5 log N Fe t O in the oxidizing zone are doubtlessly independent of variation of N CaO or N Al 2 O 3 as well as Increasing temperature from 1811 to 1927 K (1538 to 1654 • C) can result in a slightly decreasing tendency of proposed coupling relationships between L P and L S for the CaO-based slags.Thus, the proposed coupling relationships between L P and L S are not only independent of the slag oxidization ability as shown in Figure 1(f1,f2) but is also irrelevant to the mass action concentrations N i of six components over a narrow temperature range.

Influences of Reaction Abilities of Components on Coupling Relationships between Dephosphorization and Desulfurization Potentials for CaO-based Slags
The relationship of calculated [3][4][5] -   PO , determined log C after the original data from Ban-ya et al. [1], especially over the lower temperature range, is caused by the relationship [3,11] between P L and

FeS
for slags.Evidently, the accuracy of the phosphorus distribution ratio P L is very important to obtain the precise phosphate capacity

C
of slags through the relationship [3,11] between P L and   With respect to the dephosphorization potential of the CaO-based slags, it can be observed in the first layers of Figure 4 that phosphate capacity C PO 3− 4 of the CaO-based slags is almost unchangeable with the increase of N i of six components over a narrow temperature range because the comprehensive effect of iron oxides Fe t O and basic oxide CaO plays the key role in dephosphorization potential of the CaO-based slags as discussed in Section 2.3.2 and elsewhere [3].
With regard to the desulfurization potential [5] of the CaO-based slags, it can be observed in the second layers of Figure 4 that sulfide capacity C S 2− of the CaO-based slags in the reducing zone also keeps almost constant with the increase of N i of six components.However, sulfide capacity C S 2− of the CaO-based slags in the oxidizing zone displays an obviously increasing tendency with the increase of N FeO or N Fe 2 O 3 or N FeO•Fe 2 O 3 or N Fe t O over a narrow temperature range, but exhibits a largely decreasing trend with the increase of N CaO or N Al 2 O 3 , which has been explained elsewhere [5].Basic oxides CaO expressed by N CaO largely the affect desulfurization potential of the CaO-based slags in the reducing zone from the IMCT-C S 2− model [5], while ferrous oxides expressed by N FeO significantly influence the desulfurization potential of the CaO-based slags in the oxidizing zone from the IMCT-C S 2− model [5].The very small decreasing tendency of N CaO in the reducing zone in Figure 3 the corresponding phosphorus distribution ratio L P through the relationship [3,11] between L P and C PO 3− 4 for slags, meanwhile, sulfide capacity C S 2− of slags can also be determined or calculated from the sulfur distribution ratio L S through the relationship [5,7,9] between L S and C S 2− for slags.It was verified by Yang et al. [4,5] that the calculated [4] results of log L IMCT S, calculated by the IMCT-L S model are in good consistency with measured [1] ones by Ban-ya et al., meanwhile the calculated [5] results of log C IMCT S 2− , calculated by the IMCT-C S 2− model are in good accord with determined [5] log C S 2− , determined after the original data from Ban-ya et al. [1].However, it was also verified by Yang et al. [3] that the calculated results of log L IMCT P, calculated by the IMCT-L P model are not in good agreement with the measured log L P, measured by Ban-ya et al. [1], especially over the lower temperature range of 1811 to 1828 K (1538 to 1555 • C).Thus, the large deviation between calculated [3]  Ban-ya et al. [1], especially over the lower temperature range, is caused by the relationship [3,11] between L P and C  [3,5] are more accurate than those against determined ones after original data from Ban-ya et al. [1] for the CaO-based slags.

Influence of Slag Basicity on Coupling Relationships between Dephosphorization and Desulfurization Abilities for CaO-based Slags
The relationship between the simplified complex basicity (% CaO)/[(% P 2 O 5 ) + (% Al 2 O 3 )] or optical basicity Λ and calculated [3] phosphorus distribution ratio log L IMCT P, calculated for the CaO-based slags is shown in the first layers of Figure 6, respectively.Similarly, the relationship between the two kinds of slag basicity and the calculated [4] sulfur distribution ratio log L IMCT S, calculated for the CaO-based slags is also illustrated in the second layers of Figure 6, respectively.The relationship between two kinds of slag basicity and determined term log L P, measured + 5 log L S, measured or log L P, measured + log L S, measured − 5 log N Fe t O after original data from Ban-ya et al. [1], or calculated log L IMCT P, calculated + 5 log L IMCT S, calculated or log L IMCT P, calculated + log L IMCT S, calculated − 5 log N Fe t O based on results by Yang et al. [3,4] for the CaO-based slags are displayed in the first and second layers of Figure 7, respectively.It can be obtained from Figures 6 and 7 that the criterion for distinguishing, reducing and oxidizing zones corresponds to simplified complex basicity (% CaO)/[(% P 2 O 5 ) + (% Al 2 O 3 )] in 1.56 or optical basicity Λ in 0.80, respectively.It should be pointed out that the obtained criterion of optical basicity Λ as 0.80 for separating the reducing and oxidizing zones in this study is in good agreement with that by Young et al. [25] for developing the sulfide capacity C S 2− prediction model of CaO-SiO 2 -MgO-FeO-MnO-Al 2 O 3 slags.
With respect to the dephosphorization ability of the CaO-based slags, it can be observed in the first layers of Figure 6 that increasing two kinds of slag basicity can result in an exponentially growing tendency of the phosphorus distribution ratio log L P , which has been explained by Yang et al. elsewhere [3].Regarding the desulfurization ability of the CaO-based slags, it can be obtained from the second layers of Figure 6 that increasing two kinds of slag basicity can lead to a backward tick-shaped variation trend of sulfur distribution ratio log L S , which has been explained by Yang et al. elsewhere [4].Certainly, adding break symbols on the horizontal ordinates in the sub-figures of Figure 6 can only destroy the apparent relationship of the exponentially growing tendency of log L P against two kinds of slag basicity in the first layers of Figure 6 as well as the backward tick-shaped or asymmetrical relationship of log L S against two kinds of slag basicity in the second layers of Figure 6.The intrinsic relationships of two kinds of slag basicity against log L P or log L S cannot be changed through adding break symbols on the horizontal ordinates in the sub-figures of Figure 6.Yang et al. [3,4] in the second layer for CaO-FeO-Fe2O3-Al2O3-P2O5 slags equilibrated with liquid iron over a temperature range of 1811 to 1927 K (1538 to 1654 °C), respectively.With respect to the proposed coupling relationships [2] between L P and L S for the CaO-based slags, it can be observed in Figure 7 that increasing two kinds of slag basicity cannot cause a visible variation of the proposed term log L P + 5 log L S or log L P + log L S − 5 log N Fe t O for the CaO-based slags over a narrow temperature range.Thus, the proposed coupling relationships [2] between L P and L S for the CaO-based slags are also independent of simplified complex basicity (% CaO)/[(% P 2 O 5 ) + (% Al 2 O 3 )] or optical basicity Λ.

Influence of Slag Basicity on Coupling Relationship between Dephosphorization and Desulfurization Potentials for CaO-based Slags
The relationships of two kinds of slag basicity against calculated [3]  Likewise, the relationships of two kinds of slag basicity against calculated [5] sulfide capacity log C IMCT S 2− , calculated for the CaO-based slags are also illustrated in the second layers of Figure 8, respectively.
The relationships of two kinds of slag basicity against determined term log C changed through adding break symbols on the horizontal ordinates in the sub-figures of Figure 6.
With respect to the proposed coupling relationships [2] between P L and S L for the CaO-based slags, it can be observed in Figure 7  or optical basicity Λ .

Influence of Slag Basicity on Coupling Relationship between Dephosphorization and Desulfurization Potentials for CaO-based Slags
The relationships of two kinds of slag basicity against calculated [3] phosphate capacity Likewise, the relationships of two kinds of slag basicity against calculated [5] sulfide capacity  With respect to the dephosphorization potential of the CaO-based slags, it can be observed in the first layers of Figure 8 that increasing two kinds of slag basicity cannot result in an obvious With respect to the dephosphorization potential of the CaO-based slags, it can be observed in the first layers of Figure 8 that increasing two kinds of slag basicity cannot result in an obvious influence on dephosphorization potential over a narrow temperature range, which has been explained by Yang et al. elsewhere [3].With regard to the desulfurization potential of the CaO-based slags, it can be observed in the second layers of Figure 8 that the desulfurization potential of the CaO-based slags in the reducing zone keeps almost constant with the increase of two kinds of slag basicity as illustrated in the left regions of Figure 8(a2,b2); however, sulfide capacity C S 2− of the CaO-based slags in oxidizing zone displays an obviously increasing tendency with the increase of two kinds of slag basicity as illustrated in the right regions of Figure 8(a2,b2), which has been explained by Yang et al. elsewhere [5].
CaO-based slags in the reducing zone keeps almost constant with the increase of two kinds of slag basicity as illustrated in the left regions of Figures 8(a2) and 8(b2); however, sulfide capacity   [3,4] are more accurate than those against determined ones after original data from Ban-ya et al. [1] for the CaO-based slags in the reducing or oxidizing zone.Thus, the proposed coupling relationships [2] between for the CaO-based slags are also independent of two kinds of slag basicity over a narrow temperature range.

Comprehensive Effect of FetO and CaO on Coupling Relationships between Dephosphorization and Desulfurization Abilities or Potentials for CaO-based Slags
It was verified by Yang et al. [3][4][5] that the mass percentage ratios or the mass action concentration ratios of various iron oxides to basic oxide CaO can be applied to the elucidation of the comprehensive effect of iron oxides FetO and basic oxide CaO on dephosphorization and + log C IMCT S 2− , calculated − log N FeO based on the results by Yang et al. [3,4] are more accurate than those against determined ones after original data from Ban-ya et al. [1] for the CaO-based slags in the reducing or oxidizing zone.Thus, the proposed coupling relationships [2] between C PO 3− 4 and C S 2− for the CaO-based slags are also independent of two kinds of slag basicity over a narrow temperature range.

Comprehensive Effect of Fe t O and CaO on Coupling Relationships between Dephosphorization and Desulfurization Abilities or Potentials for CaO-based Slags
It was verified by Yang et al. [3][4][5] that the mass percentage ratios or the mass action concentration ratios of various iron oxides to basic oxide CaO can be applied to the elucidation of the comprehensive effect of iron oxides Fe t O and basic oxide CaO on dephosphorization and desulfurization reactions of the CaO-based slags.It was also verified by Yang et al. [4] that the mass percentage ratio (% FeO)/(% CaO) or (% Fe 2 O 3 )/(% CaO) or (% Fe t O)/(% CaO) can correlate a good linear relationship with the mass action concentration ratio N FeO /N CaO or N Fe 2 O 3 /N CaO or N Fe t O /N CaO for the CaO-based slags, respectively.Thus, the aforementioned mass action concentration ratios of various iron oxides to basic oxide CaO can be reliably substituted by the corresponding mass percentage ratios.As the newly formed structural unit FeO•Fe 2 O 3 in the CaO-based slags in terms of the IMCT [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18], the mass action concentration ratio N FeO•Fe 2 O 3 /N CaO is also applied to the evaluation of the comprehensive influence of FeO•Fe 2 O 3 and basic oxide CaO on the proposed coupling relationships [2].

Comprehensive Effect of Fe t O and CaO on Coupling Relationships between Dephosphorization and Desulfurization Abilities for CaO-based Slags
The relationship between the mass action concentration ratios of various iron oxides to basic oxide CaO, i.e., N FeO /N CaO or N Fe 2 O 3 /N CaO or N FeO•Fe 2 O 3 /N CaO or N Fe t O /N CaO and calculated [3] phosphorus distribution ratio log L IMCT P, calculated for the CaO-based slags is shown in the first layers of Figure 10, respectively.Similarly, the relationship between aforementioned four mass action concentration ratios and calculated [4] sulfur distribution ratio log L IMCT S, calculated for the CaO-based slags is also illustrated in the second layers of Figure 10, respectively.The relationships between four mass action concentration ratios and determined term log L P, measured + 5 log L S, measured or log L P, measured + log L S, measured − 5 log N Fe t O after original data from Ban-ya et al. [1], or calculated term log L IMCT P, calculated + 5 log L IMCT S, calculated or log L IMCT P, calculated + log L IMCT S, calculated − 5 log N Fe t O based on results by Yang et al. [3,4] for the CaO-based slags are displayed in the first and second layers of Figure 11, respectively.It can be observed in Figures 10 and 11 that the criterion for distinguishing the reducing and oxidizing zones corresponds to N FeO /N CaO in 0.08, N Fe 2 O 3 /N CaO in 1.59 × 10 −4 , N FeO•Fe 2 O 3 /N CaO in 5.27 × 10 −5 , and N Fe t O /N CaO in 0.082, respectively.
With respect to the dephosphorization ability of the CaO-based slags, it can be observed in the first layers of Figure 10 that increasing four mass action concentration ratios can result in an exponentially growing tendency of the phosphorus distribution ratio log L P , which has been discussed by Yang et al. elsewhere [3].With regard to the desulfurization ability of the CaO-based slags, it can be obtained from the second layers of Figure 10 that increasing four mass action concentration ratios can lead to a backward tick-shaped variation trend of sulfur distribution ratio log L S , which has been discussed by Yang et al. elsewhere [4].
On the proposed coupling relationships [2] between L P and L S for the CaO-based slags, it can be observed in Figure 11 that the proposed term log L P + 5 log L S or log L P + log L S − 5 log N Fe t O after original data from Ban-ya et al. [1] or based on results by Yang et al. [3,4] keeps almost constant with the increase of four mass action concentration ratios for the CaO-based slags in reducing and oxidizing zones over a narrow temperature range.Thus, the proposed coupling relationships [2] between L P and L S for the CaO-based slags are independent of the comprehensive influence of iron oxides Fe t O and basic oxides expressed by the mass action concentration ratio N FeO /N CaO or N Fe 2 O 3 /N CaO or N FeO•Fe 2 O 3 /N CaO or N Fe t O /N CaO , or the mass percentage ratio (% FeO)/(% CaO) or (% Fe 2 O 3 )/(% CaO) or (% Fe t O)/(% CaO).concentration ratios of various iron oxides to basic oxide CaO can be reliably substituted by the corresponding mass percentage ratios.As the newly formed structural unit FeO•Fe2O3 in the CaO-based slags in terms of the IMCT [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18], the mass action concentration ratio also applied to the evaluation of the comprehensive influence of FeO•Fe2O3 and basic oxide CaO on the proposed coupling relationships [2].[3,4] in the second layer for CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags equilibrated with liquid iron over a temperature range of1811 to 1927 K (1538 to 1654 • C), respectively.

Comprehensive Effect of Fe t O and CaO on Coupling Relationships between Dephosphorization and Desulfurization Potentials for CaO-based Slags
The relationship between the aforementioned four mass action concentration ratios of various iron oxides to basic oxide CaO and calculated [3] phosphate capacity log C IMCT PO 3−  4 , calculated for the CaO-based slags is shown in the first layers of Figure 12, respectively.Likewise, the relationship between four mass action concentration ratios and the calculated [4] sulfide capacity log C IMCT S 2− , calculated for the CaO-based slags is also illustrated in the second layers of Figure 12, respectively.The relationship between four mass action concentration ratios and the determined term log C With respect to the dephosphorization potential of the CaO-based slags, it can be observed in the first layers of Figure 12 that increasing the four mass action concentration ratios cannot result in an obvious variation of dephosphorization potential over a narrow temperature range.This result was explained by Yang et al. [3] as that greater values of calculated dephosphorization ability are the reason for larger ones of dephosphorization potential by the IMCT−C   + log C IMCT S 2− , calculated − log N FeO based on results by Yang et al. [3,4] are more accurate than those against determined terms after original data from Ban-ya et al. [1] for the CaO-based slags in the reducing and oxidizing zones.Thus, the proposed coupling relationships [2] between C  composition can significantly affect its dephosphorization and desulfurization abilities or potentials.This means that the maximum values of the sum of dephosphorization and desulfurization abilities or potentials for the assigned slags in reducing and oxidizing zones can be determined by the proposed coupling relationships [2].Additionally, the counteraction characteristics between the dephosphorization and desulfurization abilities or potentials for reducing slags can be theoretically explained and quantitatively expressed as log L P + 5 log L S or log C It has been verified by Yang et al. [3][4][5] that the IMCT-L P [3] or IMCT-C PO 3− 4 [3] or IMCT-L S [4] or IMCT-C S 2− [5] models can be accurately applied to the prediction of dephosphorization and desulfurization abilities or potentials of the assigned slags.Thus, the dephosphorization abilities or potentials of the assigned slags or fluxes can be theoretically predicted from its desulfurization abilities or potentials based on the proposed coupling relationships [2], and vice versa.This means that a new method of designing or optimizing chemical composition of slags or fluxes with the assigned dephosphorization abilities or potentials can be developed based on the proposed coupling relationships [2].
The proposed coupling relationships [2] between dephosphorization and desulfurization abilities as log L P + 5 log L S in the reducing zone and as log L P + log L S − 5 log N Fe t O in the oxidizing zone have been verified to be valid based on the reported equilibrium experiments in laboratory scale by Ban-ya et al. [1] Actually, reactions of dephosphorization and desulfurization at the final stage of many refining processes such as the dephosphorization pretreatment process of hot metal [15][16][17], the simultaneous dephosphorization and desulfurization operation of iron-based melts during secondary refining process [1][2][3][4][5], desulfurization reaction during the ladle furnace (LF) refining process [8,9], dephosphorization reaction at the blowing end-point during top-bottom combined blown converter steelmaking process [10,11], and so on can be considered to reach quasi-equilibrium at the interface between the slags and metal.It can be deduced that the proposed coupling relationships [2] are also suitable to industrial operations during the dephosphorization and desulfurization processes.

Conclusions
The proposed coupling relationships between the dephosphorization and desulfurization abilities or potentials for CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags over a large variation range of slag oxidization ability during the secondary refining process of molten steel as log L P + 5 log L S or log C (1) The proposed coupling relationships for the CaO-based slags in both the reducing and oxidizing zones are not only independent of slag oxidization ability described by the comprehensive mass action concentration N Fe t O of iron oxides but are also irrelevant to the reaction abilities of components expressed by the mass action concentrations N i over a narrow temperature range in comparison with significant influences of slag oxidization ability as well as reaction abilities of components on dephosphorization and desulfurization abilities or potentials.(2) The proposed coupling relationships for the CaO-based slags in both the reducing and oxidizing zones keep almost constant with the variation of two kinds of slag basicity as the simplified complex basicity (% CaO)/[(% P 2 O 5 ) + (% Al 2 O 3 )] and optical basicity Λ over a narrow temperature range compared with the strong effects of two kinds of slags basicity on dephosphorization and desulfurization abilities or potentials.

4 +− 4 +
log C S 2− in the reducing zone and as log L P + log L S − 5 log N Fe t O or log C PO 3log C S 2− − log N FeO in the oxidizing zone through deleting or omitting the term of slag oxidization ability represented by the comprehensive mass action concentration N Fe t O of iron oxides Fe t O based on the ion and molecule coexistence theory (IMCT)

4 = 1 .
5 log C S 2− + const.through deleting activity a O 2− of oxygen ion O 2-in slags.The defined constant term by Sano et al. [19] as log K Θ

4 +− 4 +
log C S 2− in the reducing zone and as log L P + log L S − 5 log N Fe t O or log C PO 3log C S 2− − log N FeO in the oxidizing zone based on measured log L P, measured or measured log L S, measured by Ban-ya et al.

Figure 2 .
Figure 2. Relationship of calculated [3] mass action concentration N i of CaO (a), FeO (b), Fe 2 O 3 (c), Al 2 O 3(d), FeO•Fe 2 O 3 (e), and Fe t O (f) against determined term log L P, measured + 5 log L S, measured or log L P, measured + log L S, measured − 5 log N Fe t O after Ban-ya et al.[1] in the first layer or calculated term log L IMCT P, calculated + 5 log L IMCT S, calculated or log L IMCT P, calculated + log L IMCT S, calculated − 5 log N Fe t O based on the results from Yang et al.[3,4] in the second layer for CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags equilibrated with liquid iron over a temperature range of 1811 to 1927 K (1538 to 1654 • C), respectively.

Figure 3 .
Figure 3. Relationship of calculated [3] comprehensive mass action concentration Fe O t N of iron

3 Figure 3 .
Figure 3. Relationship of calculated [3] comprehensive mass action concentration N Fe t O of iron oxides against calculated [3] mass action concentration N CaO (a) or N FeO (b) or N Fe 2 O 3 (c) or N Al 2 O 3 (d) or N FeO•Fe 2 O 3 (e) for CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags equilibrated with liquid iron over a temperature range of 1811 to 1927 K (1538 to 1654 • C), respectively.

4 + 4 +
mass action concentrations N i of six components as CaO, FeO, Fe 2 O 3 , Al 2 O 3 , FeO•Fe 2 O 3 , and Fe t O against the calculated [3] phosphate capacity log C IMCT PO 3− 4 , calculated using the IMCT-C PO 3− 4 model for the CaO-based slags are shown in the first layers of Figure 4, respectively.Similarly, the relationship of N i of six components against the calculated [5] sulfide Metals 2018, 8, 1083 10 of 27 capacity log C IMCT S 2− , calculated using the IMCT-C S 2− model for the CaO-based slags are also illustrated in the second layers of Figure 4, respectively.The relationship of N i of six components against determined log C PO 3− 4 , determined + log C S 2− , determined or log C PO 3− 4 , determined + log C S 2− , determined − log N FeO after original data from Ban-ya et al. [1], or calculated log C IMCT PO 3− 4 , calculated + log C IMCT S 2− , calculated or log C IMCT PO 3− 4 , calculated + log C IMCT S 2− , calculated − log N FeO based on results by Yang et al. [3,5] for the CaO-based slags are displayed in the first and second layers of Figure 5, respectively.In addition, the average values of term log C PO 3− log C S 2− or log C PO 3− log C S 2− − log N FeO after original data from Ban-ya et al. [1] or based on results from Yang et al. [3,5] over three sub-divided temperature ranges are also exhibited in Figure 5 by horizontal lines, respectively.Metals 2018, 8, x FOR PEER REVIEW 12 of 28

C
for slags.This means that the experimental uncertainties for dephosphorization reactions by Ban-ya et al.[1] can be effectively relieved by the predicted

− 4 +− 4 +− 4 +− 4 +
(a) cannot cause an obvious increasing tendency of desulfurization potential of the CaO-based slags in the reducing zone.Furthermore, sulfide capacity C S 2− of the CaO-based slags in the reducing zone is also independent of N FeO or N Fe 2 O 3 or N FeO•Fe 2 O 3 or N Fe t O .The decreasing tendency of the sulfide capacity C S 2− of the CaO-based slags in the oxidizing zone with the increase of N CaO or N Al 2 O 3 can be attributed to the largely decreasing trend of N Fe t O as shown in Figure 3. Increasing N FeO or N Fe 2 O 3 or N FeO•Fe 2 O 3 or N Fe t O can significantly promote the sulfide capacity C S 2− of the CaO-based slags in oxidizing zone.With regards to the proposed coupling relationships between C for the CaO-based slags, it can be observed in Figure5that the proposed terms[2] log C PO 3log C S 2− and log C PO 3log C S 2− − log N FeO are independent of N i of six components.Increasing temperature from 1811 to 1927 K (1538 to 1654 • C) can result in a decreasing tendency of proposed coupling relationships between C PO 3− 4 and C S 2− for the CaO-based slags.Thus, the proposed coupling relationships between C PO 3− 4 and C S 2− for the CaO-based slags are not only independent of slag oxidization ability as shown in Figure 5(f) but are also irrelevant to the mass action concentrations N i of six components over a narrow temperature range.However, small discrepancies of proposed terms [2] log C PO 3log C S 2− and log C PO 3log C S 2− − log N FeO based on results by Yang et al. [3,5] and that based on determined ones after original data from Ban-ya et al. [1] for the CaO-based slags can be observed in each sub-figure of Figure 5.It is widely accepted that the phosphate capacity C PO 3− 4 of slags can be determined or calculated from Evidently, the accuracy of the phosphorus distribution ratio L P is very important to obtain the precise phosphate capacity C This means that the experimental uncertainties for dephosphorization reactions by Ban-ya et al.[1] can be effectively relieved by the predicted results of log L IMCT P, calculated by the IMCT-L P[3] and log C IMCT .It can be deduced that the relationships of the mass action concentrations N i of six components against calculated coupling relationships between C based on results by Yang et al.

Figure 6 .
Figure 6.Relationship of simplified complex basicity (% CaO)/[(% P 2 O 5 ) + (% Al 2 O 3 )] (a) or optical basicity Λ (b) against the calculated [3] phosphorus distribution ratio log L IMCT P, calculated by the IMCT-L P model in the first layer or calculated [4] sulfur distribution ratio log L IMCT S, calculated by the IMCT-L S model in the second layer for CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags equilibrated with liquid iron over a temperature range of 1811 to 1927 K (1538 to 1654 • C), respectively.

Figure 7 .
Figure 7. Relationship of simplified complex basicity (% CaO)/[(% P 2 O 5 ) + (% Al 2 O 3 )] (a) or optical basicity Λ (b) against the determined term log L P, measured + 5 log L S, measured or log L P, measured + log L S, measured − 5 log N Fe t O after Ban-ya et al. [1] in the first layer or calculated term log L IMCT P, calculated + 5 log L IMCT S, calculated or log L IMCT P, calculated + log L IMCT S, calculated − 5 log N Fe t O based on results from Yang et al. [3,4] in the second layer for CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags equilibrated with liquid iron over a temperature range of 1811 to 1927 K (1538 to 1654 • C), respectively.
-based slags are shown in the first layers of Figure8, respectively.

+
+ log C S 2− , determined or log C PO 3− 4 , determined + log C S 2− , determined − log N FeO after original data from Ban-ya et al. [1], or calculated term log C IMCT log C IMCT S 2− , calculated − log N FeO based on results by Yang et al. [3,5] for the CaO-based slags are displayed in the first and second layers of Figure 9, respectively.
-based slags are shown in the first layers of Figure8, respectively.
-based slags are also illustrated in the second layers of Figure8, respectively.The relationships of two kinds of slag basicity against determined term by Yang et al.[3,5] for the CaO-based slags are displayed in the first and second layers of Figure9, respectively.

Figure 9 .
Figure 9. Relationship of simplified complex basicity (% CaO)/[(% P 2 O 5 ) + (% Al 2 O 3 )] (a) or optical basicity Λ (b) against determined term log C PO 3− 4 , determined + log C S 2− , determined or log C PO 3− 4 , determined + log C S 2− , determined − log N FeO after Ban-ya et al. [1] in the first layer or calculated term log C IMCT PO 3− 4 , calculated + log C IMCT S 2− , calculated or log C IMCT PO 3− 4 , calculated + log C IMCT S 2− , calculated − log N FeO based on results from Yang et al. [3,5] in the second layer for CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags equilibrated with liquid iron over a temperature range of 1811 to 1927 K (1538 to 1654 • C), respectively.Regarding the proposed coupling relationships [2] between C PO 3− 4 and C S 2− for the CaO-based slags, it can be observed in Figure 9 that increasing two kinds of slag basicity cannot cause a visible variation of proposed coupling relationships between C PO 3− 4 and C S 2− for the CaO-based slags over a narrow temperature range.The relationships of two kinds of slag basicity against calculated [2] term log C IMCT PO 3− 4 , calculated + log C IMCT S 2− , calculated or log C IMCT PO 3− 4 , calculated

Figure 10 .Figure 10 .
Figure 10.Relationship of the mass action concentration ratio FeO CaO N N (a) or

Figure 11 .
Figure 11.Relationship of the mass action concentration ratio FeO CaO N N (a) or

PO 3 − 4 ,+Figure 12 .Figure 12 .
Figure 12.Relationship of mass action concentration ratio FeO CaO N N (a) or lower temperature range of 1811 to 1828 K (1538 to 1555 • C).With regard to the desulfurization potential of the CaO-based slags, it can be obtained from the second layers of Figure12that increasing four mass action concentration ratios can lead to the similar variation trend of sulfide capacity C S 2− against slag oxidization ability expressed by N Fe t O of iron oxides in Figure4(f2), which has been explained by Yang et al. elsewhere[5].

Figure 13 . 4 + 4 +
Figure 13.Relationship of the mass action concentration ratio N FeO /N CaO (a) or N Fe 2 O 3 /N CaO (b) or N FeO•Fe 2 O 3 /N CaO (c) or N Fe t O /N CaO (d) against the determined term log C PO 3− 4 , determined + log C S 2− , determined or log C PO 3− 4 , determined + log C S 2− , determined − log N FeO after Ban-ya et al. [1] in the first layer or calculated term log C IMCT PO 3− 4 , calculated + log C IMCT S 2− , calculated or log C IMCT PO 3− 4 , calculated + log C IMCT S 2− , calculated − log N FeO based on results from Yang et al. [3,5] in the second layer for CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags equilibrated with liquid iron over a temperature range of 1811 to 1927 K (1538 to 1654 • C), respectively.On the proposed coupling relationships [2] between C PO 3− 4 and C S 2− for the CaO-based slags, it can be observed in Figure 13 that the proposed term log C PO 3− 4 + log C S 2− or log C PO 3− 4 + log C S 2− − log N FeOafter the original data from Ban-ya et al.[1] or based on results by Yang et al.[3,4] keeps almost for the CaO-based slags are certainly independent of the comprehensive influence of iron oxides Fe t O and basic oxides expressed by the mass action concentration ratio N FeO /N CaO or N Fe 2 O 3 /N CaO or N FeO•Fe 2 O 3 /N CaO or N Fe t O /N CaO , or the mass percentage ratio (% FeO)/(% CaO) or (% Fe 2 O 3 )/(% CaO) or (% Fe t O)/(% CaO).

3 .
Discussion on Proposed Coupling Relationships between Dephosphorization and Desulfurization Abilities or Potentials for CaO-based Slags 3.1.Magnitude of Proposed Coupling Relationships between Dephosphorization and Desulfurization Abilities for CaO-based Slags Values of the phosphorus distribution ratio log L P for the CaO-based slags in the reducing zone as shown in the first layers of Figures 1, 6 and 10 vary from 1.0 to 3.0, while data of the sulfur distribution ratio log L S for the CaO-based slags in the reducing zone, as illustrated in the second layers of Figures 1, 6 and 10, change from 1.7 to 0.9.However, results of the proposed term log L P + 5 log L S for the CaO-based slags in the reducing zone, as displayed in Figures 2, 7 and 11, fluctuate from 6.7 to 8.5.Thus, the magnitude of proposed term log L P + 5 log L S for the CaO-based slags in the reducing zone is mainly decided by that of log L S because the desulfurization ability log L S indicates a five-time contribution to the proposed term log L P + 5 log L S compared with the one-time dephosphorization ability of log L P .It is a well-known viewpoint that reducing slags exhibits good desulfurization ability with limited dephosphorization ability.This means that the magnitude of the proposed term log L P + 5 log L S for the CaO-based slags in the reducing zone is decided by desulfurization ability.Theoretically, higher temperature can promote the desulfurization reaction of the CaO-based slags.However, increasing the temperature from 1811 to 1927 K (1538 to 1654 • C) cannot cause an obvious increase of desulfurization ability for the CaO-based slags as shown in the second layers of Figures 1, 6 and 10.Furthermore, higher temperature can inhibit dephosphorization reactions of the CaO-based slags.Thus, increasing the temperature from 1811 to 1927 K (1538 to 1654 • C) can result in an effectively decreasing influence on dephosphorization ability of the CaO-based slags as illustrated in the first layers of Figures 1, 6 and 10.Evidently, increasing temperature from 1811 to 1927 K (1538 to 1654 • C) can lead to a slightly decreasing tendency of the proposed term log L P + 5 log L S for the CaO-based slags in the reducing zone in Figures 2, 7 and 11.Values of the phosphorus distribution ratio log L P for the CaO-based slags in the oxidizing zone, as shown in the first layers of Figures 1, 6 and 10 vary from 3.0 to 8.0, while the data of the sulfur distribution ratio log L S for the CaO-based slags in the oxidizing zone as illustrated in the second layers of Figures 1, 6 and 10 change from 0.7 to 1.0.However, the results of the proposed term log L P + log L S − 5 log N Fe t O for the CaO-based slags in the oxidizing zone, as displayed in Figures 2, 7 and 11, fluctuate from 9.2 to 10.6.Thus, the magnitude of proposed term log L P + log L S − 5 log N Fe t O for the CaO-based slags in the oxidizing zone is mainly decided by that of log L P .It is a widely-accepted viewpoint that oxidizing slags exhibit good dephosphorization ability with limited desulfurization ability.This indicates that the proposed term log L P + log L S − 5 log N Fe t O for the CaO-based slags in the oxidizing zone is controlled by the dephosphorization ability.This means that the temperature effect on the dephosphorization ability of the CaO-based slags can decide the influence of the increasing temperature from 1811 to 1927 K (1538 to 1654 • C) on the proposed term log L P + log L S − 5 log N Fe t O for the CaO-based slags in the oxidizing zone in Figures 2, 7 and 11.

4 +− 4 +
log C S 2− .The promotive effect of slag oxidization ability described by the comprehensive mass action concentration N Fe t O of iron oxides on the maximum values of the sum of dephosphorization and desulfurization abilities or potentials for oxidizing slags can be reasonably explained and quantitatively described as log L P + log L S − 5 log N Fe t O or log C PO 3log C S 2− − log N FeO .

4 +− 4 +
log C S 2− in the reducing zone and as log L P + log L S − 5 log N Fe t O or log C PO 3log C S 2− − log N FeO in the oxidizing zone have been further verified as valid and feasible through investigating the influence of slag chemical composition.The main summary remarks can be obtained as follows:

( 3 )
The proposed coupling relationships for the CaO-based slags in both reducing and oxidizing zones are independent of the comprehensive effect of iron oxides Fe t O and basic oxide CaO described by the mass action concentration ratio N FeO /N CaO or N Fe 2 O 3 /N CaO or N FeO•Fe 2 O 3 /N CaO or N Fe t O /N CaO , or the mass percentage ratio (% FeO)/(% CaO) or (% Fe 2 O 3 )/(% CaO) or (% Fe t O)/(% CaO) in comparison with the large influences of the aforementioned comprehensive effect of iron oxides Fe t O and basic oxide CaO on dephosphorization and desulfurization abilities or potentials.(4) Increasing the temperature from 1811 to 1927 K (1538 to 1654 • C) can result in a slightly decreasing tendency of the proposed coupling relationships for the CaO-based slags in reducing and oxidizing zones.(5) Chemical composition of slags or fluxes with the assigned dephosphorization ability or potential can be theoretically designed or optimized by its desulfurization ability or potential, and vice versa, in terms of the obtained maximum values of dephosphorization and desulfurization abilities or potentials for the CaO-based slags in both reducing and oxidizing zones.(6) The proposed coupling relationships between L P and L S for the CaO-based slags as log L P + 5 log L S and log L P + log L S − 5 log N Fe t O in reducing and oxidizing zones are recommended to design or optimize the chemical composition of slags or fluxes due to a large difference of magnitude between phosphate capacity C PO 3− 4 and sulfide capacity C S 2− .

Table 2 .
[1]parison between determined and calculated coupling relationship terms between dephosphorization and desulfurization abilities or potentials for CaO-FeO-Fe 2 O 3 -Al 2 O 3 -P 2 O 5 slags over a large range of slag oxidization ability equilibrated with liquid iron during the secondary refining process of molten steel based on measured log L P, measured or log L S, measured by Ban-ya et al.[1], predicted log L IMCT P, calculated Influence of Reaction Abilities of Components on Coupling Relationships between Dephosphorization and Desulfurization Abilities or Potentials for CaO-based Slags • C).
[3][4][5]on concentrations N i of CaO, FeO, Fe 2 O 3 , Al 2 O 3 , FeO•Fe 2 O 3 , and Fe t O are used to represent reaction abilities of components in the CaO-based slags, like the traditional applied activities a R, i of components in the classical metallurgical physicochemistry.2.1.1.Influences of Reaction Abilities of Components on Coupling Relationships between Dephosphorization and Desulfurization Abilities for CaO-based SlagsThe relationships of calculated[3][4][5]mass action concentrations, N i , of six components CaO, FeO, Fe 2 O 3 , Al 2 O 3 , FeO•Fe 2 O 3 , and Fe t O against the calculated that the criterion for distinguishing the reducing and oxidizing zones corresponds to N CaO in 0.778, N FeO in 0.0626, N Fe 2 O 3 in 1.00 × 10 −4 , N Al 2 O 3 in 1.50 × 10 −3 , N FeO•Fe 2 O 3 in 4.10 × 10 −5 , and N Fe t O in 0.0637, respectively.
(a1) is not consistent with the widely-accepted consensus that basic oxide CaO can promote dephosphorization reactions.It can be obtained from the relationship of calculated N Fe t O against N CaO or N FeO or N Fe 2 O 3 or N Al 2 O 3 or N FeO•Fe 2 O 3 for the CaO-basedslags as illustrated in Figure 3 that increasing N FeO or N Fe 2 O 3 or N FeO•Fe 2 O 3 can result in an increasing tendency of N Fe t O as shown in Figure (a1).
that increasing two kinds of slag basicity cannot cause a visible variation of the proposed term + [1]ationship of the mass action concentration ratioN FeO /N CaO (a) or N Fe 2 O 3 /N CaO (b) or N FeO•Fe 2 O 3 /N CaO (c) or N Fe t O /N CaO(d)against the determined term log L P, measured + 5 log L S, measured or log L P, measured + log L S, measured − 5 log N Fe t O after Ban-ya et al.[1]in the first layer or calculated term log L IMCT P, calculated + 5 log L IMCT S, calculated or log L IMCT P, calculated + log L IMCT S, calculated − 5 log N Fe t O based on the results from Yang et al.