Nitrogen Solubility in Liquid Manganese and Ferromanganese Alloys

EUI-JUN KIM, BYUNG-DON YOU, and JONG-JIN PAK The nitrogen solubilities in liquid manganese, manganese-iron, manganese-carbon, and manganeseiron-carbon alloys have been measured by the gas-liquid metal equilibration technique in the temperature range of 1623 to 1823 K. The equilibrium nitrogen content in pure liquid manganese at an atmospheric nitrogen pressure is high, and it does not follow Sieverts law, i.e., fN is not unity. The reduced nitrogen partial pressures by dilution with argon enabled us to obtain more reliable information on the thermodynamics of nitrogen in liquid manganese. The nitrogen dissolution follows Sieverts law at nitrogen contents below 1 wt pct. The standard free-energy change for the dissolution of nitrogen in pure liquid manganese has been determined as 67,222 30.32T J/g atom, with the standard state of nitrogen taken as a 1 wt pct solution. Carbon and iron in manganese-rich melts decrease the nitrogen solubility significantly. The first- and second-order interaction parameters between nitrogen and other elements in manganese alloy melts have been determined. The activity coefficient of nitrogen in a ferromanganese alloy melt can be expressed as log fN 0.005 (pct N) 0.029 (pct N)2 0.015 (pct Fe) 0.09 (pct C) 0.013 (pct C)2 where the interaction parameters are independent of temperature in the temperature range of 1623 to 1823 K.

I. INTRODUCTION

MANGANESE and ferromanganese alloys are widely used as additives in steelmaking processes. The increased demand for ultra-low-carbon and -nitrogen steels requires the production of high-purity ferromanganese alloys. Recently, the oxygen refining of high-carbon ferromanganese is realized as an effective process for the production of low-carbon ferromanganese alloys.[15] In this process, the oxygen-inert gas mixture is injected so that carbon is oxidized in preference to manganese, because CO is diluted with inert gases such as argon and nitrogen. Nitrogen is preferred as an inert gas due to its lower cost. However, a substantial amount of nitrogen would dissolve in molten ferromanganese alloys when nitrogen is used as the inert gas. At present, the nitrogen specification on the low-carbon ferromanganese alloy is less than 500 ppm. There will be a trend toward more stringent nitrogen specifications in ferromanganese alloys in the steel industry, due to the increased production of ultra-low-carbon and -nitrogen steel grades. An understanding of the thermodynamics of nitrogen dissolution in liquid manganese alloys is very important in manufacturing low-nitrogen ferromanganese alloys. For example, in the decarburization of a high-carbon ferromanganese melt by an oxygen-nitrogen gas mixture, the nitrogen solubility in this system varies with nitrogen partial pressure as a function of carbon content and melt temperature. There are some thermodynamic data available for the
EUI-JUN KIM, Graduate Student, and JONG-JIN PAK, Professor, are with the Division of Materials and Chemical Engineering, Hanyang University, Ansan 425 791, Korea. BYUNG-DON YOU, Professor, is with the Division of Materials Science and Engineering, Inha University, Inchon 402-751, Korea. Manuscript submitted March 29, 2000.

nitrogen solubility in pure manganese[612] and manganeseiron melts.[1016] However, there are no data available on the nitrogen solubility in manganese-carbon or manganese-ironcarbon melts. The nitrogen solubility data reported for a pure manganese melt[612] have been measured mostly at an atmospheric nitrogen pressure of 101.33 kPa. The nitrogen solubility in liquid manganese is relatively high, and it is not clear if the nitrogen dissolution follows Sieverts law. Pure liquid metals of very high nitrogen solubility, such as niobium, exhibit a large deviation from Sieverts law,[17] probably due to the interaction between nitrogen atoms in the melt. In order to determine the equilibrium constant for the nitrogen dissolution in liquid manganese, KN ( 1/2 fN (pct N)/PN2 ), the activity coefficient of nitrogen should be determined at various nitrogen contents. Such data can be obtained at reduced partial pressures of nitrogen by dilution with a noble gas. In the present study, the nitrogen solubility in pure liquid manganese was measured at nitrogen partial pressures from 3.04 to 101.33 kPa in the temperature range of 1623 to 1823 K. The effect of nitrogen partial pressure on the nitrogen dissolution behavior was examined to see if it followed Sieverts law. The equilibrium constant for the nitrogen dissolution reaction was determined from the nitrogen solubility data, where the activity coefficient of nitrogen ( fN) can be considered as unity. The temperature dependence of the equilibrium constant was measured to determine the standard free-energy change for the nitrogen dissolution in a manganese melt. The effect of carbon and iron contents on the nitrogen solubility in a manganese melt was also measured, and the interaction parameters between these elements and nitrogen were determined. The present results were used to predict the nitrogen solubility in ferromanganese melts as functions of the melt composition and temperature at given nitrogen partial pressures.

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Fig. 2Variation of nitrogen content with time in pure Mn and Fe melts.

After each experiment, the crucibles containing samples were pulled out of the furnace, quenched rapidly in a helium gas stream, and then water quenched. The time required for this sampling procedure was within 5 seconds. The nitrogen and carbon contents in the metal samples were analyzed by a nitrogen/oxygen determinator (LECO* TC-136) and a
*LECO is a trademark of LECO Corporation, St. Joseph, MI.
Fig. 1A schematic diagram of the experimental apparatus.

II. EXPERIMENTAL Figure 1 shows a schematic diagram of the experimental arrangement. Experiments were carried out in a silicon carbide resistance furnace with a mullite reaction tube. The experimental temperature range was 1623 to 1823 K. A 4 g charge consisted of electrolytic manganese (maximum 0.018 wt pct N and maximum 0.3 wt pct O), which was remelted in the tungsten arc furnace under a deoxidized Ar atmosphere, as well as electrolytic iron (99.999 pct purity) and carbon powder (99.99 pct purity). They were placed in high-purity alumina crucibles (o.d.: 13 mm, i.d.: 9 mm, and height: 25 mm). Five crucibles containing different compositions were tied up by Mo wire and placed in the hot zone of the furnace. The experiments for carbon-saturated melts were carried out in graphite crucibles. The metallic charges were heated in a deoxidized argon atmosphere. The temperature was measured with a Pt-Pt-13 pct Rh thermocouple and was controlled within 2 K. The temperature reading of the thermocouple protected with an alumina tube at the bottom of crucible was corrected by measuring the temperature inside the crucible, using a separate thermocouple, prior to experiments. When the temperature had reached a desired value, the argon gas was switched to a mixture of nitrogen and argon gases. The individual gas flow rates were controlled by the mass-flow controller (Matheson, model 8284), and the total flow rate of gas mixtures was of 500 to 1000 mL/min, depending on the mixing ratio of nitrogen in the gas, which ranged from 0.03 to 1. The gases were passed through columns of heated magnesium turnings, Drierite, and magnesium perchlorate. The mass-flow controller was calibrated at the exit of the gas inlet to within 1 pct with a precision wet-test meter.
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carbon/sulfur analyzer (LECO CS-300), respectively. The manganese and iron contents were measured by inductively coupled plasma (SPECTRO, Spectro Flame) emission spectrometry. Some of the main concerns in the equilibrium gas solubility measurement by the sampling method are how to ensure the attainment of an equilibrium value for a stagnant metallic melt and how to retain the dissolved nitrogen in metals during sampling. In order to establish the equilibration time for the nitrogen solubility measurement, separate experiments were carried out for pure manganese and iron melts. Figure 2 shows that the holding time of 12 hours is sufficient to obtain the gas-metal equilibrium for these melts. Tests were also conducted to see if any delay in quenching would result in a substantial error in determining the nitrogen solubility. Figure 3 shows the effect of the time scale for the sampling procedure on the nitrogen content in quenched manganese samples equilibrated at high and low nitrogen partial pressures at 1673 K. An extended exposure to ambient air for up to 40 seconds prior to quenching did not invalidate the results. The other experimental concern in dealing with liquid manganese or ferromanganese is its high manganese vapor pressure. The nitrogen partial pressure over the melt surface should be corrected by the following equation: PN2 (101,325 PMn) QN2
QAr QN2 [1]

where PMn is the equilibrium manganese vapor pressure of the melt (in Pascals), and QN2 and QAr are the nitrogen and argon gas flow rates (in mL/min), respectively. The value of PMn was calculated from the following equation: PMn aMn PMn [2]

where aMn is the manganese activity referred to pure liquid

METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 4Change of manganese vapor pressure with carbon content in MnC melts.

Fig. 3The effect of time scale for sampling procedure on the nitrogen content in Mn samples.

manganese in liquid manganese alloys. The term PMn is the vapor pressure of pure liquid manganese and is given by Eq. [3].[18]
log PMn 13,900 T
19.395 2.52 log T (in Pascals) [3] where T is the temperature in Kelvin. The activity data for a manganese-iron alloy may be found in the compilation of Hultgren et al.[19] According to the authors recent work,[20] the manganese activity decreases with increasing carbon content in a manganese-carbon melt. Figure 4 shows the variation of the manganese vapor pressure with carbon content in a manganese-carbon melt, calculated by Eq. [2]. III. RESULTS AND DISCUSSION The nitrogen dissolution in liquid manganese and the equilibrium constant can be expressed as 1 N 2 2(g)
KN fN (pct N) 1/2 PN2 (N)1wtpct inMn
fNKN exp GT RT

the melt surface, KN is the apparent equilibrium constant, GT is the Gibbs free-energy change for the dissolution of 1 g atom of nitrogen in liquid manganese, and R and T are the universal gas constant (8.314 J/mole K) and the absolute temperature (in Kelvin), respectively. Therefore, a plot of ln KN vs (pct N), extrapolated to (pct N) 0, would yield ln KN. The ratio of KN/KN at any concentration of nitrogen would give the value of fN. If the solution obeys Henrys law, (pct N) is proportional to the square root of the partial pressure of nitrogen gas. This is the well-known Sieverts law, and the following relationship can be derived from Eq. [5]: (pct N)
1/2 k(T )PN2

exp

HT RT

ST 1/2 PN2 R

[6]

where k(T ) is the temperature-dependent Sieverts constant, and HT and ST are the standard enthalpy and entropy changes for the nitrogen dissolution, where the standard state is a hypothetical 1 wt pct solution of nitrogen in liquid manganese, respectively. A. Pure Manganese Table I summarizes the results of the nitrogen solubility measurement in pure and carbon-saturated manganese melts, under the nitrogen partial pressures of 3.04 to 101.33 kPa at various temperatures. Based upon Eq. [6], the solubility of nitrogen at each nitrogen partial pressure and reaction temperature is plotted against the square root of the nitrogen partial pressure, as shown in Figure 5. The present results took into consideration the change in partial pressure of nitrogen near the melt surface due to the volatilization of manganese. The vapor pressure of the pure manganese melt was calculated according to Eq. [3], and PN2 was corrected by Eq. [1]. For example, the vapor pressure of the pure manganese melt at 1773 K is 2.33 kPa, and it reduces the nitrogen partial pressure about 2.3 pct. Good linear relationships are observed at nitrogen contents below 1 wt pct in the manganese melt. However, a deviation from linearity is observed at high nitrogen contents, indicating that Sieverts law does not hold at high
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[4]
[5]

where (pct N ) is the equilibrium nitrogen content in weight percent, fN is the Henrian activity coefficient of nitrogen for which the reference state is the infinitely dilute solution, i.e., fN 1 when pct N 0. The term PN2 is the nitrogen partial pressure in atmospheres (1 atm 101.325 kPa) over
METALLURGICAL AND MATERIALS TRANSACTIONS B

Table I. Nitrogen Solubility Data for Mn and Mn-Csat. Melts

[Pct N]
Temperature
1623 K

PN2 (kPa)
3.04 5.07 6.08 10.13 15.20 20.27 30.40 40.53 50.66 70.93 101.33 5.07 10.13 20.27 50.66 101.33 5.07 10.13 20.27 40.53 101.33 5.07 20.27 30.40 50.66 101.33

Pure Mn
0.640 0.844 0.928 1.130 1.920 2.654 0.732 1.022 1.330 1.868 2.400 0.563 0.782 1.086 1.410 1.929 0.478 0.945 1.120 1.361 1.710

Mn-Csat.
0.039 0.059 0.068 0.088 0.116 0.143 0.163 0.030 0.024 0.020
Fig. 5The effect of nitrogen partial pressure on the nitrogen solubility in Mn melts.

1673 K

1773 K

1823 K

nitrogen partial pressures. The nitrogen solubility in the carbon-saturated manganese melt is very low, and it follows Sieverts law over the entire range of nitrogen partial pressures. Sieverts law can only be applied at low nitrogen contents below approximately 1 wt pct. Taking Sieverts constant at each temperature, k(T ), which is the slope of the linear portion of the plots in Figure 5, the values of ln k(T ) are plotted as a function of 1/T in Figure 6. From the slope and intercept of this plot, the standard enthalpy and entropy changes for the nitrogen dissolution were calculated to be 67,222 1,437 and 30.32 0.84 J/g atom, respectively. Therefore, from Eqs. [5] and [6], the standard Gibbs freeenergy change for the dissolution of 1 g atom of nitrogen in liquid manganese can be derived as GT 67,222 30.32T J/g atom [7]

Also, the solubility of nitrogen in the pure manganese melt can be represented as a function of temperature and partial pressure of nitrogen, as follows: log (pct N) 3511 T
1.584
1 wt pct)

1 log PN2 2

Fig. 6Temperature dependency of nitrogen solubility in pure Mn melt.

[8] The temperature dependence of the nitrogen solubility in manganese melts is negative. However, KN ( 1/2 (pct N)/PN2 ) values obtained at reduced nitrogen partial pressures in the present work are significantly higher than previous results over the same temperature range. The nitrogen solubility measured by Sieverts method[6] is considerably lower than others. Gokcen[7] argued that Sieverts volumetric method is not suitable for the determination of gas solubility in manganese because the liquid metal
METALLURGICAL AND MATERIALS TRANSACTIONS B

((pct N)

where T is in Kelvin, and PN2 is in atmospheres. It must be emphasized that Eq. [8] is valid only in the range where Sieverts law is applicable and fN can be considered as unity. The equations for the nitrogen solubility polytherm in liquid manganese, determined by various investigators at different ranges of temperatures and nitrogen partial pressures, are shown for comparison in Table II and Figure 7.
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Table II. Nitrogen Solubility Data for Mn Melt Determined by Various Investigators
log KN
0.0132 3264 1.66 T
3090 T
3010 T
2785 T
3511 T

Temperature (K)
1673 1573 to 1823

KN (1823K)
1.35

PN2 (kPa)
101.33 101.33

Reference
6 10

1.55

1546 to 1773

1.40

101.33

1.457

1680 to 2000

1.56

101.33

1.33

1780 to 2080

1.59

9.12 to 101.33

11

1.584

1623 to 1823

2.19

3.04 to 20.27

present work

Fig. 7Variation of KN values with temperature determined by various investigators.

vaporizes readily and condenses in the cooler parts of the apparatus, where it can absorb large amounts of nitrogen. Gocken[7] measured the nitrogen solubility in a manganese melt at 1546 to 1773 K by bubbling pure nitrogen gas for 1 hour into the melt in an alumina crucible placed in a tubular furnace. Beer[10] bubbled pure nitrogen gas in the inductively stirred manganese melt at 1573 to 1823 K for 4 to 6 hours. Both authors[7,10] determined the nitrogen solubility at an atmospheric nitrogen pressure and obtained KN values of 1.4 and 1.35 at 1823 K, respectively. Baratashvili et al.[8] melted manganese containing initially high and low nitrogen contents using a high-frequency vacuum tube oscillator at 1680 to 2000 K under a stream of a gas mixture of nitrogen and hydrogen (1100 and 40 mL/ min, respectively). The equilibrium was obtained in 1 hour. Their nitrogen solubility of 1.56 wt pct at 1823 K is comparable to the present data of 1.71 wt pct, obtained at the atmospheric nitrogen pressure of 101.33 kPa. They determined the standard free energy of nitrogen dissolution as GT 57,656 27.8T J/g atom by taking the molten manganese in equilibrium with a nitrogen pressure of 101.33 kPa as the
METALLURGICAL AND MATERIALS TRANSACTIONS B

standard state and assuming fN is unity. However, this freeenergy data cannot be used to calculate the nitrogen solubility in a manganese melt at various nitrogen partial pressures, because fN may vary with nitrogen content in manganese melt. Grigorenko et al.[11] measured the nitrogen solubility in iron-manganese melts over a wide range of compositions by the levitation melting technique, under various nitrogen partial pressures at 1780 to 2080 K. The equation for the nitrogen solubility polytherm in pure liquid manganese, taken from their work, is also given in Table II. At this hightemperature range, the evaporation of the manganese melt was significant, and they limited the equilibration time to no longer than 30 to 40 seconds. They did not observe the deviation from Sieverts law at high nitrogen partial pressures in their temperature range. One may attribute this to relatively low nitrogen solubilities in manganese and ironmanganese melts at high temperatures. They measured the temperature of a molten specimen by an optical pyrometer. At high temperatures, the presence of a film of manganese vapor near the melt surface may cause an error in temperature measurement and control by the optical pyrometry. The standard free-energy data for the nitrogen dissolution derived in this work can be used to determine the activity coefficient of nitrogen at various nitrogen contents in a manganese melt, using Eqs. [5] and [7]. Figure 8 shows the variation of fN calculated as a function of nitrogen content in equilibrium with various nitrogen partial pressures at different temperatures. The activity coefficient of nitrogen is unity up to a 1 wt pct nitrogen content and, thereafter, it increases with nitrogen content. It is of interest to note that there was no effect of temperature on the activity coefficient. The relationship can be analytically expressed using the firstand second-order self-interaction parameters. log fN eN (pct N) N eN N
N N N N

(pct N)2

[9]

where the value of and are determined to be 0.005 and 0.029, respectively. Therefore, the equilibrium nitrogen solubility in a pure manganese melt as a function of nitrogen partial pressure can be calculated at any temperature using Eqs. [5], [7], and [9]. The solubility calculated at 1823 K is plotted as a solid
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Table III. Nitrogen Solubility Data for Mn-Fe Melts

Temperature
1623 K

PN2 (kPa)
6.08

[PctFe] in Mn-Fe alloys

0 5.9 12.6 19.7 25.2 0 5 12.2 19.1 27 0 6.3 11.4 16.8 22.6 0 5.9 11.9 18 23.5

[PctN]
0.928 0.759 0.609 0.484 0.393 0.732 0.611 0.470 0.389 0.294 0.782 0.644 0.545 0.459 0.381 0.945 0.791 0.652 0.530 0.450

1673 K

5.07

1773 K

10.13

Fig. 8Activity coefficient of nitrogen at various nitrogen contents in Mn melt.

1823 K

20.27

Fig. 9Comparison between calculated and measured nitrogen solubilities in Mn melt. Fig. 10The effect of Fe content on nitrogen solubility in Mn-Fe melts.

line together with the experimental data obtained by various authors, for comparison, in Figure 9. The solubility data measured by Baratashvili[8] and Grigorenko[11] at high nitrogen pressures are in fairly good agreement with the present result. However, Beer[10] and Gokcens data[7] are well below the other values. In their experiments, the attainment of equilibrium was not checked when bubbling nitrogen gas into the manganese melt. B. Manganese-Iron Melts Table III shows the experimental results of the nitrogen solubility measurement for manganese-iron melts as a function of the iron content at different temperatures. In this experiment, reduced nitrogen partial pressures of 5.07 to 20.27 kPa were used to keep the nitrogen content below 1 wt pct in the melt. Figure 10 shows the apparent equilibrium constant plotted against the iron content in a manganeseiron melt. The nitrogen partial pressures were also corrected for the manganese vapor pressures in manganese-iron alloy melts. The nitrogen solubility decreases linearly with iron
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content. The temperature dependence of the nitrogen solubility in these manganese-rich melts is negative. Figure 11 compares the KN values for manganese-rich manganese-iron melts with other workers results[10,1314] at 1823 K. In general, other reports agree that an addition of iron decreases the solubility, although the number of data are limited in this composition range. The KN values measured in the present work are significantly higher than others, as in the case of pure manganese melt. They determined the nitrogen solubility at an atmospheric nitrogen pressure, and their lower KN values may be attributed to the same reason as discussed in the preceding section. The activity coefficient of nitrogen in manganese-iron melts can be calculated using Eq. [5] as a function of iron content. The resulting values of log fN are plotted vs iron content in Figure 12. The activity coefficient increases linearly with iron content. Up to a 25 mass pct iron content, only the first-order interaction parameter, eFe, can be considN ered, and the second-order parameter, Fe, can be neglected. N
METALLURGICAL AND MATERIALS TRANSACTIONS B

content in Figure 14. In this calculation, the nitrogen partial pressure was also corrected for the manganese vapor pressure from the activity data in manganese-carbon melts.[20] The activity coefficient of nitrogen increases sharply with increasing carbon content. For a carbon-saturated melt, the activity coefficient of nitrogen is nearly 25. There is also no effect of temperature on the activity coefficient. The relationship can be analytically expressed using the firstand second-order interaction parameters. log fN
C eN (pct C) C N C N

(pct C)2

[11]

C where the values of eN and and 0.013, respectively.

are determined to be 0.09

D. Manganese-Iron-Carbon Alloys
Fig. 11Variation of KN values with Fe content in Mn-Fe melts determined by various investigators at 1823 K.

Table V and Figure 15 show the experimental results of nitrogen solubility measurements for manganese-ironcarbon (ferromanganese-type) melts as a function of carbon content at 1673 and 1773 K. The nitrogen partial pressure used in these experiments was 20.27 kPa. Carbon in the melts decreases the nitrogen solubility significantly. As the carbon content increases, the temperature dependence of the nitrogen solubility becomes insignificant. Figure 16 shows the activity coefficients of nitrogen plotted vs carbon content in ferromanganese-type melts. In this calculation, the nitrogen partial pressure was corrected for the manganese vapor pressure using the activity data in manganese-iron-carbon melts determined by W. Dresler.[3] The effect of temperature is not observed. Using the notation of Lupis and Elliot,[22] the activity coefficient of nitrogen in a manganese-iron-carbon ternary melt can be expressed as log fN eN (pct N) N
Fe N N N

(pct N)2

eFe (pct Fe) N

C N

(pct Fe)2

C eN (pct C)

(pct C)2 [12]

Fig. 12Variation of activity coefficient of nitrogen with Fe content in Mn-Fe melts.

Fe,C N

(pct Fe) (pct C)

There is no temperature dependency on the interaction parameter. The linear relationship in Figure 12 can be expressed as Eq. [10] using the first-order interaction parameter. log fN where the value of eFe N eFe (pct Fe) N [10] is determined to be 0.015.

C. Manganese-Carbon Alloys Table IV and Figure 13 show the nitrogen solubility in liquid manganese-carbon alloys containing various carbon contents in the temperature range of 1623 to 1823 K, under a reduced nitrogen partial pressure of 5.07 kPa. Carbon in the melt decreases the nitrogen solubility significantly, as it does in an iron melt.[21] As the carbon content increases, the temperature dependence of the nitrogen solubility becomes insignificant. The activity coefficient of nitrogen can be calculated using Eq. [5] as a function of carbon content in manganese-carbon alloy melts, and the resulting values are plotted vs carbon
METALLURGICAL AND MATERIALS TRANSACTIONS B

i i where eN and N values other than Fe,C have been deterN mined in the preceding sections. The second-order interaction parameter ( Fe,C) can be determined from the N experimental data for manganese-iron-carbon melts and from Eq. [12]. The slope of a straight line obtained by the regression of the data is zero, as shown in Figure 17. Therefore, the value of Fe,C can be neglected in ferromanganese N melts over a wide range of carbon contents. Table VI summarizes the first- and second-order interaction parameters of nitrogen determined from the present study. Using the interaction parameters and the previous analytical expression for the activity coefficient of nitrogen, the nitrogen solubility in a ferromanganese melt can be calculated by Eq. [5] at given nitrogen partial pressures and temperatures. Figure 18 shows the correlation between calculated and measured nitrogen solubilities in liquid ferromanganese alloys. It shows almost perfect agreement and suggests that these interaction parameters can be used for ferromanganese-type melts (70 to 75 wt pct Mn) over a wide range of carbon contents. Figure 19 shows a three-dimensional diagram of the nitrogen solubility in a ferromanganese melt (75 wt pct Mn) calculated for various carbon contents, melt temperatures, and nitrogen partial pressures. The nitrogen solubility

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Table IV. Nitrogen Solubility Data for Mn-C Melts (PN2

1623 K
(Pct C)
0 0.14 0.45 0.62 0.82 1.14 1.67 2.55 3.36 7.25*

5.07 kPa)
1823 K
(Pct N)
0.563 0.547 0.522 0.475 0.436 0.372 0.338 0.134 0.024

1673 K
(Pct N)
0.844 0.814 0.746 0.725 0.692 0.626 0.541 0.403 0.299 0.039

1773 K
(Pct N)
0.732 0.731 0.723 0.687 0.664 0.656 0.506 0.470 0.216 0.030

(Pct C)
0 0.03 0.16 0.17 0.22 0.56 1.42 1.70 3.80 7.45*

(Pct C)
0 0.14 0.28 0.51 1.04 1.58 1.96 4.39 7.62*

(Pct C)
0 0.07 0.17 0.57 0.97 1.19 1.50 4.84 7.67*

(Pct N)
0.478 0.464 0.462 0.432 0.366 0.341 0.296 0.100 0.020

*Carbon saturation.

Table V. Nitrogen Solubility Data for Mn-Fe-C Melts (PN2 20.27 kPa)
Pct in Mn-Fe-C Alloys
Temperature
1673 K

[Fe]
24.6 24.7 24.8 24.6 25.1 24.2 24.6 24.8 24.3 22.4 25.1 25.0 25.4 25.3 25.3 26.1 25.0 23.8 22.6

[C]
0.10 0.40 0.71 0.88 0.99 1.56 1.92 2.43 3.04 6.87* 0.10 0.33 0.57 0.81 1.11 1.71 2.49 4.34 7.26*

[Pct N]
0.597 0.554 0.514 0.506 0.475 0.419 0.376 0.323 0.253 0.037 0.461 0.449 0.421 0.394 0.359 0.308 0.254 0.124 0.029

1773 K

Fig. 13The effect of carbon content on nitrogen solubility in Mn-C melts.

*Carbon saturation.

Fig. 14Variation of activity coefficient of nitrogen with carbon content in Mn-C melts.
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Fig. 15The effect of carbon content on nitrogen solubility in ferromanganese melts.

METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 16Variation of activity coefficient of nitrogen with carbon content in ferromanganese melts.

Fig. 18Correlation between calculated and measured nitrogen solubilities in ferromanganese melts.

Fig. 17Plot of log fN 0.005[pct N ] 0.029[pct N ]2 0.09[pct C] 0.013[pct C ]2 vs [pct Fe][pct C ].

0.015[pct Fe]

Table VI. Interaction Parameters of Nitrogen in Mn Alloy Melts

System
Mn-N Mn-Fe-N Mn-C-N Mn-Fe-C-N
j eN j N

Values
0.005 0.029 0.015 0 0.09 0.013 0

Reference
present work present work present work present work
Fig. 19Calculated values of nitrogen solubility in ferromanganese melt as functions of carbon content and melt temperature at different nitrogen partial pressures.

eN N e Fe N eC N

N N

Fe N

C N Fe,C N

increases rapidly as the carbon content decreases. Increasing the melt temperature decreases the nitrogen solubility, and the effect of temperature is more significant at low carbon contents. In most cases, the actual nitrogen content in the ferromanganese melt would be below the solubility, due to the kinetic factors. However, the present results suggest that nitrogen can be used as an inert gas during the early stage of the
METALLURGICAL AND MATERIALS TRANSACTIONS B

oxygen-refining process for high-carbon ferromanganese. In the later stage of refining, when the carbon content is low, argon can be used to control the nitrogen content in the melt. Also, high operating temperatures would be desirable to keep the nitrogen content low during the refining process. IV. CONCLUSIONS The nitrogen solubilities in pure manganese, manganeseiron, manganese-carbon, and manganese-iron-carbon melts
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have been measured at various partial pressures of nitrogen in the temperature range of 1623 to 1823 K. The nitrogen dissolution follows Sieverts law at nitrogen contents below 1 wt pct. The standard free-energy change for the dissolution of nitrogen in pure liquid manganese has been determined to be 67,222 30.32T J/g atom, with the standard state taken to be 1 wt pct nitrogen in solution. Carbon and iron in manganese-rich melts decrease the nitrogen solubility significantly. The first- and second-order interaction parameters between nitrogen and other elements in manganese melts have been determined. They are temperature-independent in the temperature range of 1623 to 1823 K. The nitrogen solubility in a ferromanganese alloy melt at any nitrogen partial pressure can be estimated as a function of the melt composition and temperature.

REFERENCES
1. D.S. Kozak and L.R. Matricardi: Iron Steelmaker, 1981, vol. 8 (4), pp. 28-31. 2. E. Schurmann, A. Ender, E. Hoffken, H. Litterscheld, and C.H. Schutz: Stahl Eisen., 1993, vol. 113, pp. 77-82. 3. W. Dresler: Can. Metall. Q., 1989, vol. 28, pp. 109-15. 4. B.D. You, K.Y. Park, J.J. Pak, and J.W. Han: Met. Mater., 1999, vol. 5, pp. 395-99.

5. B.D. You, J.W. Han, and J.J. Pak: Steel Res., 2000, vol. 71 (12), pp. 22-26. 6. T. Saito: Res. Inst. Tohoku Univ., 1949, vol. 1, pp. 411-19. 7. N.A. Gokcen: Trans. TMS-AIME, 1961, vol. 221, pp. 200-01. 8. I.B. Baratashvili, V.P. Fedotov, A.M. Samarin, and V.M. Berezhiani: Dokl. Akad. Nauk SSSR, 1961, vol. 139, pp. 1354-55. 9. Y. Tsu and T. Saito: Suppl. Trans. ISIJ, 1971, vol. 11, pp. 461-66. 10. S.Z. Beer: Trans. TMS-AIME, 1961, vol. 221, pp. 2-8. 11. G.M. Grigorenko, Y.M. Pomarin, V.I. Lakomskiy, and A.V. Sherevera: Metally, 1974, vol. 6, pp. 9-13 (English translation). 12. H. Wada and R.D. Pehlke: Plasma Fusion of Metallic Materials, Soviet-American Cooperative Research, 1979, pp. 233-36. 13. R.A. Dodd and N.A. Gokcen: Trans. TMS-AIME, 1961, vol. 221, pp. 233-36. 14. I.B. Baratashvili, V.P. Fedotov, A.M. Samarin, and V.M. Berezhiani: Dokl. Akad. Nauk SSSR, 1961, vol. 140, pp. 423-25. 15. V.S. Shitikov: Metally, 1970, No. 4, pp. 27-30 (English translation). 16. C. Qiu: Metall. Trans. A, 1993, vol. 24A, pp. 629-45. 17. H.G. Park, A.B. Gokhale, P. Kumar, and R. Abbaschian: Metall. Trans. B, 1990, vol. 21B, pp. 845-53. 18. C.J. Smithells: in Smithells Metals Reference Book, 7th ed., E.A. Brandes and G.B. Brook, eds., Butterworth-Heinemann Ltd., Oxford, United Kingdom, 1992. 19. R. Hultgren, P.D. Desai, D.T. Hawkins, M. Gleiser, and K.K. Kelley: Selected Values of the Thermodynamic Properties of the Elements, ASM, Metals Park, OH, 1973. 20. E.J. Kim, J.J. Pak, and B.D. You: Hanyang University, Ansan, Korea, unpublished research, 1999. 21. R.D. Pehlke and J.F. Elliott: Trans. TMS-AIME, 1960, vol. 218, pp. 1088-101. 22. C.H.P. Lupis and J.F. Elliott: Acta Metall., 1966, vol. 14, pp. 529-38.

668VOLUME 32B, AUGUST 2001

METALLURGICAL AND MATERIALS TRANSACTIONS B