The rate of absorption of nitrogen into liquid iron containing oxygen and sulfur

The rate of nitrogen absorption into and desorption from liquid iron containing sulfur and/or oxygen was measured by employing a constant-volume technique with a highly sensitive pressure transducer. Critical evaluation of the results demonstrated conclusively that the chemical rate at high oxygen or sulfur contents is second order with respect to nitrogen content in the metal and probably controlled by the dissociation of the nitrogen molecule on the surface. The effect of sulfur on the rate is complex because of the influence of 1) liquid-phase mass transfer at low sulfur contents, 2) the chemical rate on vacant iron sites at intermediate sulfur contents, and 3) the rate on the adsorbed sulfur layer or the limiting rate at high sulfur contents. However, at intermediate concentrations the limiting case for the adsorption isotherm for sulfur is adhered to and the rate is inversely proportional to the sulfur concentration. For Fe-O melts the rate is inversely proportional to the oxygen content except at low oxygen levels where mass transfer affects the rate. The rate for Fe-S-O melts can be calculated reasonably well from the results for the Fe-S and Fe-0 alloys, assuming that oxygen does not effect the adsorption of sulfur andvice versa and that there is nearly complete coverage of the surface with oxygen and sulfur atoms.     

The kinetics of nitrogen absorption and desorption from a plasma arc by molten iron

A plasma torch and refractory-lined furnace with a 10 kg capacity were used to study the kinetics of nitrogen absorption and desorption in molten iron. In this study, melts containing both oxygen and sulfur were used. In accord with earlier studies, a limiting rate constant of 0.020 cm/s-pct was observed at high oxygen and/or sulfur contents. At lower oxygen and/or sulfur contents, the measured desorption rates are smaller than most of the reported values and appear to be limited by mixed melt, mass transfer chemical control. Absorption of nitrogen from the plasma arc is limited by mass transfer in the melt. The dominant form of convection in the vicinity of jet impingement is surface tension driven flow. The reaction N(g)=N(pct) appears to be responsible for the enhanced nitrogen content of the melt. The nitrogen content of a melt in equilibrium with the atomic nitrogen content of an Ar-5 pct N₂ plasma jet was determined to be 0.30 wt pct or thirty times the equilibrium value. T. B. KING, formerly Professor of Metallurgy at the Massachusetts Institute of Technology, Cambridge, MA, is deceased. This paper is based on a presentation made in the T.B. King Memorial Symposium on “Physical Chemistry in Metals Processing” presented at the Annual Meeting of The Metallurgical Society, Denver, CO, February, 1987, under the auspices of the Physical Chemistry Committee and the PTD/ISS.     

The rate of absorption of hydrogen into iron and of nitrogen into Fe-Cr and Fe-Ni-Cr alloys containing sulfur

The rate of absorption of hydrogen into liquid iron and of nitrogen into liquid Fe-Cr alloys containing various levels of sulfur was measured by using a constant-volume Sieverts apparatus employing a sensitive pressure transducer. The rate for the absorption of hydrogen was measured by using H2 containing a small amount of H₂S(<0.2 pct) such that the activity of sulfur on the surface of the melt was the same as in the bulk metal. The hydrogen-absorption rate for Fe-S melts containing up to 0.72 pet sulfur was virtually independent of sulfur content and controlled by liquid-phase mass transfer. The liquidphase mass-transfer coefficient for hydrogen in liquid iron, calculated from the results, was comparable to that for nitrogen transfer in liquid iron. The rate of absorption of nitrogen into Fe-Cr melts with low-sulfur contents was controlled by liquid-phase mass transfer. For melts containing significant amounts of sulfur it was controlled by both mass transfer and the chemical rate of the dissociation of nitrogen on the surface in series. Equations were developed to calculate the chemical rate from the measured rate, correcting for mass transfer. The chemical rate decreased with increasing sulfur content as expected, because sulfur is strongly adsorbed on the surface and increased with chromium content at constant sulfur activity, possibly because available Cr sites promote nitrogen dissociation. Formerly with United States Steel Corporation, Monroeville, PA     

A mathematical approach for the mass transfer between liquid steel and an ascending bubble

A mathematical model which is adaptable to practical conditions has been put forward to deseribe adequately the purging of liquid steel with an inert gas. The mass transfer between liquid steel with varying C, O, H, N, and S contents and an ascending argon bubble has been investigated. The simultaneous mass transfer of all possible gaseous compounds is considered as a function of the initial bubble mass, height of the steel bath, the bulk concentrations in the melt, and the external pressure. The model takes into account the change in size and form of the bubble resulting from its rise and the mass transfer between the bubble and the melt, and also the influence of surface active agents such as sulfur and oxygen. The following general conclusions can be drawn: 1) the gases flushed (out of the melt) by the bubble can be related to the amount of argon injected into the bath. 2) Increase in the initial bubble size and the content of the gas in the bath to be purged, and decrease in the external pressure result in more pronounced deviations from equilibrium saturation within the bubble. 3) Lower external pressure, increasing supersaturation of CO, and greater amounts of purging gas at higher dispersion are the chief factors responsible for increasing, purging efficiency for H, N₂, CO in steel melts. 4) Surface-active agents decrease the purging ratio for nitrogen in a carbon-free melt, but, in carbon-containing melts, increasing amounts of oxygen alone lead to a considerable increase in the purging ratios for nitrogen due to the high mass transfer of CO to the bubble. In the latter case, the effect of increasing sulfur content on the purging ratios is of no significance. KAZUO OKOHIRA, formerly Graduate Student at the Institut für Eisenhüttenkunde at Aachen HERMANN SCHENCK, Dr.-Ing., Dr.-Ing. E.h., Dr.h.e., formerly Director of the Institut für Eisenhüttenwesen, President of the German Iron and Steel Institute (VDEh) from 1950 to 1968 This paper is based in part on a thesis submitted by KAZUO OKOHIRA in partial fulfillment of the requirements for degree of Doktor-Ingenieur at the Technische Hochschale, Aachen.     

Rate of nitrogen desorption from liquid iron-carbon and iron-chromium alloys with argon

The rate of nitrogen desorption from inductively stirred liquid iron, iron-carbon, and iron-chromium alloys with argon carrier gas has been measured by the sampling method for a wide range of nitrogen, carbon, and chromium contents mainly at 1600 °C. The results obtained by the present work and other data of previous investigators are used to clarify the reaction mechanism of nitrogen desorption from liquid iron. The rate of nitrogen desorption from liquid iron and iron alloys is second order with respect to nitrogen content in the metal under the present condition, and mutual relationships among interfacial chemical reaction, liquid-phase mass transfer, and gas-phase mass transfer are elucidated. The effects of oxygen and sulfur on the rate of nitrogen desorption are given byk _' ^{c ’} = 3.15?_N ² [1/(1 + 300a₀ + 130a_s)]. Carbon dissolved in iron increases the rate of nitrogen desorption, and chromium decreases it. The effects of these alloying elements can be explained by the change of the nitrogen activity in the metal.     

Rate of nitrogen desorption from CaO-Al2O3 melts to gas phase

There is a limit to lowering the nitrogen level in steel, because of pickup from the atmosphere during and after degassing. Therefore, the nitride capacity of various fluxes has been measured in order to examine the possibility of nitrogen removal by using slag. It is necessary to take into account the nitrogen reaction rate between the gas and slag phases for the efficient removal of nitrogen in practical steelmaking processes. In this study, the nitrogen desorption rate from CaO-Al₂O₃ melts to gas phase has been examined at 1873 K. The mass-transfer coefficient of nitrogen in the melts increases as the CaO content increases, and the dependence is related to the viscosity of the melts. The reaction-rate constant of nitrogen desorption is found to be proportional to the 3/2 power of the oxygen partial pressure and increases as the CaO content increases under constant oxygen partial pressure.     

Rate of nitrogen desorption from liquid iron-carbon and iron-chromium alloys with argon

The rate of nitrogen desorption from inductively stirred liquid iron, iron-carbon, and iron-chromium alloys with argon carrier gas has been measured by the sampling method for a wide range of nitrogen, carbon, and chromium contents mainly at 1600 °C. The results obtained by the present work and other data of previous investigators are used to clarify the reaction mechanism of nitrogen desorption from liquid iron. The rate of nitrogen desorption from liquid iron and iron alloys is second order with respect to nitrogen content in the metal under the present condition, and mutual relationships among interfacial chemical reaction, liquid-phase mass transfer, and gas-phase mass transfer are elucidated. The effects of oxygen and sulfur on the rate of nitrogen desorption are given byk _' ^{c ’} = 3.15ƒ_N ² [1/(1 + 300a₀ + 130a_s)]. Carbon dissolved in iron increases the rate of nitrogen desorption, and chromium decreases it. The effects of these alloying elements can be explained by the change of the nitrogen activity in the metal. This paper is based on a presentation made at the G. R. Fitterer Symposium on Nitrogen in Metals and Alloys held at the 114th annual AIME meeting in New York, February 24–28, 1985, under the auspices of the ASM-MSD Thermodynamic Activity Committee.     

Denitrogenation of steel melts with oxygen and sulphur by injection of argon under reduced pressure

Denitrogenation of steel melts with oxygen and sulphur was studied under reduced pressure by injection of argon. The rate of nitrogen desorption was found to obey a reaction of second order. The macrokinetic rate increases with increasing Ar flowrate until bubble coalescence occurs in the melts. The effects of sulphur and oxygen on nitrogen desorption were evaluated from the experimental data. The dimensionless rate constant for nitrogen is described by . A reasonable agreement was obtained in comparison with the results of other investigators.     

Impact of boron on melt properties and structurization of iron and nickel-based steels and alloys

Comparison of the results obtained from studies of the effect of boron microadditives on the structure and properties of liquid melts and of the alloys crystallizing out of such melts indicates that the reactions between boron and other highly active surfactants such as oxygen’ sulfur’ phosphorus’ nitrogen’ and carbon must be taken into account when determining the optimum amount of boron to be added. Thus’ in order for boron to have a greater effect on steel structurization and properties’ the most active surfactants — oxygen and sulfur — must be removed before the boron is added to the liquid metal.     

Effect of the metal charge mass and the slag thickness on the process of steelmaking in an arc furnace

The effect of the metal charge mass and the foamed slag thickness on the sulfur, phosphorus, nitrogen, and hydrogen contents in a metal produced in a 120-t arc steel-melting furnace is studied. It is shown that the sulfur and nitrogen contents in the steel increase and the phosphorus and hydrogen contents decrease as the metal charge mass increases or the slag thickness (mass) decreases.     

Mathematical model for nitrogen control in oxygen steelmaking

A mathematical model was developed to quantify the effects of different operational parameters on the nitrogen content of steel produced during oxygen steelmaking. The model predicts nitrogen removal by the CO produced during decarburization and how the final nitrogen content is affected by different process variables. These variables include the type of coolants used (scrap, direct reduced iron (DRI), etc.), the sulfur content of the metal, combined gas blowing practices, and the nitrogen content in the hot metal, scrap and oxygen blown. The model is a mixed control model that incorporates mass transfer and chemical kinetics. It requires a single parameter that reflects the surface area and mass-transfer coefficient that is determined from the rate of decarburization. The model also computes the rate of decarburization and the change in surface active elements, such as sulfur and oxygen, that affect the rate of the nitrogen reaction. Nitrogenization of steel in the converter is also predicted with the model. The computed results are in good agreement with plant data and observations.     

Oxygen and nitrogen reactions in Fe-X and Fe-Cr-Ni-X melts

A modified ? formalism is developed to perform thermodynamic analysis for metallic solutions. The model calculation is successfully applied to describe oxygen and nitrogen equilibria in both liquid iron and alloyed steel melts. Relations between oxygen activities or contents and composition of Fe-O-X (X = Si, Cr, Ti and Al) melts are given quantitatively. The results are widely supported by the available experimental results. Nitrogen solubilities in Fe-Cr and Fe-Cr-Ni melts predicted by the present model calculation feature good agreement with experimental results.     

Nitrogenation and decarburization of stainless steel

The rate of nitrogenation of iron alloys by nitrogen bubbling was determined. The rate of nitrogen pickup in iron with high oxygen activities was controlled by a chemical reaction at the gas bubble-metal interface. For an 18-8 type stainless steel and for iron containing between 50 and 400 ppm oxygen, the rate is controlled by a chemical reaction and liquid-phase mass transfer in series. The rate equation for this case was developed. The rates calculated from existing rate data and the fluid dynamic properties of the system were in good agreement with the experimental results. When argon-oxygen mixtures are bubbled through shallow (7.5 cm) stainless-steel melts, the rate of oxidation of chromium is considerably faster than that of carbon. It is suggested that oxygen primarily oxidizes chromium and iron and as the oxides are carried through the bath by argon bubbles they oxidize the carbon.     

Change of Nitrogen Content in the Molten Steel during CaO Powder Blowing

The rates of nitrogen desorption from molten steel were measured with the blow of CaO powder or argon gas onto the melts under reduced pressure. 15kg of electrolytic iron was melted in a MgO crucible by a high frequency induction furnace and the temperature of the melt was held at 1873 K. A mathematical model was developed with the consideration of the chemical reaction between sulphur in molten steel and CaO powder and the desorption of nitrogen at gas‐metal interface. The calculated results were in good agreement with the measured ones. The apparent rate constant of nitrogen desorption and the rate controlling step were examined.     

Nitrogen Desorption in Molten Stainless Steel during Immersion Argon Blowing

The behavior of nitrogen desorption reaction in molten stainless steel for AISI 304 and 316 during immersion argon blowing through an immersed alumina nozzle with 3 mm in I.D. has been investigated by sampling method. Some kinetic parameters such as reaction order, rate constant and apparent activation energy of nitrogen desorption reaction for AISI 304 and 316 have been obtained. Results show that nitrogen desorption reaction from molten stainless steel for AISI 304 and 316 is the second order reaction. The rate constant at 1550 ℃ and 1580 ℃ for AISI 316 is 0.08407%-1·min-1 and 0.82370%-1·min-1, respectively. The rate constant at 1550 ℃ for AISI 304 is 0.4166%-1·min-1. The apparent activation energy Ea of nitrogen desorption reaction for AISI 316 is 2136.47 kJ/mol. This huge value of apparent activation energy verifies that the nitrogen desorption reaction has a complex and multistep reaction mechanism. The rate of nitrogen desorption reaction from molten stainless steel is mixed controlled by the desorption reaction of diatomic molecule nitrogen or of monatomic nitrogen from molten metal at the gas-metal interface and the mass transfer of nitrogen in molten metal. The rate equation of process for nitrogen desorption has been deduced.     

铝镇静钢氮含量控制分析

在炼钢过程中,将成品氮质量分数稳定控制在0.003%以下存在一定难度。对铝镇静钢而言,常规生产流程为BOF-RH-CC,增氮和脱氮在每个工艺环节都可能会发生。本研究进行了9炉工业试验以研究冶炼全过程中氮含量的变化。结果表明,转炉冶炼终点钢中氮含量随碳氧积的增加而增加,而碳氧积反映了转炉底吹搅拌效果。出钢过程发生了增氮现象,合金化时间越长,转炉终点碳含量越低,出钢口的使用炉数越多,增氮量越大。对于RH过程中脱氮行为,RH浸渍管越新,脱氮越多。根据所得结论,提出了控制钢中氮含量的可行措施。     

转炉炼钢过程渣钢间硫的分配比

采用热力学分析的方法研究了300t转炉渣钢间脱硫反应。发现渣中氧传质控制转炉炼钢脱硫反应,转炉终点渣钢间硫分配比与（FeO）-O-S热力学模型计算结果相符,说明脱硫反应接近平衡。定量分析结果表明,转炉渣钢间硫分配比主要受碱度、FeO含量、MgO含量及温度的影响。根据生产数据回归得到了对生产指导性较强的渣钢间硫分配比计算...     

A simplified model for the oxidation of disintegrated steel streams

A model is suggested for calculation of oxidation of disintegrated steel streans by mass transfer of oxygen to the droplets. The mass transfer of oxygen into the cylindrical space occupied by droplets and gas occurs by bulk flow and diffusion. Driving force for the bulk flow of air is the suction developed by the consumption of oxygen molecules and by acceleration. The differential equations describing the vertical gas velocity and the oxygen concentration of the gas phase are solved simultaneously. The increase of oxygen content of the metal phase is computed for a steel stream disintegrated into droplets of various sizes.     

脉冲熔融-飞行时间质谱法同时测定钢铁中氧、氮和氢

采用脉冲熔融-飞行时间质谱法同时测定钢铁中氧、氮和氢三种元素,通过对比空白和样品的质谱图,选择C+,N+,H2+作为质谱分析的谱线。对一系列标准样品中的氧、氮和氢进行测定,根据分析谱线的离子数及元素的质量绘制校准曲线。通过对空白的标准偏差计算得氧、氮和氢的检出限分别为0.000 015%,0.000 02%,0.000 003%,测定氧、氮和氢的范围分别为0.000 05%~0.2%,0.000 06~0.2%,0.000 01~0.05%。方法用于标准样品的分析,测定结果与认定值一致,相对标准偏差为1.4%~7.4%。该方法把质谱检测器用于钢铁材料中氧、氮和氢的同时、定量分析,测定结果的允许误差符合国家标准的规定。     

A Coupled Thermodynamic Model for Prediction of Inclusions Precipitation during Solidification of Heat-resistant Steel Containing Cerium

A coupled thermodynamic model of inclusions precipitation both in liquid and solid phase and microsegregation of solute elements during solidification of heat-resistant steel containing cerium was established.Then the model was validated by the SEM analysis of the industrial products.The type and amount of inclusions in solidification structure of 253 MA heat-resistant steel were predicted by the model,and the valuable results for the inclusions controlling in 253 MA steel were obtained.When the cerium addition increases,the types of inclusions transform from SiO2 and MnS to Ce2O3 and Ce2O2S in 253 MA steel and the precipitation temperature of SiO2 and MnS decreases.The inclusions CeS and CeN convert to Ce2O3 and Ce2O2S as the oxygen content increases and Ce2O3 and CeN convert to Ce2O2 S,Ce3S4,and MnS as the sulfur content increases.The formation temperature of SiO2 increases when the oxygen content increases and the MnS precipitation temperature increases when the sulfur content increases.There is only a small quantity of inclusions containing cerium in 253 MA steel with high cleanliness,i.e.,low oxygen and sulfur contents.By contrast,a mass of SiO2,MnS and Ce2O2 S are formed in steel when the oxygen and sulfur contents are high enough.The condition that MnS precipitates in 253 MA steel is 1.2 w[O]+w[S]0.01%and SiO2 precipitates when 2 w[O]+w[S]0.017%(w[S]0.005%)and w[O]0.006%(w[S]0.005%).