STEEL MAKING

Steel making (introduction)

Steel is an alloy of iron, containing up to 2% of carbon (usually up to 1%). Steel contains lower (compared to pig iron) quantities of impurities like phosphorous, sulfur and silicon. Steel is produced from pig iron by processes, involving reducing the amounts of carbon, silicon and phosphorous. The main steel making methods are: Basic Oxygen Process (BOP) Electric-arc furnace Ladle refining (ladle metallurgy, secondary refining)

Basic Oxygen Process (BOP)

The Basic Oxygen Process is the most powerful and effective method of steel manufacturing.

The scheme of the Basic Oxygen Furnace (BOF) (basic oxygen furnace, basic oxygen converter) is presented in the picture. Typical basic oxygen converter has a vertical steel shell lined with refractory lining. The furnace is capable to rotate about its horizontal axis on trunnions. This rotation is necessary for charging raw materials and fluxes, sampling the melt and pouring the steel and the slag out of the furnace. The Basic Oxygen is equipped with the water cooled oxygen lance for blowing oxygen into the melt.

The basic oxygen converter uses no additional fuel. The pig iron impurities (carbon, silicon, manganese and phosphorous) serve as fuel. The steel making process in the oxygen converter consists of: Charging steel scrap. Pouring liquid pig iron into the furnace. Charging fluxes. Oxygen blowing. Sampling and temperature measurement Tapping the steel to a ladle. De-slagging.

The iron impurities oxidize, evolving heat, necessary for the process. The forming oxides and sulfur are absorbed by the slag. The oxygen converter has a capacity up to 400 t and production cycle of about 40 min.

Electric-arc furnace

The electric-arc furnace employs three vertical graphite electrodes for producing arcs, striking on to the charge and heating it to the required temperature. As the electric-arc furnace utilizes the external origin of energy (electric current), it is capable to melt up to 100% of steel scrap. The steel making process in the electric-arc furnace consists of: Charging scrap metal, pig iron, limestone

Lowering the electrodes and starting the power (melting) Oxidizing stage

At this stage the heat, produced by the arcs, causes oxidizing phosphorous, silicon and manganese. The oxides are absorbed into the slag. By the end of the stage the slag is removed. De-slagging Reducing stage

New fluxes (lime and anthracite) are added at this stage for formation of basic reducing slag. The function of this slag is refining of the steel from sulfur and absorption of oxides, formed as a result of deoxidation. Tapping Lining maintenance

The advantages of the electric-arc furnace are as follows: Unlimited scrap quantity may be melt; Easy temperature control; Deep desulfurization; Precise alloying.

Ladle refining (ladle metallurgy, secondary refining)

Ladle refining is post steel making technological operations, performed in the ladle prior to casting with the purposes of desulfurization, degassing, temperature and chemical homogenization, deoxidation and others. Ladle refining may be carried out at atmospheric pressure, at vacuum, may involve heating, gas purging and stirring. Sulfur refining (desulfurization) in the ladle metallurgy is performed by addition of fluxes (CaO, CaF2 and others) into the ladle and stirring the steel together with the slag, absorbing sulfur. In the production of high quality steel the operation of vacuum treatment in ladle is widely used. Vacuum causes proceeding chemical reaction within the molten steel: [C] + [O] = {CO} This reaction results in reduction of the quantity of oxide inclusions. The bubbles of carbon oxide remove Hydrogen, diffusing into the CO phase. An example of ladle refining method is Recirculation Degassing (RH) vacuum degasser, which consists of a vacuum vessel with two tubes (snorkels), immersed in the steel. In one of the tubes argon is injected.

Argon bubbles, moving upwards, cause steel circulation through the vacuum vessel. Additions of fluxes in the vacuum vessel permits conducting desulfurization treatment by this method.

Basic Oxygen Furnace (BOF)

Basic Oxygen Furnace (BOF) is a steel making furnace, in which molten pig iron and steel scrap convert into steel due to oxidizing action of oxygen blown into the melt under a basic slag. The Basic Oxygen Process (Basic Oxygen Furnace, Basic Oxygen Steelmaking, Basic Oxygen Converter) is the most powerful and effective steel making method. About 67% of the crude steel in the world is made in the Basic Oxygen Furnaces (BOF). Furnace structure Refractory lining Chemical and physical processes Operation

Structure of a Basic Oxygen Furnace

The scheme of a Basic Oxygen Furnace (BOF) is presented in the picture. Typical basic oxygen furnace has a vertical vessel lined with refractory lining. Only 8-12% of the furnace volume is filled with the treated molten metal. The bath depth is about 4-6.5 ft (1.21.9 m). The ratio between the height and diameter of the furnace is 1.2-1.5. The typical capacity of the Basic Oxygen Furnace is 250-400 t. The vessel consists of three parts: spherical bottom, cylindrical shell and upper cone. The vessel is attached to a supporting ring equipped with trunnions. The supporting ring provides stable position of the vessel during oxygen blowing. The converter is capable to rotate about its horizontal axis on trunnions driven by electric motors. This rotation (tilting) is necessary for charging raw materials, sampling the melt and pouring the steel out of the converter.

The top blown basic oxygen furnace is equipped with the water cooled oxygen for blowing oxygen into the 3 3 melt through 4-6 nozzles. Oxygen flow commonly reaches 200-280 ft /(min*t) (6-8 m /(min*t)). The oxygen pressure is 150-220 psi (1-1.5 MPa). Service life of oxygen lance is about 400 heats. The bottom blown basic oxygen furnace is equipped with 15-20 tuyeres for injection of oxygen (or oxygen with lime powder). The tuyeres are cooled by either hydrocarbon gas (propane, methane) or oil supplied to the outer jacket of the tube.

Refractory lining of a Basic Oxygen Furnace

The refractory lining of basic oxygen furnaces work in severe conditions of high temperature and oxidizing atmosphere. The lining wear is fastest in the zone of contact with the oxidizing slag (slag line). Refractory bricks for lining basic oxygen furnaces are made of either resin bonded magnesite or tar bonded mixtures of magnesite (MgO) and burnt lime (CaO). The bonding material (resin, tar) is coked and turns into a carbon network binding the refractory grains, preventing wetting by the slag and protecting the lining the from chemical attack of the molten metal. The following measures allows to prolong the service life of the lining: Control of the content of aggressive oxidizing oxide FeO in the slags at low level. Addition of MgO to the slags. Performing slag splashes - projecting residual magnesia saturated slag to the lining walls by Nitrogen blown through the lance. Repair the damaged zones of the lining by gunning refractory materials.

Properly maintained lining may serve 20000 heats. Chemical and physical processes in a Basic Oxygen Furnace The basic oxygen furnace uses no additional fuel. The pig iron impurities (carbon, silicon, manganese and phosphorous) serve as fuel. Iron and its impurities oxidize evolving heat necessary for the process. Oxidation of the molten metal and the slag is complicated process proceeding in several stages and occurring simultaneously on the boundaries between different phases (gas-metal, gas-slag, slag-metal). Finally the reactions may be presented as follows: (square brackets [ ] - signify solution in steel, round brackets ( ) - in slag, curly brackets {} - in gas) 1/2{O2} = [O] [Fe] + 1/2{O2} = (FeO) [Si] + {O2} = (SiO2) [Mn] + 1/2{O2} = (MnO) 2[P] + 5/2{O2} = (P2O5) [C] + 1/2{O2} = {CO} {CO} + 1/2{O2} = {CO2} Most oxides are absorbed by the slag. Gaseous products CO and CO2 are transferred to the atmosphere and removed by the exhausting system.

Oxidizing potential of the atmosphere is characterized by the post-combustion ratio: {CO2}/({CO2}+{CO}). Basic Oxygen Process has limiting ability for desulfurization. The most popular method of desulfurization is removal of sulfur from molten steel to the basic reducing slag. However the slag formed in the Basic Oxygen Furnace is oxidizing (not reducing) therefore maximum value of distribution coefficient of sulfur in the process is about 10, which may be achieved in the slags containing high concentrations of CaO.

Operation of a Basic Oxygen Furnace

Charging steel scrap (25-30% of the total charge weight). Pouring molten pig iron from blast furnace. Charging fluxes. Starting oxygen blowing. Duration of the blowing is about 20 min. Sampling. Temperature measurements (by disposable thermocouple) and taking samples for chemical analysis are made through the upper cone in tilted position of the furnace. Tapping - pouring the steel to a ladle. Special devices (plugs, slag detectors) prevent penetration (carry-over) of the slag into the ladle. De-slagging - pouring the residual slag into the slag pot. The furnace is turned upside down in the direction opposite to the tapping hole.

The Basic Oxygen Furnace has a capacity up to 400 t and production cycle (tap-to-tap) of about 40 min.

Electric Arc Furnace (EAF)

Electric Arc Furnace (EAF) is a steel making furnace, in which steel scrap is heated and melted by heat of electric arcs striking between the furnace electrodes and the metal bath. Two kinds of electric current may be used in Electric Arc Furnaces: direct (DC) and alternating (AC). Three-phase AC Electric Arc Furnaces with graphite electrodes are commonly used in steel making. The main advantage of the Electric Arc Furnaces over the Basic Oxygen Furnaces (BOF) is their capability to treat charges containing up to 100% of scrap. About 33% of the crude steel in the world is made in the Electric Arc Furnaces (EAF). Capacity of Electric Arc Furnace may reach 400 t. Structure of an Electric Arc Furnace Refractory lining of an Electric Arc Furnace Chemical and physical processes in an Electric Arc Furnace Operation of an Electric Arc Furnace

Structure of an Electric Arc Furnace

The scheme of a Electric Arc Furnace (EAF) is presented in the picture. The furnace consists of a spherical hearth (bottom), cylindrical shell and a swinging water-cooled dome-shaped roof. The roof has three holes for consumable graphite electrodes held by a clamping mechanism. The mechanism provides independent lifting and lowering of each electrode. The water-cooled electrode holders serve also as contacts for transmitting electric current supplied by watercooled cables (tubes). The electrode and the scrap form the star connection of three-phase current, in which the scrap is common junction. The furnace is mounted on a tilting mechanism for tapping the molten steel through a tap hole with a pour spout located on the back side of the shell. The charge door, through which the slag components and alloying additives are charged, is located on the front side of the furnace shell. The charge door is also used for removing the slag (de-slagging). The scrap is charged commonly from the furnace top. The roof with the electrodes is swung aside before the scrap charging. The scrap arranged in the charge basket is transferred to the furnace by a crane and then dropped into the shell.

Refractory lining of an Electric Arc Furnace

Refractory linings of Electric Arc Furnaces are made generally of resin-bonded magnesia-carbon bricks. Fused magnesite grains and flake graphite are used as raw materials. When the bricks are heated the bonding material is coked and turns into a carbon network binding the refractory grains, preventing wetting by the slag and protecting the lining the from erosion and chemical attack of the molten metal and slag.

Chemical and physical processes in an Electric Arc Furnace

Melting Melting process starts at low voltage (short arc) between the electrodes and the scrap. The arc during this period is unstable. In order to improve the arc stability small pieces of the scrap are placed in the upper layer of the charge. The electrodes descend melting the charge and penetrating into the scrap forming bores. The molten metal flows down to the furnace bottom. When the electrodes reach the liquid bath the arc becomes stable and the voltage may be increased (long arc). The electrodes are lifting together with the melt level. Most of scrap (85%) melt during this period.

Temperature of the arc reaches 6300F (3500C).

Oxidizing stage
At this stage excessive carbon, phosphorous, silicon and manganese oxidize. The process is similar to that in Basic Oxygen Furnace. Basic oxidizing slag composed of lime (CaO) and ion ore (FeO) is used during the oxidizing period. Gaseous oxygen may be blown into the melt for additional oxidizing. Iron oxide causes increase of Oxygen content in the molten steel according to the reaction: (square brackets [ ] - signify solution in steel, round brackets ( ) - in slag, curly brackets {} - in gas) (FeO) = [Fe] + [O] Oxygen dissolved in the melt oxidizes carbon, phosphorous, silicon and manganese: [C] + [O] = {CO} [Si] + {O2} = (SiO2) [Mn] + 1/2{O2} = (MnO) 2[P] + 5/2{O2} = (P2O5) Carbon monoxide partially burns in the atmosphere: {CO} + {O2} = {CO2} The formed oxides are absorbed by the slag. CO bubbles floating up through the melt result in refining of the steel from non-metallic inclusions and hydrogen removal. Gaseous products CO and CO2 are removed by the exhausting system. Oxidizing potential of the atmosphere is characterized by the post-combustion ratio: {CO2}/({CO2}+{CO}). The oxidizing slag enriched with phosphorous and other oxides formed during this period is removed from the furnace to a slag pot (de-slagging).

Reducing stage
New slag composed mainly of lime (CaO), CaF2 (as slag fluidizer) is added at this stage for formation of basic reducing conditions. The function of this slag is refining of the steel from sulfur and absorption of oxides, formed as a result of deoxidation (killing). The excessive oxygen dissolved in the melt during oxidizing period is removed by metallic deoxidizers Mn, Si, Al: [Mn] + [O] = (MnO) [Si] + 2[O] = (SiO2) 2[Al] + 3[O] = (Al2O3) Basic reducing slag is favorable for desulfurization in accordance to the reaction:

[S] + (CaO) = (CaS) + [O] Oxide and sulfide non-metallic inclusions are absorbed by the slag. Alloying elements (Cr, Ni, Mo, V, etc.) are added after deoxidation. In many cases the processes of killing (deoxidation), desulfurization, alloying and final heating are performed outside of the furnace - Ladle refining.

Operation of an Electric Arc Furnace

Scrap charging; Melting; Sampling and chemical analysis of the melt; Oxidizing slag formation; Oxidation of C, P, Mn, Si, Al. Sampling and temperature measurement; De-slagging; Basic slag formation; Deoxidizing (killing); Alloying; Tapping the steel; Refractory lining maintenance.

Ladle refining
Vacuum ladle degassing o Recirculation Degassing (RH) o Recirculation Degassing with oxygen top lance (RH-OB) o Ladle Degassing (VD, Tank Degassing) o Vacuum Oxygen Decarburization (VOD) Ladle Furnace (LF) Ladle desulfurization by injection of active agents o Powder injection o Cored wire injection Ladle-to-mold degassing

Vacuum ladle degassing

Methods of vacuum ladle degassing utilize the reaction of deoxidation by carbon dissolved in steel according to the equation: [C] + [O] = {CO} where: [C] and [O] - carbon and oxygen dissolved in liquid steel; {CO} - gaseous carbon monoxide. Vacuum treatment of molten steel decreases the partial pressure of CO, which results in shifting equilibrium of the reaction of carbon oxidation. Bubbles of carbon monoxide form in the liquid steel, float up and then they are removed by the vacuum system. In addition to deoxidation vacuum treatment helps to remove Hydrogen dissolved in liquid steel. Hydrogen diffuses into the CO bubbles and the gas is then evacuated by the vacuum pump.

Movement of the molten steel caused by CO bubbles also results in refining the steel from non-metallic inclusions, which agglomerate, float up and are absorbed by the slag. CO bubbles also favor the process of floating and removal of nitride inclusions and gaseous Nitrogen. Steels refined in vacuum are characterized by homogeneous structure, low content of non-metallic inclusions and low gas porosity. Vacuum degassing methods are used for manufacturing large steel ingots, rails, ball bearings and other high quality steels.

Vacuum ladle degassing methods:

Recirculation Degassing (RH)

Recirculation degassing unit uses a vacuum chamber having two snorkels connected to the chamber bottom. One of the snorkels is equipped with pipes supplying Argon through its refractory lining. The snorkels of the vacuum chamber are immersed into the ladle with molten steel. Liquid metal fills the chamber to a level determined by the atmospheric pressure (4.2ft/1.3m). Argon bubbles floating up in one of the snorkels (up-leg) force the melt to rise in the snorkel. Through the second snorkel (down-leg) the molten steel flows down back to the ladle producing circulation. The circulation rate may reach 150-200 t/min. The recirculation degassing vacuum chambers are usually equipped with addition hoppers, through which alloying elements or/and desulfurization slag may be added.

Benefits of Recirculation Degassing (RH):

-Hydrogen removal (degassing); -Oxygen removal (deoxidation); -Carbon removal (decarburization); -Sulfur removal (desulfurization); -Precise alloying; -Non-metallic inclusions removal; -Temperature and chemical homogenizing. Recirculation Degassing with oxygen top lance (RH-OB)

In this method a conventional Recirculation degassing (RH) vessel (chamber) is equipped with a vertical water cooled lance for blowing oxygen on the molten steel surface. Oxygen intensifies the reaction [C] + [O] = {CO} resulting in fast and effective decarburization. Oxygen also oxidizes phosphorus like in Basic Oxygen Process (BOP) or in oxidizing slag stage in Electric-arc furnace. Oxidation reactions have also heating effect therefore the treated metal may be heated to a required temperature without any additional energy source.

Benefits of Recirculation degassing with oxygen top lance (RH-OB):

-Hydrogen removal (degassing); -Fast carbon removal (decarburization); -Phosphorus removal (dephosporization); -Sulfur removal (desulfurization); -Reheating; -Precise alloying; -Non-metallic inclusions removal; -Temperature and chemical homogenizing. Ladle Degassing (VD, Tank Degassing)

In the Tank Degassing method the ladle with molten steel is placed into a vacuum chamber. The ladle is equipped with a porous refractory plug mounted in the ladle bottom. Through the plug argon is supplied during vacuum treatment. There is an addition hopper with vacuum lock on the chamber cover. The hopper is used for adding alloying elements and/or slag components. The reaction [C] + [O] = {CO} starting in the steel under vacuum conditions causes stirring, which is additionally intensified by argon blown through the bottom porous plug. Intensive stirring of the melt and the slag results in deep desulfurization of the steel. Desulfurizing slags possessing high sulfur solubility are used in this process. Argon and CO bubbles also favor the process of floating and removal of nitride inclusions and gaseous nitrogen.

Benefits of Ladle Degassing (VD, Tank Degassing):

-Hydrogen removal (degassing); -Oxygen removal (deoxidation); -Deep sulfur removal (desulfurization); -Carbon removal (decarburization); -Precise alloying; -Non-metallic inclusions (oxides and nitrides) removal; -Temperature and chemical homogenizing. Vacuum Oxygen Decarburization (VOD)

In this method a conventional Ladle Degassing (VD, Tank Degassing) chamber is equipped with a vertical water cooled lance for blowing oxygen on the molten steel surface. Vacuum Oxygen Decarburization (VOD) method is used for manufacturing Stainless steels. Oxidation of liquid steel components under vacuum differs from that at normal pressure: oxygen is consumed mainly by the reaction [C] + [O] = {CO} rather than by oxidation of chromium, which is the main constituent of stainless steels. VOD process allows to decarburize the steel with minor chromium losses. Oxidation reactions have also heating effect therefore the treated metal may be heated to a required temperature without any additional energy source. After having the decarburization (oxidation) stage completed deoxidizers are added to the steel in order to remove excessive oxygen. Then a Desulfurizing slag is added to the molten steel surface. Stirring of the melt and the slag caused by argon blown through the porous bottom plug results in deep desulfurization of the steel.

Benefits of Vacuum Oxygen Decarburization (VOD):

-Deep carbon removal (decarburization); -Low losses of chromium in treatment of stainless steels; -Hydrogen removal (degassing); -Sulfur removal (desulfurization); -Precise alloying; -Reheating; -Non-metallic inclusions (oxides and nitrides) removal; -Temperature and chemical homogenizing.

Ladle Furnace (LF)

Molten steel in a ladle may be treated (refined) in a device called Ladle Furnace (LF). The ladle is transported to the Ladle Furnace stand where it is placed under a cover equipped with three graphite electrodes connected to a three-phase arc transformer. The ladle bottom has a porous refractory plug, which is connected to the argon supply pipe at the Ladle Furnace stand. The LF stand is also equipped with an addition hopper mounted on the cover and a lance for injection of desulfurizing agents. Fumes formed during the operation are extracted through the cover. Molten steel treated in Ladle Furnace is covered by a layer of desulfurizing slag. The graphite electrodes are submerged into the slag, which protects the ladle lining from overheating produced by the electric arcs. The arcs are capable to heat the steel at the rate about 5F/min (3C/min). During the treatment process argon is blown through the bottom porous plug providing continuous metal stirring. Stirring results in distribution of heat produced by the arcs, chemical homogenization and desulfurization of the steel by the slag. Alloying elements and/or slag components may be added through the addition hopper. If deep desulfurization is required active desulfurizing agents are injected into the melt through the injection lance or in form of cored wire. Besides refining operations Ladle Furnace (LF) may serve as a buffer station before Continuous casting.

Benefits of Ladle Furnace (LF):

Deep sulfur removal (desulfurization); Controllable reheating by electric power;

Alloying; Temperature and chemical homogenizing; Non-metallic inclusions removal.

Ladle Furnace process is used for refining a wide variety of steels, in which degassing (hydrogen removal) is not required.

Ladle desulfurization by injection of active agents

Injection of desulfurizing agents (Ca, Mg, CaSi, CaC2, CaF2+CaO) to a molten steel is the most effective method of sulfur removal. Injection methods usually combine supply of a disperse desulfurizing agent (powder) with stirring by argon blowing. A ladle with deoxidized (killed) molten steel is transported to the injection stand where it is placed under a cover, through which the injection lance may lower and immerse into the melt. Steel treated in the stand is covered by a layer of desulfurizing slag having high solubility of sulfur and capable to absorb sulfides formed as a result of active agents injection. Desulfurization agents are injected in argon stream. Argon bubbles produce stirring of the molten steel and the slag promoting desulfurization. Stirring also provides thermal and chemical homogenization of the melt. When the desulfurizing agents are injected into molten steel in form of a cored wire containing powder of desulfurizing agent stirring by argon bubbling from the porous plug mounted in the ladle bottom is used. Fumes formed during the operation are extracted through the cover. Injection of desulfurizing agents allows to achieve ultra-low concentrations of sulfur in steel (0.0002%). Benefits of Ladle desulfurization by injection of active agents: Deep sulfur removal (desulfurization); Temperature and chemical homogenizing; Non-metallic inclusions removal.

Ladle-to-mold degassing

Ladle-to-mold degassing is a vacuum degassing method, in which the mold is placed in a vacuum chamber. The molten steel is poured from a tundish attached to the cover of the chamber. The tundish is continuously filled with the melt poured from the ladle. The steel stream boils when it is falling to the mold cavity in vacuum due to the deoxidation reaction [C] + [O] = {CO}. Hydrogen dissolved in steel diffuses into the CO bubbles and the gas is then evacuated by the vacuum pump. Intensity of the deoxidation and degassing during Ladle-to-mold pouring is indicated by the angle, at which the melt stream opens as a result of CO bubbles formation.

Deoxidation of steel
The main sources of Oxygen in steel are as follows: Oxygen blowing (example: Basic Oxygen Furnace (BOF)); Oxidizing slags used in steel making processes(example: Electric-arc furnace; Atmospheric oxygen dissolving in liquid steel during pouring operation; Oxidizing refractories (lining of furnaces and ladles); Rusted and wet scrap.

Solubility of oxygen in molten steel is 0.23% at 3090F (1700C). However it decreases during cooling down and then drops sharply in Solidification reaching 0.003% in solid steel. Oxygen liberated from the solid solution oxidizes the steel components (C, Fe, alloying elements) forming gas pores (blowholes) and non-metallic inclusions entrapped within the ingot structure. Both blowholes and inclusions adversely affect the steel quality.

In order to prevent oxidizing of steel components during solidification the oxygen content should be reduced. Deoxidation of steel is a steel making technological operation, in which concentration (activity) of oxygen dissolved in molten steel is reduced to a required level. There are three principal deoxidation methods: Deoxidation by metallic deoxidizers Deoxidation by vacuum Diffusion deoxidation

Deoxidation by metallic deoxidizers

This is the most popular deoxidation method. It uses elements forming strong and stable oxides. Manganese (Mn), silicone (Si), aluminum (Al), cerium (Ce), calcium (Ca) are commonly used as deoxidizers. Deoxidation by an element (D) may be presented by the reaction: n[D] + k[O] = (DnOk) The equilibrium constant KD-O of the reaction is: KD-O = aox/(aD x aO ) or log KD-O = log aox - n*log aD - k*log aO where: aox - activity of the oxide (DnOk) in the resulted non-metallic inclusion; aD - activity of the deoxidizer in liquid steel; aO - activity of oxygen in liquid steel. Thermodynamic activity of a solute in a solution is a parameter related to the solute concentration. Activity substitutes concentration in thermodynamic equations describing chemical reactions in non-ideal solutions (activities of solutes in a diluted solution are close to their concentrations). The equilibrium constant of a deoxidation reaction is determined by the steel temperature: log KD-O = AD/T - BD where: AD, BD - characteristic parameters determined for the particular deoxidizer D; T - steel temperature, K The table presents parameters of the deoxidation reactions for some metallic oxidizers: Deoxidizer Silicone Reaction [Si] + 2[O] = (SiO2) A B Equilibrium constant at 1873 K (2912F, 1600C)
n k

Manganese [Mn] + [O] = (MnO) 12440 5.33 1.318 30000 11.5 4.518 Aluminum 2[Al] + 3[O] = (Al2O3) 62780 20.5 13.018

Values of the equilibrium constant parameters are used for calculation of equilibrium concentrations of oxygen and the deoxidizer by the equation: AD/T - BD = log aox - n*log aD - k*log aO

In the simplest case aox=1, aD=[D], aO=[O], therefore: AD/T - BD = n*log [D] - k*log [O] According to the degree of deoxidation Carbon steels may be subdivided into three groups: Killed steels - completely deoxidized steels, solidification of which does not cause formation of carbon monoxide (CO). Ingots and castings of killed steel have homogeneous structure and no gas porosity (blowholes). Semi-killed steels - incompletely deoxidized steels containing some amount of excess oxygen, which forms carbon monoxide during last stages of solidification. Rimmed steels - partially deoxidized or non-deoxidized low carbon steels evolving sufficient amount of carbon monoxide during solidification. Ingots of rimmed steels are characterized by good surface quality and considerable quantity of blowholes.

Deoxidation in vacuum
Method of deoxidation in vacuum utilizes carbon dissolved in steel as the deoxidizer according to the equation: [C] + [O] = {CO} where: [C] and [O] - carbon and oxygen dissolved in liquid steel; {CO} - gaseous carbon monoxide. The equilibrium constant of this chemical reaction is expressed as follows: KCO = pCO/(aC x aO) where: pCO - partial pressure of carbon monoxide in the atmosphere; aC and aO - activities of carbon and oxygen in liquid steel. Temperature dependence of KCO is insufficient. For approximate calculations the following equation may be used: [C]*[O] = 0.0025*pCO at 2948F (1620C) According to the above expressions the oxygen activity (concentration) is proportional to the partial pressure of carbon monoxide therefore decrease of the latter will cause reduction of the oxygen activity. Vacuum treatment of molten steel decreases the partial pressure of CO, which results in shifting equilibrium of the reaction of carbon oxidation. Bubbles of carbon monoxide form in the liquid steel, float up and then they are removed by the vacuum system. In addition to deoxidation vacuum treatment helps to remove Hydrogen dissolved in liquid steel. Hydrogen diffuses into the CO bubbles and the gas is then evacuated by the vacuum pump. Vacuum deoxidation is used mainly in Ladle refining. Steels deoxidized in vacuum are characterized by homogeneous structure, low content of non-metallic inclusions and low gas porosity. Vacuum treatment is used for manufacturing large steel ingots, rails, ball bearings and other high quality steels.

Diffusion deoxidation
Oxygen dissolves in both steel and slag. Equilibrium between the two systems may be presented by the equation: [O] = (O) The equilibrium constant of the reaction: KFeO = a[O]/a(O) or a[O] = KFeO*a(O) Thus reduction of the oxygen activity (concentration) in steel may be achieved by decreasing the oxygen activity in the slag. When the oxygen activity in the slag is reduced oxygen ions dissolved in steel begin to diffuse from the steel into the slag, and the equilibrium conditions are restored. In other words, deoxidation of slag results in deoxidation of the steel. Carbon (coke), silicone, aluminum and other elements are used for slag deoxidation. Since deoxidizers in the difusion method are not introduced directly into the steel melt, oxide non-metallic inclusions do not form. Diffusion deoxidation allows to produce steel less contaminated by non-metallic inclusions.

Desulfurization of steel
Sulfur in steel Desulfurization of steel by slags Desulfurization of steel by injection of active agents

Sulfur in steel
Sulfur (S) may dissolve in liquid iron (Fe) at any concentration. However solubility of sulfur in solid iron is limited: 0.002% in -iron at room temperature and 0.013% in -iron at 1832F (1000C). When a liquid steel cools down and solidifies the solubility of sulfur drops and it is liberated from the solution in form of iron sulfide (FeS) forming an eutectic with the surrounding iron. The eutectic is segregated at the iron grain boundaries. The eutectic temperature is relatively low - about 1810F (988C). Fe-FeS eutectic weakens the bonding between the grains and causes sharp drop of the steel properties (brittleness) at the temperatures of hot deformation (Rolling, Forging etc.). Brittleness of steel at hot metal forming operations due to the presence of low-melting iron sulfides segregated at grain boundaries is called hot shortness. In order to prevent formation of low-melting iron sulfide manganese (Mn) is added to steel to a content not less than 0.2%. Manganese actively reacts with iron sulfides during solidification of steel transforming FeS to MnS according to the reaction: (FeS) + [Mn] = (MnS) + Fe (square brackets [ ] - signify concentration in steel, round brackets ( ) signify concentration in slag) The melting temperature of manganese sulfide is relatively high - about 2930F (1610C) therefore the steels containing manganese may be deformed in hot state (no hot shortness). Unfortunately MnS inclusions are:

Brittle (less ductile than steel); They may have sharp edges; They are located between the steel grains.

All these factors determine negative influence of sulfide inclusions on the mechanical properties. Cracks may be initiated at brittle sharp edge inclusions. Sulfide inclusions especially arranged in a chain form also make easier the cracks propagation along the grain boundaries. The negative effect of sulfur on the steel properties becomes more significant in large ingots and castings, some zones of which are enriched by sulfur (macrosegregation of sulfur). The properties negatively affected by sulfur: Ductility; Impact toughness; corrosion resistance; Weldability.

Desulfurization of steel by slags

The most popular method of desulfurization is removal of sulfur from molten steel to the basic reducing slag. Basic slag is a slag containing mainly basic oxides: CaO, MgO, MnO, FeO. A typical basic slag consists of 35-60% CaO + MgO, 10-25% FeO, 15-30% SiO2, 5-20% MnO. Transition of sulfur from steel to slag may be presented by the chemical equation: [S] + (CaO) = (CaS) + [O] The equilibrium constant KS1 of the reaction is: KS1 = a[O]*a(CaS)/a[S]*a(CaO) Where: a[O], a[S] - activities of oxygen and sulfur in the liquid steel; a(CaS), a(CaO) - activities of CaS and CaO in the slag. The same reaction in ionic form: [S] + (O ) = (S ) + [O] The equilibrium constant KS2 of the reaction is: KS2 = a[O]*a(S2-)/a[S]*a(O2-) Where: 22a(S2-), a(O2-) - activities of S and O in the slag. Capability of a slag to remove sulfur from steel is characterized by the distribution coefficient of sulfur: LS = (S)/[S] Where: (S) - concentration of sulfur in slag; [S] - concentration of sulfur in steel;
22-

As appears from the above equations desulfurization is effective in deoxidized (low (O)) basic (high (CaO)) slags. Therefore ability of Basic Oxygen Process (BOP) to remove sulfur is low due to its highly oxidized slag. Desulfurization may be effectively conducted in the reducing slag stage of the steel making process in Electricarc furnace. At this stage the oxidizing slag is removed and then lime flux is added to form basic slag with high CaO content. Deep desulfurization by slags may be achieved in ladle: The refining (desulfurizing) slag with high content of CaO and no FeO is prepared and placed in an empty ladle. The molten steel is poured into the ladle filled with the refining slag. Energy of the falling steel stream causes mixing the slag with the steel, during which sulfur is removed from the steel to slag phase.

Effect of desulfurization may be enhanced by additional stirring, for which electromagnetic (induction) stirrers or argon bubbling are used.

Desulfurization of steel by injection of active agents

Injection of desulfurizing agents to a molten steel is the most effective method of sulfur removal. Injection methods usually combine supply of a disperse desulfurizing agent (powder) with stirring by argon blowing. Deep desulfurization by injection of active agents are achieved due to the following factors: High chemical activity of the desulfurization agents (Ca, Mg); High contact area between the steel and slag phases; Stirring providing good kinetic conditions of desulfurization; Presence of basic non-oxidized slag capable to absorb the products of the desulfurization reaction (CaS, MgS).

The following materials are used as desulfurizing agents: Slag mixtures CaO (50-90%) + CaF2 (10-20%) + A2lO3 (0-30%); CaSi; CaC2; CaC2 + Mg; Lime (CaO) + Mg; Ca + Al; Ca; Mg.

The desulfurizing agents are injected into molten steel either in form of powder transported by an argon blown to the steel through a lance or in form of a cored wire containing powder of desulfurizing agent. In the latter method stirring by argon bubbling from the porous plug mounted in the ladle bottom is used.

Chemical reactions between desulfurizing agents and sulfur dissolved in steel may be presented by the following equations: Ca + [S] = (CaS) Mg + [S] = (MgS) Injection of desulfurizing agents allows to achieve ultra-low concentrations of sulfur in steel (0.0002%).

Non-metallic inclusions in steel

Non-metallic inclusions are chemical compounds of metals (Fe, Mn, Al, Si, Ca) with non-metals (O, S, C, H, N). Non-metallic inclusions form separate phases. The non-metallic phases containing more than one compound (eg. different oxides, oxide+sulfide) are called complex non-metallic inclusions (spinels, silicates, oxysulfides, carbonitrides). Despite of small content of non-metallic inclusions in steel (0.01-0.02%) they exert significant effect on the steel properties such as: Tensile strength Deformability (ductility) Toughness Fatigue strength corrosion resistance Weldability Polishability Machinability

Depending on the source, from which non-metallic inclusion are derived, they are subdivided into two groups: indigenous and exogenous inclusions.

Indigenous inclusions are formed in liquid, solidified or solid steel as a result of chemical reactions (deoxidation, desulfurization) between the elments dissolved in steel. Exogenous inclusions are derived from external sources such as furnace refractories, ladle lining, mold materials etc. Amount of exogenous inclusions and their influence on the steel properties are insufficient. Types of non-metallic inclusions Formation of non-metallic inclusions Morphology of non-metallic inclusions Distribution of non-metallic inclusions

Types of non-metallic inclusions

Oxides

FeO, Al2O3, SiO2, MnO, Cr2O3 etc. Al2O3*SiO2, Al2O3*FeO, Cr2O3*FeO, MgO*Al2O3, MnO*SiO2 etc. Sulfides

FeS, MnS, CaS, MgS, Ce2S3 etc. Oxysulfides

MnS*MnO, Al2O3*CaS, FeS*FeO etc. Carbides

Fe3C, WC, Cr3C2, Mn3C, Fe3W3C etc. Nitrides

TiN, AlN, VN, BN etc. Carbonitrides

Titanium carbonitrides, vanadium carbonitrides, niobium carbonitrides etc. Phosphides

Fe3P, Fe2P, Mn5P2

Formation of non-metallic inclusions

There are three stages of inclusions formation: 1. Nucleation At this stage nuclei of new phase are formed as a result of supersaturation of the solution (liquid or solid steel) with the solutes (eg. Al and O) due to dissolution of the additives (deoxidation or desulfurization reagents) or cooling down of the metal. The nucleation process is determined by surface tension on the boundary inclusion-liquid steel. The less the surface tension, the lower supersaturation is required for formation of the new phase nuclei. The nucleation process is much easier in the presence of other phase (other inclusions) in the melt. In this case

the new phase formation is determined by the wetting angle between a nucleus and the substrate inclusion. Wetting condition (low wetting angle) are favorable for the new phase nucleation. 2. Growth Growth of a separate inclusion continues until the chemical equilibrium is achieved (no supersaturation). Growth of inclusions in solid steel is very slow process therefore a certain level of non-equilibrium supersaturation may be retained (eg. martensite). 3. Coalescence and agglomeration Motion of the molten steel due to thermal convection or forced stirring causes collisions of the inclusions, which may result in their coalescence (merging of liquid inclusions) or agglomeration (merging of solid inclusions). The coalescence/agglomeration process is driven by the energetic benefit obtained from decrease of the boundary surface between the inclusion and the liquid steel. Inclusions with higher surface energy have higher chance to merge when collide. Large inclusions float up faster than the smaller ones. The floating inclusions are absorbed by the slag. The floating process may be intensified by moderate stirring. Vigorous stirring will result in breaking the large inclusions into small droplets/fragments. Gas bubbles moving up through the molten steel also promote the inclusions floating and absorption by the slag. Blowing inert gas in Ladle Furnace (LF) or Vacuum ladle degassing of steel in result in obtaining cleaner steel.

Morphology of non-metallic inclusions

Globular shape of inclusions is preferable since their effect on the mechanical properties of steel is moderate. Spherical shape of globular inclusions is a result of their formation in liquid state at low content of aluminum. Examples of globular inclusions are manganese sulfides and oxysulfides formed during solidification in the spaces between the dendrite arms, iron aluminates and silicates. Platelet shaped inclusions. Steels deoxidized by aluminum contain manganese sulfides and oxysulfides in form of thin films (platelets) located along the steel grain boundaries. Such inclusions are formed as a result of eutectic transformation during solidification. Platelet shaped inclusions are most undesirable. They considerably weaken the grain boundaries and exert adverse effect on the mechanical properties particularly in hot state (hot shortness). Dendrite shaped inclusions. Excessive amount of strong deoxidizer (aluminum) results in formation of dendrite shaped oxide and sulfide inclusions (separate and aggregated). These inclusions have melting point higher than that of steel. Sharp edges and corners of the dendrite shaped inclusions may cause local concentration of internal stress, which considerably decrease of ductility, toughness and fatigue strength of the steel part. Polyhedral inclusions. Morphology of dendrite shaped inclusions may be improved by addition (after deep deoxidation by aluminum) of small amounts of rare earth (Ce,La) or alkaline earth (Ca, Mg) elements. Due to their more globular shape polyhedral inclusions exert less effect on the steel properties than dendrite shape inclusions.

Distribution of non-metallic inclusions

Besides of the shape of non-metallic inclusions their distribution throughout the steel grain structure is very important factor determining mechanical properties of the steel. Homogeneous distribution of small inclusions is the most desirable type of distribution. In some steels microscopic carbides or nitrides homogeneously distributed in the steel are created by purpose in order to increase the steel strength. Location of inclusions along the grain boundaries is undesirable since this type of distribution weakens the metal.

Clusters of inclusions are also unfavorable since they may result in local drop of mechanical properties such as toughness and fatigue strength.

Distribution of non-metallic inclusions may change as a result of metal forming (eg. Rolling). Ductile inclusions are deformed and elongated in the rolling direction. The less ductile inclusions are breaking forming chains of fragments. Elongated inclusions and chains result anisotropy of mechanical and other properties. Mechanical properties in transverse direction are lower than those parallel to the rolling direction.

Structure of killed steel ingot

Typical ingot structure consists of five zones:

Zone of small equiaxed grains

The thin layer of small crysrtals forms when a melt comes to a contact with a wall of a cold metallic mold. The crystals (grains) have no favorable direction (equiaxed) and their chemical composition is close to that of the liquid steel. Heat liberated as a result of Crystallization depresses the nucleation and crystal growth.

Zone of columnar grains

Columnar grains start to grow when a stable and directed heat flow is formed as a result of heat transfer through the zone of small equiaxed grains. Direction of the columnar grains growth is oppsite to the direction of heat flow. Columnar grains continue to grow untill the heat flow decreases due to the following causes: Large width of the solidified metal; Heating the mold wall; Formation of an air gap between the ingot and the mold wall. The air gap is a result of shrinkage caused by solidification.

When the temperature of the melt, adjacent to the solidification front, increases due to the liberation of the latent heat, constitutional undercooling will end and the columnar grains growth will stop.

Zone of large equiaxed grains

Low temperature gradient (low heat flow) and low cooling rate of the solute-enriched liquid in the cenral zone of the ingot result in formation of equiaxed grains. This process is slow due to slow heat extraction therefore the number of nuclei (seed crystals) is low and the grains size is large. Zone of large equiaxed grains is enriched by the impurities (sulfur, phosphorous, carbon).

Bottom cone

This cone-shaped zone is a mixture of small equiaxed garins grown as a result of the contact with a bottom of a cold metallic mold and crystals and crystals fragments, which sedimintate from other ingot zones. Bottom cone is characterized by negative segregation of the impurities.

Shinkage cavity zone

Shrinkage cavity is located in the top part of the ingot (which is later discarded) where last portion of liquid solidifies. The mold design should provide upwards direction of solidification at its last stage. Below the shrinkage cavity the zone of shrinkage porosity is located. This zone forms when the feeding of solidifying metal by the residual liquid is insufficient. Isolated pockets of liquid metal separated from the liquid pool by bridges form their own shrinkage cavities (shrinkage pores). The mold shape, which is wider in upper levels and thermal isolation of the hot top favor to diminish the shrinkage porosity.

Macrosegregation in steel ingots

Solidification of a liquid alloy is characterized by a phenomenon called segregation. Segregation is a separation of impurities and alloying elements in different regions of solidified alloy. Segregation is caused by the rejection of the solutes from a solidified alloy into the liquid phase. This rejection is a result of different solubility of impurities in liquid and solid phases at the equilibrium temperature. Partition of solutes between the dendrite arms and interdendritic liquid is called Microsegregation. Causes of macrosegregation Macrosegregation zones in steel ingot

Causes of macrosegregation
Microsegregation is the basic cause of macrosegregation. Microsegregation results in formation of numerous small volumes of liquid enriched with the solute. The liquid is surrounded by the solid dendrites having low solute concentration (solute-poor). Transfer of the solute-rich liquid phase or solute-poor solid phase to large distances over the solidifying mass results in enrichment (positive macrosegregation) or impoverishment (negative macrosegregation) of particular zones of the ingot/casting with the solute. The macro movements of the liquid and solid phases may be caused by the following effects:

Solidification shrinkage

Shrinkage of solidifying alloy causes suction of the liquid phase through the interdendritic structure. The moving liquid feeds the shrinking metal.

Buoyancy forces

Liquid phase may move as a result of a gradient of the density caused by gradients of temperature and solute concentration.

Zone melting effect

A separate volume of the liquid phase having different temperatures at its opposite sides may move in the direction of the higher temperature. The volume solidifies at the colder side and melts solid phase at the hotter side like in zone melting.

CO bubbles

CO bubbles form in solidifying steel as a result of either low content of metallic deoxidizers in rimmed steel or Ladle-to-mold degassing in vacuum. Floating gas bubbles cause movement of the solidifying alloy.

External forces

Metal movement may be caused by the energy of the stream poured into the mold from the ladle. Solidified metal may be also forced by electro-magnetic field, mechanical stirrers, vibration.

Sedimentation of solid phase

Solid crystals homogeneously nucleated in liquid phase and fragments of broken or melted off dendrites settle down (they are commonly heavier than liquid.

Macrosegregation zones in steel ingot

Development of macrosegregation zones in a steel ingot and their locations are associated with the ingot grain structure.

Bottom negative segregation

Bottom negative segregation is a result of low solute concentration in the crystals formed in the early stage of solidification and comprising bottom cone. The bottom cone is a mixture of small equiaxed garins grown as a result of the contact with a bottom of a cold metallic mold and crystals and crystals fragments, which sedimintate from other ingot zones.

V-segregation

The central zone of ingot is enriched with solute rejected by the solidification front progressing from the mold wall to its center. The central zone consists of large equiaxed grains, which settle down to the V-shaped solidification front. The residual liquid surrounding the large equiaxed grains is solute-rich and it forms Vsegregates when solidifies.

A-segregation

A-segregates (freckles) form in the Zone of columnar grains at the regions with structure characterized by the transition from the columnar grains to large equiaxed grains. A-segrgates present channels enriched by sulfur, carbon, phosphorus and other impurities.

Hot top segregation

Hot top segregation zone is located in the top central ingot region below the shrinkage cavity. Hot top segregation is formed at the final solidification stage from the residual liquid enriched by the solutes as a result of microsegregation (rejection by solidifying dendrites) followed by penetration of the liquid through the dendrite skeleton.

Fabrication of large steel ingots

Large steel ingots are required for manufacturing electric power plant turbine shafts, generator rotor shafts, nuclear pressure vessels, chemical pressure vessels, ship parts and other heavy machinery parts. Metalforming technology used for final shaping of large ingots is Forging. The largest ingot (570 metric tons) was produced in 1980 by Kawasaki Steel (Japan). Solidification of a large mass of steel is characterized by significant development of micro and macro-defects of the ingot structure: Non-metallic inclusions Macrosegregation Hydrogen in steel

The structure defects decrease the reliability of the part manufactured from the ingot. Since such parts work in equipment, failure of which is potentially catastrophic (nuclear equipment, electric power plants, chemical equipment, large scale machinery), Technology of large ingots fabrication should provide minimum degree of steel structure defects.

Non-metallic inclusions
Non-metallic inclusions in steel are chemical compounds of metals (Fe, Mn, Al, Si, Ca) with non-metals (O, S, C, H, N). Non-metallic inclusions form separate phases. The non-metallic phases containing more than one compound (eg. different oxides, oxide+sulfide) are called complex non-metallic inclusions (spinels, oxysulfides, carbonitrides). Despite small content of non-metallic inclusions in steel (0.01-0.02%) they exert significant effect on the steel properties such as: Tensile strength Deformability (ductility) Toughness Fatigue strength corrosion resistance Weldability Polishability Machinability

The following parameters of non-metallic inclusions influence on the properties of parts made of large steel ingots: Chemical composition (oxides, sulfides etc.) o Oxides o Sulfides o Oxysulfides o Carbides o Nitrides o Carbonitrides o Phosphides Inclusions size

Size of non-metallic inclusions is determined by the processes of nucleation, growth and coalescence/agglomeration. High surface energy causes the nucleation at higher supersaturation of the solutes (oxygen, sulfur, nitrogen, aluminum, silicon, titanium, vanadium, etc.) and favors coalescence and agglomeration of the inclusions. Shape (morphology) of non-metallic inclusions o Globular inclusion form in liquid state at low concentration of aluminum. Globular shape inclusions exert moderate influence on the steel properties therefore globular morphology is preferable. o Platelet shaped inclusions form at the grain boundaries as a result of eutectic transformation during solidification. Platelet shaped inclusion exert adverse effect on the steel properties and therefore this morphology is undesirable. o Dendrite shaped inclusions form at high concentration of aluminum. Their shape is characterized by sharp edges, which may cause concentration of stresses during the ingot forging and decrease of ductility, toughness and fatigue strength of the steel part fabricated from the ingot. o Polyhedral inclusions are result of modification of the dendrite shaped inclusions by addition of strong deoxidizers and rare earth (Ce,La) or alkaline earth (Ca, Mg) elements. The effect of polyhedral inclusions on the steel properties is less than that of the dendrite shaped inclusions. Distribution (homogeneous, clusters, chains)

Homogeneous distribution of non-metallic inclusions is most desirable. Clusters of inclusions are unfavorable since they may result in local drop of mechanical properties such as toughness and fatigue strength. Physical and mechanical properties (hardness, ductility, melting point)

Microscopic hard inclusions (carbides, nitrides) strengthen the metal however larger hard inclusions may cause drop of the steel ductility without increase of the strength and hardness. Ductile and brittle inclusions behave different during plastic deformation (steel Forging). Ductile inclusions elongate in the direction of deformation. Brittle inclusions break to fragments and form chains.

Macrosegregation
The following factors favors macrosegregation in large steel ingots: Large absolute amount of solutes (sulfur, phosphorous, carbon). Steel is being enriched with the solutes rejected by the moving solidification front therefore at the final solidification stage the residual liquid contain large solute content. Low cooling rate of the metal in the central ingot zone. Low cooling rate results in larger spaces between the dendrite arms filled with the liquid metal enriched with the solutes. Partition of solutes between the dendrite arms and interdendritic liquid is called Microsegregation, which is the main cause of macrosegregation. Additionally solidification conditions at low cooling rate are closer to equilibrium resulting in decrease of Equilibrium Partition Coefficient and higher microsegregation. Large distances, which liquid metal and separate dendrite crystals and their fragments may be transferred. Transfer of liquid and solid phases in a solidifying ingot is the result of solidification shrinkage, buoyancy forces acting on the liquid metal, sedimentation of solid crystals homogeneously nucleated in liquid phase and fragments of broken or melted off dendrites.

Development of macrosegregation zones in a steel ingot and their locations are associated with the ingot grain structure. Bottom negative segregation

Bottom negative segregation is a result of low solute concentration in the crystals formed in the early stage of solidification and comprising bottom cone. The bottom cone is a mixture of small equiaxed garins grown as a result of the contact with a bottom of a cold metallic mold and crystals and crystals fragments, which sedimintate from other ingot zones. V-segregation

The central zone of ingot is enriched with solute rejected by the solidification front progressing from the mold wall to its center. The central zone consists of large equiaxed grains, which settle down to the V-shaped solidification front. The residual liquid surrounding the large equiaxed grains is solute-rich and it forms Vsegregates when solidifies. A-segregation

A-segregates (freckles) form in the Zone of columnar grains at the regions with structure characterized by the transition from the columnar grains to large equiaxed grains. A-segrgates present channels enriched by sulfur, carbon, phosphorus and other impurities. Hot top segregation

Hot top segregation zone is located in the top central ingot region below the shrinkage cavity. Hot top segregation is formed at the final solidification stage from the residual liquid enriched by the solutes as a result of microsegregation (rejection by solidifying dendrites) followed by penetration of the liquid through the dendrite skeleton. Factors allowing to diminish macrosegregation in large steel ingots: Lowering contents of impurities. Steel for large ingots is treated in the melting furnace and in Ladle refining stands in order to remove undesirable impurities such as sulfur (desulfurization]]), phosphorous (dephosphorization), hydrogen (degassing). Steel for large steel ingots commonly contains not more than 0.005% of sulfur, 0.005 of phosphorous and up to 2 ppm of hydrogen. Alloying of steel by alkaline (Ca, Mg) or rare earth (Ce,La) elements in amount of about 2*[S]. Low concentration of silicon in steel (about 0.1%). Using steel grades with lower carbon content. Modification of the ingot dimensions. If low level of A-segregation is required the ratio of the ingot height to its diameter should be as low as possible (about 1.0-1.2). Decrease of the pouring temperature. Lower pouring temperature results in increase of the cooling rate, which is favorable for depressing macrosegregation.

Hydrogen in steel
Sources of hydrogen in liquid steel: Damp scrap; Fluxes and alloying additives; Furnace and ladle refractories; Atmospheric humidity; Fuel (if used).

Hydrogen is easily dissolved in liquid steel in dissociated (atomic) state. Solubility of hydrogen in steel drops sharply during solidification resulting in formation of gaseous hydrogen form H 2. In solid steel hydrogen is dissolved in form of interstitial solution. Carbon, nickel, chromium (up to 10%), vanadium, titanium, zirconium, columbium, tantalum increase the

solubility of hydrogen in solid steel. Silicon, aluminum, tungsten, chromium (10% and higher) decrease the solubility of hydrogen in solid steel. Solubility of hydrogen in austenite is much higher than in ferrite. Both gaseous and dissolved forms of hydrogen exert adverse effect on mechanical properties of steels:

Hydrogen flakes

Solubility of hydrogen decrease during solidification and cooling down of steel ingot. Hydrogen atoms possessing high mobility are collected at internal voids such as non-metallic inclusions (sulfides, oxides) and their clusters, shrinkage pores, cracks caused by internal stresses. Hydrogen atoms collected at internal voids combine and form gaseous hydrogen H 2, which may cause formation of cracks (flakes) when the gas pressure exceeds the steel strength. Hydrogen flakes is particularly dangerous for parts fabricated from large ingots. Vacuum ladle degassing methods allow to decrease the content of hydrogen to 2 ppm, which does not cause flaking formation.

Hydrogen embrittlement

Hydrogen in dissolved form also decreases steel properties such as ductility, Fracture Toughness and fatigue strength.

Technology of large ingots fabrication

The following tasks are accomplished by the technology of large ingots fabrication: Dephosphorization (to about 0.005%) in a steel making furnace (melting furnace). Desulfurization of steel (to about 0.005%) in the melting furnace and then by a ladle refining desulfurization method (eg. Ladle desulfurization by injection of active agents, Ladle Furnace (LF)). Deoxidation of steel by metallic deoxidizers to the required concentrations of aluminum, silicon and other deoxidizing elements. Removal of non-metallic inclusions from the liquid steel in both melting furnace and Ladle refining stand. Vacuum treatment of steel in ladle by one of the degassing methods: Recirculation Degassing (RH), Ladle Degassing (VD). *Achievement of the required temperature of steel before pouring to the mold by using Ladle Furnace (LF). Final vacuum treatment of the steel in the Ladle-to-mold degassing operation. Providing non-intermittent supply of liquid steel to the pouring-to-mold operation.

The possible technological schemes of large steel ingots fabrication are presented in the figure:

Electroslag Remelting
Electroslag Remelting (ESR) is a process of remelting a consumable electrode utilizing the heat generated by an electric current passing through a molten slag between the electrode and the solidifying ingot. ESR process description Advantages of Electroslag Remelting Applications of Electroslag Remelting Electroslag Remelting under controllable atmosphere

ESR process description

The consumable electrods are as cast or forged cylindrical parts made of an alloy to be remelt. An electroslag remelting process (ESR) starts when the lower tip of a consumable electrode is immersed into a pool of molten slag. The premelted slag possessing electrical conductivity is located on the water-cooled mold base connected to a power supply. The electric current (commonly AC) passing through the the slag keeps it at high temperature, which is about 360F (200C) higher than the melting point of the remelted metal. The electrode tip is heated by the hot slag and starts to melt forming droplets of liquid metal, which disconnect from the electrode and sink through the slag layer. The slag composition is based on calcium fluoride (CaF2), lime (CaO) and alumina (Al2O3). The slag composition provides the following properties: Melting point lower than that of the remelted alloy; Required level ov viscosity; Required level of electrical conductivity; High solubility of sulfur; Capability to adsorb non-metallic inclusions.

The molten steel in form of both liquid film on the electrode tip and descending droplets contacts with the slag and get refined due to desulfurization and removal of non-metallic inclusions (sulfides and oxides). The droplets enters the molten steel pool, bottom of which is progressively solidifying. The water-cooled copper mold provides relatively high gradient of temperature resulting in high solidification rate. Solidification front is moving upwards (unidirectional solidification) forming sound homogeneous metal structure. The ingot has a good surface quality due to a thin slag film covering it.

Advantages of Electroslag Remelting

Deep desulfurization; Refining non-metallic inclusions; Homogeneous Distribution of non-metallic inclusions Fine Grain structure; No Shrinkage defects; Low macrosegregation; Good surface quality; Controllable process.

Applications of Electroslag Remelting

Superalloys (nickel base alloys possessing high strength, Creep resistance and oxidation resistance at high temperatures. Large Forging ingots. Fabrication of large steel ingots requires technologies providing high purity steel with low level of macrosegregation and shrinkage porosity. The technology of electroslag remelting (ESR) meets these demands. Ingots up to 200 metric tons are produced by electroslag remelting utilizing simultaneous remelting of tens of electrodes. The ingots are used for manufacturing heavy parts for electric power generating units (turbine shafts, generator rotor shafts). Rolling mill rolls. Tool and die steels. Stainless steels. Titanium alloys for aerospace applications. Titanium scrap remelting. Titnanium machining turnings and foundry scrap may be recycled by ESR providing cost effective secondary titanium.

Electroslag Remelting under controllable atmosphere

Electroslag Remelting under vacuum. The main limitation of the conventional ESR process is difficulty of removal of hydrogen exerting adverse effect on mechanical properties of steels. Low content of Hydrogen in conventional ESR is obtained by control of hydrogen in the consumable electrode. Additionally Electroslag Remelting under atmospere may cause oxidation by Oxygen penetrating into the slag contacting the pool of liquid metal. Electroslag Remelting under vacuum provides both vacuum degassing and oxidation protection of the remelted metal. Electroslag Remelting under inert gas atmosphere . Inert gas protects the slag and the metal from oxidation and from pick-up of atmospheric hydrogen. The method is simpler and cheaper than ESR under vacuum but it does not allow hydrogen removal. Electroslag Remelting under increased pressure. The method is used for remelting nitride hardened steels (alloyed by Nitrogen). During ESR process such steels are continuously alloyed by nitrogen containing compounds. Increased pressure prevents removal of dissolved nitrogen from the liquid steel to the atmosphere.