Deoxidization
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Deoxidization is a method used in
metallurgy Metallurgy is a domain of materials science and engineering that studies the physical and chemical behavior of metallic elements, their inter-metallic compounds, and their mixtures, which are known as alloys. Metallurgy encompasses both the ...
to remove the rest of
oxygen Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), group in the periodic table, a highly reactivity (chemistry), reactive nonmetal (chemistry), non ...
content from previously reduced iron ore during steel manufacturing. In contrast,
antioxidant Antioxidants are Chemical compound, compounds that inhibit Redox, oxidation, a chemical reaction that can produce Radical (chemistry), free radicals. Autoxidation leads to degradation of organic compounds, including living matter. Antioxidants ...
s are used for stabilization, such as in the storage of food. Deoxidation is important in the
steelmaking Steelmaking is the process of producing steel from iron ore and/or scrap. Steel has been made for millennia, and was commercialized on a massive scale in the 1850s and 1860s, using the Bessemer process, Bessemer and open hearth furnace, Siemens-M ...
process as oxygen is often detrimental to the quality of steel produced. Deoxidization is mainly achieved by adding a separate chemical species to neutralize the effects of oxygen or by directly removing the oxygen.


Oxidation

Oxidation Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
is the process of an element losing electrons. For example, iron will transfer two of its electrons to oxygen, forming an
oxide An oxide () is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion (anion bearing a net charge of −2) of oxygen, an O2− ion with oxygen in the oxidation st ...
. This occurs all throughout as an unintended part of the steelmaking process. Oxygen blowing is a method of steelmaking where oxygen is blown through
pig iron Pig iron, also known as crude iron, is an intermediate good used by the iron industry in the production of steel. It is developed by smelting iron ore in a blast furnace. Pig iron has a high carbon content, typically 3.8–4.7%, along with si ...
to lower the carbon content. Oxygen forms oxides with the unwanted elements, such as
carbon Carbon () is a chemical element; it has chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 ...
,
silicon Silicon is a chemical element; it has symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic lustre, and is a tetravalent metalloid (sometimes considered a non-metal) and semiconductor. It is a membe ...
,
phosphorus Phosphorus is a chemical element; it has Chemical symbol, symbol P and atomic number 15. All elemental forms of phosphorus are highly Reactivity (chemistry), reactive and are therefore never found in nature. They can nevertheless be prepared ar ...
, and
manganese Manganese is a chemical element; it has Symbol (chemistry), symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese was first isolated in the 1770s. It is a transition m ...
, which appear from various stages of the manufacturing process. These oxides will float to the top of the steel pool and remove themselves from the pig iron. However, some of the oxygen will also react with the iron itself. Due to the high temperatures involved in smelting, oxygen in the air may dissolve into the molten iron while it is being poured.
Slag The general term slag may be a by-product or co-product of smelting (pyrometallurgical) ores and recycled metals depending on the type of material being produced. Slag is mainly a mixture of metal oxides and silicon dioxide. Broadly, it can be c ...
, a byproduct left over after the smelting process, is used to further absorb impurities such as
sulfur Sulfur ( American spelling and the preferred IUPAC name) or sulphur ( Commonwealth spelling) is a chemical element; it has symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms ...
or oxides and protect steel from further oxidation. However, it can still be responsible for some oxidation. Some processes, while still able to lead to oxidation, are not relevant to the oxygen content of steel during its manufacture. For example,
rust Rust is an iron oxide, a usually reddish-brown oxide formed by the reaction of iron and oxygen in the catalytic presence of water or air moisture. Rust consists of hydrous iron(III) oxides (Fe2O3·nH2O) and iron(III) oxide-hydroxide (FeO(OH) ...
is a red iron oxide that forms when the iron in steel reacts with the oxygen or water in the air. This usually only occurs once the steel has been in use for varying lengths of time. Some physical components of the steelmaking process itself, such as the
electric arc furnace An electric arc furnace (EAF) is a Industrial furnace, furnace that heats material by means of an electric arc. Industrial arc furnaces range in size from small units of approximately one-tonne capacity (used in foundry, foundries for producin ...
, may also wear down and oxidize. This problem is typically dealt with by the use of
refractory metals Refractory metals are a class of metals that are extraordinarily resistant to heat and wear. The expression is mostly used in the context of materials science, metallurgy and engineering. The definitions of which elements belong to this group di ...
, which resist environmental conditions. If steel is not properly deoxidized, it will have lost various properties such as tensile strength,
ductility Ductility refers to the ability of a material to sustain significant plastic Deformation (engineering), deformation before fracture. Plastic deformation is the permanent distortion of a material under applied stress, as opposed to elastic def ...
, toughness, weldability, polishability, and
machinability Machinability is the ease with which a metal can be cut ( machined) permitting the removal of the material with a satisfactory finish at low cost.Degarmo, p. 542. Materials with good machinability (free-machining materials) require little power t ...
. This is due to forming
non-metallic inclusions Non-metallic inclusions are chemical compounds and nonmetals that are present in steel and other alloys. They are the product of chemical reactions, physical effects, and contamination that occurs during the melting and pouring process. These inc ...
and gas pores, bubbles of gas that get trapped during the solidification process of steel.


Types of deoxidizers


Metallic deoxidizers

This method of deoxidization involves adding specific metals into the steel. These metals will react with the unwanted oxygen, forming a strong oxide that, compared to pure oxygen, will reduce the steel's strength and qualities by a lesser amount. The chemical equation for deoxidization is represented by: nD + mO \longrightarrow D_ nO_m where n and m are coefficients, D is the deoxidizing agent, and O is oxygen. Thus, the
chemical equilibrium In a chemical reaction, chemical equilibrium is the state in which both the Reagent, reactants and Product (chemistry), products are present in concentrations which have no further tendency to change with time, so that there is no observable chan ...
equation involved is: K_ = a_ / (a_D^n * a_O^m ) where aox is the activity, or concentration, of the oxide in the steel, aD is the activity of the deoxidizing agent, and aO is the activity of the oxygen. An increase in the
equilibrium constant The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency ...
Keq will cause an increase in aox, and thus more of the oxide product. Keq can be manipulated by the steel temperature via the following equation: log K_ = A_D / T - B_D where AD and BD are parameters specific to different deoxidizers and T is the temperature in K°. Below are the values for certain deoxidizers at a temperature of 1873 K°. Below is a list of commonly used metallic deoxidizers: *
Ferrosilicon Ferrosilicon is an ferroalloy, alloy of iron and silicon. It has a typical silicon content of 15–90% by weight and a high proportion of iron silicides. Production and reactions Ferrosilicon is produced by reduction of silica or sand with coke ...
,
ferromanganese Ferromanganese is an alloy of iron and manganese, with other elements such as silicon, carbon, sulfur, nitrogen and phosphorus. The primary use of ferromanganese is as a type of processed manganese source to add to different types of steel, such ...
, calcium silicide - used in steelmaking in production of
carbon steel Carbon steel is a steel with carbon content from about 0.05 up to 2.1 percent by weight. The definition of carbon steel from the American Iron and Steel Institute (AISI) states: * no minimum content is specified or required for chromium, cobalt ...
s,
stainless steel Stainless steel, also known as inox, corrosion-resistant steel (CRES), or rustless steel, is an iron-based alloy that contains chromium, making it resistant to rust and corrosion. Stainless steel's resistance to corrosion comes from its chromi ...
s, and other ferrous alloys * Manganese - used in steelmaking *
Silicon carbide Silicon carbide (SiC), also known as carborundum (), is a hard chemical compound containing silicon and carbon. A wide bandgap semiconductor, it occurs in nature as the extremely rare mineral moissanite, but has been mass-produced as a powder a ...
,
calcium carbide Calcium carbide, also known as calcium acetylide, is a chemical compound with the chemical formula of . Its main use industrially is in the production of acetylene and calcium cyanamide. The pure material is colorless, while pieces of technica ...
- used as ladle deoxidizer in steel production * Aluminum dross - also a ladle deoxidizer, used in secondary steelmaking *
Calcium Calcium is a chemical element; it has symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to it ...
- used as a deoxidizer, desulfurizer, or decarbonizer for ferrous and non-ferrous alloys *
Titanium Titanium is a chemical element; it has symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in ...
- used as a deoxidizer for steels * Phosphorus, copper(I) phosphide - used in production of
oxygen-free copper Oxygen-free copper (OFC) or oxygen-free high thermal conductivity (OFHC) copper is a group of wrought high-conductivity copper alloys that have been electrolytically refined to reduce the level of oxygen to 0.001% or below. Oxygen-free copper ...
* Calcium hexaboride - used in production of oxygen-free copper, yields higher conductivity copper than phosphorus-deoxidized *
Yttrium Yttrium is a chemical element; it has Symbol (chemistry), symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and has often been classified as a "rare-earth element". Yttrium is almost a ...
- used to deoxidize
vanadium Vanadium is a chemical element; it has Symbol (chemistry), symbol V and atomic number 23. It is a hard, silvery-grey, malleable transition metal. The elemental metal is rarely found in nature, but once isolated artificially, the formation of an ...
and other non-ferrous metals *
Zirconium Zirconium is a chemical element; it has Symbol (chemistry), symbol Zr and atomic number 40. First identified in 1789, isolated in impure form in 1824, and manufactured at scale by 1925, pure zirconium is a lustrous transition metal with a greyis ...
*
Magnesium Magnesium is a chemical element; it has Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 ...
* Carbon *
Tungsten Tungsten (also called wolfram) is a chemical element; it has symbol W and atomic number 74. It is a metal found naturally on Earth almost exclusively in compounds with other elements. It was identified as a distinct element in 1781 and first ...


Vacuum deoxidation

Vacuum deoxidation is a method which involves using a
vacuum A vacuum (: vacuums or vacua) is space devoid of matter. The word is derived from the Latin adjective (neuter ) meaning "vacant" or "void". An approximation to such vacuum is a region with a gaseous pressure much less than atmospheric pressur ...
to remove impurities. A portion of the carbon and oxygen in steel will react, forming
carbon monoxide Carbon monoxide (chemical formula CO) is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the si ...
. CO gas will float up to the top of the liquid steel and be removed by a vacuum system. As the chemical reaction involved in vacuum deoxidation is: C + O \longrightarrow CO the reaction between carbon and oxygen is represented by the following chemical equilibrium equation: K_ = P_/(a_C * a_O) where PCO is the
partial pressure In a mixture of gases, each constituent gas has a partial pressure which is the notional pressure of that constituent gas as if it alone occupied the entire volume of the original mixture at the same temperature. The total pressure of an ideal g ...
of the carbon monoxide formed. Decreasing the oxygen activity(aO) will raise the higher equilibrium constant, increasing CO production. To achieve this, subjecting the pool of steel to vacuum treatment decreases the value of PCO, allowing for more CO gas to be produced.


Diffusion deoxidation

This method relies on the idea that deoxidation of slag will lead to the deoxidation of steel. The chemical equilibrium equation used for this process is: K_ = a_ / a_ where a /sub> is the activity of the oxygen in the slag, and a(O) is the activity of oxygen in the steel. Reducing the activity in the slag (a /sub>) will lower the oxygen levels in the slag. Afterwards, oxygen will
diffuse Diffusion is the net movement of anything (for example, atoms, ions, molecules, energy) generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical p ...
from the steel into the lesser concentrated slag. This method is done by using deoxidizing agents on the slag, such as coke or silicon. As these agents do not come into direct contact with the steel, non-metallic inclusions will not form in the steel itself.


See also

*
Smelting Smelting is a process of applying heat and a chemical reducing agent to an ore to extract a desired base metal product. It is a form of extractive metallurgy that is used to obtain many metals such as iron-making, iron, copper extraction, copper ...


References

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See also

*
Desulfurization Desulfurization or desulphurisation is a chemical process for the removal of sulfur from a material. The term usually refers to the removal of sulfur from a molecule or a material by hydrogenolysis: : Hydrogen is the ultimate sulfur acceptor. A ...
is the process of decreasing the sulfur content of steel. *
Decarburization Decarburization (or decarbonization) is the process of decreasing carbon content, which is the opposite of carburization. The term is typically used in metallurgy, describing the decrease of the content of carbon in metals (usually steel). Decar ...
is the process of decreasing the carbon content in metallurgy. *
Deoxidized steel Deoxidized steel (also known as killed steel) is steel that has some or all of the oxygen removed from the melt during the steelmaking process. Liquid steels contain dissolved oxygen after their conversion from molten iron, but the solubility of o ...
s are steels categorized by level of deoxidization treatment. *
Vacuum engineering Vacuum engineering is the field of engineering that deals with the practical use of vacuum in industrial and scientific applications. Vacuum may improve the productivity and performance of processes otherwise carried out at normal air pressure, or ...
** Vacuum metallurgy Industrial processes Metallurgy Steelmaking