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 sci ...
to remove the
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as we ...
content during steel manufacturing. In contrast,
antioxidant
Antioxidants are compounds that inhibit oxidation, a chemical reaction that can produce free radicals. This can lead to polymerization and other chain reactions. They are frequently added to industrial products, such as fuels and lubricants ...
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 carbon/or scrap. In steelmaking, impurities such as nitrogen, silicon, phosphorus, sulfur and excess carbon (the most important impurity) are removed from the sourced iron, and allo ...
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, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a ...
is the process of an element losing electrons. For example, iron will transfer two of its electrons to oxygen, forming an
oxide. 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 product of the iron industry in the production of steel which is obtained by smelting iron ore in a blast furnace. Pig iron has a high carbon content, typically 3.8–4.7%, along with sil ...
to lower the carbon content. Oxygen forms oxides with the unwanted elements, such as
carbon
Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon makes ...
,
silicon
Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic ...
,
phosphorus
Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ea ...
, and
manganese
Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy u ...
, 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
Slag is a by-product of smelting ( pyrometallurgical) ores and used metals. Broadly, it can be classified as ferrous (by-products of processing iron and steel), ferroalloy (by-product of ferroalloy production) or non-ferrous/ base metals (by ...
, a byproduct left over after the smelting process, is used to further absorb impurities such as
sulfur
Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formul ...
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 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 foundries for producing cast iron products) up to ...
, 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 definition of which elements belong to this group dif ...
, which resist environmental conditions.
If steel is not properly deoxidized, it will have lost various properties such as tensile strength,
ductility
Ductility is a mechanical property commonly described as a material's amenability to drawing (e.g. into wire). In materials science, ductility is defined by the degree to which a material can sustain plastic deformation under tensile str ...
, toughness,
weldability The weldability, also known as joinability,. of a material refers to its ability to be welded. Many metals and thermoplastics can be welded, but some are easier to weld than others (see Rheological weldability). A material's weldability is used t ...
, 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 to ...
. This is due to forming
non-metallic inclusions 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:
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 reactants and products are present in concentrations which have no further tendency to change with time, so that there is no observable change in the properties of the ...
equation involved is:
where a
ox is the
activity, or concentration, of the oxide in the steel,
a
D is the activity of the deoxidizing agent,
and a
O 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 ...
K
eq will cause an increase in a
ox, and thus more of the oxide product.
K
eq can be manipulated by the steel temperature via the following equation:
where A
D and B
D 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 alloy of iron and silicon with a typical silicon content by weight of 15–90%. It contains a high proportion of iron silicides.
Production and reactions
Ferrosilicon is produced by reduction of silica or sand with coke in t ...
, ferromanganese
Ferromanganese is a ferroalloy with high manganese content (high-carbon ferromanganese can contain as much as 80% Mn by weight). It is made by heating a mixture of the oxides MnO2 and Fe2O3, with carbon (usually as coal and coke) in either a bl ...
, 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, coba ...
s, stainless steels, 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 semiconductor, it occurs in nature as the extremely rare mineral moissanite, but has been mass-produced as a powder and crystal ...
, calcium carbide
Calcium carbide, also known as calcium acetylide, is a chemical compound with the chemical formula of Ca C2. Its main use industrially is in the production of acetylene and calcium cyanamide.
The pure material is colorless, while pieces of te ...
- used as ladle deoxidizer in steel production
* Aluminum dross - also a ladle deoxidizer, used in secondary steelmaking
* Calcium
Calcium is a chemical element with the 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 t ...
- used as a deoxidizer, desulfurizer, or decarbonizer for ferrous and non-ferrous alloy
In metallurgy, non-ferrous metals are metals or alloys that do not contain iron (allotropes of iron, ferrite, and so on) in appreciable amounts.
Generally more costly than ferrous metals, non-ferrous metals are used because of desirable proper ...
s
* Titanium
Titanium is a chemical element with the Symbol (chemistry), 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, resista ...
- used as a deoxidizer for steels
* Phosphorus, copper(I) phosphide
Copper phosphide, , also copper(I) phosphide, cuprous phosphide, cuprophosphorus and phosphor copper, is a compound of copper and phosphorus, a phosphide of copper. It has the appearance of yellowish-grey very brittle mass of crystalline structure ...
- 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.
Specification
Ox ...
* Calcium hexaboride - used in production of oxygen-free copper, yields higher conductivity copper than phosphorus-deoxidized
* Yttrium
Yttrium is a chemical element with the 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 always found in c ...
- used to deoxidize vanadium
Vanadium is a chemical element with the 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 oxide layer ( pass ...
and other non-ferrous metals
* Zirconium
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name ''zirconium'' is taken from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian '' zargun'' (zircon; ''zar-gun'' ...
* Magnesium
Magnesium is a chemical element with the 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 of the periodic ...
* Carbon
* Tungsten
Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isol ...
Vacuum deoxidation
Vacuum deoxidation is a method which involves using a vacuum
A vacuum is a space devoid of matter. The word is derived from the Latin adjective ''vacuus'' for "vacant" or " void". An approximation to such vacuum is a region with a gaseous pressure much less than atmospheric pressure. Physicists often di ...
to remove impurities. A portion of the carbon and oxygen in steel will react, forming carbon monoxide
Carbon monoxide ( chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is 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:
the reaction between carbon and oxygen is represented by the following chemical equilibrium equation:
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 result in a higher equilibrium constant, thus more product, CO. 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:
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.[
]
References
{{Reflist
See also
* Desulfurization Desulfurization or desulphurisation is a chemical process for the removal of sulfur from a material. This involves either the removal of sulfur from a molecule (''e.g.'' A=S → A:) or the removal of sulfur compounds from a mixture such as oil refin ...
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). Deca ...
is the process of decreasing the carbon content in metallurgy.
* Deoxidized steels are steels categorized by level of deoxidization treatment.
* Vacuum engineering
** Vacuum metallurgy
Industrial processes
Metallurgy
Steelmaking