Ferritic nitrocarburizing or FNC, also known by the proprietary names Tenifer, Tufftride and Melonite as well as ARCOR,
[Other trade names include Tuffride/ Tuffrider, QPQ, Sulfinuz, Sursulf, Meli 1, and Nitride, among others] is a range of proprietary
case hardening
Case-hardening or surface hardening is the process of Hardening (metallurgy), hardening the surface of a metal object while allowing the metal deeper underneath to remain soft, thus forming a thin layer of hardness, harder metal at the surface. Fo ...
processes that diffuse
nitrogen
Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at seve ...
and
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 ...
into
ferrous
In chemistry, the adjective Ferrous indicates a compound that contains iron(II), meaning iron in its +2 oxidation state, possibly as the divalent cation Fe2+. It is opposed to "ferric" or iron(III), meaning iron in its +3 oxidation state, suc ...
metals at sub-
critical temperatures during a salt bath. Other methods of ferric nitrocarburizing include gaseous process such as
Nitrotec and ion (plasma) ones. The processing temperature ranges from to , but usually occurs at . At this temperature steels and other ferrous alloys remain in the
ferritic
A ferrite is a ceramic material made by mixing and firing large proportions of iron(III) oxide (Fe2O3, rust) blended with small proportions of one or more additional metallic elements, such as strontium, barium, manganese, nickel, and zinc. ...
phase region. This allows for better control of the dimensional stability that would not be present in case hardening processes that occur when the alloy is transitioned into the
austenitic phase.
[.] There are four main classes of ferritic nitrocarburizing: ''gaseous'', ''salt bath'', ''ion'' or ''plasma'', and ''fluidized-bed''.
[.]
The process is used to improve three main
surface integrity Surface integrity is the surface condition of a workpiece after being modified by a manufacturing process. The term was coined by Michael Field and John F. Kahles in 1964..
The surface integrity of a workpiece or item changes the material's propert ...
aspects including scuffing resistance,
fatigue
Fatigue describes a state of tiredness that does not resolve with rest or sleep. In general usage, fatigue is synonymous with extreme tiredness or exhaustion that normally follows prolonged physical or mental activity. When it does not resolve ...
properties, and
corrosion resistance
Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engi ...
. It has the added advantage of inducing little shape distortion during the hardening process. This is because of the low processing temperature, which reduces thermal shocks and avoids
phase transition
In chemistry, thermodynamics, and other related fields, a phase transition (or phase change) is the physical process of transition between one state of a medium and another. Commonly the term is used to refer to changes among the basic states ...
s in steel.
History
The first ferritic nitrocarburizing methods were done at low temperatures, around , in a liquid salt bath. The first company to successfully commercialize the process was the
Imperial Chemical Industries
Imperial Chemical Industries (ICI) was a British chemical company. It was, for much of its history, the largest manufacturer in Britain.
It was formed by the merger of four leading British chemical companies in 1926.
Its headquarters were at M ...
in
Great Britain
Great Britain is an island in the North Atlantic Ocean off the northwest coast of continental Europe. With an area of , it is the largest of the British Isles, the largest European island and the ninth-largest island in the world. It is ...
. ICI called their process "the cassel" due to the plant where it was developed or "Sulfinuz" treatment because it had sulfur in the salt bath. While the process was very successful with high-speed spindles and
cutting tool
In the context of machining, a cutting tool or cutter is typically a hardened metal tool that is used to cut, shape, and remove material from a workpiece by means of machining tools as well as abrasive tools by way of shear deformation. The majori ...
s, there were issues with cleaning the solution off because it was not very water
soluble
In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution.
The extent of the solub ...
.
Because of the cleaning issues the Joseph Lucas Limited company began experimenting with gaseous forms of ferritic nitrocarburizing in the late 1950s. The company applied for a patent by 1961. It produced a similar surface finish as the Sulfinuz process with the exception of the formation of sulfides. The atmosphere consisted of
ammonia
Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogeno ...
,
hydrocarbon
In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ...
gases, and a small amount of other carbon-containing gases.
This spurred the development of a more environmentally friendly salt bath process by the German company
Degussa after acquiring ICI patents. Their process is the widely known as the Tufftride or Tenifer process. Following this the ion nitriding process was invented in the early 1980s. This process had faster cycle times, required less cleaning and preparation, formed deeper cases, and allowed for better control of the process.
Processes
Despite the naming the process is a modified form of
nitriding and not
carburizing
Carburising, carburizing (chiefly American English), or carburisation is a heat treatment process in which iron or steel absorbs carbon while the metal is heated in the presence of a carbon-bearing material, such as charcoal or carbon monoxid ...
. The shared attributes of this class of this process is the introduction of nitrogen and carbon in the ferritic state of the material. The processes are broken up into four main classes: ''gaseous'', ''salt bath'', ''ion'' or ''plasma'', or ''fluidized-bed''. The trade name and patented processes may vary slightly from the general description, but they are all a form of ferritic nitrocarburizing.
Salt bath ferritic nitrocarburizing
Salt bath ferritic nitrocarburizing is also known as liquid ferritic nitrocarburizing or liquid nitrocarburizing
[.] and is also known by the trademarked names Tufftride
and Tenifer.
The simplest form of this process is encompassed by the trademarked Melonite process, also known as Meli 1. It is most commonly used on steels,
sintered
Clinker nodules produced by sintering
Sintering or frittage is the process of compacting and forming a solid mass of material by pressure or heat without melting it to the point of liquefaction.
Sintering happens as part of a manufacturing ...
irons, and
cast iron
Cast iron is a class of iron– carbon alloys with a carbon content more than 2%. Its usefulness derives from its relatively low melting temperature. The alloy constituents affect its color when fractured: white cast iron has carbide impu ...
s to lower
friction
Friction is the force resisting the relative motion of solid surfaces, fluid layers, and material elements sliding (motion), sliding against each other. There are several types of friction:
*Dry friction is a force that opposes the relative la ...
and improve
wear
Wear is the damaging, gradual removal or deformation of material at solid surfaces. Causes of wear can be mechanical (e.g., erosion) or chemical (e.g., corrosion). The study of wear and related processes is referred to as tribology.
Wear in ...
and corrosion resistance.
[.]
The process uses a salt bath of
alkali
In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of ...
cyanate
Cyanate is an anion with the structural formula , usually written . It also refers to any salt containing it, such as ammonium cyanate.
It is an isomer of the much less stable fulminate anion .William R. Martin and David W. Ball (2019): "Sm ...
. This is contained in a steel pot that has an
aeration
Aeration (also called aerification or aeriation) is the process by which air is circulated through, mixed with or dissolved in a liquid or other substances that act as a fluid (such as soil). Aeration processes create additional surface area i ...
system. The cyanate thermally reacts with the surface of the workpiece to form alkali
carbonate
A carbonate is a salt of carbonic acid (H2CO3), characterized by the presence of the carbonate ion, a polyatomic ion with the formula . The word ''carbonate'' may also refer to a carbonate ester, an organic compound containing the carbonat ...
. The bath is then treated to convert the carbonate back to a cyanate. The surface formed from the reaction has a compound layer and a diffusion layer. The compound layer consists of iron, nitrogen, and oxygen, is abrasion resistant, and stable at elevated temperatures. The diffusion layer contains
nitride
In chemistry, a nitride is an inorganic compound of nitrogen. The "nitride" anion, N3- ion, is very elusive but compounds of nitride are numerous, although rarely naturally occuring. Some nitrides have a find applications, such as wear-resista ...
s and
carbide
In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece.
Interstitial / Metallic carbides
The carbides of th ...
s. The
surface hardness ranges from 800 to 1500 HV depending on the
steel grade
Steel grades to classify various steels by their composition and physical properties have been developed by a number of standards organizations.
Steel grades standards by country
* For alloys in general (including steel), unified numbering system ...
. This also inversely affects the depth of the case; i.e. a high carbon steel will form a hard, but shallow case.
A similar process is the trademarked Nu-Tride process, also known incorrectly as the Kolene process (which is actually the company's name), which includes a preheat and an intermediate quench cycle. The intermediate quench is an
oxidizing
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 d ...
salt bath at . This quench is held for 5 to 20 minutes before final quenching to room temperature. This is done to minimize distortion and to destroy any lingering cyanates or cyanides left on the workpiece.
Other trademarked processes are Sursulf and Tenoplus. Sursulf has a sulfur compound in the salt bath to create surface sulfides which creates
porosity
Porosity or void fraction is a measure of the void (i.e. "empty") spaces in a material, and is a fraction of the volume of voids over the total volume, between 0 and 1, or as a percentage between 0% and 100%. Strictly speaking, some tests measure ...
in the workpiece surface. This porosity is used to contain lubrication. Tenoplus is a two-stage high-temperature process. The first stage occurs at , while the second stage occurs at .
Gaseous ferritic nitrocarburizing
Gaseous ferritic nitrocarburizing is also known as controlled nitrocarburizing, soft nitriding, and vacuum nitrocarburizing or by the tradenames UltraOx, Nitrotec, Nitemper, Deganit, Triniding, Corr-I-Dur, Nitroc, NITREG-C, Nitrowear, and Nitroneg.
The process works to achieve the same result as the salt bath process, except gaseous mixtures are used to diffuse the nitrogen and carbon into the workpiece.
[.]
The parts are first cleaned, usually with a
vapor degreasing process, and then nitrocarburized around , with a process time that ranges from one to four hours. The actual gas mixtures are proprietary, but they usually contain ammonia and an
endothermic
In thermochemistry, an endothermic process () is any thermodynamic process with an increase in the enthalpy (or internal energy ) of the system.Oxtoby, D. W; Gillis, H.P., Butler, L. J. (2015).''Principle of Modern Chemistry'', Brooks Cole. p. ...
gas.
Plasma-assisted ferritic nitrocarburizing
Plasma-assisted ferritic nitrocarburizing is also known as ion nitriding, plasma ion nitriding or glow-discharge nitriding. The process works to achieve the same result as the salt bath and gaseous process, except the reactivity of the media is not due to the temperature but to the gas ionized state. In this technique intense electric fields are used to generate ionized molecules of the gas around the surface to diffuse the nitrogen and carbon into the workpiece. Such highly active gas with ionized molecules is called
plasma, naming the technique. The gas used for plasma nitriding is usually pure nitrogen, since no spontaneous decomposition is needed (as is the case of gaseous ferritic nitrocarburizing with ammonia). Due to the relatively low temperature range ( to ) generally applied during plasma-assisted ferritic nitrocarburizing and gentle cooling in the furnace, the distortion of workpieces can be minimized. Stainless steel workpieces can be processed at moderat