Last updated
Martensite in AISI 4140 steel Martensite.jpg
Martensite in AISI 4140 steel
0.35% carbon steel, water-quenched from 870 degC Steel 035 water quenched.png
0.35% carbon steel, water-quenched from 870 °C

Martensite is a very hard form of steel crystalline structure. It is named after German metallurgist Adolf Martens. By analogy the term can also refer to any crystal structure that is formed by diffusionless transformation. [1]



Martensite is formed in carbon steels by the rapid cooling (quenching) of the austenite form of iron at such a high rate that carbon atoms do not have time to diffuse out of the crystal structure in large enough quantities to form cementite (Fe3C). Austenite is gamma-phase iron (γ-Fe), a solid solution of iron and alloying elements. As a result of the quenching, the face-centered cubic austenite transforms to a highly strained body-centered tetragonal form called martensite that is supersaturated with carbon. The shear deformations that result produce a large number of dislocations, which is a primary strengthening mechanism of steels. The highest hardness of a pearlitic steel is 400  Brinell, whereas martensite can achieve 700 Brinell. [2]

The martensitic reaction begins during cooling when the austenite reaches the martensite start temperature (Ms), and the parent austenite becomes mechanically unstable. As the sample is quenched, an increasingly large percentage of the austenite transforms to martensite until the lower transformation temperature Mf is reached, at which time the transformation is completed. [1]

For a eutectoid steel (0.78% C), between 6 and 10% of austenite, called retained austenite, will remain. The percentage of retained austenite increases from insignificant for less than 0.6% C steel, to 13% retained austenite at 0.95% C and 30–47% retained austenite for a 1.4% carbon steel. A very rapid quench is essential to create martensite. For a eutectoid carbon steel of thin section, if the quench starting at 750 °C and ending at 450 °C takes place in 0.7 seconds (a rate of 430 °C/s) no pearlite will form, and the steel will be martensitic with small amounts of retained austenite. [2]

For steel with 0–0.6% carbon, the martensite has the appearance of lath and is called lath martensite. For steel with greater than 1% carbon, it will form a plate-like structure called plate martensite. Between those two percentages, the physical appearance of the grains is a mix of the two. The strength of the martensite is reduced as the amount of retained austenite grows. If the cooling rate is slower than the critical cooling rate, some amount of pearlite will form, starting at the grain boundaries where it will grow into the grains until the Ms temperature is reached, then the remaining austenite transforms into martensite at about half the speed of sound in steel.

In certain alloy steels, martensite can be formed by the working the steel at Ms temperature by quenching to below Ms and then working by plastic deformations to reductions of cross section area between 20% to 40% of the original. The process produces dislocation densities up to 1013/cm2. The great number of dislocations, combined with precipitates that originate and pin the dislocations in place, produces a very hard steel. This property is frequently used in toughened ceramics like yttria-stabilized zirconia and in special steels like TRIP steels. Thus, martensite can be thermally induced or stress induced. [1] [3]

The growth of martensite phase requires very little thermal activation energy because the process is a diffusionless transformation, which results in the subtle but rapid rearrangement of atomic positions, and has been known to occur even at cryogenic temperatures. [1] Martensite has a lower density than austenite, so that the martensitic transformation results in a relative change of volume. [4] Of considerably greater importance than the volume change is the shear strain, which has a magnitude of about 0.26 and which determines the shape of the plates of martensite. [5]

Martensite is not shown in the equilibrium phase diagram of the iron-carbon system because it is not an equilibrium phase. Equilibrium phases form by slow cooling rates that allow sufficient time for diffusion, whereas martensite is usually formed by very high cooling rates. Since chemical processes (the attainment of equilibrium) accelerate at higher temperature, martensite is easily destroyed by the application of heat. This process is called tempering. In some alloys, the effect is reduced by adding elements such as tungsten that interfere with cementite nucleation, but more often than not, the nucleation is allowed to proceed to relieve stresses. Since quenching can be difficult to control, many steels are quenched to produce an overabundance of martensite, then tempered to gradually reduce its concentration until the preferred structure for the intended application is achieved. The needle-like microstructure of martensite leads to brittle behavior of the material. Too much martensite leaves steel brittle; too little leaves it soft.

See also

Related Research Articles

Steel Metal alloy made by combining iron with other elements

Steel is an alloy of iron with typically a few percent of carbon to improve its strength and fracture resistance compared to iron. Many other additional elements may be present or added. Stainless steels that are corrosion and oxidation resistant need typically an additional 11% chromium. Because of its high tensile strength and low cost, steel is used in buildings, infrastructure, tools, ships, trains, cars, machines, electrical appliances, and weapons. Iron is the base metal of steel and it can take on two crystalline forms : body centred cubic and face-centred cubic. These forms depend on temperature. In the body-centred cubic arrangement, there is an iron atom in the centre and eight atoms at the vertices of each cubic unit cell; in the face-centred cubic, there is one atom at the centre of each of the six faces of the cubic unit cell and eight atoms at its vertices. It is the interaction of the allotropes of iron with the alloying elements, primarily carbon, that gives steel and cast iron their range of unique properties.

Heat treating Process of heating something to alter it

Heat treating is a group of industrial, thermal and metalworking processes used to alter the physical, and sometimes chemical, properties of a material. The most common application is metallurgical. Heat treatments are also used in the manufacture of many other materials, such as glass. Heat treatment involves the use of heating or chilling, normally to extreme temperatures, to achieve the desired result such as hardening or softening of a material. Heat treatment techniques include annealing, case hardening, precipitation strengthening, tempering, carburizing, normalizing and quenching. Although the term heat treatment applies only to processes where the heating and cooling are done for the specific purpose of altering properties intentionally, heating and cooling often occur incidentally during other manufacturing processes such as hot forming or welding.


Cementite (or iron carbide) is a compound of iron and carbon, more precisely an intermediate transition metal carbide with the formula Fe3C. By weight, it is 6.67% carbon and 93.3% iron. It has an orthorhombic crystal structure. It is a hard, brittle material, normally classified as a ceramic in its pure form, and is a frequently found and important constituent in ferrous metallurgy. While cementite is present in most steels and cast irons, it is produced as a raw material in the iron carbide process, which belongs to the family of alternative ironmaking technologies. The name cementite originated from the research of Floris Osmond and J. Werth, where the structure of solidified steel consists of a kind of cellular tissue in theory, with ferrite as the nucleus and Fe3C the envelope of the cells. The carbide therefore cemented the iron.

Austenite Metallic, non-magnetic allotrope of iron or a solid solution of iron, with an alloying element

Austenite, also known as gamma-phase iron (γ-Fe), is a metallic, non-magnetic allotrope of iron or a solid solution of iron, with an alloying element. In plain-carbon steel, austenite exists above the critical eutectoid temperature of 1000 K (727 °C); other alloys of steel have different eutectoid temperatures. The austenite allotrope is named after Sir William Chandler Roberts-Austen (1843–1902); it exists at room temperature in some stainless steels due to the presence of nickel stabilizing the austenite at lower temperatures.


Bainite is a plate-like microstructure that forms in steels at temperatures of 125–550 °C. First described by E. S. Davenport and Edgar Bain, it is one of the products that may form when austenite is cooled past a temperature where it no longer is thermodynamically stable with respect to ferrite, cementite, or ferrite and cementite. Davenport and Bain originally described the microstructure as being similar in appearance to tempered martensite.


Pearlite is a two-phased, lamellar structure composed of alternating layers of ferrite and cementite that occurs in some steels and cast irons. During slow cooling of an iron-carbon alloy, pearlite forms by a eutectoid reaction as austenite cools below 723 °C (1,333 °F). Pearlite is a microstructure occurring in many common grades of steels.

Carbon steel Steel in which the main interstitial alloying constituent is carbon

Carbon steel is a steel with carbon content from about 0.05% up to 2.1% by weight. The definition of carbon steel from the American Iron and Steel Institute (AISI) states:

Quenching Rapid cooling of a workpiece to obtain certain material properties

In materials science, quenching is the rapid cooling of a workpiece in water, oil or air to obtain certain material properties. A type of heat treating, quenching prevents undesired low-temperature processes, such as phase transformations, from occurring. It does this by reducing the window of time during which these undesired reactions are both thermodynamically favorable, and kinetically accessible; for instance, quenching can reduce the crystal grain size of both metallic and plastic materials, increasing their hardness.

Maraging steel

Maraging steels are steels that are known for possessing superior strength and toughness without losing ductility. Aging refers to the extended heat-treatment process. These steels are a special class of low-carbon ultra-high-strength steels that derive their strength not from carbon, but from precipitation of intermetallic compounds. The principal alloying element is 15 to 25 wt% nickel. Secondary alloying elements, which include cobalt, molybdenum and titanium, are added to produce intermetallic precipitates. Original development was carried out on 20 and 25 wt% Ni steels to which small additions of aluminium, titanium, and niobium were made; a rise in the price of cobalt in the late 1970s led to the development of cobalt-free maraging steels.

Tempering (metallurgy) Process of heat treating used to increase toughness of iron-based alloys

Tempering is a process of heat treating, which is used to increase the toughness of iron-based alloys. Tempering is usually performed after hardening, to reduce some of the excess hardness, and is done by heating the metal to some temperature below the critical point for a certain period of time, then allowing it to cool in still air. The exact temperature determines the amount of hardness removed, and depends on both the specific composition of the alloy and on the desired properties in the finished product. For instance, very hard tools are often tempered at low temperatures, while springs are tempered at much higher temperatures.

Hardenability Depth to which a metal is hardened after being submitted to a thermal treatment

The hardenability of a metal alloy is the depth to which a material is hardened after putting it through a heat treatment process. It should not be confused with hardness, which is a measure of a sample's resistance to indentation or scratching. It is an important property for welding, since it is inversely proportional to weldability, that is, the ease of welding a material.

Cryogenic hardening is a cryogenic treatment process where the material is cooled to approximately −185 °C (−301 °F), usually using liquid nitrogen. It can have a profound effect on the mechanical properties of certain steels, provided their composition and prior heat treatment are such that they retain some austenite at room temperature. It is designed to increase the amount of martensite in the steel's crystal structure, increasing its strength and hardness, sometimes at the cost of toughness. Presently this treatment is being practiced over tool steels, high-carbon, high-chromium steels and in some cases to cemented carbide to obtain excellent wear resistance. Recent research shows that there is precipitation of fine carbides in the matrix during this treatment which imparts very high wear resistance to the steels.

Hardening is a metallurgical metalworking process used to increase the hardness of a metal. The hardness of a metal is directly proportional to the uniaxial yield stress at the location of the imposed strain. A harder metal will have a higher resistance to plastic deformation than a less hard metal.

In metallurgy and materials science, annealing is a heat treatment that alters the physical and sometimes chemical properties of a material to increase its ductility and reduce its hardness, making it more workable. It involves heating a material above its recrystallization temperature, maintaining a suitable temperature for an appropriate amount of time and then cooling.


In iron and steel metallurgy, ledeburite is a mixture of 4.3% carbon in iron and is a eutectic mixture of austenite and cementite. Ledeburite is not a type of steel as the carbon level is too high although it may occur as a separate constituent in some high carbon steels. It is mostly found with cementite or pearlite in a range of cast irons.

Isothermal transformation diagram

Isothermal transformation diagrams are plots of temperature versus time. They are generated from percentage transformation-vs time measurements, and are useful for understanding the transformations of an alloy steel at elevated temperatures.

Diffusionless transformation

A diffusionless transformation is a phase change that occurs without the long-range diffusion of atoms but rather by some form of cooperative, homogeneous movement of many atoms that results in a change in crystal structure. These movements are small, usually less than the interatomic distances, and the atoms maintain their relative relationships. The ordered movement of large numbers of atoms leads some to refer to these as military transformations in contrast to civilian diffusion-based phase changes.

Martempering is also known as stepped quenching or interrupted quenching. In this process, steel is heated above the upper critical point and then quenched in a salt, oil, or lead bath kept at a temperature of 150-300 °C. The workpiece is held at this temperature above martensite start (Ms) point until the temperature becomes uniform throughout the cross-section of workpiece. After that it is cooled in air or oil to room temperature. The steel is then tempered. In this process, Austenite is transformed to martensite by step quenching, at a rate fast enough to avoid the formation of ferrite, pearlite or bainite.


Austempering is heat treatment that is applied to ferrous metals, most notably steel and ductile iron. In steel it produces a bainite microstructure whereas in cast irons it produces a structure of acicular ferrite and high carbon, stabilized austenite known as ausferrite. It is primarily used to improve mechanical properties or reduce / eliminate distortion. Austempering is defined by both the process and the resultant microstructure. Typical austempering process parameters applied to an unsuitable material will not result in the formation of bainite or ausferrite and thus the final product will not be called austempered. Both microstructures may also be produced via other methods. For example, they may be produced as-cast or air cooled with the proper alloy content. These materials are also not referred to as austempered.

TRIP steel are a class of high-strength steel alloys typically used in naval and marine applications and in the automotive industry. TRIP stands for "Transformation induced plasticity," which implies a phase transformation in the material, typically when a stress is applied. These alloys are known to possess an outstanding combination of strength and ductility.


  1. 1 2 3 4 Khan, Abdul Qadeer (March 1972) [1972], "3", The effect of morphology on the strength of copper-based martensites (in German and English), 1 (1 ed.), Leuven, Belgium: A.Q. Khan, University of Leuven, Belgium, p. 300
  2. 1 2 Baumeister, Avallone, Baumeister (1978). "6". Marks' Standard Handbook for Mechanical Engineers, 8th ed . McGraw Hill. pp.  17, 18. ISBN   9780070041233.CS1 maint: multiple names: authors list (link)
  3. Verhoeven, John D. (2007). Steel Metallurgy for the Non-Metallurgist. American Society for Metals. pp. 26–31. ISBN   9780871708588.
  4. Ashby, Michael F.; David R. H. Jones (1992) [1986]. Engineering Materials 2 (with corrections ed.). Oxford: Pergamon Press. ISBN   0-08-032532-7.
  5. Bhadeshia, H. K. D. H. (2001) [2001]. Geometry of Crystals (with corrections ed.). London: Institute of Materials. ISBN   0-904357-94-5.