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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.


Properties

Martensite is formed in carbon steels by the rapid cooling (
quench In materials science, quenching is the rapid cooling of a workpiece in water, oil, polymer, air, or other fluids to obtain certain material properties. A type of heat treating, quenching prevents undesired low-temperature processes, such as p ...
ing) of the
austenite 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 ...
form of
iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundanc ...
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 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, bri ...
(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 In crystallography, the cubic (or isometric) crystal system is a crystal system where the unit cell is in the shape of a cube. This is one of the most common and simplest shapes found in crystals and minerals. There are three main varieties of ...
austenite transforms to a highly strained
body-centered tetragonal In crystallography, the tetragonal crystal system is one of the 7 crystal systems. Tetragonal crystal lattices result from stretching a cubic lattice along one of its lattice vectors, so that the cube becomes a rectangular prism with a squa ...
form called martensite that is supersaturated with
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 mak ...
. 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. The martensitic
reaction Reaction may refer to a process or to a response to an action, event, or exposure: Physics and chemistry *Chemical reaction *Nuclear reaction * Reaction (physics), as defined by Newton's third law *Chain reaction (disambiguation). Biology and m ...
begins during cooling when the
austenite 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 ...
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. For a
eutectoid A eutectic system or eutectic mixture ( ) is a homogeneous mixture that has a melting point lower than those of the constituents. The lowest possible melting point over all of the mixing ratios of the constituents is called the ''eutectic tempe ...
steel (0.76% 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. For steel with 0–0.6% carbon, the martensite has the appearance of
lath A lath or slat is a thin, narrow strip of straight-wood grain, grained wood used under roof shingles or tiles, on lath and plaster walls and ceilings to hold plaster, and in Latticework, lattice and Trellis (architecture), trellis work. ''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 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 Yttria-stabilized zirconia (YSZ) is a ceramic in which the cubic crystal structure of zirconium dioxide is made stable at room temperature by an addition of yttrium oxide. These oxides are commonly called "zirconia" ( Zr O2) and "yttria" ( Y2 O3 ...
and in special steels like
TRIP steel 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, typicall ...
s. Thus, martensite can be thermally induced or stress induced. The growth of martensite phase requires very little thermal
activation energy In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules p ...
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. Martensite has a lower density than austenite, so that the martensitic transformation results in a relative change of volume. Of considerably greater importance than the volume change is the
shear strain In physics, deformation is the continuum mechanics transformation of a body from a ''reference'' configuration to a ''current'' configuration. A configuration is a set containing the positions of all particles of the body. A deformation can ...
, which has a magnitude of about 0.26 and which determines the shape of the plates of martensite. 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 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 ...
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 A material is brittle if, when subjected to stress, it fractures with little elastic deformation and without significant plastic deformation. Brittle materials absorb relatively little energy prior to fracture, even those of high strength. Br ...
; too little leaves it soft.


See also

* Eutectic *
Eutectoid A eutectic system or eutectic mixture ( ) is a homogeneous mixture that has a melting point lower than those of the constituents. The lowest possible melting point over all of the mixing ratios of the constituents is called the ''eutectic tempe ...
*
Ferrite (iron) At atmospheric pressure, three allotropic forms of iron exist, depending on temperature: alpha iron (α-Fe), gamma iron (γ-Fe), and delta iron (δ-Fe). At very high pressure, a fourth form exists, called epsilon iron (ε-Fe). Some controvers ...
*
Maraging steel Maraging steels (a portmanteau of " martensitic" and "aging") 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 cla ...
*
Spring steel Spring steel is a name given to a wide range of steels used in the manufacture of different products, including swords, saw blades, springs and many more. These steels are generally low-alloy manganese, medium-carbon steel or high-carbon stee ...
*
Tool steel Tool steel is any of various carbon steels and alloy steels that are particularly well-suited to be made into tools and tooling, including cutting tools, dies, hand tools, knives, and others. Their suitability comes from their distinctive har ...


References


External links


Comprehensive resources on martensite from the University of CambridgeYouTube Lecture by Prof. HDKH Bhadeshia , from the University of Cambridge

Metallurgy for the Non-Metallurgist from the American Society for MetalsPTCLab---Capable of calculating martensite crystallography with single shear or double shear theory
{{Authority control Metallurgy Metals Steel Ceramic materials