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R. V.

COLLEGE OF ENGINEERING,
BANGALORE.







MATERIAL SCIENCE AND METALLURGY

ASSIGNMENT ON


INDUSTRIAL PROCESS OF MARTENSITE
FORMATION





By
Abhishek Kumtakar (1RV11ME004)
Amit Vijay Dodmani (1RV11ME016)
Brian Nikil Quadras (1RV11ME036)
G K Shivakumar (1RV11ME044)
3
rd
Sem A Section
I n d u s t r i a l P r o c e s s O f M a r t e n s i t e F o r m a t i o n P a g e | 2
Contents:
Introduction
Properties
Terminology
Tempering in steel
Quenched steel
Welded steel
Quench and self tempering
Blacksmithing
Martempeting
Interrupted Quenching
Quench Hardening
Effect of Quench Hardening










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Introduction
Martensite, named after the German metallurgist Adolf Martens (18501914), most
commonly refers to a very hard form of steel crystalline structure, but it can also refer to any
crystal structure that is formed by displacive transformation. It includes a class of hard minerals
occurring as lath- or plate-shaped crystal grains. When viewed in cross section, the lenticular
(lens-shaped) crystal grains are sometimes incorrectly described as Acicular (needle-shaped).

Martensite in AISI 4140 steel
In the 1890s, Martens studied samples of different steels under a microscope, and found that
the hardest steels had a regular crystalline structure. He was the first to explain the cause of the
widely differing mechanical properties of steels. Martensitic structures have since been found in
many other practical materials, including shape memory alloys and transformation-toughened
ceramics.

microstructue

Properties
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The martensite is formed by rapid cooling (quenching) of austenite which traps
carbon atoms that do not have time to diffuse out of the crystal structure. This martensitic
reaction begins during cooling when the austenite reaches the martensite start
temperature (M
s
) and the parent austenite becomes mechanically unstable. At a constant
temperature below M
s
, a fraction of the parent austenite transforms rapidly, then no
further transformation will occur.

When the temperature is decreased, more of the austenite transforms to martensite.
Finally, when the martensite finish temperature (M
f
) is reached, the transformation is
complete. Martensite can also be formed by application of stress (this property is
frequently used in toughened ceramics like yttria-stabilized zirconia and in special steels
like TRIP steels (i.e. transformation induced plasticity steels). Thus, Martensite can be
thermally induced or stress induced.

One of the differences between the two phases is that martensite has a body-centered
tetragonal (BCT) crystal structure, whereas austenite has a face-centered cubic (FCC)
structure. The transition between these two structures requires very little thermal
activation energy because it 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 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
allowing sufficient time for diffusion, whereas martensite is usually formed by swift
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 temperingaa.

In some alloys, the effect is reduced by adding elements such as tungsten that interfere
with cementite nucleation, but, more often than not, the phenomenon is exploited instead.
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 right structure for the intended application is achieved. Too much martensite leaves
steel brittle, too little leaves it soft.



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Crystal
Structure


FCC BCC BCT


0.35%C Steel, water-quenched from 870C



Tempering
Tempering is a process of heat treating, which is used to increase the toughness of iron-based
alloys. It is also a technique used to increase the toughness of glass. For metals, tempering is
usually performed after hardening, to reduce some of the excess hardness, and is done by heating
the metal to a much lower temperature than was used for hardening.
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 to
much higher temperatures. In glass, tempering is performed by heating the glass and then quickly
cooling the surface, increasing the toughness.
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Differentially tempered steel. The various colors produced indicate the temperature to which the steel was
heated. Light-straw indicates 204 C (399 F) and light blue indicates 337 C (639 F).


Photomicrograph of martensite, a very hard microstructure formed when steel is quenched. Tempering
reduces the hardness in the martensite by transforming it into various forms of tempered martensite.
Tempering is a heat treatment technique applied to ferrous alloys, such as steel or cast iron,
to achieve greater toughness by decreasing the hardness of the alloy. The reduction in hardness is
usually accompanied by an increase in ductility, thereby decreasing the brittleness of the metal.
Tempering is usually performed after quenching, which is rapid cooling of the metal to put it in
its hardest state. Tempering is accomplished by controlled heating of the quenched work-piece to
a temperature below its "lower critical temperature".
This is also called the lower transformation temperature or lower arrest (A
1
) temperature;
the temperature at which the crystalline phases of the alloy, called ferrite and cementite, begin
combining to form a single-phase solid solution referred to as austenite.
Precise control of time and temperature during the tempering process is critical to achieve the
desired balance of physical properties. Low tempering temperatures may only relieve some of
the internal stresses, decreasing brittleness while maintaining a majority of the hardness. Higher
tempering temperatures tend to produce a greater reduction in the hardness, sacrificing some
yield strength and tensile strength for an increase in elasticity and plasticity.
However, in some low alloy steels, containing other elements like chromium and molybdenum,
tempering at low temperatures may produce an increase in hardness, while at higher
temperatures the hardness will decrease. Many steels with high concentrations of these alloying
elements behave like precipitation hardening alloys, which produce the opposite effects under
the conditions found in quenching and tempering, and are referred to as maraging steels.
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In carbon steels, tempering alters the size and distribution of carbides in the martensite, forming
a microstructure called "tempered martensite". Tempering is also performed on normalized steels
and cast irons, to increase ductility, machinability, and impact strength.
Steel is usually tempered evenly, called "through tempering," producing a nearly uniform
hardness, but it is somethimes heated unevenly, referred to as "differential tempering," producing
a variation in hardness. In tempered glass, tempering is accomplished by creating internal
stresses in the amorphous structure, to increase both impact resistance and safety in the event of
breakage.

Terminology
In metallurgy, one may encounter many terms that have very specific meanings within the field,
but may seem rather vague when viewed from outside. Terms such as "hardness," "impact
resistance," "toughness," and "strength" can carry many different connotations, making it
sometimes difficult to discern the specific meaning. Some of the terms encountered, and their
specific definitions are:
Strength: Also called rigidity, this is resistance to permanent deformation. Strength, in
metallurgy, is still a rather vague term, so is usually divided into yield strength (resistance
to compression), shear strength (resistance to transverse, or cutting forces), and tensile
strength (resistance to stretching).
Toughness: Resistance to fracture, as measured by the Charpy test. Toughness often
increases as strength decreases.
Hardness: Hardness is often used to describe strength or rigidity but, in metallurgy, the
term is usually used to describe resistance to scratching or abrasion.
Brittleness: Brittleness describes a material's tendency to break before bending or
deforming either elastically or plastically. Brittleness increases with decreased toughness,
but is greatly affected by internal stresses as well.
Plasticity: The ability to mold, bend or deform in a manner that does not spontaneously
return to its original shape. This is proportional to the ductility or malleability of the
substance.
Elasticity: Also called flexibility, this is the ability to deform, bend, compress, or stretch
and return to the original shape once the external stress is removed. Elasticity is related to
the Young's modulus of the material.
Impact resistance: Usually synonymous with high-strength toughness, it is the ability
resist shock-loading with minimal deformation.
Wear resistance: Usually synonymous with hardness, this is resistance to erosion,
ablation, spalling, or galling.
Structural integrity: The ability to withstand a maximum-rated load while resisting
fracture, resisting fatigue, and producing a minimal amount of flexing or deflection, to
provide a maximum service life.
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Tempering in steel
Very few metals react to heat treatment in the same manner, or to the same extent, that steel
does. Steel can be softened to a very malleable state through annealing, or it can be hardened to a
state nearly as rigid and brittle as glass by quenching. However, in its hardened state, steel is
usually far too brittle, lacking the structural integrity to be useful for most applications.
Tempering is a method used to decrease the hardness, thereby increasing the ductility of the
quenched steel, to impart some springiness and malleability to the metal. This allows the metal to
bend before breaking. Depending on how much temper is imparted to the steel, it may bend
elastically (the steel returns to its original shape once the load is removed), or it may bend
plastically (the steel does not return to its original shape, resulting in permanent deformation),
before fracturing.
Tempering is used to precisely balance the mechanical properties of the metal, such as shear
strength, yield strength, hardness, ductility and tensile strength, to achieve any number of a
combination of properties, making the steel useful for a wide variety of applications. Tools such
as hammers and wrenches require good resistance to abrasion, impact resistance, and resistance
to deformation. Springs do not require as much rigidity, but must deform elastically before
breaking. Automotive parts tend to be a little less rigid, but need to deform plastically before
breaking.
Except in rare cases where maximum rigidity and hardness are needed, such as the untempered
steel used for files, quenched steel is almost always tempered to some degree. However, steel is
sometimes annealed through a process called normalizing, leaving the steel only partially
softened. Tempering is sometimes used on normalized steels to further soften it, increasing the
malleability and machinability for easier metalworking. Tempering may also be used on welded
steel, to relieve some of the stresses and excess hardness created in the heat affected zone around
the weld.

Quenched-steel
Tempering is most often performed on steel that has been heated above its upper critical (A
3
)
temperature and then quickly cooled, in a process called quenching, using methods such as
immersing the red-hot steel in water, oil, or forced-air. The quenched-steel, being placed in, or
very near, its hardest possible state, is then tempered to incrementally decrease the hardness to a
point more suitable for the desired application.
The hardness of the quenched-steel depends on both cooling speed and on the composition of
the alloy. Steel with a high carbon-content will reach a much harder state than steel with a low
carbon-content. Likewise, tempering high-carbon steel to a certain temperature will produce steel
that is considerably harder than low-carbon steel that is tempered at the same temperature. The
amount of time held at the tempering temperature also has an effect.
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Tempering at a slightly elevated temperature for a shorter time may produce the same effect as
tempering at a lower temperature for a longer time. Tempering times vary, depending on the
carbon content, size, and desired application of the steel, but typically range from a few minutes
to a few hours.
Tempering quenched-steel at very low temperatures, between 66 and 148 C (151 and 298 F),
will usually not have much effect other than a slight relief of some of the internal stresses.
Tempering at higher temperatures, from 148 to 205 C (298 to 401 F), will produce a slight
reduction in hardness, but will primarily relieve much of the internal stresses. Tempering in the
range of 260 and 340 C (500 and 644 F) causes a decrease in ductility and an increase in
brittleness, and is referred to as the "tempered martensite embrittlement" (TME) range.
This range is usually avoided. Steel requiring more strength than toughness, such as tools, are
usually not tempered above 205 C (401 F). When increased toughness is desired at the expense
of strength, higher tempering temperatures, from 370 to 540 C (698 to 1,004 F), are used.
Tempering at even higher temperatures, between 540 and 600 C (1,004 and 1,112 F), will
produce excellent toughness, but at a serious reduction in the strength and hardness. At 600 C
(1,112 F), the steel experiences another stage of embrittlement, called "temper embrittlement"
(TE), so heating above this temperature is also avoided.
.
Welded steel
Steel that has been arc welded, gas welded, or welded in any other manner besides forge welded,
is affected in a localized area by the heat from the welding process. This localized area, called
the heat-affected zone (HAZ), consists of steel that varies considerably in hardness, from
normalized steel to steel nearly as hard as quenched steel near the edge of this heat-affected
zone. The uneven heating and cooling also creates internal stresses in the metal, both within and
surrounding the weld. Tempering is sometimes used in place of stress relieving to both reduce
the internal stresses and to decrease the brittleness around the weld. Tempering temperatures for
this purpose are generally around 205 C (401 F) and 343 C (649 F).
Quench and self-temper
Modern reinforcing bar of 500 MPa strength can be made from expensive microalloyed steel or
by a quench and self-temper (QST) process. After the bar exits the final rolling pass, where the
final shape of the bar is applied, the bar is then sprayed with water which quenches the outer
surface of the bar. The bar speed and the amount of water are carefully controlled in order to
leave the core of the bar unquenched. The hot core then tempers the already quenched outer part,
leaving a bar with high strength but with a certain degree of ductility too.
Blacksmithing
Tempering was originally a process used and developed by blacksmiths (forgers of iron). The
process was most likely developed by the Hittites of Anatolia (modern-day Turkey), in the
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twelfth or eleventh century BC. Without knowledge of metallurgy, tempering was originally
devised through a trial-and-error method.
Because few methods of precisely measuring temperature existed until modern times,
temperature was usually judged by watching the tempering colors of the metal. Tempering often
consisted of heating above a charcoal or coal forge, or by fire, so holding the work at exactly the
right temperature for the correct amount of time was usually not possible. Tempering was
usually performed by slowly, evenly overheating the metal, as judged by the color, and then
immediately cooling, either in open air or by immersing in water.
This produced much the same effect as heating at the proper temperature for the right amount of
time. However, although tempering-color guides exist, this method of tempering usually requires
a good amount of practice to perfect, because the final outcome depends on many factors,
including the composition of the steel, the speed at which it was heated, the type of heat source
(oxidizing or carburizing), the cooling rate, oil films or impurities on the surface, and many other
circumstances which vary from smith to smith or even from job to job. The thickness of the steel
also plays a role. With thicker items, it becomes easier to heat only the surface to the right
temperature, before the heat can penetrate through. However, very thick items may not be able to
harden all the way through during quenching.

Tempering colors

Pieces of through-tempered steel flatbar. The first one, on the left, is normalized steel. The second is
quenched, untempered martensite. The remaining pieces have been tempered in an oven to their
corresponding temperature, for an hour each. "Tempering standards" like these are sometimes used by
blacksmiths for comparison, ensuring that the work is tempered to the proper color.
If steel has been freshly ground, sanded, or polished, it will form an oxide layer on its surface
when heated. As the temperature of the steel is increased, the thickness of the iron oxide will also
increase. Although iron oxide is not normally transparent, such thin layers do allow light to pass
through, reflecting off both the upper and lower surfaces of the layer.
This causes a phenomenon called thin-film interference, which produces colors on the surface.
As the thickness of this layer increases with temperature, it causes the colors to change from a
very light yellow, to brown, then purple, then blue. These colors appear at very precise
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temperatures, and provide the blacksmith with a very accurate gauge for measuring the
temperature. The various colors, their corresponding temperatures, and some of their uses are:
Faint-yellow 176 C (349 F) engravers, razors, scrapers
Light-straw 205 C (401 F) rock drills, reamers, metal-cutting saws
Dark-straw 226 C (439 F) scribers, planer blades
Brown 260 C (500 F) taps, dies, drill bits, hammers, cold chisels
Purple 282 C (540 F) surgical tools, punches, stone carving tools
Dark blue 310 C (590 F) screwdrivers, wrenches
Light blue 337 C (639 F) springs, wood-cutting saws
Grey-blue 371 C (700 F) and higher structural steel
Beyond the grey-blue color, the iron oxide loses its transparency, and the temperature can no
longer be judged in this way. The layer will also increase in thickness as time passes, which is
another reason overheating and immediate cooling is used. Steel in a tempering oven, held at 205
C (401 F) for a long time, will begin to turn brown, purple or blue, even though the
temperature did not exceed that needed to produce a light-straw color. Oxidizing or carburizing
heat sources may also affect the final result. The iron oxide layer, unlike rust, also protects the
steel from corrosion through passivation.
[12]

DIFFERENTIAL TEMPERING


Differential tempering is often used for tempering cutting tools, such as this cold chisel.
Differential tempering is a method of providing different amounts of temper to different parts of
the steel. The method was often used in bladesmithing, for making knives and swords, to provide
a very hard edge while softening the spine or center of the blade. This increased the toughness
while maintaining a very hard, sharp, impact-resistant edge, helping to prevent breakage. This
technique was more often found in Europe, as opposed to the differential hardening techniques
more common in Asia, such as in Japanese swordsmithing.
Differential tempering consists of applying heat to only a portion of the blade, usually the spine,
or the center of double-edged blades. For single-edged blades, the heat, often in the form of a
flame or a red-hot bar, is applied to the spine of the blade only. The blade is then carefully
watched as the tempering colors form and slowly creep toward the edge. The heat is then
removed before the light-straw color reaches the edge. The colors will continue to move toward
the edge for a short time after the heat is removed, so the smith typically removes the heat a little
early, so that the pale-yellow just reaches the edge, and travels no farther. A similar method is
used for double-edged blades, but the heat source is applied to the center of the blade, allowing
the colors to creep out toward each edge.
[

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Interrupted quenching
Interrupted quenching methods are often referred to as tempering, although the processes are
very different from traditional tempering. These methods consist of quenching to a specific
temperature that is above the martensite start (M
s
) temperature, and then holding at that
temperature for extended amounts of time. Depending on the temperature and the amount of
time, this allows either pure bainite to form, or holds-off forming the martensite until much of
the internal stresses relax. These methods are known as austempering and martempering.
MARTEMPERING

Martempering is similar to austempering, in that the steel is quenched in a bath of molten metal
or salts to quickly cool it past the pearlite-forming range. However, in martempering, the goal is
to create martensite rather than bainite. The steel is quenched to a much lower temperature than
is used for austempering; to just above the martensite start temperature. The metal is then held at
this temperature until the temperature of the steel reaches an equilibrium.
The steel is then removed from the bath before any bainite can form, and then is allowed to air-
cool, turning it into martensite. The interruption in cooling allows much of the internal stresses to
relax before the martensite forms, decreasing the brittleness of the steel. However, the
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martempered steel will usually need to undergo further tempering to adjust the hardness and
toughness.

Physical processes
Tempering involves a three-step process in which unstable martensite decomposes into ferrite
and unstable carbides, and finally into stable cementite, forming various stages of a
microstructure called tempered martensite. The martensite typically consists of laths (strips) or
plates, sometimes appearing acicular (needle-like) or lenticular (lens-shaped). Depending on the
carbon content, it also contains a certain amount of "retained austenite."
Retained austenite are crystals which are unable to transform into martensite, even after
quenching below the martensite finish (M
f
) temperature. An increase in alloying agents or carbon
content causes an increase in retained austenite, lowering the wear resistance of the steel,
although some or most of the retained austenite can be transformed into martensite by cold and
cryogenic treatments prior to tempering.
The martensite forms during a diffusionless transformation, in which the transformation occurs
due to shear-stresses created in the crystal lattices rather than by chemical changes that occur
during precipitation. The shear-stresses create many defects, or "dislocations," between the
crystals, providing less-stressful areas for the carbon atoms to relocate.
Upon heating, the carbon atoms first migrate to these defects, and then begin forming unstable
carbides. This reduces the amount of total martensite by changing some of it to ferrite. Further
heating reduces the martensite even more, transforming the unstable carbides into stable
cementite.
The first stage of tempering occurs between room-temperature and 200 C (392 F). In the first
stage, carbon precipitates into -carbon (Fe
24
C). In the second stage, occurring between 150 C
(302 F) and 300 C (572 F), the retained austenite transforms into a form of lower-bainite
containing -carbon rather than cementite.
The third stage occurs at 200 C (392 F) and higher. In the third stage, -carbon precipitates into
cementite, and the carbon content in the martensite decreases. If tempered at higher
temperatures, between 650 C (1,202 F) and 700 C (1,292 F), or for longer amounts of time,
the martensite may become fully ferritic and the cementite may become coarser or spheroidize.
In spheroidized steel, the cementite recedes into rods or spherical shaped globules, and the steel
becomes softer than annealed steel; nearly as soft as pure iron, making it very easy to form or
machine.
Quenching

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Coke being pushed into a quenching car, Hanna furnaces of the Great Lakes Steel Corporation, Detroit,
Michigan, November 1942.
In materials science, quenching is the rapid cooling of a workpiece to obtain certain material
properties. It prevents low-temperature processes, such as phase transformations, from occurring
by only providing a narrow window of time in which the reaction is both thermodynamically
favorable and kinetically accessible. For instance, it can reduce crystallinity and thereby increase
toughness of both alloys and plastics (produced through polymerization).
In metallurgy, it is most commonly used to harden steel by introducing martensite, in which case
the steel must be rapidly cooled through its eutectoid point, the temperature at which austenite
becomes unstable. In steel alloyed with metals such as nickel and manganese, the eutectoid
temperature becomes much lower, but the kinetic barriers to phase transformation remain the
same.
This allows quenching to start at a lower temperature, making the process much easier. High
speed steel also has added tungsten, which serves to raise kinetic barriers and give the illusion
that the material has been cooled more rapidly than it really has. Even cooling such alloys slowly
in air has most of the desired effects of quenching.
Extremely rapid cooling can prevent the formation of all crystal structure, resulting in amorphous
metal or "metallic glass".

Quench hardening
Quench hardening is a mechanical process in which steel and cast iron alloys are strengthened
and hardened. These metals consist of ferrous metals and alloys. This is done by heating the
material to a certain temperature, depematerial. This produces a harder material by either surface
hardening or through-hardening varying on the rate at which the material is cooled. The material
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is then often tempered to reduce the brittleness that may increase from the quench hardening
process. Items that may be quenched include gears, shafts, and wear blocks.
Process
Quenching metals is a progression; the first step is soaking the metal, i.e. heating it to the
required temperature. Soaking can be done by air (air furnace), or a bath. The soaking time in air
furnaces should be 1 to 2 minutes for each millimeter of cross-section. For a bath the time can
range a little higher. The recommended time allotment in salt or lead baths is 0 to 6 minutes.
Uneven heating or overheating should be avoided at all cost. Most materials are heated from
anywhere to 815 to 900 C (1,500 to 1,650 F).
The next item on the progression list is the cooling of the part. Water is one of the most efficient
quenching media where maximum hardness is acquired, but there is a small chance that it may
cause distortion and tiny cracking. When hardness can be sacrificed, whale, cottonseed and
mineral oils are used. These often tend to oxidize and form a sludge, which consequently lowers
the efficiency. The quenching velocity (cooling rate) of oil is much less than water. Intermediate
rates between water and oil can be obtained with water containing 10-30% UCON from DOW, a
substance with an inverse solubility which therefore deposits on the object to slow the rate of
cooling.
To minimize distortion, long cylindrical workpieces are quenched vertically; flat workpieces are
quenched on edge; and thick sections should enter the bath first. To prevent steam bubbles the
bath is agitated.

Effect of Quench Hardening
Before the material is hardened, the microstructure of the material is a pearlite grain structure
that is uniform and lamellar. Pearlite is a mixture of ferrite and cementite formed when steel or
cast iron are manufactured and cooled at a slow rate. After quench hardening, the microstructure
of the material form into martensite as a fine, needle-like grain structure.
[1]

Before using this technique it is essential to look up the rate constants for the quenching of the
excited states of metal ions.

When quenching, there are numerous types of media. Some of the more common
include: air, brine (salt water), oil and water
Bibliography

I n d u s t r i a l P r o c e s s O f M a r t e n s i t e F o r m a t i o n P a g e | 16
1) www.industrialheating.com
2) steel.keytometals.com
3) www.scientfic.net
4) www.metalpass.com
5) Image Courtesy:
www.google.co.in