Unit-2

Heat Treatment of Metals and Alloys

Introduction: Heat treatment involves various heating and cooling procedures performed to effect
microstructural changes in a material, which in turn affect its mechanical properties. Its most common
application are on metals. Heat treatment operations can be performed on a metallic workpart at various
times during its manufacturing sequence. In some cases, the treatment is applied before shaping (e.g., to
soften the metal so that it can be more easily formed while hot). In other cases, heat treatment is used to
relieve the effects of strain hardening that occur during forming, so that the material can be subjected to
further deformation. Heat treatment can also be accomplished at or near the end of the sequence to
achieve the final strength and hardness required in the finished product. The principal heat treatments
are annealing, martensite formation in steel, precipitation hardening, and surface hardening.

Iron-Carbide Equilibrium Diagram: The iron-carbon equilibrium diagram. Many of the basic features of
this system influence the behaviour of even the most complex of alloy steels. The phases found in the
simple binary Fe-C system persist in complex steels, but it is necessary to examine the effects alloying
elements have on the formation and properties of these phases. The iron-carbon diagram provides a
valuable foundation on which to build knowledge of both plain carbon and alloy steels in their immense
variety. As shown in the iron–carbon phase diagram, when steel alloys are heated sufficiently above the
A3 temperature, they transform to the FCC austenite (γ) structure. On slow cooling, the structure
transforms back into the BCC ferrite (α) structure, along with cementite (Fe3C), to form a structure called
pearlite. This transformation forms the basis for heat treatment by quenching and tempering. If the steel
is austenitized at a temperature sufficiently above 1333° F for some period of time and then quenched to
room temperature, it does not convert to the normal BCC structure. Instead, it converts to a body
centered tetragonal (BCT) structure called martensite. This transformation is shown in the isothermal
transformation diagram for 4340 steel in Fig. 5.3. The BCT martensite structure is essentially a BCC
structure distorted by interstitial carbon atoms into a tetragonal structure. The distortion severely strains
the crystalline lattice and dramatically increases the strength and hardness. Unfortunately, it also makes
the steel extremely brittle; therefore, the steel is reheated, or tempered, at intermediate temperatures
to restore some ductility and toughness, although the strength also decreases as the tempering
temperature is increased. A key variable in heat treating alloy steels is the cooling rate during quenching.
The quench rate that will provide the desired hardness for a given thickness is determined primarily by
alloying additions. Some alloys require a water quench, others an oil quench, and some are so highly
alloyed that they can be air cooled to room temperature to form a martensitic structure. Since the cooling
rate is also dependent on section size, the quench may have to be changed as the thickness increases, for
example, a steel that could be through-hardened with an oil quench at a thickness of 1/2 in. may have to
be water quenched when the thickness is increased to an inch.

While some steels are hardened by the conversion of austenite to martensite through a quench and
temper process, others, such as the maraging and precipitation hardening steels, are strengthened by
precipitation hardening. The maraging steels, with nominal nickel contents of 18% and carbon contents
of only 0.03%, will form martensite on air cooling from the austenitizing temperature. Even very slow
cooling of heavy sections produces a fully martensitic structure. However, this low carbon martensite is
not the high strength marten-site that forms in the higher carbon alloy steels.. The low carbon martensite
that is formed is a tough and ductile iron–nickel martensite. The strength in the maraging steels results
during age hardening at 850–950° F to form precipitates of Ni3Mo and Ni3Ti. Since the carbon content is
extremely low, maraging steels are characterized by a combination of high strength, ductility, and
excellent toughness.

T-T-T Diagram (Time –Temperature- Transformation Diagram):

The TTT curve shows how cooling rate affects the transformation of austenite into various possible phases.
The phases can be divided between (1) alternative forms of ferrite and cementite and (2) martensite. Time
is displayed (logarithmically for convenience) along the horizontal axis, and temperature is scaled on the
vertical axis. The curve is interpreted by starting at time zero in the austenite region (somewhere above
theA1 temperature line for the given composition) and proceeding downward and to the right along a
trajectory representing how the metal is cooled as a function of time. The TTT curve shown in the figure
is for a specific composition of steel (0.80% carbon). The shape of the curve is different for other
compositions. At slow cooling rates, the trajectory proceeds through the region indicating transformation
into pearlite or bainite, which are alternative forms of ferrite–carbide mixtures. Because these
transformations take time, the TTT diagram shows two lines—the start and finish of the transformation
as time passes, indicated for the different phase regions by the subscripts s and f, respectively. Pearlite is
a mixture of ferrite and carbide phases in the form of thin parallel plates. It is obtained by slow cooling
from austenite, so that the cooling trajectory passes through Ps above the ‘‘nose’’ of the TTT curve. Bainite
is an alternative mixture of the same phases that can be produced by initial rapid cooling to a temperature
above Ms, so that the nose of the TTT curve is avoided; this is followed by much slower cooling to pass
through Bs and into the ferrite–carbide region. Bainite has a needle-like or feather-like structure
consisting of fine carbide regions. If cooling occurs at a sufficiently rapid rate indicated by the dashed line
austenite is transformed into martensite. Martensite is a unique phase consisting of an iron–carbon
solution whose composition is the same as the austenite from which it was derived. The face-centered
cubic structure of austenite is transformed into the body-centered tetragonal (BCT) structure of
martensite almost instantly—without the time-dependent diffusion process needed to separate ferrite
and iron carbide in the preceding transformations.

During cooling, the martensite transformation begins at a certain temperature Ms ,and finishes at a lower
temperature Mf, as shown in our TTT diagram. At point’s between these two levels, the steel is a mixture
of austenite and martensite. If cooling is stopped at a temperature between the Ms and Mf lines, the
austenite will transform to bainite as the time-temperature trajectory crosses the Bs threshold. The level
of the Ms line is influenced by alloying elements, including carbon. In some cases, the Ms line is depressed
below room temperature, making it impossible for these steels to form martensite by traditional heat-
treating methods.

The extreme hardness of martensite results from the lattice strain created by carbon atoms trapped in
the BCT structure, thus providing a barrier to slip. Shows the significant effect that the martensite
transformation has on the hardness of steel for increasing carbon contents.
Annealing Process: Annealing consists of heating the metal to a suitable temperature, holding at that
temperature for a certain time (called soaking), and slowly cooling.
It is performed on a metal for any of the following reasons:

 To reduce hardness and brittleness,

 To alter microstructure so that desirable mechanical properties can be obtained,
 To soften metals for improved machinability or formability,
 To recrystallize cold-worked(strain-hardened) metals
 To relieve residual stresses induced by prior processes .Different terms are used in annealing,
depending on the details of the process and the temperature used relative to the recrystallization
temperature of the metal being treated.

Full annealing is associated with ferrous metals (usually low and medium carbon steels); it involves
heating the alloy into the austenite region, followed by slow cooling in the furnace to produce coarse
pearlite. Normalizing involves similar heating and soaking cycles, but the cooling rates are faster. The
steel is allowed to cool in air to room temperature. This results in fine pearlite, higher strength and
hardness, but lower ductility than the full anneal treatment.

Cold-worked parts are often annealed to reduce effects of strain hardening and increase ductility. The
treatment allows the strain-hardened metal to recrystallize partially or completely, depending on
temperatures, soaking periods, and cooling rates.

When annealing is performed to allow for further cold working of the part, it is called a process anneal.
When performed on the completed (cold-worked) part to remove the effects of strain hardening and
where no subsequent deformation will be accomplished, it is simply called anneal. The process itself
is pretty much the same, but different terms are used to indicate the purpose of the treatment.

If annealing conditions permit full recovery of the cold-worked metal to its original grain structure,
then recrystallization has occurred. After this type of anneal, the metal has the new geometry created
by the forming operation, but its grain structure and associated properties are essentially the same
as before cold working. The conditions that tend to favor recrystallization are higher temperature,
longer holding time, and slower

Cooling rate. If the annealing process only permits partial return of the grain structure toward its
original state, it is termed a recovery anneal. Recovery allows the metal to retain most of the strain
hardening obtained in cold working, but the toughness of the part is improved.

The preceding annealing operations are performed primarily to accomplish functions other than
stress relief. However, annealing is sometimes performed solely to relieve residual stresses in the
work piece. Called stress-relief annealing, it helps to reduce distortion and dimensional variations that
might otherwise occur in the stressed parts.

Heat Treatment: Metals and alloys are heat treated to improve their mechanical properties, to relieve
internal stresses or to improve their machinability. The properties of carbon steels can also be altered
significantly by subjecting them to heat treatment processes.

Heat treatment consists of three basic steps:

(i) Heat the metal/alloy to a predetermined temperature. This temperature will, ideally, depend upon
the actual composition of carbon steel (i.e. carbon percentage),
(ii) Soaking or holding the metal/alloy at that temperature for some time, so that the temperature
across the entire cross-section becomes uniform, and

(iii) Cooling the metal/alloy at a predetermined rate in a suitable medium like water, oil or air. The
rate of cooling is the most important factor.

Normalizing: Normalizing entails heating to the same temperatures as recommended for annealing
(except for high carbon steel specimens, which are to be heated to much higher temperatures than
for annealing particularly as carbon percentage in sample increases), soaking and then cooling the
sample in still air. Main object of normalizing is getting rid of internal stresses and grain-refinement.

Tempering: Tempering means giving up a certain amount of hardness but shedding a great deal of
brittleness acquired in the process of hardening. It is a tradeoff between hardness and brittleness, so
that hardened component may give useful service without failure.

Tempering involves heating the carbon steel part to a temperature varying from 150°–600°C
(depending upon how much tradeoff is required) and cooling the component in an oil or salt bath or
even in air

Surface hardening techniques: Surface hardening refers to any of several thermochemical treatments
applied to steels in which the composition of the part surface is altered by addition of carbon,
nitrogen, or other elements. The most common treatments are carburizing, nitriding, and
carbonitriding.

These processes are commonly applied to low carbon steel parts to achieve a hard, wear-resistant
outer shell while retaining a tough inner core. The term case hardening is often used for these
treatments.

Carburizing: It is the most common surface-hardening treatment. It involves heating a part of low
carbon steel in the presence of a carbon-rich environment so that C is diffused into the surface. In
effect the surface is converted to high carbon steel, capable of higher hardness than the low-C core.
The carbon-rich environment can be created in several ways. One method involves the use of
carbonaceous materials such as charcoal or coke packed in a closed container with the parts. This
process, called pack carburizing, produces a relatively thick layer on the part surface, ranging from
around 0.6 to 4 mm (0.025 to 0.150 in). Another method, called gas carburizing, uses hydrocarbon
fuels such as propane (C3H8) inside a sealed furnace to diffuse carbon into the parts. The case
thickness in this treatment is thin, 0.13 to 0.75 mm (0.005 to 0.030 in). Another process is liquid
carburizing, which employs a molten salt bath containing sodium cyanide (NaCN), barium chloride
(BaCl2), and other compounds to diffuse carbon into the steel. This process produces surface layer
thicknesses generally between those of the other two treatments. Typical carburizing temperatures
are 875o to 925oC (1600o to1700oF), well into the austenite range.

Carburizing followed by quenching produces a case hardness of around HRC=60.However, because

the internal regions of the part consist of low carbon steel, and its hardenability is low, it is unaffected
by the quench and remains relatively tough and ductile to withstand impact and fatigue stresses.

Nitriding: Nitriding is a treatment in which nitrogen is diffused into the surfaces of special alloy steels
to produce a thin hard casing without quenching. To be most effective, the steel must contain certain
alloying ingredients such as aluminum (0.85% to 1.5%) or chromium (5%or more).These elements
form nitride compounds that precipitate as very fine particles in the casing to harden the steel.
Nitriding methods include: gas nitriding, in which the steel parts are heated in an atmosphere of
ammonia (NH3) or other nitrogen rich gas mixture; and liquid nitriding, in which the parts are dipped
in molten cyanide salt baths. Both processes are carried out at around 500oC (950oF). Case thicknesses
range as low as 0.025 mm (0.001 in) and up to around 0.5 mm (0.020 in), with harnesses up to HRC
70.

Carbonitriding: It is a treatment in which both carbon and nitrogen are absorbed into the steel
surface, usually by heating in a furnace containing carbon and ammonia. Case thicknesses are usually
0.07 to 0.5mm (0.003 to 0.020 in), with harnesses comparable with those of the other two treatments.

Two additional surface-hardening treatments diffuse chromium and boron, respectively, into the steel
to produce casings that are typically only 0.025 to 0.05 mm (0.001 to0.002 in) thick.

Chromizing: It requires higher temperatures and longer treatment times than the preceding surface-
hardening treatments, but the resulting casing is not only hard and wear resistant, it is also heat and
corrosion resistant. The process is usually applied to low carbon steels. Techniques for diffusing
chromium into the surface include: packing the steel parts in chromium-rich powders or granules,
dipping in a molten salt bath containing Cr and Cr salts, and chemical vapor deposition

Boronizing: It is performed on tool steels, nickel- and cobalt-based alloys, and cast irons, in addition
to plain carbon steels, using powders, salts, or gas atmospheres containing boron. The process results
in a thin casing with high abrasion resistance and low coefficient of friction. Casing hardnesses reach
70HRC.When boronizing is used on low carbon and low alloy steels, corrosion resistance is also
improved.

Heat treatment for non-ferrous alloys and Stainless steels: Nonferrous alloys and some stainless
steels cannot be heat treated by the techniques used for ferrous alloys. The reason is that nonferrous
alloys do not undergo phase transformations like those in steels the hardening and strengthening
mechanisms for these alloys are fundamentally different. Heat-treatable aluminum alloys, copper
alloys, martensitic stainless steels, and some other stainless steels are hardened and strengthened by
a process called precipitation hardening. This heat treatment is a technique in which small particles
of a different phase, called precipitates, are uniformly dispersed in the matrix of the original phase. In
this process, precipitates form because the solid solubility of one element (one component of the
alloy) in the other is exceeded.

Three stages are involved in precipitation hardening; they can best be described by reference to the
phase diagram for the aluminum-copper system. For an alloy with the composition 95.5% Al-4.5% Cu,
a single-phase (kappa phase) sub-stitutional solid solution of copper (solute) in aluminum (solvent)
exists between 500°and 570°C. This kappa phase is aluminum rich, has an FCC structure, and is ductile.

Below the lower temperature (that is, below the lower solubility curve) there are two phases: kappa
(K) and theta (6), which is a hard intermetallic compound of CuAl2.

This alloy can be heat treated, and its properties are modified by two different methods:

i) Solution treatment
ii) Precipitation hardening.

a b

Fig a) Phase diagram for the aluminum-copper alloy system. b) Various microstructures obtained
during the age-hardening process.

Solution Treatment: In solution treatment, the alloy is heated to within the solid-solution kappa phase
around 54O°C and then cooled rapidly-for instance, by quenching it in water. The structure obtained
soon after quenching consists only of the single phase kappa, this alloy has moderate strength and
considerable ductility.

Precipitation Hardening: The structure obtained in fig b with A structure can be made stronger by
precipitation hardening. In this process, the alloy is reheated to an intermediate temperature and
then held there for a period of time, during which precipitation takes place. The copper atoms diffuse
to nucleation sites and combine with aluminum atoms, this process produces the theta phase, which
forms as submicroscopic precipitates (shown in B by the small dots within the grains of the kappa
phase). This structure is stronger than that in A, although it is less ductile. The increase in strength is
due to increased resistance to dislocation movement in the region of the precipitates.