Basic principles of heat treatment

Heat treatment of a metal or alloy is a technological procedure, including controlled

heating and cooling operations, conducted for the purpose of changing the alloy
microstructure and resulting in achieving required properties.

There are two general objectives of heat treatment: hardening and annealing.

Hardening

Hardening is a process of increasing the metal hardness, strength, toughness, fatigue

resistance.

• Strain hardening (work hardening) – strengthening by

cold-work (cold plastic deformation).

Cold plastic deformation causes increase of concentration of dislocations, which

mutually entangle one another, making further dislocation motion difficult and
therefore resisting the deformation or increasing the metal strength.

• Grain size strengthening (hardening) – strengthening by

grain refining.

Grain boundaries serve as barriers to dislocations, raising the stress required to cause
plastic deformation.

• Solid solution hardening – strengthening by dissolving an

alloying element.

Atoms of solute element distort the crystal lattice, resisting the dislocations motion.
Interstitial elements are more effective in solid solution hardening, than substitution
elements.

• Dispersion strengthening – strengthening by addition of

second phase into metal matrix.

The second phase boundaries resist the dislocations motions, increasing the material
strength. The strengthening effect may be significant if fine hard particles are added to
a soft ductile matrix (composite materials).

• Hardening as a result of Spinodal decomposition.

Spinodal structure is characterized by strains on the coherent
boundaries between the spinodal phases causing hardening of the
alloy.
 • Precipitation hardening (age hardening) – strengthening
by precipitation of fine particles of a second phase from a
supersaturated solid solution.

The second phase boundaries resist the dislocations motions, increasing the material
strength.

The age hardening mechanism in Al-Cu alloys may be illustrated by the phase
diagram of Al-Cu system (see figure below)

When an alloy Al-3%Cu is heated up to the temperature TM, all CuAl2 particles are
dissolved and the alloy exists in form of single phase solid solution (α-phase). This
operation is called solution treatment.

Slow cooling of the alloy will cause formation of relatively coarse particles of CuAl2
intermetallic phase, starting from the temperature TN.

However if the the cooling rate is high (quenching), solid solution will retain even at
room temperature TF. Solid solution in this non-equilibrium state is called
supersaturated solid solution.

Obtaining of supersaturated solid solution is possible when cooling is considerably

faster, than diffusion processes.

As the diffusion coefficient is strongly dependent on the temperature, the precipitation

of CuAl2 from supersaturated solution is much faster at elevated temperatures (lower
than TN).This process is called artificial aging. It takes usually a time from several
hours to one day.

When the aging is conducted at the room temperature, it is called natural aging.
Natural aging takes several days or more.
Precipitation from supersaturated solid solution occurred in several steps:

• Segregation of Cu atoms into plane clusters. These clusters

are called Guinier-Preston1 zones (G-P1 zones).

• Diffusion of Cu atoms to the G-P1 zones and formation larger

clusters, called GP2 zones or θ” phase. This phase is coherent with
the matrix .

• Formation of θ’ phase which is partially coherent with the

matrix. This phase provides maximum hardening.

Annealing

Annealing is a heat treatment procedure involving heating the alloy and holding it at
a certain temperature (annealing temperature), followed by controlled cooling.

Annealing results in relief of internal stresses, softening, chemical homogenizing and

transformation of the grain structure into more stable state.

Annealing stages:

• Stress relief (recovery) – a relatively low temperature

process of reducing internal mechanical stresses, caused by cold-
work, casting or welding.

During this process atoms move to more stable positions in the crystal lattice.
Vacancies and interstitial defects are eliminated and some dislocations are
annihilated.

Recovery heat treatment is used mainly for preventing stress-corrosion cracking and
decreasing distortions, caused by internal stresses.

• Recrystallization – alteration of the grain structure of the

metal.

If the alloy reaches a particular temperature (recrystallization or annealing

temperature) new grains start to grow from the nuclei formed in the cold worked
metal. The new grains absorb imperfections and distortions caused by cold
deformation. The grains are equi-axed and independent to the old grain structure.

As a result of recrystallization mechanical properties (strength, ductility) of the alloy

return to the pre-cold-work level.

The annealing temperature and the new grains size are dependent on the degree of
cold-work which has been conducted. The more the cold-work degree, the lower the
annealing temperature and the fine recrystallization grain structure. Low degrees of
cold-work (less than 5%) may cause formation of large grains.

Usually the annealing temperature of metals is between one-third to one-half of the

freezing point measured in Kelvin (absolute) temperature scale.
 • Grain growth (over-annealing, secondary
recrystallization) – growth of the new grains at the expense of
their neighbors, occurring at temperature, above the
recrystallization temperature.

This process results in coarsening grain structure and is undesirable.

Annealing

Annealing is a heat treatment procedure involving heating the alloy and holding it at
a certain temperature (annealing temperature), followed by controlled cooling.

Annealing results in relief of internal stresses, softening, chemical homogenizing and

transformation of the grain structure into more stable state.

Annealing increases an extent of equilibrium of the metal structure resulting in

softening and high ductility.

Annealing temperature and the control cooling rate depend on the alloy composition
and the type of the annealing treatment.

The following types of annealing are used in heat treatment of alloys:

• Full annealing is a process in which a ferrous alloy (commonly

hypoeutectoid steel) is heated to about 100°F (55°C) above the upper critical
temperature, followed by soaking and slow cooling in the furnace or in some
medium to a temperature below the critical temperature.

For the non-ferrous alloys full annealing means full softening after cold work in
contrast to partial annealing meaning partial softening.

• Subcritical annealing is annealing of cold-worked steel below the

critical temperature on the iron-carbon phase diagram.

• Recrystallization annealing is a process of heating a cold worked

metal to a temperature above the recrystallization temperature followed by
soaking for a time required for the grain structure transformation.

Recrystallization annealing is widely used as an intermediate softening treatment

between stages of cold work (cold rolling, drawing).

Combination of recrystallization annealing and cold work allows to control the

microstructure grains size.

• Stress relief (recovery) – a relatively low temperature process of

reducing internal mechanical stresses, caused by cold work, casting or
welding.

The stress relief temperature is lower than the recrystallization temperature.

 • Spheroidizing annealing is a process of controlled heating and
cooling high carbon steels (tool steels) to produce spherical (globular) form of
cementite inclusions.

This treatment improves the machining characteristics of the steel.

• Bright annealing is an annealing treatment which is carried out in

furnaces with reducing atmosphere preventing surface oxidation of the steel
parts.

• Homogenizing annealing is a durable high temperature annealing

treatment intended to decrease chemical segregation by diffusion.

Homogenizing annealing is used for steel and aluminum ingots and castings.

More homogeneous intercrystalline distribution of carbon, phosphorus sulfur and

alloying elements in steel ingots is achieved in annealing at 2000°F -2370°F (1100°C
- 1300°C) for 20-50 hrs.

Aluminum alloys are treated at 790°F - 970°F (420°C - 520°C) for 16-30 hrs.

Normalizing
Normalizing is a process in which a steel is heated to about 100°F (55°C) above the
upper critical temperature, followed by soaking and cooling in still air at room
temperature.

Normalizing treatment is similar to the full annealing treatment. The difference is in

the cooling method and rate – full annealing involves slow controlled cooling if the
furnace or in some medium providing slow cooling rate.

As normalizing requires less time, it is more economically efficient heat treatment

method than full annealing.

Normalizing relieves internal stresses caused by cold work while grain growth is
limited by the relatively high cooling rate therefore the mechanical properties
(strength, hardness) of a normalized steel are better than in an annealed steel.

Since the cooling rate in the normalizing heat treatment is not controlled, the resulting
structure is dependent on the thickness of the steel part, therefore the effect of
increased mechanical properties is greater in thin parts.

Quality of surface after machining of a normalized part is also better than in an

annealed part. This effect is caused by increased ductility of annealed steel favoring
formation of tearing on the machined surface.

Hardening
Hardening is a heat treatment process involving heating a steel above the phase
transformation temperature (upper critical temperature, A3), followed by soaking and
then rapid cooling (quenching).

When steel is heated above the upper critical temperature, its structure becomes
entirely austenitic.

Then the article is cooled at a rate exceeding the critical rate value.

Critical cooling rate is a function of the chemical composition and the grain size of
austenite.

If the critical cooling rate is not achieved, a mixture of ferrite and cementite forms.

Depending on the cooling rate the following ferrite-cementite structures may form:

• pertlite – ferrite-cementite structure, forming as a result of

decomposition of austenite at slow cooling in annealing treatment;

• sorbite- ferrite-cementite perlite-like structure with finer (than in

perlite) grain structure, forming as a result of decomposition of austenite at
relatively high cooling rate (cooling in air);

• trostite–fine ferrite-cementite perlite-like structure forming as a result

of decomposition of austenite at high (but lower than critical) cooling rate
(cooling in oil);

• bainite– very fine ferrite-cementite mixture, forming in a mechanism

similar to the mechanism of martensite transformation, as a result of
decomposition of austenite at high (but lower than critical) cooling rate
(cooling in a quenching medium);

Cooling in water usually provides cooling rate higher than the critical value.

The structure forming as a result of quenching in water is called martensite

(supersaturated solid solution of carbon in α-iron). Martensite is hard and brittle
phase, having hardness varying between 500 HB to 710 HB depending on the carbon
content.

The temperature interval at which the austenite-martensite transformation occurs is

about 480°F - 400°F (250°C - 200°C).

Hardening temperature is the temperature to which a steel is heated before

quenching.

If the hardening temperature of a hypoeutectoid steel is at least 100°F (55°C) above

the upper critical temperature, quencing will result in complete austenite-martensite
transformation (full hardening).
If the hypoeutectoid steel is heated to a temperature, lying between the upper critical
temperature (A3) and the lower critical temperature (A1), quenching will result in
formation of martensite with some amount of ferrite (partial hardening). This structure
is softer than full-hard martensite structure.

In the case of hypereutectoid steel partial hardening results in formation of a mixture

of martensite and cementite, which is harder than full-hard martensite structure.

Hardenability is the property of steel indicating the depth to which hardening effect
penetrates. Hardenability depends on the chemical composition of the steel, hardening
temperature, dimensions and shape of the article and other factors.

Hardenability is detrmined by the Jominy test, in which a steel bar of 1 inch in

diameter and 4 inch long is heated above the upper critical point and then one end of
the bar is quenched by water jet. Results of the hardness measurements conducted
along the bar after quenching indicate the hardenability of the steel.

Isothermal hardening is a hardening method involving quenching in a medium (oil

or molten salt) to minimize the part cracking and distortion.

There are two pricipal isothermal methods:

• Martempering is the isothermal hardening method, in which a part is

quenched in a quenching medium (oil or molten salt) and is left in it reaching
uniform temperature distribution. The part is removed from the quenching
medium before the bainite formation.

• Austempering is the isothermal hardening method, in which a part is

quenched in a quenching medium (oil or molten salt) and is left in it reaching
uniform temperature distribution. The part is removed from the quenching
medium after the complete bainite formation.

Case hardening
Case hardening is the diffusion heat treatment operation which involves two stages:

• Heating a steel part to a temperature above the upper critical

temperature in a medium, containing an element capable to
saturate the surface layer of the part through diffusion;

• Heat treatment of the part in order to obtain the desired

combination of mechanical properties of the hard outer “case” and
the ductile “core”.

As a medium for the case hardening solid, liquid and gaseous substances may be used.

The most widely used case hardening methods are: carburizing, nitriding and
carbonitriding.
 • Carburizing
• Nitriding
• Carbonitriding

Carburizing

Carburizing is the process of diffusion enrichment of the surface layer of a part with
carbon followed by heat treatment of the part.

As carburizing medium the following substances are used:

• Charcoal or other carbon-containing solids mixed with sodium

carbonate and barium carbonate accelerating the process of
dissolving the carbon in steel.

The process is carried out in steel or cast iron boxes placed into a furnace at the
temperature 1650°F - 1750°F (900°C - 950°C) resulting in formation of hard case of
the thickness 0.02”-0.08” (0.5mm – 2mm) and containing 0.8-1% of carbon.

• Kerosene or benzene – liquid carbonizing mediums, which are

usually used in dispersed form;
• Methane (CH4), propane (C3H8) – gaseous carbonizing
mediums.

The process is carried out in a furnace (batch or continuous) at the temperature

1650°F - 1750°F (900°C - 950°C) for 3-4 hrs.

Thickness of the hard layer formed in the gaseous carburizing may reach 0.15”
(4mm).

Heat treatment after carburizing involves hardening-tempering treatments with

purpose of controlling structure and properties of both the hard layer and the ductile
core.

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Nitriding

Nitriding is the process of diffusion enrichment of the surface layer of a part with
Nitrogen.

Gas nitriding is carried out at 930°F - 1110°F (500°C - 600°C) for 40-100 hrs.in the
atmosphere of Ammonia, which dissociates to Hydrogen and nitrogen. The latter
diffuses into the steel forming nitrides of iron, aluminum, chromium and vanadium.

Ion nitriding (plasma nitriding) is a surface Hardening heat treatment, in which

Nitrogen is delivered to the workpiece surface in form of ionized gas (plasma).

The case formed as a result of nitriding has a hardness of about 1100 HV which is
higher than the hardness after carburizing.
Nitrided part possess also better wear resistance, increased fatigue strength, enhanced
toughness and good resistance to corrosion.

No additional heat treatment is required after nitriding.

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Carbonitriding

Carbonitriding is the process of diffusion enrichment of the surface layer of a part

with carbon and nitrogen.

Gaseous carbonitriding is carried out in gaseous medium, consisting of carburizing

gas (methane, propane) with addition of 3-8% of Ammonia.

There are two principal methods of the gaseous carbonitriding:

• Low temperature gaseous carbonitriding, conducted at 930°F

- 1110°F (500°C - 600°C). The steel surface is enriched mostly with
nitrogen in this process.
• High temperature gaseous carbonitriding, conducted
at1470°F - 1750°F (800°C - 950°C). The steel surface is enriched
mostly with carbon in this process. This process is followed by heat
treatment.

Cyaniding is the carbonitriding process, conducted in molten salt, containing 20-25%

of sodium cyanide (extremely toxic substance).

The process is carried out at the temperatures 1500°F - 1580°F (820°C - 860°C) for 1
hour.

Carbonitrided parts possess better (than

carburized parts) wear resistance.

Ion nitriding

Ion nitriding (plasma nitriding) is a surface Hardening heat treatment, in which

Nitrogen is delivered to the workpiece surface in form of ionized gas (plasma).

Ion nitriding produces high surface hardness, good wear resistance, increased fatigue
strength and toughness.

• Ion nitriding process

• Advantages of ion nitriding
• Applications of ion nitriding
Ion nitriding process

Ion nitriding is performed in a vacuum chamber at a pressure 1-10 torr.

A DC voltage 100-700 V is applied between the workpiece and the chamber wall. The
workpiece is connected to the negative terminal (cathode). The chamber wall is the
anode (positive terminal). The wall is usually grounded.

The air is first evacuated from the chamber to 0.1 torr, which is then backfilled with a
mixture of nitrogen, a Hydrogen containing gas (eg., methane) and an inert gas. The
gas mixture is continuously supplied to the chamber, pressure of which (1-10 torr) is
controlled by the gas flow rate and the vacuum system.

Electrostatic field between the cathode and anode ionizes the gas forming a glow
discharge plasma at the workpiece surface.
Positively charged ions of hydrogen and nitrogen are attracted by the negatively
charged workpiece. They are accelerated by the electric field.
The nitrogen ions move towards the cathode and bombard its surface where they
dissolve and chemically react with the steel components (iron, chromium, aluminum,
vanadium, molybdenum).

Most of nitrides formed in the surface layer (case) are iron nitrides Fe2N, Fe3N, Fe4N.

Hydrogen contained in the gas mixture is required for cleaning the metal surface from
the oxides. Oxide-free and activated surface easily reacts with the nitrogen ions.

The steel workpiece is heated by the glow discharge plasma to a temperature 700-
1200°F (370-650°C). Titanium alloys are treated at higher temperatures (up to
1600°F/870°C).

The temperature determines the speed at which the depth of the white layer (case
depth) increases.
Typically the case depth is within the range 0.004-0.025” (0.1-0.6 mm).
The treatment time is commonly 10-50 hrs.

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Advantages of ion nitriding

Advantages of ion nitriding over ammonia nitriding are as follows:

• Shorter (by 20-50%) treatment cycle.

• Better process control and automation. The process
parameters (pressure, voltage, temperature, gas flow, DC current)
are easily controlled.
• Higher surface hardness may be achieved due to lower
process temperature (up to 1200 HV).
• Better dimensional stability (lower distortions) due to lower
process temperature and uniform heating.
• Cases with uniform depth are formed even over parts with
complex shapes.
 • Easier masking for selective nitriding.
• Lower energy consumption due to lower temperature and
shorter treatment cycle.
• Reduced gas consumption.
• Safer operation.
• Lower environment pollution.

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Applications of ion nitriding

Ion nitriding is used for Case hardening of Alloy steels, Stainless steels, Titanium
alloys.

Ion nitriding is effectively used when high surface hardness, good wear resistance,
increased fatigue strength and toughness are required.

The following parts are processed by ion nitriding:

• Cutting tools
• Forging dies
• Drawing dies
• Molds for Transfer molding and Compression molding of
polymers
• Machine and automotive parts subject to wear under friction
(gear wheels, valves, lifters, cams, rocker arms, crankshafts)

Tempering

Tempering is a heat treatment operation involving reheating hardened steel to a

certain temperature below the lower critical point (A1) followed by soaking and then
cooling.

The steel structure after hardening consists mainly of martensite which is hard and
brittle. Tempering is carried out in order to change the martensite structure and obtain
a desired combination of strength and ductility.

The object of tempering is also to reduce the internal stresses caused by quenching.

Depending on the tempering temperature, the following stages of tempering take

place:

• Tempering at temperatures 300°F - 480°F (150°C - 250°C). The

soaking time is commonly about 1-3 hrs. At these temperatures low carbon
(0.25%) tempered martensite and fine dispersed carbides form. The internal
stresses are partially reduced and some softening (by 2-3 HB) occurs at this
stage.
 • Tempering at temperatures 570°F - 750°F (300°C - 400°C).
Soaking time varies from 2 to 8 hours depending on the parts size. At these
temperatures martensite transforms to trostite (very fine mixture of ferrite and
cementite). Trostite is softer than martensite and more ductile.
• Tempering at temperatures higher than 750°F (400°C) but lower
than lower critical point(A1). Soaking time varies from 2 to 8 hours
depending on the parts size. At these temperatures martensite transforms to
sorbite (fine mixture of ferrite and cementite). Sorbite and trostite are
principally similar structures differing only in the particles size. Sorbite is
more ductile and less strong than trostite. This kind of tempering is used for
the parts exposed to impacts.

If the tempering temperature is above 1020°F (550°C) strength decreases sharply

without any notable increase of ductility.

Batch type furnaces ( either air atmosphere or liquid bath) are used for the tempering
heat treatment.

Oil baths are widely used for tools tempering at relatively low tempering temperatures
300°F - 600°F (150°C - 315°C).

In order to prevent cracking the steel part should be preheated before immersing to
hot oil.

Molten salt baths are used for tempering at temperatures 400°F - 1020°F (200°C -
550°C). Mixtures of sodium nitrate and potassium nitrate are suitable as the bath
medium

Precipitation hardening

Precipitation hardening (age hardening) – strengthening by precipitation of fine

particles of a second phase from a supersaturated solid solution.

The precipitation hardening heat treatment involves the following stages:

Solution treatment

During solution treatment a part is heated to a temperature above the solvus

temperature in order to dissolve the second phase in the solid solution.

The part is held at this temperature for a time varying from 1hour to 20 hrs. until the
dissolving has been accomplished.

The temperature and the soaking time of solution treatment should not be too high to
prevent excessive growth of the grains.
Quenching

Quenching is carried out in water, water-air mixture or sometimes in air.

Object of the quenching operation is obtaining supersaturation solid solution at room

temperature.

Since the second phase retains dissolved at this stage, hardness of the quenched alloy
is lower than after age precipitation, however higher than hardness of the alloy in
annealed state.

Aging

Depending on the temperature at which this operation is carried out aging may be
artificial or natural.

• Artificial aging.

At this stage the part is heated up to a temperature below the solvus temperature,
followed by soaking for a time varying between 2 to 20 hours.

The soaking time depends on the aging temperature (the higher the temperature, the
lower the soaking time).

The aging temperature and the soaking time are also determined by the desired
resulted combination of the strength and ductility of the alloy.

Too high aging temperature and time result in overaging – decrease of the strength
and increase of ductility.

• Natural aging.

Natural aging is conducted at room temperature and it takes a relatively long period of
time (from several days to several weeks).

Precipitation hardening heat treatment is commonly used for the following alloys:

• Aluminum alloys: Al-Cu, Al-Mg-Si, Al-Cu-Mg, Al-Zn.

• Copper alloys: beryllium bronze,aluminum bronze, aluminum-

nickel bronze, chromium copper.

• Stainless steels: iron-chromium-nickel alloys with additions of

copper, aluminum, titanium and niobium. The precipitation
hardening stainless steels are either austenitic or martensitic.

• Nickel alloys: nickel-copper alloys with additions of titanium,

aluminum and iron.
 • Titanium alloys: titanium-aluminum alloys, titanium-
vanadium alloys.

Cryogenic treatment of steel

Cryogenic treatment (tempering) is a processing of the material at a temperature
below 80K (-315°F / -193°C) resulting in modification of its microstructure and
improvement of its properties.

• Effects of cryogenic treatment on steel microstructure

• Benefits of cryogenic treatment
• Applications of cryogenic treatment of steels

Effects of cryogenic treatment on steel microstructure

Cryogenic tempering of a steel is carried out as a supplemental process following

after the conventional heat treatment procedure (Hardening).

Hardening treatment comprises heating the steel above the phase transformation
temperature (upper critical temperature), followed by soaking and then rapid cooling
(quenching).

When steel is heated above the upper critical temperature, its structure becomes
entirely austenitic, which transforms into martensite (supersaturated solid solution of
carbon in α-iron) after quenching.
Austenite-martensite transformation is never complete - a certain percentage of
austenite is retained in the resulting microstructure. Austenite has face centered cubic
(FCC) structure, which is denser than the body centred tetragonal (BCT) structure of
martensite. The densities difference causes internal stresses in heat treated steels.
Austenite is softer than martensite therefore high percentage of retained martensite
decreases the steel hardness and wear resistance.

Cryogenic treatment results in the following effects of the steel microstructure:

• Transformation of retained austenite into martensite;

• Internal stresses relief affecting most mechanical properties;
• Precipitation of fine carbide particles (ETA-carbides) uniformly
distributed in the martensite grains.
• More homogeneous microstructure due to reduction of micro-
voids (pores, cracks).

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Benefits of cryogenic treatment

• Wear resistance (due to higher hardness and the presence of

hard ETA-carbides);
• Mechanical strength;
 • Toughness;
• Fatigue strength (due to low residual stresses and
homogeneous structure);
• Creep;
• Low coefficient of friction (due to higher hardness and the
presence of hard ETA-carbides);
• Machining, grinding and polishing finish (due to no/little soft
austenite);

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Applications of cryogenic treatment of steels

• Cutting tools for different machining operations: sawing,

milling, drilling, broaching, turning, slitting, shearing;
• Metal forming tools: dies, molds, punches.
• High precision parts: gauges, guides, shafts;
• Parts of high performance (sport) car engines and
transmissions: crankshafts, connecting rods, piston rings, engine
blocks, gear parts, camshafts.

Salt bath heat treatment

Salt bath heat treatment is a heat treatment process comprising an immersion of the
treated part into a molten salt (or salts mixture).

• Benefits of heat treatment in salt baths

• Compositions of salt baths
• Heat treatments conducted in salt baths

Benefits of heat treatment in salt baths

• Fast heating. A work part immersed into a molten salt is

heated by heat transferred by conduction (combined with
convection) through the liquid media (salt bath). The heat transfer
rate in a liquid media is much greater than that in other heating
mechanisms: radiation, convection through a gas (e.g., air).
• Controlled cooling conditions during quenching. In
conventional quenching operation either water or oil are used as
the quenching media. High cooling rate provided by water/oil may
cause cracks and distortions. Cooling in molten salt is slower and
stops at lower temperature.
• Low surface oxidation and decarburization. The contact
of the hot work part with the atmosphere is minimized when the
part is treated in the salt bath.

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Compositions of salt baths
No Compositi Approximate Work temperature
. on melting poing range

NaOH 75%
320-752ºF (160-
1 KOH 19% 284ºF (140ºC)
280ºC)
H2O 6%

KOH 50-
60%% 572-752ºF (300-
2 -
NaOH 50- 400ºC)
40%

662-930ºF (350-
3 KNO3 100% 639ºF (337ºC)
500ºC)

KNO3 50-
60% 320-1022ºF (160-
4 275ºF (135ºC)
NaNO2 50- 550ºC)
40%

NaNO3 50-
60% 311-932ºF (150-
5 293ºF (145ºC)
NaNO2 50- 500ºC)
40%

KNO3 50-
60% 500-1112ºF (260-
6 437ºF (225ºC)
NaNO3 50- 600ºC)
40%

NaNO3 752-1110ºF (400-

7 698ºF (370ºC)
100% 600ºC)

NaCl 10-
15%
KCl 20-30%
932-1472ºF (500-
8 BaCl2 40- 752ºF (400ºC)
800ºC)
50%
CaCl2 15-
20%

NaCO3 45-
1022-1652ºF (550-
9 55% 842ºF (450ºC)
900ºC)
KCl 55-45%
 BaCl2 50%
1058-1652ºF (570-
10 KCl2 30% 1004ºF (540ºC)
900ºC)
NaCl 20%

BaCl2 70-
1112-1472ºF (600- 1292-2282ºF (700-
11 96%
800ºC) 1250ºC)
NaCl 30-4%

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Heat treatments conducted in salt baths

• Quenching of steels. Quenching is rapid cooling from the

temperature above A3 (upper critical temperature). Relatively slow
cooling rate provided by molten salts prevents the work part from
cracking and distortion.
• Austempering. Austempering is the isothermal hardening
method in which a part is quenched in a quenching medium (molten
salt) and is left in it reaching uniform temperature distribution. The
part is removed from the quenching medium after the complete
bainite formation. Tha austempering temperature range is 400-
750°F (204-399°C). Nitrate salts No. 4-6 are used for austempering
treatment.
• Martempering. Martempering is the isothermal hardening
method in which a part is quenched in a quenching medium (molten
salt) and is left in it reaching uniform temperature distribution. The
part is removed from the quenching medium before the bainite
formation. Martempering is performed at a temperature above the
the temperature of martensite formation (austenite-martensite
transformation), which is 400-480°F (200-250°C). Nitrate salts No.
4-6 are used for martempering treatment of most alloys. Sodium
nitrate (No.7) a potassium nitrate (No.3) are used for martempering
tool steels (hot-work and high speed steel).
• Hardening. Hardening is performed at 1400-2300°F (760-
1260°C) in chloride salts (No.8-11).
• Nitriding. Liquid nitriding is the process of diffusion
enrichment of the surface layer of a part with Nitrogen provided by
a molten cyanide base salt (extremely toxic substance). The
process is carried out at the temperatures 950-1075°F (510-580°C)
for about 4 hour.
• Carbonitriding. Liquid carbonitriding is the process of
diffusion enrichment of the surface layer of a part with carbon and
nitrogen provided by a molten salt containing 20-25% of sodium
cyanide (extremely toxic substance). The process is carried out at
the temperatures 1500-1580°F (820-860°C).
 • Carburizing. Liquid carburizing is the process of diffusion
enrichment of the surface layer of a part with carbon provided by a
molten salt containing 10-25% of sodium cyanide (extremely toxic
substance). The process is carried out at the temperatures 1562-
1742°F (850-950°C).
• Solution treatment of Aluminum alloys. Solution
treatment is the operation of heating the work park to a
temperature at which the hardening second phase particles dissolve
in the matrix. Solution treatment of heat treatable aluminum alloys
is carried out at 900-1025°F (482-551°C). Fast solution heat
treatment may be achieved by heating an aluminum alloy part in a
molten salt bath. Nitrate salts No.4,5,6 are used for solution
treatment of aluminum alloys.
• Deep brazing. Brazing is a method of joining two metal
work pieces by means of a filler material at a temperature above its
melting point but below the melting point of either of the materials
being joined. Dip brazing is a brazing method in which the work
pieces together with the filler metal are immersed into a bath with a
molten salt. The filler material melts and flows into the joint.
Chloride salts with addition of reactive agents are used for deep
brazing.
• Cleaning. Polymeric contamination on metal parts surfaces
may be effectively removed by immersion of the part into a molten
salt. Polymers decompose and burn at the temperature of the
molten salt. Mixtures of hydroxides and nitrates at a temperature
within 650-950°F (343-510°C) are used for cleaning operation.

Furnaces for heat treatment

Batch furnaces

• Car bottom furnace

Furnaces of this type have a movable bottom (car). The car goes out of the furnace
and may be loaded or unloaded with treated parts.

The heating method may be either electric resistance or fuel/gas.

Car bottom furnaces are suitable for various heat treatment operations of large and
heavy parts.

• Bell type furnace

Furnaces of this type have a movable vertically heating bell and a stationary bottom
with the treated parts.

The heating method may be either electric resistance or fuel/gas.

Bell type furnaces are suitable for coiled strip annealing and other heat treatments
including operations in controllable atmosphere.

• Vertical pit furnace

Furnaces of this type are used for heat treatment of shaft like parts (generator rotors,
steam turbine rotors) which are loaded vertically through the top of the furnace.

The heating method may be either electric resistance or fuel/gas.

Continuous furnaces

• Belt furnace

Furnaces of this type have a mesh belt conveyor moving through a long tube like
furnace.

The heating method may be either electric (resistance or induction) or fuel/gas.

Belt furnaces are suitable for heat treatment of relatively small parts.

• Roller furnace

Furnaces of this type have heat resistant steel rollers moving the parts through a long
tube like furnace.

The heating method may be either electric or fuel/gas.

Roller furnaces are suitable for heat treatment of sheets, tubes and other long parts.

• Pusher furnace

Furnaces of this type have a pusher located at the furnace end and moving the parts
through the furnace.

The heating method may be either electric or fuel/gas.

Pusher furnaces are generally used for heating parts before hot deformation.

• Continuous strip annealing furnace

Coled rolled strip in uncoiled state passes through the long tube like or looped furnace
with controlled reducing atmospere (commonly a mixture of Hydrogen and Nitrogen)
preventing oxidation of the steel surface..

The heating method may be either electric or fuel/gas.

Grain structure
Grain is a small region of a metal, having a given and continuous crystal lattice
orientation. Each grain represents small single crystal.

Grains form as a result of solidification or other phase transformation processes.

Grains shape and size change in course of thermal treatment processes (for example
recrystallization annealing). The normal grain size varies between 1µm to 1000 µm.

Grain structure of a solid is an arrangement of differently oriented grains,

surrounded by grain boundaries.

Formation of a boundary between two grains may be imagined as a result of rotation

of crystal lattice of one of them about a specific axis.

Depending on the rotation axis direction, two ideal types of a grain boundary are
possible:

• Tilt boundary – rotation axis is parallel to the boundary plane;

• Twist boundary - rotation axis is perpendicular to the boundary plane;

• An actual boundary is a “mixture” of these two ideal types.

Grain boundaries are called large-angle boundaries if misorientation of two

neighboring grains exceeds 10º-15º.

Grain boundaries are called small-angle boundaries if misorientation of two

neighboring grains is 5º or less.

Grains, divided by small-angle boundaries are also called subgrains.

Grain boundaries accumulate crystal lattice defects (vacancies, dislocations) and other
imperfections, therefore they effect on the metallurgical processes, occurring in alloys
and their properties.

Since the mechanism of metal deformation is a motion of crystal dislocations through

the lattice, grain boundaries, enriched with dislocations, play an important role in the
deformation process.

Diffusion along grain boundaries is much faster, than throughout the grains.

Segregation of impurities in form of precipitating phases in the boundary regions

causes a form of corrosion, associated with chemical attack of grain boundaries. This
corrosion is called Intergranular corrosion.

Crystallization
Some metallurgical processes involve phase transition.

The typical example of phase transition is crystallization.

Crystallization is transformation of liquid phase to solid crystalline phase.

There are two general stages of phase transformation (crystallization) process –

nucleation and growth:

1. Nucleation

Nucleation is a process of formation of stable crystallization centers of a new phase.

Nucleation may occur by either homogeneous or heterogeneous mechanism,

depending on the value of undercooling of the liquid phase (cooling below the
equilibrium freezing point).

Presence of foreign particles or other foreign substance in the liquid alloy (walls of
the casting mold) allows to initiate crystallization at minor value of undercooling (few
degrees below the freezing point). This is heterogeneous nucleation.

If there is no solid substance present, undercooling of a hundred degrees is required in

order to form stable nuclei or “seeds” crystals, providing following crystal growth
(homogeneous nucleation)
Undercooling value determines quantity of nuclei, forming in the crystallizing alloy.
When a liquid comes into a contact with cold and massive mold wall (chill zone), it
cools fast below the freezing point, resulting in formation of a large quantity of stable
nuclei crystals.

In order to promote the nucleation process, surface-active additives are used. They
decrease interfacial energy of the nuclei crystals, causing formation of many more
new stable nuclei.

2. Crystal growth

Number of stable nuclei per unit volume of crystallizing alloy determines the grain
size.

When a large number of stable nuclei are present in chill zone of mold, fine equiaxed
grains form. Latent crystallization heat, liberating from the crystallizing metal,
decreases the undercooling of the melt and depresses the fast grains growth.

At this stage some of small grains, having favorable growth axis, start to grow in the
direction opposite to the direction of heat flow. As a result columnar crystals
(columnar grains) form.

Contrary to the pure metals, in alloys different type of undercooling takes place. It is
called constitutional undercooling.

Constitutional undercooling

Since solubility of an alloying element in solid is lower, than in liquid at the same
temperature, this element (solute) is rejected by the solidifying metal to the liquid
phase, enriching the region of liquid adjacent to the crystallization front.
For the most of the alloys: the higher the concentration of alloying element in the
alloy, the lower its liquidus temperature (temperature at which crystallization of the
alloy starts).

Thus crystallization temperature of the liquid, adjacent to the crystallization front,

rises with increasing the distance from the front surface. Therefore there is a layer of
the liquid, where its temperature is lower, than its crystallization temperature. This is
the region of constitutional undercooling (see the figure below).

Dendrites

If a protruding finger forms on the solidifying surface, its tip may reach the region of
constitutional undercooling . In this case the protuberance starts accelerated growth,
forming the main dendrite arms. Under certain conditions the same process may
occur on the surface of the main dendrite arms, causing branching off the secondary
arms and then arms of higher orders.

Process of solidification is considered in the article Solidification.

Imperfections of crystal structure

There are three conventional types of crystal imperfections:

Point defects

The simplest point defects are as follows:

• Vacancy – missing atom at a certain crystal lattice position;

• Interstitial impurity atom – extra impurity atom in an

interstitial position;

• Self-interstitial atom – extra atom in an interstitial

position;

• Substitution impurity atom – impurity atom, substituting

an atom in crystal lattice;

• Frenkel defect – extra self-interstitial atom, responsible for

the vacancy nearby.
Line defects

Linear crystal defects are edge and screw dislocations.

• Edge dislocation is an extra half plane of atoms “inserted”

into the crystal lattice. Due to the edge dislocations metals possess
high plasticity characteristics: ductility and malleability.

• Screw dislocation forms when one part of crystal lattice is

shifted (through shear) relative to the other crystal part. It is called
screw as atomic planes form a spiral surface around the dislocation
line.

For quantitative characterization of a difference between a crystal distorted by a

dislocation and the perfect crystal the Burgers vector is used.

The dislocation density is a total length of dislocations in a unit crystal volume. The
dislocation density of annealed metals is about 1010 - 1012 m−². After work
hardening the dislocation density increases up to 1015 - 1016 m-². Further increase of
dislocation density causes crackes formation and fracture.

Planar defects

Planar defect is an imperfection in form of a plane between uniform parts of the

material. The most important planar defect is a grain boundary. Formation of a
boundary between two grains may be imagined as a result of rotation of crystal lattice
of one of them about a specific axis. Depending on the rotation axis direction, two
ideal types of a grain boundary are possible:

• Tilt boundary – rotation axis is parallel to the boundary

plane;

• Twist boundary - rotation axis is perpendicular to the

boundary plane:
 • An actual boundary is a “mixture” of these two ideal types.
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Grain boundaries are called large-angle boundaries if misorientation of two

neighboring grains exceeds 10º-15º.

Grain boundaries are called small-angle boundaries if misorientation of two

neighboring grains is 5º or less.

Grains, divided by small-angle boundaries are also called subgrains.

Grain boundaries accumulate crystal lattice defects (vacancies, dislocations) and other
imperfections, therefore they effect on the metallurgical processes, occurring in alloys
and their properties.

Since the mechanism of metal deformation is a motion of crystal dislocations through

the lattice, grain boundaries, enriched with dislocations, play an important role in the
deformation process.

Diffusion along grain boundaries is much faster, than throughout the grains.

Segregation of impurities in form of precipitating phases in the boundary regions

causes a form of corrosion, associated with chemical attack of grain boundaries. This
corrosion is called Intergranular corrosion.