Cătălin CROITORU

E-mail: c.croitoru@unitbv.ro
Office: Colina UnitBv, room GI23
Thermal (heat) treatments of steels
Heat treatments are a set of operations of heating and cooling used for
changing the structure and properties of an alloy as required by the
application domain.
There are three types of thermal treatment: strengthening thermal
processing, which increases hardness, strength and wear resistance; softening
treatment, which increases ductillity and toughness, but reduces hardness
and resistance to deformation and rupture and structure/composition
refining thermal treatments (grain growth/structure formation and
homogenization of the material’s structure).
All three variants of thermal processing are widely applied to steel products.
It is possible to present any operation of thermal processing graphically in
the form of a curve in “temperature – time” coordinates, including periods of
heating, holding and cooling. The main parameters, defining the result of the
thermal processing, are the heating temperature th, holding time h and
cooling rate vc

Graphical representation of the heat treatment

regime
Non-equilibrium constituents in steels
Pearlite (the mechanical mixture composed of ferrite and cementite
lamellae stacked together) can be formed from austenite () under slow
cooling (the so-called equilibrium cooling conditions) under the
eutectoid temperature, 727C.
If the cooling of austenite is performed at very high rates (very fast),
then another constituent may be formed in steel, called martensite (M).
The technological process (thermal treatment) involving cooling steel
in various cooling media (water, oil, molten salts, etc.) at very high rates
is called quenching (ro: călire).
 Eutectoid steel solidification from Fe-C melt (~0.8%C)

Hypoeutectoid steel solidification from Fe-C melt

(< 0.8% C)
 Quenching (călirea)
Quenching consists in heating the steel above the eutectoid temperature (cca. 723C) to
convert its microstructure to austenite with subsequent fast enough cooling. The purpose is to
obtain the non-equilibrium structure: a supersaturated solid solution of carbon in -iron,
called martensite. Martensite formation allows for obtaining the maximum hardness
possible for the given steel type.
Rapid cooling upon quenching is necessary, so that carbon has no time to diffuse from the
solid solution – austenite – and remains in the lattice after cooling. The minimum cooling
rate at which quenching occurs is called the critical cooling rate.
Critical cooling rate during quenching of carbon steels is not lower 400 С/s. Such a value is
attained upon cooling in water or aqueous salt solutions (NaCl) or alkali (NaOH) solutions,
increasing the cooling capacity of water. The quenching cooling medium is often called a
quenching medium or hardening medium. While quenching, it is necessary to move the
workpiece vigorously in the cooling liquid to reduce steam buildup on the metal’s surface
because it retards the cooling (steam is thermally-insulative).
Critical cooling rate of alloying steel is much lower therefore it is possible to apply milder
cooling mediums such as mineral oils or polymer solutions in water.
Most of the time, quenching is simply a function
of how fast you cool the material.

Generally, the only way to control cooling speed

is with the quenching medium (that’s the stuff in
the bucket). In theory you could change the
temperature of the quenching medium, but you
already have a hot metal, so a few degrees change
in the water temperature doesn’t really matter. On
the other hand, differences in specific heat or
boiling point can make a large difference in
cooling rate.
Water and brine (NaCl in water) have the highest
heat dissipating abilities, so quenching speeds are
the highest with these.
 Cooling rate of austenite în steels

retained austenite
If the cooling rate is slow, diffusion of C atoms occur and the
normal (equilibrium) constituents are formed, ferrite,
cementite and pearlite

If the atoms are not allowed to move (i.e., the material is

cooled very fast) then we have a difussionless
transformation. The C and Fe atoms do not have enough
time to regroup, so a distorted FCC lattice occurs in the
quenched material, called body centered tetragonal (BCT).
This distorted FCC crystal lattice is typical of martensite.
Formation of quench cracks caused by residual stresses produced during quenching.
The figure illustrates the development of stresses as the austenite transforms to
martensite during cooling.
When quenching steel, martensite is formed by straining austenite. This
strain (called the Bain strain) forms martensite lamellae of different shapes.
Formation of a martensite lamellae work-hardens the surrounding austenite
so this will become more strain-resistant and therefore will not transform to
martensite. In quenched steels we always have some residual amount of
non-transformed austenite, which is called retained austenite (ro: austenită
reziduală).
Martensite is named after the German metallurgist Adolf Martens. It is very
hard (BH=700) and brittle, so a quenched steel containing high amount of
martensite will be very brittle. Usually, a supplementary thermal treatment is
neccesary to ”soften” the steel, so it can be machined and plastically
deformed without fracturing. During this operation, martensite decomposes
to other equilibrium or non-equilibrium constituents, depending on the
conditions. Content of carbon
0.2 0.3 0.4 0.5 0.6 0.8 1.0
in martensite, %
wt.
Hardness, НRC 40 48 55 59 62 65 66
Three main quenching methods are distinguished:
1. Continuous quenching (quenching in one hardening medium or single
quench hardening). It is the simplest type of quenching but may result in
generation of high internal stresses inside the work-piece (because the
surface of the material cools much faster than the interior).
2. Quenching in two hardening mediums (double quench hardening), or
broken quenching. The steel is quickly cooled in the range of temperatures
750-400 С (in a molten salts bath), and then the workpiece is immersed
into another hardening medium at room temperature, such as water or oil.
3. Isothermal quenching: the steel is quenched in a molten salt bath at a
specific temperature until full decomposition of austenite into another non-
equilibrium constituent called bainite. In all previous cases quenching
produced martensite structure, and in this case it gives bainite. Upon
isothermal quenching the stresses in steel are minimum, formation of cracks
is excluded, deformation is low. For some alloyed steels (spring and die
steels) this quenching allows for an optimum combination of strength and
plasticity.
 Formation of martensite from austenite by straining:
It’s like forming mountains by crimping of the Earth’s crust

The martensite grains grow at a very high rate equal to the velocity of sound within the austenite matrix
(>5 km/s). Sometimes there is a sound effect produced.
For steel with 0–0.6% carbon, the martensite has the appearance of laths
(fine lamellae) and is called lath martensite. For steel with greater than 1%
carbon, it will form a plate-like (coarse lamellae) structure called plate
martensite. Between those two percentages, the physical appearance of the
grains is a mix of the two.

Lath martensite in a steel with 0.4% C Mixed martensite in a tool steel Plate martensite in a tool steel
with 0.8 % C with 1.2% C
 Applying a thermal treatment to quenched steel can decompose the martensite
into other types of products, with good hardness and higher ductility (low
brittleness). This thermal treatment is called tempering (ro: revenire).
At martensite heating carbon is precipitated out of the  (austenite) solid
solution, forming thus cementite Fe3C. Martensite dissolves into a ferrite and
cementite mix, with different morphologies than the lamellar pearlite.
Depending on temperature and time of transformation, spheroidal structures or
fine lamellar structures can form – tempered sorbite or troostite (ro: sorbită
sau troostită de revenire).
So, on martensite tempering the following processes can
occur:
1) decrease of carbon content in martensite and cementite formation;
2) reduction of internal stresses;
3) growth of cementite particles;
4) transformation of retained austenite to martensite (it is important for
steels with the carbon content > 0.6 % wt. and especially for alloyed
steels).
 Mild Steel has only a very small amount of carbon
(less than 0.5%) and cannot be hardened and tempered
but tool steel with a carbon content of around 0.5% or
more can (i.e. 0.5% - 1.5%).

If Tool Steel is heated to Red Heat and then plunged

into water to cool it quickly, it will become hard and
very brittle, making it unusable for most purposes.

Tempering is a process whereby the hardened steel is

heated again and cooled from a lower temperature.
This increases the Toughness at the expense of losing
some Hardness. In industry, the correct temperature
would be set by the oven or kiln but, with experience,
the changing oxide colours can be used to judge when
it is reached sufficiently accurately for craft work.
Bainite is a plate-like non-equilibrium microstructure that forms in steels at
temperatures of 125–550 °C (depending on alloy and C content). First described
by Edgar Bain, it is one of the products that may form when austenite is cooled
past a temperature where it no longer is thermodynamically stable with respect to
ferrite, cementite, or ferrite and cementite.
The hardness of bainite can be between that of pearlite and martensite. This is the
most desired constituent in many types of steel (including steel for automotive
applications).
It is formed from very fine cementite needles or plates
embedded in ferrite (the type of bainite formed depends
on the isothermal quenching temperature.
Japanese swords were made by quenching at a gradient. They coated their blades with clay so that the back of the sword
quenched more slowly, so it had more tough ferrite. The edge of the sword would be pure, hard martensite while the core
of the blade was tougher and more ductile.
Alloy steels
• These are steels in which elements other than carbon are added in
sufficient quantity, to obtain special properties.
The alloying of steel is generally done to increase its
• Strength (yield strength, UTS)
• Hardness
• Toughness
• Resistance to corrosion, abrasion and wear
• Improving electrical and magnetic properties.
The various alloying elements in steels are:
• Nickel
• Chromium
• Molybdenum
• Cobalt
• Vanadium
• Manganese
• Silicon
• Titanium and
• Tungsten.

Effects of alloying elements on steel:

• dislocation movement impeding, Fe allotropic transformation temperature modification,
• alpha or gamma solutions stabilizers,
• formation and stability of carbides (chemical compounds of alloying elements with the C from steel),
• grain growth,
• displacement of the eutectoid point, retardation of the transformation rates on quenching,
• improvement in corrosion resistance,
• mechanical properties improving.
Constituents found in alloy steels:
• Alloyed solid solutions: nearly all alloying elements are able to form
substitutional solid solutions from plain ferrite or austenite. It results
that the solid solutions present in alloyed steels are much tougher and
harder than in plain carbon steels (sometimes with up to 200%). Boron
(B) can form interstitial solid solutions with -Fe, resulting in an
interstitially-alloyed ferrite;
• Chemical compounds: usually carbides, but in some cases also
intermetallic compounds. Carbides of Mn and partly of Cr can
”dissolve” in cementite (thus forming an ”alloyed” cementite);
• Mechanical mixtures: carbides (spheroidal or lamellar) and alloyed
solid solutions or cementite/alloyed cementite and alloyed solid
solutions resembling pearlite or other non-equilibrium compounds.
Vickers hardness of some common carbides in alloy steels
 • Dislocation movement impeding: Because of alloying, these atoms form
substitutional solutions with iron, thus the movement of dislocations is difficult,
leading to an increase in the strength of steels.
• Alpha and gamma stabilizers: alpha (ferrite) stabilizers such as Cr, Si, Mo,
Nb have bcc structure (same as that of alpha iron) while gamma (austenite)
stabilizers such as Mn, Ni, Co, Cu have fcc structure (as gamma iron) and
stabilize this phase at lower temperatures.
• Formation and stability of carbides: stable carbides are formed by alloying
elements with the combination of carbon. The carbides which are formed
generally have high wear resistance and extremely hard. Carbides increase
resistance to softening at elevated temperatures and prevent grain coarsening.
• Effect on grain growth:

The smaller the grains, the higher

the mechanical properties !!!
Improving the quenching ability of steels:

Addition of alloying elements retards the critical cooling rate to obtain martensite in quenching. This means that slow rate
of cooling by oil quenching (or) air quenching leads to the formation of martensitic structure.

Improvement in corrosion resistance:

Generally, addition of alloying elements such as chromium, aluminum, silicon to steel improves the corrosion resistance.
These elements form a thin dense and adherent oxide film on the surface of steel, which in turn prevents the corrosion to
greater extent.

Mechanical properties:

Mechanical properties of steels such as strength, hardness, wear resistance, corrosion resistance is improved by the addition
of alloying elements such as manganese, nickel, cobalt, vanadium etc., Addition of lead and bismuth improves the
machinability of steel. The strength and quenching ability of steel are improved by addition of silicon and chromium
respectively.
• Manganese (Mn) steels
Manganese increases strength and hardness of the steel.
It forms manganese carbide when it joins with iron carbide (a complex unit).
Manganese carbide raises the solubility of carbon in austenite, ans lowers the
austenite to pearlite transformation temperature.
Manganese is a deoxidizer and desulphurizer for steels at low concentrations.
The manganese alloy steels containing over 1.5% manganese with a carbon
range of 0.4% to 0.55% are widely used for gears, axles, shafts, tough mining
equipment, steel containers and other parts (called Hardox steels).
Steels containing manganese varying from 11 to 14% and carbon from 1% to
1.3% form an alloy steel (called Hadfield steel), which is extensively hard
and tough and has a high resistance to abrasion.
The lower percentage of manganese increases hardness, strength, wear
resistance and tensile strength. The higher percentages of manganese render
the steel practically non-magnetic and increase its work hardening properties.
• Nickel (Ni) steels:
Nickel is one of the oldest, most fundamental steel alloying element.
It is generally added in quantities up to 5%.
Nickel is a solid solution strengthener. Its addition lowers the critical
temperatures, which retards the decomposition of austenite and does not form
any carbides.
Nickel also increases the amount of pearlite at a given %C, in oposition to
plain carbon steels.
Nickel steels are characterized by high tensile strength, increased toughness
values, improved fatigue strength and have high impact resistance.
3.5% nickel steels with low carbon are used for carburizing of drive gears and
connecting rods.
5% nickel steels are used in heavy duty applications such as bus and truck
gears, cams and crankshafts.
Nickel confers dimensional stability to steel (i.e., low thermal expansion
coefficients).
• Silicon (Si) steels:
Silicon increases the strength and hardness of steel without lowering its ductility. Silicon in
small amounts are frequently used in many alloy steels but the percentage does not usually
exceed about 0.8%.
In heat resisting stainless steel, silicon may be used up to 3%. Silicon is present in steels with
varying amount and it acts a deoxidizer.
Silicon does not form carbides at heat treating temperatures and is responsible for
decomposition of other components by its presence. Although silicon improves the quenching
abillity and ultimate strength in steel, its biggest role is as a deoxidizing agent and in high
percentages, increases several magnetic properties of steel.
Silicon added steels can withstand impact and fatigue even at elevated temperatures. These
steels are principally used for generator and transformers in the form of laminated cores.
A steel containing 1 to 2% silicon known as navy steel is used for structural applications
requiring a high yield point.
The proper combination of manganese and silicon produces a steel with unusually high
strength and with good ductility and toughness.
• Chromium (Cr) steels
Chromium is one of the cheapest alloying elements, and it increases strength
and hardness when added to steel. It forms chromium carbide in the steel and
increases the hardening property of steel.
It increases the hardness, decreases the ductility and increases the tensile
strength and elastic limit but the toughness is slightly lowered.
It also imparts corrosion resisting properties to steel. A chromium alloy steel
containing 0.5 to 2% chromium is used for bearings, permanent magnets etc.
• Nickel-chromium steels
In these steels, the ratio of nickel to chromium is approximately 2.5.
Ni-Cr steels exhibit good mechanical properties, excellent corrosion and
oxidation resistance.
Ni-Cr steels are used in the manufacturing of worm drives, piston pins,
connecting rods and drive shafts etc.
• Molybdenum (Mo) steels:
Molybdenum is a ferrite stabilizer and forms hard carbides.
Molybdenum content varies from 0.20 to 0.70 percent.
This element dissolves both in gamma and alpha iron.
Molybdenum finds the greatest use in conjunction with other alloys. It is
particularly valuable in increasing tensile strength and hardenability
(quenching abillity) of steel.
The addition of molybdenum to steel increases wear resistance.
In present day use of steels for sustaining loads at high temperatures, failures
due to creep are avoided or minimized by alloying steel with molybdenum.
This element finds wide use in making of high speed steels (ro: oțeluri
rapide). Molybdenum steels are used for airplane and automobile parts.
The presence of molybdenum in nickel-chromium steel increases the
hardenability.
What Is High Speed Steel ?
It is an alloy tool steel that retains much of its hardness and toughness at red heat after heat treatment, allowing
tools made of it to cut at high speeds even while red-hot through friction.

High-speed steel (HSS or HS) is a subset of tool steels, which is commonly used as cutting tool material.

High speed steels (HSS ) get their name from the fact that they may be operated as cutting tools at much higher
cutting speeds than is possible with plain carbon tool steels. High-speed steels operate at cutting speed 2 to 3
times higher than for carbon steels.

When a hard material is machined at high speed with heavy cuts, sufficient heat may be developed to cause the
temperature of the cutting edge to reach a red heat. This temperature would soften carbon tool steel containing
even up to 1.5 per cent carbon to the extent of destroying their cutting ability. Certain highly alloyed steels,
designated as high-speed steels, therefore, have been developed which must retain their cutting properties at
temperatures up 600°C to 620°C.
• Vanadium (V) steels:
The percentage of vanadium in steels varies from 0.1 to 2.0. Vanadium forms
complex carbides with carbon, and these carbides together with chromium and
nickel greatly strengthen the steel.
Vanadium is a ferrite-stabilizer and forms a strong carbide. It acts as an expensive
deoxidizer and nitrogen-remover.
It produces fine-grained dispersion-strengthened steels in amounts of 0.1% as V4C3
particles which act as grain size refiners
The addition of a very small amount of vanadium, say less than 0.20%, produces a
marked increase in tensile strength, elastic limit, yield strength, resistance to shock,
hardness and fatigue strength and good wearability.
In construction steels, vanadium is added to an extent of 0.25% while for tool steels
and other special steels an increased percentage of vanadium is used.
Vanadium steels are largely used for making spring steels, high speed tool steels,
crankshafts, locomotives and wagon axles.

• Titanium (Ti) steels:

Titanium is a very strong carbide as well as nitride forming element which increases
the wear and abrasion resistance of the steel. Titanium is added to stainless steels to
prevent the precipitation of chromium carbides.
• Wolfram (tungsten) W steels:
W is an expensive metal and dissolves in ferrite and austenite. It forms
carbides and increase the strength of steel.
W amount in steels varies from 0.4 to 22.0 percent.
The addition of W increases the strength of alloyed steels at higher
temperature.
Wolfram imparts cutting hardness and abrasion resistance to steel.
When W is added up to 5% to 6%, it imparts special magnetic properties
to steel. W-alloy steels are commonly used for magnets, electrical
instruments etc.
The presence of W in steel improves the hardenabillity.
In general, the effect of adding W is to increase heat resistance, wear
resistance, tensile strength, shock resistance and thermal stability.
• Stainless steels (ro: oțeluri inoxidabile sau inoxuri)
Stainless steels are alloyed steels, with chromium and other elements (mainly Ni and Mo).
The stainless steels are highly resistant to corrosion (rusting) in a variety of environments.
Their predominant alloying element is chromium. A minimum concentration of at least 11% by weight Cr
is required for stainless steel. Their corrosion resistance can be improved by nickel and molybdenum
additions. Stainless steels are generally chosen for service conditions where corrosion resistance,
oxidation resistance and creep strength are important.
Chromium forms a protective passive film on the steel surface and thereby helps to prevent oxidation,
giving them their remarcable corrosion resistance.

Depending on their structure, there are three types of stainless stels:

• Austenitic stainless steels: this is the largest family of stainless steels, making up about two-thirds of
all stainless steel production. They possess an austenitic microstructure, achieved by alloying steel with
sufficient nickel to maintain an austenitic microstructure at all temperatures, ranging from the cryogenic
region to the melting point. Austenitic stainless steels are not hardenable by heat treatment since they
possess the same microstructure at all temperatures.
• Ferritic stainless steels: possess a ferrite microstructure like carbon steel, and contain between 10.5%
and 27% chromium with very little or no nickel. This microstructure is present at all temperatures due
to the chromium addition, so they are not hardenable by heat treatment. They cannot be strengthened by
cold work to the same degree as austenitic stainless steels. They are magnetic.
• Martensitic stainless steels: offer a wide range of properties and are used as stainless engineering
steels, stainless tool steels, and creep-resistant steels. They are magnetic, and not as corrosion-resistant
as ferritic and austenitic stainless steels due to their low chromium content. They are used as tool steels.
Microstructure of an austenitic stainless Microstructure of an ferritic stainless Microstructure of an martensitic stainless
steel steel steel
Unlike carbon steel, stainless steels contain sufficient chromium to
undergo passivation, spontaneously forming a microscopically thin inert
surface film of chromium oxide by reaction with the oxygen in the air and
even the small amount of dissolved oxygen in the water. This passive film
prevents further corrosion by blocking oxygen diffusion to the steel surface
and thus prevents corrosion from spreading into the bulk of the metal. This
film is self-repairing, even when scratched.
Applications of stainless steels:

• Austenitic stainless steels: are used in the manufacture of pump sets, rail road, car
frames, screw nuts and bolts etc. They are also used in chemical plants, appliances,
storage and transport tanks for chemical industries, utensils and cutlery, household and
sanitary fittings.
• Ferritic stainless steels: are used in the manufacture of valves and pipes in the chemical
and food plant equipment to resist nitric acid corrosion. They are also used in highly
stressed fittings of engines and machines, in the manufacture of bars, sheets, strips,
wires etc. These steels can be welded, forged, rolled and machined.
• Martensitic stainless steels: are used for making steam valves, turbine blades, shafts,
scissors, knives, gears, ball bearings, springs, cutlery and other purposes where hard
edges are required.