Heat Treatment Course No MME 321

Hardening Processes

Dr. SASIKUMAR, Asst Prof., MME

Department of Materials & Metallurgical Engineering (MME)
MAULANA AZAD NATIONAL INSTITUTE OF TECHNOLOGY
Bhopal, M.P., India
 HARDENING BY QUENCHING
 Hardening treatment consists of heating to a
predetermined temperature, usually known as
hardening temperature, holding at that
temperature, followed by rapid cooling such as
quenching in water, oil or salt baths.
 Rapid cooling – i.e. cooling rate is equal or more
than critical cooling rate.
 Stainless and high-alloy steels may be
quenched to minimize the presence of grain
boundary carbides or to improve the ferrite
distribution but most steels including carbon,
low-alloy, and tool steels, are quenched to Temp. range for hardening heat treatment
produce controlled amounts of martensite in the  Rapid cooling results in the transformation of
microstructure.
austenite into non-equilibrium products such
 Successful hardening usually means achieving as martensite or bainite
the required microstructure, hardness, strength,
or toughness while minimizing residual stress,
 Hypo-eutectoid steel – heated 30-50 C above
A3 i.e. upper critical temp.
distortion, and the possibility of cracking.
 Hyper-eutectoid steel – heated about 30-50 C
above lower critical temp.
FACTORS AFFECTING HARDENING PROCESS
 Chemical composition of steel- alloying elements

 Size and Shape of the part - variable cross sections

 Hardening cycle i.e. heating rate, hardening temp., holding time and
cooling rate - larger cooling rate, slow heating, fast heating, heating to
an intermediate temp., holding time and nature of the austenite

 homogeneity and grain size of austenite

 Quenching media – temp., specific heat, thermal conductivity, Hv

 Surface condition of steel part – oil, grease, oxides

QUENCHING METHODS
 Conventional or Direct Quenching
 Time Quenching (or ) Quenching with self tempering
 Selective Quenching
 Spray Quenching
 Fog Quenching
 Interrupted Quenching (Quenching in stages in sequence in different
media )

Austempering or Isothermal Quenching

Martempering or Stepped Quenching

 CONVENTIONAL /DIRECT QUENCHING
 Direct quenching refers to quenching directly from the austenitizing temperature and is
by far the most widely used practice. The term direct quenching is used to differentiate
this type of cycle from more indirect practices which might involve carburizing, slow
cooling, reheating, followed by quenching.
 Quenching a steel from hardening temp. in the quenching medium

 allowed to cool in the media

 internal stresses – distortion, cracking (less severe media)

 small sections can be hardened – lesser quenching power

 Simpler shapes , not for intricate components.

TIME QUENCHING
 TIME QUENCHING
 Time quenching is used when the cooling rate of the part being quenched needs
to be abruptly changed during the cooling cycle.

 The change in cooling rate may consist of either an increase or a decrease in

the cooling rate depending on which is needed to attain desired results.

 The usual practice is to lower the temperature of the part by quenching in a

medium with high heat removal characteristics (for example, water) until the part
has cooled below the nose temperature, and then to transfer the part to a second
medium (for example, oil), so that it cools more slowly through the martensite
formation range.

 In some applications, the second medium may be air or an inert gas.

 Time quenching is most often used to minimize distortion, cracking, and

dimensional changes.
 TIME QUENCHING OR QUENCHING WITH SELF
TEMPERING
 soft and tough core with
hardened and toughened case
 self tempering – time quenching –
quenched from hardening temp.,
withdrawing from quenching bath
after some time without allowing it
to cool completely in quenching
medium.
 heat retained in the central portion

now cooled in mild quenching medium oil/air

First quenching – martensite – depth depends on time period.
Second quench – homogenisation of temp.
Results in tough core with hardened and toughened case.
 SELECTIVE QUENCHING
 Selective quenching is used when it is desirable for certain areas of a part to be
relatively unaffected by the quenching medium.
 This can be accomplished by insulating an area to be more slowly cooled so the
quenchant contacts only those areas of the part that are to be rapidly cooled.
SPRAY QUENCHING
 SPRAY QUENCHING
 The term spray quenching refers to a wide variety of quenching processes that
involve heat removal facilitated by the impingement of a quenchant medium on a hot
metal surface.
 Spray quenching involves directing high-pressure streams of quenching liquid onto
areas of the workpiece where higher cooling rates are desired.
 The cooling rate is faster because the quenchant droplets formed by the high-
intensity spray impact the part surface and remove heat very effectively.
 One advantage of spray quenching, relative to other quench methods, is that a large
and adjustable range of cooling rates is achievable by simple changes in flow rates
and pressures. The high rates of heat extraction possible with sprays are critical for
attaining a good depth of hardness.
 Rate of heat extraction is much higher
 No formation of liquid vapour film over the surface.
 Best suited for selective hardening
 water as quenching media
COOLING RATE AND HARDNESS IN SPRAY
QUENCHING
WATER-COOLING CONFIGURATIONS

The three main water-cooling configurations on runout tables. From left to

right: spray, laminar, and water curtain.
 FOG QUENCHING
 Fog quenching utilizes a fine fog or mist of
liquid droplets in a gas carrier as the cooling
agent.
 Although similar to spray quenching, fog
quenching produces lower cooling rates
because of the relatively low liquid content of
the stream.
INTERRUPTED QUENCHING/ QUENCHING IN STAGES
 Interrupted quenching refers to the rapid cooling of the metal from the
austenitizing temperature to a point above the Ms where it is held for a specified
period of time, followed by cooling in air.
 There are three types of interrupted quenching: austempering, marquenching
(martempering), and isothermal quenching.
 The temperature at which the quenching is interrupted, the length of time the
steel is held at temperature, and the rate of cooling can vary depending on the
type of steel and workpiece thickness.
 Quenching in stages in sequence in different media
 Steel part – hardening temp. – bath (T1 higher than Ms) - mild quenching
medium (room temp.)
 Oil / air media
 internal stresses are considerably less
 COMPARISONS OF DIRECT AND INTERRUPTED QUENCH
CYCLES

Fig. Comparison of cooling rates and temperature gradients as workpieces pass into and through martensite
transformation range for a conventional quenching and tempering process and for interrupted quenching
processes. (a) Conventional quenching and tempering processes that use oil, water, or polymer quenchants.
(b) Marquenching, which uses either salt or hot oil as a quenchant. (c) Austempering, which uses a salt as a
quenchant. (d) Isothermal quenching, which uses either salt or hot oil as a quenchant.
INTERRUPTED QUENCHING/ QUENCHING IN
STAGES
 Cooling from the marquenching bath to room temperature is usually conducted in still
air. Deeper hardening steels are susceptible to cracking while martensite forms if the
cooling rate is too rapid. Alloy carburizing steels, which have a soft core, are
insensitive to cracking during martensite formation, and the rate of cooling from the
Ms temperature is not critical.
 Marquenching does not remove the necessity for subsequent tempering. The
structure of the metal is essentially the same as that formed during direct quenching.

 Isothermal quenching is also similar to austempering in that the steel is rapidly

quenched through the ferrite and pearlite formation range to a temperature just
above Ms. However, isothermal quenching differs from austempering in that two
quench baths are employed. After the first quench, and before transformation has
time to begin, the workpiece is transferred to a second bath at a somewhat higher
temperature where it is isothermally transferred, followed by cooling in air.
 INTERRUPTED QUENCHING/ QUENCHING IN
STAGES
 Austempering consists of rapidly cooling the metal part from the austenitizing
temperature to about 230 to 400 °C (depending on the transformation characteristics
of the particular steel involved), holding at a constant temperature to allow isothermal
transformation, followed by air cooling.
 Austempering is applicable to most medium-carbon steels and alloy steels. Low-alloy
steels are usually restricted to 9.5 mm ( 3/8 in.) or thinner sections, while more
hardenable steels can be austempered in sections up to 50 mm (2 in.) thick.
 Molten salt baths are usually the most practical for austempering applications. Oils
have been developed that suffice in some cases, but molten salts possess better heat-
transfer properties and eliminate the fire hazard.
 Marquenching. The marquenching (martempering) process is similar to austempering in
that the workpiece is quenched rapidly from the austenitizing range into an agitated
bath held near the Ms temperature. It differs from austempering in that the workpiece
remains at temperature only long enough for the temperature to be equalized
throughout the workpiece. When the temperature has attained equilibrium but before
transformation begins, the workpiece is removed from the salt bath and air cooled to
room temperature. Oils are used successfully for marquenching, but molten salt is
usually preferred because of its better heat-transfer properties.
TEMPERING
WHY TEMPERING IS REQUIRED ?
Quench cracks

Martensite

Metastable Phases ,
Retained Austenite
MARTENSITE
 Steel gains its high quenched hardness through the formation of martensite during
cooling of the high temperature austenite
 More carbon in martensite means higher hardness. Hardness/strength is increased by
making it more difficult for “dislocations” to move within the material, which are line
defects in the atomic structure.
 Dislocation motion is prevented in martensite because of solid solution strengthening of
carbon, high dislocation density, “tetragonality” of martensite, and the many packet and
block boundaries.
 When the transformation to martensite is incomplete any remaining austenite is known
as “retained austenite”. such a steel, may develop distortion and cracks due to stresses
induced in steels during quenching,
 Metastable martensite and the retained austenite may slowly decompose which may
cause dimensional changes due to differences in specific volumes of the parent and the
product phases, which may create stresses.
 The quenching process, martensite formation, and supersaturated carbon leads to brittle
steel. The primary reason to temper the steel is to decrease its brittleness, or in other
words, increase its toughness of the steel.
TEMPERING OF STEEL
 TEMPERING OF STEEL is a process in which previously hardened or
normalized steel is usually heated to a temperature below the lower critical
temperature and cooled at a suitable rate, primarily to increase ductility and
toughness, but also to increase the grain size of the matrix.
 Steels are tempered by reheating after hardening to obtain specific values
of mechanical properties and also to relieve quenching stresses and to
ensure dimensional stability.
 Tempering usually follows quenching from above the upper critical
temperature; however, tempering is also used to relieve the stresses and
reduce the hardness developed during welding and to relieve stresses
induced by forming and machining.
MICROSTRUCTURAL CHANGE DURING TEMPERING
MICROSTRUCTURAL CHANGE DURING TEMPERING
CLASSIFICATION OF TEMPERING:
CLASSIFICATION OF TEMPERING:
PRINCIPAL VARIABLES
 Variables associated with tempering that affect the microstructure and the
mechanical properties of a tempered steel include:

 Tempering temperature
 Soaking time at temperature
 Cooling rate from the tempering temperature
 Composition of the steel, including carbon content, alloy content, and residual
elements
EFFECTS OF TEMPERING
 In a steel quenched to a microstructure consisting essentially of martensite, the iron
lattice is strained by the carbon atoms, producing the high hardness of quenched
steels.
 Upon heating, the carbon atoms diffuse and react in a series of distinct steps that
eventually form Fe3C or an alloy carbide in a ferrite matrix of gradually decreasing
stress level.
 The properties of the tempered steel are primarily determined by the size, shape,
composition, and distribution of the carbides that form, with a relatively minor
contribution from solid-solution hardening of the ferrite.
 These changes in microstructure usually decrease hardness, tensile strength, and
yield strength but increase ductility and toughness.
 Under certain conditions, hardness may remain unaffected by tempering or may even
be increased as a result of it. For example, tempering a hardened steel at very low
tempering temperatures may cause no change in hardness but may achieve a desired
increase in yield strength.
 Also, those alloy steels that contain one or more of the carbide-forming elements
(chromium, molybdenum, vanadium, and tungsten) are capable of secondary
hardening; that is, they may become somewhat harder as a result of tempering.
EFFECTS OF TEMPERING
 The tempered hardness values for several quenched steels are presented in Table 1.
Temperature and time are interdependent variables in the tempering process.
 Within limits, lowering temperature and increasing time can usually produce the same
result as raising temperature and decreasing time.
 However, minor temperature changes have a far greater effect than minor time
changes in typical tempering operations.
 With few exceptions, tempering is done at temperatures between 175 and 705 °C (350
and 1300 °F) and for times from 30 min to 4 h.
 DIMENSIONAL CHANGES
 Martensite transformation is associated with an increase in volume. During tempering,
martensite decomposes into a mixture of ferrite and cementite with a resultant decrease
in volume as tempering temperature increases.
 The retained austenite in plain carbon steels and low-alloy steels transforms to bainite
with an increase in volume, in stage II of tempering. When certain alloy steels are
tempered, a precipitation of finely distributed alloy carbides occurs, along with an
increase in hardness, called secondary hardness, and an increase in volume.
 With the precipitation of alloy carbides, the Ms temperature (temperature at which
martensite starts to form from austenite upon cooling) of the retained austenite will
increase and transform to martensite during cooling from the tempering temperature.
 STAGES OF TEMPERING:
 During heating for tempering, intention is to allow the diffusion processes, the
nature of which depends on the temperature of tempering.
 Tempering of carbon steels takes place in four distinct but overlapping stages:
 1. Stage I:
 Up to 200°C- Precipitation of ε (epsilon)-carbide due to decrease of tetragonality
of martensite.
 2. Stage II :
 200° to 300°C- Decomposition of retained-austenite (The transformation of retained
austenite to ferrite and cementite).
 3. Stage III :
 200° to 350°C- The replacement of transition carbides and low-temperature martensite
by cementite and ferrite (Formation of rods, or plates of cementite with compete loss
of tetragonality of martensite and dissolution of e-carbide).
 4. Stage IV:
 350°C to 700°C- Coarsening and spheroidisation of cementite along with
recovery and recrystallisation of ferrite .
 precipitation of finely dispersed alloy carbides, exists for high-alloy steels.
TEMPERING TEMPERATURE
 The tempering temperature is decided by the strength (or hardness) and
toughness required in service for a given application.

Purpose of tempering
1. To relieve internal stresses developed during hardening.
2. To restore ductility and toughness at the cost of hardness and strength.
3. To improve dimensional stability by the decomposition of retained austenite.
4. To improve magnetic properties by transforming non-magnetic austenite to magnetic
product.
EFFECT OF TEMPERING TEMPERATURE ON MECHANICAL
PROPERTIES
EXAMPLE 1: EFFECT OF HARDENING AND TEMPERING ON THE
DIMENSIONS OF O1 TOOL STEEL PLATES.

 Dimensional changes that occur in O1 tool steel (Bofors RT 1733) when heat treated at two hardening
temperatures and two soak times using two tempering methods, (a) oil quenching, and (b) martempering.
Specimen dimensions were 100 × 50 × 18 mm (4 × 2 × 0.7 in.). Steel was rolled in the longitudinal direction.
EFFECT OF TEMPERING TEMPERATURE ON ROOM-TEMPERATURE
MECHANICAL PROPERTIES OF 1050 STEEL.

Effect of tempering temperature on room-temperature mechanical properties of 1050

steel. Properties summarized are for one heat of 1050 steel that was forged to 38 mm
(1.50 in.) in diameter, then water quenched and tempered at various temperatures.
Composition of heat: 0.52% C, 0.93% Mn
EFFECT OF TEMPERING TEMPERATURE ON THE
MECHANICAL PROPERTIES OF OIL-QUENCHED 4340
STEEL BAR

Effect of tempering temperature on the

mechanical properties of oil-quenched 4340 steel
bar.
Single heat results: ladle composition, 0.41% C,
0.67% Mn, 0.023% P, 0.018% S, 0.26% Si, 1.77%
Ni, 0.78% Cr, 0.26% Mo;
grain size, ASTM 6 to 8;
critical points, Ac1, 730 °C (1350 °F); Ac3, 770
°C (1415 °F); Ar3, 475 °C (890 °F); Ar1, 380 °C
(720 °F); treatment, normalized at 870 °C (1600
°F), reheated to 800 °C (1475 °F),
quenched in agitated oil; cross section, 13.46 mm
(0.530 in.) diam; round treated, 12.83 mm (505
in.) diam; round tested; as-quenched hardness,
601 HB.
 NOTCH TOUGHNESS AS A FUNCTION OF TEMPERING
TEMPERATURE FOR 4140

Notch toughness as a function of tempering temperature for 4140 (UNS G41400) ultrahigh-strength steel tempered 1 h
There is no decrease in ductility in the temperature range of tempered martensite embrittlement, or TME (also known
as 500 °F embrittlement or one-step temper embrittlement) because the tensile tests are performed on smooth, round
specimens at relatively low strain rates.
However, in impact loading, catastrophic failure may result when alloy steel is tempered in the tempered martensite
embrittlement range (260 to 370 °C).
Both plain carbon and alloy steels respond to tempering in this manner. The phenomenon of impact energy minima
centered around 300 °C (570 °F) is called tempered martensite embrittlement (TME) or 500 °F embrittlement.
TEMPERING TIME.

Effect of time at four tempering temperatures on room-temperature hardness of quenched 0.82% C

steel. Note nearly straight lines on logarithmic time scale.
RELATIONSHIP BETWEEN CARBON CONTENT AND ROOM
TEMPERATURE HARDNESS FOR STEELS COMPRISING 99.9%
UNTEMPERED MARTENSITE
ALLOY CONTENT

Strong carbide-forming elements such as chromium, molybdenum, and vanadium are most effective
in increasing hardness at higher temperatures above 205 °C (400 °F). Silicon was found to be most
effective in increasing hardness at 315 °C (600 °F). The increase in hardness caused by
phosphorus, nickel, and silicon can be attributed to solid-solution strengthening. Manganese is more
effective in increasing hardness at higher tempering temperatures.
 SECONDARY-HARDENING EFFECT
 The carbide-forming elements retard coalescence of
cementite during tempering and form numerous small
carbide particles.
 Under certain conditions, such as with highly alloyed
steels, hardness may actually increase. This effect,
mentioned previously, is known as secondary
hardening.
 As the alloy content increases, the magnitude of the
secondary-hardening effect increases. Synergistic
effects of various combinations of alloying elements
can occur: Influence of molybdenum content on the
 Chromium tends to produce secondary hardening at softening of quenched 0.35% C steels with
increasing
a lower temperature than does molybdenum, and the
tempering temperature
combination of chromium and molybdenum produces
a rather flat tempering curve, with the peak hardness
occurring at a somewhat lower temperature than
when only molybdenum is present.
 H11 steel is a widely used hot-working die steel that
H11 steel.
contains nominally 0.35% C, 5% Cr, 1.5% Mo, and
0.4% V. Figure
 TEMPERING PROCEDURES
 Tempering can be accomplished by soaking entire parts in the furnace for enough time
to bring the tempering mechanism to the desired point of completion or by selective
heating of certain portions of the part to achieve toughness or plasticity in those areas.
EQUIPMENT FOR
TEMPERING
TEMPER COLOURS

 Hardened steel, when heated in oxidizing atmosphere for the purpose of

tempering, exhibits various colors on the surface.
 The colours are caused by the formation of iron oxide film.
 TEMPER EMBRITTLEMENT
 When carbon or low-alloy steels are cooled slowly from tempering above 575 °C
(1065 °F) or are tempered for extended times between 375 and 575 °C, a loss in
toughness occurs that manifests itself in reduced notched-bar impact strength
compared to that resulting from normal tempering cycles and relatively fast cooling
rates .
The cause of temper embrittlement is believed to be the precipitation of
compounds containing trace elements such as tin, arsenic, antimony, and
phosphorus, along with chromium and/or manganese.
The intergranular nature of the fracture suggests that the embrittlement occurs at
the prior austenite grain boundaries. Although manganese and chromium cannot
be restricted, a reduction of the other elements and quenching from above 575 °C
are the most effective remedies for this type of embrittlement.
Effect of temper embrittlement on notch toughness. Variation in
Charpy V-notch impact energy with temperature for 5140 steel
hardened and tempered at 620 °C
 Hydrogen Embrittlement: Hydrogen produces severe embrittlement in many
metals. Even very small amount of hydrogen can cause cracking in steel and
titanium. It may be introduced during melting and entrapped during
solidification, or it may be picked up during heat treatment, acid pickling,
electroplating or welding.
 2.Tempered Martensite Embrittlement: Tempering some steels within °C results
in temper brittlement, which is manifested by increase in impact transition
temperature. It is due to segregation of certain elements to grain boundaries,
giving local hardening to fracture.
 3.Blue Brittleness: Low-carbon steels exhibit two types of aging which causes
an increase in transition temperature: quench aging & strain aging. Strain aging
is the slow increase in hardness in steels finished by cold work (mainly cold
rolling). Blue brittleness is attributed to strain aging caused by heating cold
worked steel to around the temperature range of 230 to 370 °C.
 Brindley et al. indicated that the mechnisms by which strain aging increases the flow
stress were the creation of an extra dislocation density and the precipitation of nitrogen
on the dislocations.
 Generally, it is believed that the blue-brittle behaviour is due mainly to nitrogen
TEMPER BRITTLENESS OR TEMPER
EMBRITTLEMENT
 Certain types of steels, either on
cooling slowly or on holding
prolonged periods within a specific
tempering temperature range (375-
575OC) , show decrease in toughness
values.
 This phenomenon is known as
temper embrittlement.
o Temper brittleness does not occur in carbon steel, but widely observed in
alloy
steels.
o Steels with Phosphorous, antimony, tin and arsenic are highly prone to this.
o In order to assess susceptibility to temper embrittlement in Cr-Mo steels, two
compositional parameters are commonly employed, the Watanabe J
factor and the Bruscato X factor .
J=(Mn + Si)(P + Sn) x104 (in wt %) X=(10P + 5Sb + 4Sn + As)/100 (in ppm),
If J is less than or equal to 180, or if X is less than 20, the risk of temper
TEMPERING:
 The tempering changes in hardness as a function of tempering temperature, where
tempering time is kept constant of 1 hour at each temperature.
 Hollomon and Jaffe’s “tempering parameter” may be used for this purpose as it relates
the hardness, tempering temperature and tempering time.
 For a thermally activated process, the usual rate equation is:

 where, t is the time of tempering to develop a given hardness, and Q is the ’empirical
activation energy.’ ‘Q’ is not constant in the complex tempering process but varies with
hardness.
 Thus, hardness was assumed to be a function of time and temperature:

 Interestingly, [t e-Q/RT] is a constant, and let it be t0. Equating the eqns

 As t0 is a constant, then-
 H = f[T(C + In t)]
 where, C is a constant, whose value depends on the composition of austenite. The
single parameter which expresses two variables time and the temperature, i.e., T (C + In
t] is called the Hollomon and Jaffe tempering parameter.
 MODIFIED MARTEMPERING

Time temperature transformation diagrams with superimposed cooling curves showing quenching
and tempering. (a) Conventional process. (b) Martempering. (c) Modified martempering

The lower temperature increases the severity of quenching. This is important for steels of lower
hardenability that require faster cooling in order to harden to sufficient depth, or when the Ms is high
and some bainite is detrimental to the finished part. Therefore, modified martempering is applicable
to a greater range of steel compositions than is the standard process.