Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering

Alexey Sverdlin
Department of Mechanical Engineering, Milwaukee School of Engineering, Mequon,
Wisconsin, U.S.A.

Abstract
In the as-quenched state, martensite, in addition to being very hard, is so brittle that it cannot be used for
most applications. The formation of martensite is accompanied by severe matrix distortions. The hardness
and strength of martensite increase sharply with the increase in carbon content. In this case, “as-quenched”
martensite is reheated to a suitable temperature below the lower critical temperature A1. This heat
treatment following quench-hardening is termed tempering. Tempering is accomplished by heating a
martensitic steel to a temperature below the eutectoid for a specified time period. Normally, tempering is
carried out at temperatures between 250
C and 650
C (480
F and 1200
F). This tempering heat treatment
allows, by diffusional processes, the formation of tempered martensite, where the single-phase BCT
martensite, which is supersaturated with carbon, transforms into the tempered martensite, composed of
the stable ferrite and cementite phases. The process of tempering is mainly involved with the precipitation
and coalescence of the various carbides of iron and alloying elements.

TEMPERING OF ALLOY STEELS
The addition of alloying elements to steel has a substantial
effect on the kinetics of the γ!α transformation and also
of the pearlite reaction. Most of the common alloying
elements move the TTT curves to longer times. This essen-
tially gives higher hardenability, as martensite structures
can be achieved at slower cooling rates, and in practical
terms, thicker specimens can be made fully martensitic.
Alloying elements have also been shown to have a signif-
icant effect on the decrease in Ms temperature.[2]
Similar to hardenability, alloying elements have a sig-
Carbon–Iron—Carburized
The structural changes during the early stage of tem-
pering are difficult to follow. It is clear that certain ele-
ments, notably silicon, can stabilize the ε-iron carbide
to such an extent that it is still present in the microstruc-
ture after tempering at 400
C in steels with 1–2 wt.% Si
and at even higher temperatures if the silicon is further
increased. It is also clear that the transformation of ε-iron
carbide to cementite is delayed considerably. Although the
tetragonality of martensite disappears at 300
C in plain
carbon steels, in steels containing some alloying elements,
such as Cr, Mo, W, V, Ti, and Si, the tetragonal lattice is
still observed after tempering at 450
C and even as high as
500
C. These alloying elements increase the stability of

nificant influence on the tempering properties and the

nature and amount of carbides present.[4] They retard the
rate of softening during tempering by stabilizing both
the transition carbides and the supersaturated martensitic
structure to higher tempering temperature, by delaying
the precipitation and growth of cementite. With steels of
low- and medium-carbon contents, moderate amounts of
alloying elements may slightly increase the initial maxi-
mum hardness brought about by effective quenching. With
higher carbon, they are likely to slightly reduce the hard-
ness achieved, by an increase in the proportion of retained
austenite. Otherwise, the elements have little effect on
the as-quenched hardness; probably no wrought steel ever
exceeds the maximum hardness attainable in a high-
carbon steel as measured at ordinary temperatures. Unless
the proportion of austenite is very high, a tempering at
~400
F reduces the hardness of all ordinary alloy steels,
but seemingly, the presence of any alloying elements
retards, at least slightly, the loss of hardness and strength.
the supersaturated iron–carbide solid solution. In contrast,
Mn and Ni decrease the stability (Fig. 1).
The general effects on tempering of the more common
alloying elements, such as C, Mn, Cr, Mo, and Ni, found
in steels are summarized in Table 1.
Alloying elements also greatly influence the proportion
of austenite retained on quenching. Typically, a steel with
4.0% Mo and 0.2% C in the martensitic state contains
<2.0% austenite, and ~5.9% is detected in a steel with
1.0% V and 0.2% C.[4]
Alloying elements can also restrain the coarsening of
cementite in the range of 400700
C, which is a basic
process during the fourth stage of tempering. Several
alloying elements, notably Si, Cr, Mo, and W, cause the
cementite to retain its fine Widmanstätten structure to
higher temperatures, either by entering into the cementite
structure or by segregating at the carbideferrite inter-
faces. In plain carbon steels, cementite particles begin to

Encyclopedia of Iron, Steel, and Their Alloys DOI: 10.1081/E-EISA-120053682

498 Copyright © 2015 by Taylor & Francis. All rights reserved.
 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering
1.14
1.4% C
1.12 1.05% C, 1.38% Ti
1.09% C, 1.7% Mn
1.10
Martensize c/a ratio
1.08
1.06
1.04
1.02
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1.00
100 200 300 400
Temperature (°C)
Fig. 1 The effect of Ti and Mn on the tetragonality of martens-
ite during tempering.
Source: Sverdlin and Ness.[2]
coarsen in the temperature range of 350400
C, and the
addition of Cr, Si, Mo, or W delays the coarsening to the
range of 500–550
C. It should be emphasized that up to
500
C, the only carbides to form are those of iron. How-
ever, they will take varying amounts of alloying elements
into the solid solution and may reject other alloying ele-
ments as they grow.[8]
Fig. 2 shows as to how increasing proportions of silicon
act to increase the hardness of tempered steels that have
been suitably quenched. As silicon is not soluble in any
large proportion in the carbide, it strengthens the ferrite in
which the gradually coarsening carbide particles are dis-
persed. Nickel and manganese, also largely dissolved in
iron rather than in carbide, act in a similar manner,
although they are less effective at the same content, nickel
being particularly moderate in this respect. The softening
of an ordinary 0.45% C steel is compared with a steel that
has the same amount of manganese and carbon but has
3.5% Ni and is shown in the curves of Fig. 3. Nickel is not
a special potent ferrite strengthener. The slightly greater
effect of increase from 0.76% to 1.78% Mn is shown in
Fig. 4.
With carbon content much above 0.90% and particu-
larly with over 1.0% Mn or considerable nickel, the tem-
pering curve may possibly reflect the release of retained
austenite by a slight retardation of softening. This effect is
so small with moderate amounts of retained austenite,
which is probably attributed to an error in the hardness
measurement. However, marked the effect of retained
austenite fostered by nickel and manganese on other
499
properties, in ordinary steels with these elements, the
hardness and strength fall off gradually with the increase
in tempering temperature. This is not true for another class
of elements.
Fig. 5 illustrates the softening patterns of a series of
chromium steels and a plain carbon steel with about the
same carbon content, 0.35%. Chromium contents were
0.50%, 3.0%, 4.0%, and 12.0%. In chromium steels, two
chromium carbides are very often encountered: Cr7C6
(Trigonal) and Cr23C6 (complex cubic). The normal car-
bide sequence during tempering is expressed as follows:
Matrix ! ðFeCrÞ3 C ! Cr7 C3 ! Cr23 C6
Chromium is a weaker carbide former than vanadium,
which is shown by the fact that Cr7C3 does not normally
occur until the chromium content of the steel exceeds 1
wt.% at a carbon level of ~0.2 wt.%. The heating for
500 carbide; the quenching developed nearly, though not quite,
the quenching was such as to insure the solution of sub-
stantially all the maximum martensitic hardness possible
for the compositions. The 12.0% Cr steel, a typical cutlery
stainless steel, is particularly interesting because it defi-
nitely preserves a moderate amount of retained austenite,
which is sufficient to lower the initial hardness below that
of the other members of the series. The release of this
retained austenite may possibly have augmented the effect
of secondary hardness (Fig. 6).
The carbide-forming elements, although powerful in
deep-hardening influence, are not so effective in retaining
austenite as that of nickel and manganese. The effect of a
stronger carbide former, molybdenum, is shown in Fig. 7.
The effect of a still smaller addition of molybdenum
(0.24%) in a fine-grained 0.400.45% C steel is detect-
Carbon–Iron—Carburized
able in the softening characteristics shown in Fig. 8. Even
with ~1.0% Cr and 0.2% Mn makes its presence felt in
tempering, as shown in Fig. 9, which compares steels 5140
and 4140 with all elements except molybdenum at almost
identical values. The superimposition of the molybdenum
effect on that of 0.50% Cr is shown in Fig. 10. With a
uniform 2.0% Cr and 0.35% C, the reluctance to soften is
marked indeed as the molybdenum content increases and
is shown in Fig. 11. The alloys having 4.05.0% Cr sus-
tain a high hardness in proportion to molybdenum content
and present a series of steels with exceptional retention of
strength after a high reheating temperature (Fig. 12).
Vanadium is a strong carbide former and, in steel with
as small as 0.1 wt.% V, the FCC vanadium carbide VC is
formed. It is not of stoichiometeric composition, being
often nearer V4C3, but with other elements in the solid
solution within the carbide.[8] Vanadium carbide forms as
small platelets, which are initially <5 nm across and not
>1 nm thick.
Many steels containing vanadium will exhibit exten-
sive vanadium carbide precipitation on tempering,
 500 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering

Table 1 The effect of common alloying elements during tempering.

Element Tempering
Carbon In plain carbon steels, C precipitates from martensite as iron carbide. With the increase in temperature,
the hardness decreases as the carbides coarsen. At a high temperature (e.g., 600
C) spheroidal carbides
are formed. Alloying elements reduce the carbide coarsening rate and increase the temper resistance.
With carbide-forming elements, the tempering resistance is increased substantially and with sufficient
element a fine dispersion of carbides promotes secondary hardening.
Silicon Si increases the temper resistance, especially in combination with molybdenum. It has a solid solution
strengthening effect in ferrite.
Manganese Mn has a very weak effect on temper resistance and may promote grain boundary segregation of
elements promoting temper embrittlement (e.g., P).
Phosphorus P migrates rapidly to grain boundaries and interfaces and is a primary cause for temper embrittlement
in ferritic steels.
P may be added up to ~0.1 wt.% in certain austenitic stainless steels age hardened by carbide
precipitation, where it is believed to assist intergranular rather than intergranular precipitation of
carbide.
Sulfur No effect.
Nickel Compared with the carbide-forming elements, nickel has little effect on the temper resistance, but at
higher levels it may modify the precipitation of alloy carbides. Because nickel lowers the Ac1
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temperature, the maximum utilizable tempering temperature is lowered as nickel increases. For
example, in a 4 wt.% Ni alloy, especially those containing larger amounts of carbon, reversion to
austenite may occur as low as 680
C. In 9 wt.% Ni alloys this effect used to form a stable retained
austenite on tempering (for toughness). In 18 wt.% Ni maraging steels, reversion of austenite to
martensite occurs at even lower temperatures.
Carbide forming elements (Cr, Carbide-forming elements increase the resistance to tempering by modifying the precipitation of
Mo, V, W) carbides, which form as alloy carbides. Because the carbides formed are stable, their coarsening rate is
reduced. The composition of the carbides formed varies with tempering temperature. They tend to be
carbon-rich at lower temperatures, where the alloying element diffuses less easily, with increasing
alloy in the carbide as the tempering temperature increases. In a multi-alloy system, the relative
proportion of different alloys in the carbides changes with tempering temperature.
Secondary hardening from the precipitation of fine carbides will occur in steels rich in Cr, Mo, V, and
W with sufficient carbon. Temper resistance and the propensity for secondary hardening increases in
tile order shown. The temperature for optimum secondary hardening with increasing carbide stability.
Molybdenum Mo has a stronger effect than Cr on temper resistance. Particularly, it delays the onset of temper
embrittlement, and therefore, it is used in nitriding steels, for example, with the dual role of forming
nitrides.
Vanadium Vanadium has a very strong effect on the temper resistance of quenched and tempered steels. The
effect is most noticeable in steels tempered at high temperatures (550650
C, whereas the effects of
Carbon–Iron—Carburized

Cr and Mo would appear at lower temperatures.

Tungsten
Boron Boron has no effect on temper resistance, and it precipitates with the carbide.
Aluminum When present in nitriding steels, up to ~1 wt.%, Al combines with the nitrogen to precipitate as a
nitride, producing an intense hardening reaction.

because of the stability of this carbide, not only with
respect to cementite but also with respect to the several
chromium carbides and molybdenum carbide (Fig. 20).
Because of its ability to maintain a fine carbide dispersion,
even at temperatures approaching 700
C, vanadium is an
important constituent of steels for an elevated temperature
service.
A strong resistance to softening at temperatures
~1000
F is offered by small proportions of vanadium,
provided the vanadium-rich carbide is first largely
dissolved (Fig. 13). The vanadium effect is observable
even when the two steels shown in Fig. 14 are quenched
from 1625
F. The remarkable resistance to softening con-
tributed by vanadium is also illustrated in Fig. 15. The
effects of the solution of molybdenum in austenite are
shown in Figs 16 and 17. The effects of high heating
temperature on the hardening of the steels with consider-
able amount of carbide-forming elements, such as vana-
dium and molybdenum, are shown in Figs. 18 and 19.
The Formation of Alloy Carbides and Secondary
Hardening
A number of familiar alloying elements in steels form
carbides that are thermodynamically more stable than
cementite. It is also true for a number of nitrides and
borides. N and B are increasingly used in steels in small
but significant concentrations. The enthalpies of formation
of some of these compounds are shown in Fig. 20, in
which iron carbide is the least stable compound placed on
 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering 501

Temperature (°C) Temperature (°C)

100 200 300 400 500 600 700 100 200 300 400 500 600 700
65 60
0.50 – 0.55% C

60 55

3.8% Si
55 50

2.3% Si
50 45

Hardness, rockwell C
SAE 2340 (3.5% Ni)
Hardness, rockwell C

45 40
SAE 1040
40 35
1.3% Si
35 30
0.5% Si
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30 25

25 20
1 hr 0.40 – 0.45 %C
20 15
0 200 400 600 800 1000 1200
0 200 400 600 800 1000 1200 Tempering temperature (F)

Tempering temperature (F)

Fig. 2 Softening, with the increase in tempering temperature,
of quenched 0.500.55% C steels as influenced by the silicon
content.
the right-hand side of the diagram. All the alloying ele-
ments, such as Cr, Mo, V, W, and Ti, form carbides with
Fig. 3 Softening, with the increase in tempering temperature,
of quenched 0.400.45% C steels as influenced by ~3.5% Ni.
Mo, V, W, Ti, and Cr steels at a higher alloy
concentration.[8]
This secondary hardening process is a type of age-
hardening reaction, in which a relatively coarse cementite

substantially higher enthalpies of formation, whereas the
elements Ni, Co, and Cu do not form carbide phases. Mn
is a weak carbide former, which is found in a solid solu-
tion in cementite and not in a separate carbide phase.
It would be expected that when strong carbide-forming
elements are present in steel in sufficient concentration,
their carbides would be formed in preference to cementite.
Nevertheless, during the tempering of all alloy steels,
alloy carbides are not formed until the temperature range
of 500600
C because below this temperature, the metal-
lic alloying elements cannot diffuse sufficiently rapidly to
allow alloy carbides to nucleate. Higher temperatures are
needed for the necessary diffusion of the alloying ele-
ments before the nucleation and the growth of the alloy
carbides, and for most of the carbide-forming elements,
this is in the range of 500600
C.
The formation of alloy carbides between 500
C and
600
C is accompanied by a marked increase in strength,
which is often in excess of that of the as-quenched mar-
tensite (Fig. 21). This phenomenon, which is referred to as
secondary hardening, is best shown in steels containing
Carbon–Iron—Carburized
dispersion is replaced by a new and much finer alloy
carbide dispersion. The process is both time- and
temperature-dependent; therefore, both variables are often
combined in a parameter as follows:
P ¼ T ðk þ logtÞ
where T is the absolute temperature; t is the tempering
time in hours; and k is a constant, which is ~20 for alloy
steels. It is usually referred to as the HollomanJaffe
parameter, and this can be plotted against hardness to give
one typical curve for a particular steel (Fig. 22).
Noncarbide-forming elements, such as Ni, Co, and Si, do
not give secondary hardening.
The circumstances under which Cr, Mo, W, V, and Ti
retard softening are most easily conjectured by regarding
tempering as a classical precipitation-hardening process,
including the “overaging” phenomenon. In the presence of
a dissolve element, on heating to 500600
F, martensite
softens in the same manner as that of a corresponding
carbon steel, although perhaps to a lesser degree. Let us
 502 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering

Temperature (°C) Temperature (°C)

100 200 300 400 500 600 700 100 200 300 400 500 600 700
60 60

55 55

50 50 2.9% Cr

SAE T1340 (1.75% Mn) 1% Cr

45 45
Hardness, rockwell C

Hardness, rockwell C
Carbon steel
40 40
SAE 1040 (0.75% Mn)
35 35

30 30
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25 25

20 20
0.40 – 0.45%C 0.40 – 0.45% C
15 15
0 200 400 600 800 1000 1200 Q 200 400 600 800 1000 1200
Tempering temperature (F) Tempering temperature (F)

Fig. 4 Softening, with the increase in tempering temperature, Fig. 6 Softening, with the increase in tempering temperature,
of quenched 0.400.45% C steels as influenced by an increase in of quenched 0.400.45% C steels as influenced by the chro-
manganese from ~0.75% to 1.75%. mium content.

Temperature (°C)
Temperature (°C)
200 300 400 500 600 700
60 200 300 400 500 600 700
60
Carbon–Iron—Carburized

12%Cr 5% Mo

50
4%Cr 50 2% Mo
Hardness, rockwell C
Hardness, rockwell C

2%Cr
40 0.5%Cr 40
0.5% Mo

Carbon steel
30 30
Carbon steel

20 20

0.35% C 0.35% C

10 10
0 400 600 800 1000 1200 Q 400 600 800 1000 1200
Tempering temperature (F) Tempering temperature (F)

Fig. 5 Softening, with the increase in tempering temperature, Fig. 7 Softening, with the increase in tempering temperature,
of quenched 0.35% C steels as influenced by the chromium of quenched 0.35% C steels as influenced by the molybdenum
content. content.
 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering 503

Temperature (°C) Temperature (°C)

100 200 300 400 500 600 700 100 200 300 400 500 600 700
60 60

0.40 – 0.45% C
55 55

50 50
0.24% Mo
45 45
SAE 4140

Hardness, rockwell C
Hardness, rockwell C

SAE 1040
40 40
SAE 5140
35 35

30 30
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25 25

20 20 1 hr
0.40 – 0.45% C
15 15
0 200 400 600 800 1000 1200
0 200 400 600 800 1000 1200
Tempering temperature (F)
Tempering temperature (F)

Fig. 8 Softening, with the increase in tempering temperature, Fig. 9 Softening, with the increase in tempering temperature,
of quenched 0.400.45% C steels as influenced by ~0.24% Mo. of quenched 0.400.45% C, 1.0% Cr steels as influenced by
0.20% Mo.

consider the softening of a 0.35% C, 5.0% Mo steel at

several temperatures, as shown in Fig. 36. Between ~2
Temperature (°C)
and 1500 hr of reheating, the specimen held at 660
F was
softened more than that of the one tempered at 840
F. 60
200 300 400 500 600 700
Heating at 1200
F produced a harder product than that

Carbon–Iron—Carburized
5% Mo
heated at 660
F when the tempering interval ranged
between ~10 sec and 20 min.
50
In the 4.0% Cr steel shown in Fig. 23, considerable 2% Mo
retardation is evident. Tempering for a few minutes at
840
F causes retention of a hardness greater than that for
Hardness, rockwell C

0.5% Mo
the same interval at 660
F. When 2.0% Mo is present 40
along with 5.0% Cr, the different retarding effects of the 0% Mo
two elements appear to supplement each other and result
in the softening effects recorded in Fig. 24, in which tem- 30
pering at 840
F brings about a hardness superior to that
tempering at 660
F over a wide range of time intervals.
The more or less constant level of hardness maintained
20
over long periods is seemingly a feature of the combina-
tion of two or more alloying elements, for 2.0% Mo alone 0.35% C
0.50% Cr
brings a sharper rise in secondary hardness, as shown in
10
Fig. 25. With 2.0% Cr, even 0.5% Mo contributes a Q 400 600 800 1000 1200
marked reluctance to softening at both 840
F and 1020
F Tempering temperature (F)
(Figs. 26 and 27). Finally, in Fig. 28, a room-temperature
hardness in excess of HRC55 is found in a 5.0% Cr, 5.0% Fig. 10 Softening, with the increase in tempering temperature,
Mo steel after 1000 hr at 840
F, whereas the same of quenched 0.35% C, 0.50% Cr steels as influenced by molyb-
quenched steel held at only 660
F is considerably softer, denum content.
 504 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering

Temperature (°C) Temperature (°C)

200 300 400 500 600 700 100 200 300 400 500 600 700
60

60 55 0.40 – 0.45%C
1% Cr
5% Mo

2% Mo 50
50
0.5% Mo
Hardness, rockwell C

Hardness, rockwell C
45
SAE 6140
40 0% Mo
40

SAE 5140
30 35

30
20
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0.35% C 25 1 hr
2% Cr
10 20
Q 400 600 800 1000 1200 Q 200 400 600 800 1000 1200
Tempering temperature (F) Tempering temperature (F)

Fig. 11 Softening, with the increase in tempering temperature, Fig. 13 Softening, with the increase in tempering temperature,
of quenched 0.35% C, 2.0% Cr steels as influenced by molybde- of quenched 0.400.45% C, 1.0% Cr steels as influenced by
num content. 0.16% V. High quenching temperature applied to the vanadium
steel.

because the temperature is too low to develop secondary

Temperature (°C)
hardening in 1000 hr.
200 300 400 500 600 700
During increasing temperatures, the Fe3C formed from
ε-carbide between 395
F and 575
F grows larger until at
60 750
F. It has the form of rods ~3000 Å long and few
5% Mo
hundred Angstroms thick. Above 750
F, these rods begin
Carbon–Iron—Carburized

2% Mo to dissolve and new carbides that are <50 Å in size appear

in the microstructure. This stage of visibility is usually at
50
0.5% Mo or just beyond the condition of peak hardness and is shown
Hardness, rockwell C

in Fig. 29 for a special molybdenumtantalum steel.

0% Mo Vanadium in amount of 1.0% will cause secondary hard-
40 ening. Chromium often causes only a retardation of soft-
ening. Vanadium is known to form a dispersed array of
small carbides that contribute considerably to hardness
30 and do not coarsen easily (Fig. 30); chromium carbide
coarsens significantly in 100 hr at 950
F. Molybdenum
acts slightly similar to vanadium.
20
0.35% C
4 – 5% Cr STRUCTURAL CHANGES ON TEMPERING
10
Q 400 600 800 1000 1200 Tempering is a thermal martensitic treatment of quenched
Tempering temperature (F) steels. The basic process that takes place during tempering
is martensite precipitation. The first structural change dur-
Fig. 12 Softening, with the increase in tempering temperature, ing tempering is carbon segregation at dislocations. The
of quenched 0.35% C, 4.05.0% Cr steels as influenced by the second stage of tempering is the precipitation of interme-
molybdenum content. diate
 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering 505

Temperature (°C) Temperature (°C)

100 200 300 400 500 600 700 100 200 300 400 500 600 700
60 70

0.40 – 0.45% C 18-4-1 high speed steel

55 1% Cr 65

6.0% V, 1.0% C
50 60
SAE 6140
Hardness, rockwell C

45 55

SAE 5140 0.27% V, 0.9% C

Hardness, rockwell C
40 50

0.9% C
35 45

30 40
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1 hr 35
25

30
20
Q 200 400 600 800 1000 1200 1 hr
Tempering temperature (F) 25

Fig. 14 Softening, with the increase in tempering temperature,

20
of quenched 0.400.45% C, 1.0% Cr steels as influenced by 200 400 600 800 1000 1200
0.16% V. Both steels are quenched from 1625
F. Tempering temperature (F)

ε-carbide with a hexagonal lattice, which forms under

heating above 100
C (212
F). During the third stage,
cementite precipitates above ~250
C (~480
F). At the
final stage of tempering above 350
C (660
F), cementite
particles coagulate and spheroidize.
Consider the changes that take place in martensite
and austenite structures at different stages of tempering.
Fig. 15 Softening, with the increase in tempering temperature,
of quenched 0.90% C steels as influenced by 0.27% V. For
comparison, the softening of a 1.0% C, 6.0% V steel, a typical
high-speed steel, is also shown.
precipitation of carbon was found to occur at 400
C
(750
F). A further increase in temperature leads only to

During the first stage, beginning at 80
C (175
F) and up
to 170
C (330
F), the c parameter of the martensite lattice
decreases. The ratio c/a becomes close to unity. Tetrago-
nal martensite transforming to a cubic form is called
tempered martensite. The decrease of tetragonality is
connected with the precipitation of carbon from the
solution.
Heating steels over 200
C (390
F) and up to 300
C
(570
F) activates the transformation of retained austenite
to a heterogeneous mixture composed of a supersaturated
α-solution and the Fe3C carbide. This means that the
retained austenite transforms to a tempered martensite as
follows:
Feγ ðCÞ ! Feα ðCÞ þ Fe3 C
By the end of transformation (~300
C; 570
F), the
retained austenite contains about 0.15–0.20% C.
Heating above 300
C (570
F) leads to a further pre-
cipitation of carbon and the relaxation of internal
stresses arising from previous transformations. Complete
Carbon–Iron—Carburized
coagulation of ferrite and cementite particles.
During tempering, cementite acquires a globular form
when a ferritecementite mixture is formed from martens-
ite. The different forms of cementite in the ferritecementite
mixture determine the difference in properties.
TEMPERING OF MARTENSITE
The influence of alloying elements on transformations
during tempering depends on whether they dissolve in
ferrite and cementite or form special carbides. The diffu-
sion mobility of atoms of alloying elements dissolved in
α-Fe by the substitutional method is many orders of mag-
nitude lower than the diffusion mobility of carbon atoms
dissolved by the interstitial method. Therefore, at a tem-
perature below 400
C (750
F), no diffusion redistribution
of alloying elements in the matrix takes place. First the
ε-carbide and subsequently the cementite precipitate
from the α-solid solution. The concentration of alloying
 506 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering

Temperature (F) 2600

Grain coarsening begins 1400
400 600 800 1000 1200

2400 1300

60

Quenching temperature (°C)

Quenching temperature (F)
2200 1200

Q Carbides dissolved
2000 1100
Hardness, rockwell C

50
1000
1800
Incomplete solution

40 900
1600

800
To secure Rockwell C 60 after quench
1400
30
1% C 700
0.35 C 1Hr 1200
5% Mo 0 1 2 3 4 5 6
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20 Vanadium (%)
0 200 300 400 500 600 700
Tempering temperature (°C)
Fig. 18 Heating temperature range for 1.0% C steels of
indicted vanadium content. Upper curve: maximum to just avoid
Fig. 16 Softening, with the increase in tempering temperature, undue coarsening; lower curve: maximum to secure hardness
of quenched 5.0% Mo steel as influenced by the extent of carbide HRC 60 with drastic quench.
solution. 2200
F quench (upper curve); 1740
F quench (lower
curve).
elements in them is the same as that in martensite. Atoms
of alloying elements in the ε-carbide and cementite lattice
formed below 400
C (750
F) partly replace iron atoms.
Complex carbides such as (Fe, Cr)3C and (Fe, V)3C are
formed. The structural changes that occur on tempering
Temperature (F)
may be considered to take place in four stages:
400 600 800 1000 1200
Carbon–Iron—Carburized

60
Q Carbide dissolved
Hardness, rockwell C

50
Incomplete solution

40

30
0.35% C
5% Cr 1hr
5% Mo
20
0 200 400 600 800 1000 1200
Tempering temperature (°C)

Fig. 17 Softening, with the increase in tempering temperature, Fig. 19 Softening, with the increase in tempering temperature,
of quenched 5.0% Mo, 5.0% Cr steel as influenced by the extent of quenched CrMoV steel as influenced by the degree of
of carbide solution. 2200
F quench (upper curve); 1740
F carbide solution, which, in turn, is dependent on the heating
quench (lower curve). temperature.
 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering 507

TiB2 60
Logarithmic scale
ZrB2 NbB2
HfB2 TaB2
55
840 F
160 120 80 40 0
Cr23C6
VCX Cr7C3 50 660 F
TiC Fe3C
(Cr3C2)

Hardness, rockwell C
ZrC NbC Mo2C 45
(Nb2C) (MoC)
HfC TaC W2C
40
(Ta2C) (WC) 1020 F

35
160 120 80 40 0
TiN VN Cr2N
1200 F
30
ZrN NbN (Mo2N)?
0.35%C
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5% Mo
HfN TaN 25
Q 6 1 10 1 10 100 1000
Sec Min Hr
160 120 80 40 0
Time at temperature
–ΔH298K (kJ mol–1)

Fig. 22 Softening, with the increase in time, at four tempera-

Fig. 20 The enthalpies of the formation of carbides, nitrides, tures in a quenched 5.0% Mo steel.
and borides. Source: From Irving and Pickering.[14]
Source: From Schick.[13]

Logarithmic scale
60
1h at temperature (°C)
400 500 600 700
55

600

Carbon–Iron—Carburized
50 640 F
Hardness, rockwell C

500 45
840 F
Hardness (HVN)

3.07% Mo
2.05% Mo 40
400 1.50% Mo
0.90% Mo
0.47% Mo
35

300
30
1020 F

200 25
0.35% C
4% Cr
20
14 16 18 20 22
Q 6 1 10 1 10 100 1000
T(20+log t) × 10–3 Sec Min Hr
Time at temperature
Fig. 21 The effect of molybdenum on the tempering of
quenched 0.1 wt.% C steels. Fig. 23 Softening, with the increase in time, at three tempera-
Source: From Irving and Pickering.[14] tures in a quenched 4.0% Cr steel.
 508 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering

60
Logarithmic scale Logarithmic scale
60
55

55 840 F
50
660 F 840 F

Hardness, rockwell C
50
1020 F 45
660 F
Hardness, rockwell C

45
40
1020 F
40
35
1200 F
35
30
0.35% C
Downloaded by [Cornell University] at 21:59 02 October 2016

30 2% Mo
1200 F
25
Q 6 1 10 1 10 100 1000
25
0.35% C Sec Min Hr
2% Mo Time at temperature
5% Cr
20
Fig. 25 Softening, with the increase in time, at four tempera-
tures in a quenched 2.0% Mo steel.
Q 6 1 10 1 10 100 1000
Sec Min Hr
Time at temperature

Fig. 24 Softening, with the increase in time, at four tempera-

tures in a quenched 5.0% Cr, 2.0% Mo steel.
Logarithmic scale
60
 Stage 1: up to 250
C—the precipitation of ε-iron car-
bide; partial loss of tetragonality in martensite
Carbon–Iron—Carburized

 Stage 2: between 200
C and 300
C—the decomposi- 55

tion of retained austenite
 Stage 3: between 200
C and 350
C—the replacement
2% Cr, 2% Mo
of ε-iron carbide by cementite; martensite loses
Hardness, rockwell C

50
tetragonality
2% Cr, 0.5% Mo
 Stage 4: above 350
C—cementite coarsens and
45
spheroidizes; recrystallization of ferrite.[8]
2% Cr
Stage 1. Martensite formed in medium- and high-carbon 40
steels (0.31.5 wt.% C) is not stable at room temperature
because interstitial carbon atoms can diffuse in the tetrag-
onal martensite lattice at this temperature. At this stage, 35
fine particles of the carbide phase (ε-carbide) of composi-
tion about Fe2.4C precipitate, with the corresponding for- 30
mation of low-carbon martensite (Fig. 31). This low-
0.35% C
carbon martensite grows at the expense of the high-carbon
martensite until, at the end of this stage, the structure 25
Q 6 1 10 1 10 100 1000
consists of retained austenite, ε-carbide, and martensite of Sec Min Hr
reduced tetragonality. The first stage of transformations in Time at 840 F
martensite (the formation of tempered martensite) at a
temperature of <150
C (300
F) is affected little by Fig. 26 Softening, with the increase in time, at 840
F in three
alloying elements. At this stage of tempering, nucleation quenched 2.0% Cr steels, with 0, 0.5, and 2.0% Mo.
 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering 509

60
Logarithmic scale Logarithmic scale
60
840 F
55

55

50
660 F
50
2% Cr, 2% Mo
45
45 1020 F
Hardness, rockwell C

Hardness, rockwell C
40
40

2% Cr, 0.5% Mo
35 35
2% Cr

30 30
Downloaded by [Cornell University] at 21:59 02 October 2016

1200 F

25
25
0.35% C
0.35% C 5% Mo
20 5% Cr
20

15
Q 6 1 10 1 10 100 1000 Q 6 1 10 1 10 100 1000
Sec Min Hr Sec Min Hr
Time at 1020 F Time at temperature

Fig. 27 Softening, with the increase in time, at 1020
F in three Fig. 28 Softening, with the increase in time, at four tempera-
quenched 2.0% Cr steels, with 0, 0.5, and 2.0% Mo. tures in a quenched 5.0% Cr, 5.0% Mo steel.

of carbide particles depends basically on the supersatura-

tion of the α-solution with carbon. At the end of Stage 1,

Carbon–Iron—Carburized
the martensite still possesses a tetragonality, indicating a
carbon content of ~0.25 wt.%. It follows the fact that
steels with lower carbon contents are unlikely to precipi-
tate ε-carbide. This stage of tempering possesses an acti-
vation energy between 60 and 80 kJ mol1, which is in the
right range for diffusion of carbon in martensite.
Stage 2. During this stage, any retained austenite in the
steel begins to transform isothermally to bainite. This
stage of martensite precipitation is strongly influenced by
a number of alloying elements. They retard the growth of
carbide particles, and consequently, supersaturation of the
α-solution with carbon is preserved. Thus, the state of
tempered martensite is retained up to temperatures of
450–500
C (840–930
F). The additions of Cr, W, Mo, V,
Co, and Si bring about this effect.
Stage 3. The third stage is marked by the formation of
cementite platelets. The precipitation of cementite is
accompanied by a dissolution of the ε-carbide phase so Fig. 29 The electron microstructure or a 0.2% C, 3.6% Mo,
that the martensites loses its remaining tetragonality and 0.20% Ta steel quenched and tempered 10 hr at 1100
F. The
becomes BCC ferrite. The twins occurring in the higher acicular particles are Mo2C, and the massive particles are
carbon martensites are also sites for the nucleation and M6C, · 12,000.
 510
Downloaded by [Cornell University] at 21:59 02 October 2016
Fig. 30 The electron microstructure of a 0.23% C, 0.97% V
steel quenched and tempered 100 hr at 950
F. Note the very
small acicular particles of V4C3, 200,000.
growth of cementite, which tends to grow along the twin
boundaries, forming colonies of similarly oriented lath-
shaped particles (Fig. 32 Steels) of [112]a habit, which
can be readily distinguished from that of the normal
Widmanstätten habit.[8] The orientation relationship with
the ferritic matrix is the same in both these cases.
The third site for the nucleation of cementite is the
grain boundary regions (Fig. 33), which include both the
interlath boundaries of the martensite and the original
austenite grain boundaries. The cementite can form as
very thin films that are difficult to detect, which gradually
spheroidize to give rise to well-defined particles of Fe3C
Carbon–Iron—Carburized
in the grain boundary regions.
0.5 μm
Fig. 31 Fe-0.8C quenched and tempered at 250
C. The
precipitates of ε-carbide and cementite.
Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering
0.5 μm
Fig. 32 Fe-0.8C quenched and tempered at 450
C Fe3C
growing along the twin boundaries.
Stage 4. At this stage, the cementite particles undergo a
coarsening process and essentially lose their crystallo-
graphic morphology, becoming spheroidized. The coars-
ening took place between 300
C and 400
C, whereas
spheroidization took place at a temperature of 700
C. At
the higher end of this range of temperature, the martensite
lath boundaries are replaced by more equiaxed ferrite
grain boundaries by a process that is best described as
recrystallization (Fig. 34).[8] The original martensite lath
boundaries remain stable up to ~600
C; however, in the
range of 350600
C, there is considerable rearrangement
of the dislocations within the laths and at those lath bound-
aries that are essentially low-angle boundaries.
This process, which is essentially one of the recoveries,
is replaced between 600
C and 700
C by recrystallization,
which results in the formation of equiaxed ferrite grains
with spheroidal Fe3C particles in the boundaries and
1 μm
Fig. 33 Fe-0.8C quenched and tempered at 250
C. The grain
boundary precipitation of cementite.
 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering 511

enable the improvement in ductility to be achieved at higher

tempering temperatures.
Alloying elements lower the Ms temperatures, and
consequently, greater stresses and distortion are intro-
duced during quenching. This can be minimized by
austempering and martempering. Alloying elements
should be chosen to produce the maximum retardation of
tempering for a minimum depression of Ms. Table 2 sum-
marizes that carbon should be as low as possible; silicon
and cobalt are particularly effective; and molybdenum is
the preferred element among the molybdenum, tungsten,
and vanadium group, as it is easier to take into solution
than vanadium and is cheaper than tungsten.
A delay in martensite precipitation can be explained by
two factors. Firstly, one of the alloying elements lowers
the rate of carbon diffusion in the α-solution. Secondly,
the other elements can increase the strength of interatomic
bonds in the α-solution lattice. This will prevent the atoms
Downloaded by [Cornell University] at 21:59 02 October 2016

from crossing the α-solution carbide interface. Both fac-

Fig. 34 Fe-0.17C water quenched from 900
C and tempered
5 hr at 650
C. Spheroidized Fe3C in equiaxed ferrite.
within the grains. This process occurs most readily in low-
carbon steels (Fig. 34). At higher carbon contents, the
increased density of Fe3C particles is much more effective
in pinning the ferrite boundaries; therefore, recrystalliza-
tion is much more sluggish. The final process is the con-
tinued coarsening of the Fe3C particles and gradual ferrite
grain growth (Fig. 34).
The degree to which these four stages overlap will
depend on the temperature of the annealing and the carbon
content. The final structure produced will be governed by
the initial choice of steel and the properties, and hence
tors impede precipitation of martensite.
Alloying elements affect carbide transformation tem-
pering under 450
C (840
F) when their diffusion move-
ment becomes possible. In this case, special carbides are
formed. With an increase in the tempering temperature,
intermediate metastable carbides stabilize. For example,
when molybdenum and tungsten steels are tempered,
Me2C (Mo2C and W2C) is formed first, then Me23C6
appears, and finally Me6C emerges. The sequence of their
formation can be expressed as follows:
Fe3 C ! Me2 C þ Me23 C6 ! Me6 C
Alloying elements affect the coagulation rate of carbide
particles. Nickel accelerates the coagulation rate, whereas
chromium, molybdenum, vanadium, and other elements

Carbon–Iron—Carburized
thermal treatment, required. Alloying elements, except Cr, slow it down. Owing to the low diffusion rate of alloying
affect the tempering of martensite. Plain carbon steels soften elements, the coagulation of special carbides proceeds
above 100
C owing to the early formation of ε-carbide, slowly. Even alloyed cementite (Fe, Cr)C3 coagulates
whereas in Si-content steels the softening is delayed to much more slower than Fe3C in a carbon steel.
above 250
C, as Si stabilizes ε-carbide and delays its trans- The additions of alloying elements slow down recrys-
formation to cementite. Alloying additions (Table 2) thus tallization and polygonization. The atoms of these ele-
ments form impurity atmospheres near dislocations and
prevent their movement during polygonization. The dis-
Table 2 The influence of alloying elements on tempering. perse particles of special carbides retard the movement of
The retardation in The ratio of retardation large-angle boundaries during polygonization.
tempering per 1.0% of tempering to
Element addition depression of Ms
Carbon 40 Negative THE TRANSFORMATION OF RETAINED
Cobalt 8 >8
AUSTENITE (SECONDARY TEMPERING)
Chrome 0 0
Manganese 8 0.24
Molybdenum 17 0.8 Alloying elements have the greatest influence on the mar-
Nickel 8 0.5 tensite transformation temperature. This affects the
Silicon 20 1.8 amount of retained austenite in alloy steel. Some elements
Vanadium 30 >1.0 (e.g., cobalt) raise the point Ms, thus decreasing the
Tungsten 10 0.9 amount of retained austenite. Others (e.g., silicon) have
Source: From Hosford.[7] no influence on Ms. However, the majority of elements
 512 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering

decrease the martensite point and increase the amount of eliminate the retained austenite. To obtain a complete
retained austenite in quenched steel. Up to 60% of transformation, it is necessary to perform double temper-
retained austenite is left in high-carbon steels during ing. Double tempering favors additional precipitation of
quenching and 10–15% in a large number of structural special carbides and decreases the degree of austenite
alloy steels. alloying. This causes another increase in the transforma-
During tempering of carbon and low-alloy steels, tion temperature Ms. Sometimes, multiple tempering is
retained austenite transforms over the temperature interval required to realize the most complete transformation of
of 230–280
C (440–540
F) or at lower temperatures if the retained austenite.
holding time is extended. Alloying elements, especially Cr
and Si, inhibit that transformation, shifting it to higher
temperatures and longer tempering time. The transforma-
TIMETEMPERATURE RELATIONSHIPS IN
tion kinetics of retained austenite during tempering is sim-
TEMPERING
ilar to those of undercooled austenite. Steels with two
clearly distinguished transformation ranges (pearlite and
The kinetics of structural transformations during temper-
bainite) also exhibit two regions of fast transformation of
ing is described by temperaturetime curves that are sim-
retained austenite during tempering that are separated by a
ilar to the curves shown in Fig. 35. After quenching from
zone of high stability of retained austenite.
900
C (1650
F), steels with 0.7% C, 1% Cr, and 3% Ni
When alloy steels are tempered at 500–600
C (930–
contain 30% of retained austenite. When plotting the
Downloaded by [Cornell University] at 21:59 02 October 2016

1110
F), in many cases, the transformation of retained

curve and diagram, the nontransformed austenite (30%)
austenite is not complete. The retained austenite that did
was taken to be 100%. It is found that at 600
C (1110
F),
not precipitate at these tempering temperatures transforms
5% of primary austenite transforms in 7 min and 5% of
during cooling from those temperatures (secondary
retained austenite transforms in 30 sec. However, after
quenching). The phenomenon is most pronounced in high-
10–15% of the retained austenite is transformed, the trans-
speed and high-chromium steels. The secondary martensite
formation rate of retained austenite becomes smaller than
transformation during cooling after tempering is caused by
that of the initial austenite. The transformation of retained
the depletion of austenite in carbon and alloy elements in
austenite is not complete. It is inhibited on reaching
the course of tempering. As a result, the temperature of
45% at 500
C (930
F) and 60% at 550
C (1020
F). The
retained austenite Ms during cooling is increased.
retained austenite that does not precipitate immediately at
Secondary quenching (double tempering) is also
these tempering temperatures transforms during cooling
observed in structural steels. It takes place if the primary
after tempering. The transformation rate of retained aus-
quenching is accompanied by a partial intermediate trans-
tenite in the intermediate range is much higher than that of
formation, leading to an increase in the carbon content of
the initial austenite; about 25% of the initial austenite
austenite. During tempering at 500–550
C (930–1020
F),
transforms at 300
C (570
F) in 75 min and the same
retained austenite with a high content of carbon yields
amount of retained austenite in 15 sec and about 75% of
carbides intensively, and the martensite transformation
the initial austenite transforms in 220 min and 75% of the
Carbon–Iron—Carburized

temperature Ms increases. As a result, the secondary mar-

retained austenite in 9.5 min. In a typical structural steel
tensite transformation takes place during cooling after
(0.37% C, 1% Cr, 1% Mn, and 1% Si), 5% of the initial
tempering.
austenite transforms in 19 min at 600
C (1110
F) or in
In high-alloy steels, e.g., high-speed steels, even a very
5 min at 400
C (750
F) and 5% of the retained austenite at
long tempering at high temperatures does not completely
the same temperature transforms in a few seconds.

600 1
2
500
25%
75
t,8C 400 5 25 5
25
300 75

200 5 25 75

100

1 23 5 10 20 30 50 1 235 10 20 30 1 23 5 10
s m h
Fig. 35 The timetemperature transformation
Time
curves.
 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering
Another specific feature of the retained austenite trans-
formation of this steel in the intermediate range is the
lowering of the transformation limit. For example, at
350
C (660
F), 70% of the initial austenite and only 40%
of the retained austenite transform. This difference
decreases with an increase in temperatures.
THE ESTIMATION OF HARDNESS AFTER
TEMPERING
Hardness decreases noticeably when alloy steels and addi-
tion-free steels are subjected to tempering at 500–600
C
(930–1110
F). This decrease in hardness is due to the
precipitation of martensite and coagulation of cementite.
However, when the tempering temperature is higher, the
hardness of steels with additions of titanium, molybde-
num, vanadium, or tungsten increases. This phenomenon
Downloaded by [Cornell University] at 21:59 02 October 2016
is called secondary hardening.
Secondary hardening is caused by the formation of
clusters of atoms of alloying elements and carbon (a max-
imum hardness often corresponds to the clusters) and the
replacement of relatively coarse particles of cementite by
much more disperse precipitates of special carbides (TiC,
VC, Mo2C, and W2C). When these particles coagulate,
hardness decreases. The particles of Me6C are rather
coarse and do not add to strengthening.
The chromium additive causes a small secondary hard-
ening. This is connected with a rapid coagulation of the
Cr7C3 carbide at 550
C (1020
F) as opposed to Mo2C and
especially W2C. During secondary hardening, an increase
in the yield stress is accompanied by an increase in tough-
ness owing to dissolution of coarse cementite particles.
THE EFFECT OF TEMPERING ON MECHANICAL
PROPERTIES
The manner in which structural changes that take place
during tempering affect the properties of steels depends on
the particular tempering conditions. The general tendency
of changes in mechanical properties of carbon steels dur-
ing tempering is that as the tempering temperature is ele-
vated, the strength parameters σ e and σ 0.2 (fracture stress
and yield stress) decrease, whereas the elasticity parame-
ters δ and ψ (percent elongation and percent reduction of
area) are improved. However, these properties change
nonmonotonically, and the variation depends on the tem-
pering temperature intervals.
Low-temperature tempering (120–250
C; 250–480
F)
is used for the treatment of high-strength structural and
tool steels. Medium-temperature tempering (350–450
C;
660–840
F) is applied mainly to spring steels to achieve
high elasticity. High-temperature tempering (450–650
C;
840–1200
F) is widely used for products made of
513
structural steels combining a relatively high strength with
resistance to dynamic loads.
Alloying of high-strength steels preserves high-strength
characteristics up to 400
C (750
F). In steels containing
additions of chromium, nickel, tungsten, and aluminum,
it is possible to obtain a very favorable combination of
strength (σ e, σ 0.2), ductility (δ, ψ), and impact strength
under low-temperature tempering (160–200
C; 320–
390
F). In low-carbon martensitic steels containing chro-
mium, manganese, nickel, and molybdenum, the tensile
strength remains unchanged up to 400–500
C (750–
930
F). In steels with secondary hardening (e.g., in steels
with 0.26% C, 5% Cr, 1% Mo, 1.2% V, and 1.4% Si), the
strength and impact strength increase under high-tempera-
ture tempering.
These data suggest that mechanical properties of every
type of steel exhibit certain specific features that vary with
the tempering temperature. These features are determined
by the influence of alloying elements on the kinetics of
phase transformations: the change in the martensite point
Ms, the stabilization of retained austenite, and the carbide
formation.
The influence of structural evolution on properties
during tempering can be completely understood through
the example of a maraging (martensite-aging) alloy
containing 0.020.03% C and also Co, Mo, Ti, and Al.
Alloying with cobalt increases the temperature Ms and
provides 100% martensite after cooling. The tensile
strength reaches 1000–1100 MPa. The subsequent temper-
ing (aging) at temperatures of 450500
C (840–930
F)
results in considerable strengthening. Thus, σ e can reach
1900–2100 MPa, σ 0.2 = 1800–2000 MPa, and δ = 8–10%.
Such high-strength properties are due to the segregation of
impurity atoms during aging (initial stages) and then to
Ni3Ti, Ni3Mo, Fe2Mo, etc. phases coherently bound with
Carbon–Iron—Carburized
the matrix. The size of particles is approximately 100 nm.
The coagulation of the precipitates with an increase in
temperature leads to a decrease in the strength character-
istics and an increase in the ductility.
EMBRITTLEMENT DURING TEMPERING
When carbon and alloy steels are tempered over the tem-
perature interval of 250–400
C (480–750
F), a dramatic
drop in impact strength is observed. If the steel is
subjected to a higher temperature tempering and then tem-
pering is repeated at 250–400
C, the brittle state is not
recovered. Therefore, this phenomenon has been called
irreversible tempering brittleness. Such tempering brittle-
ness is typical of almost all carbon steels and alloys. High-
temperature mechanical treatment and refinement of
grains weaken this type of brittleness.
Although cleavage fracture in steels is a common form
of embrittlement, in many cases, the embrittlement is
intergranular. It takes place along the grain boundaries,
 514
Downloaded by [Cornell University] at 21:59 02 October 2016
Fig. 36 Intergranular embrittlement of an Fe-0.26P wt.% alloy
after holding at 500
C, 80.
usually the former austenitic boundaries (Fig. 36).[8] This
behavior is encountered in as-quenched steels, on temper-
ing (temper embrittlement), after heating at very high
austenitizing temperatures. Many alloy steels when tem-
pered in the range of 500650
C following quenching to
form martensite become progressively embrittled in an IG
manner. A similar phenomenon can also occur when the
steels are continuously cooled through the critical range.
Carbon–Iron—Carburized
Fig. 37 The temper embrittlement of a 4.5Ni1.5Cr0.3C wt.%
steel fractured at 77 K, 800.
Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering
It is revealed by the effect on the notched bar impact test,
where the transition temperature is increased and the shelf
energy is decreased, the transgranular fracture mode being
replaced by an intergranular mode below the transition
temperature (Fig. 36).
In high-purity steels, embrittlement does not occur at
all. The embrittlement may be caused by nonuniform pre-
cipitation of martensite at the second stage of tempering.
This structure has a lower resistance to dynamic loads.
This effect is enhanced when the initial grain boundaries
of austenite get saturated with impurities under quenching
heating. The alloying elements, which retard the second
stage of martensite precipitation, shift the interval of irre-
versible brittleness toward higher temperatures.
Another drop in the impact strength is found at temper-
ing temperatures of 450–600
C (840–1110
F). A very
significant feature of embrittlement is its reversibility
under high-temperature tempering. If a steel that has
undergone tempering embrittlement is heated to a temper-
ature of >600
C (1110
F) and then cooled rapidly, its
impact strength is restored. Therefore, such brittleness is
termed reversible (Fig. 37).
In the state of reversible tempering embrittlement, steel
possesses a structure that consists of ferrite and carbide.
When subjected to impact tests, fracture occurs mainly
along the boundaries of the initial austenite grains.
With the individual elements, the tendency to embrittle
appears to increase with both group and period number of
elements in the Periodic Table of elements; i.e., S, Se, and
Te (Group VIB) in increasing order are the most surface
active elements in iron. Although the elements in Groups
18
16
14
12
Atomic % Ni
Ni-Sb
Ni-Sn
10
6 Ni-P
0 2 4 6 8 10 12 14 16
Atomic % P, Sn, Sb
Fig. 38 The interelation between the concentrations of Sn, Sb,
and P and of Ni at grain boundaries in NiCr steels of constant
hardness and grain size.
Source: From McMahon.[33]
 Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering
500
Transition temperature (°C)
400
Sb Sn
300
P 2012.
300
100
0
0 2 4 6
Grain boundary concentration (at%)
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Fig. 39 The effect of grain boundary concentrations of P, Sb,
and Sn on the ductility of NiCr steels of constant hardness and
grain size.
Source: From McMahon.[33]
IVB (C, Si, Ge, and Sn) and VB (N, P, As, Sb, and Bi) are
less surface active, they play a greater role in embrittle-
ment because they interact with certain metallic elements,
e.g., Ni and Mn, which are common alloying elements in
steels. These interactions lead to cosegregation of alloy
element and impurity elements at the grain boundaries,
and to resultant lowering of cohesion by the impurity
element. The analysis of the composition of grain bound-
aries by Auger spectroscopy has confirmed strong interac-
tions between NiSb, NiP, NiSn, and MnSb
(Figs. 38 and 39).[8]
Embrittlement over a certain temperature interval is
typical of not only martensitically hardened steels but also
shows up, although to a lesser degree, in steels with the
bainite structure and is least pronounced in steels with the
pearlite structure. The additions of chromium, nickel, and
manganese facilitate tempering embrittlement. Small
additions of molybdenum (not >0.2–0.3%) weaken tem-
pering embrittlement. The presence of Sb, P, Sn, and As in
industrial steels makes these steels most susceptible to
tempering embrittlement.
The optimum temperature range for temper embrittle-
ment is between 500
C and 575
C. However, in some
steels, embrittlement occurs in the range of 250400
C.
This phenomenon is called 350
C (500
F) embrittlement
and occurs at a very low temperature to attribute it to the
diffusion of metalloids, such as Sb, to the austenite grain
more mobile atoms, e.g., P, which would be rejected during
the grain boundary growth of iron carbide that takes place in
this temperature range.[8] However, the morphology of the
grain boundary Fe3C, if predominantly sheet-like, could be
a prime cause of low ductility in this temperature ranges.
515
REFERENCES
Sb
Sn
1. Kurdjumov, J. Transformations in Iron and Steel, J. Iron
P
Steel Inst. 1960, 195, 26.
2. Sverdlin, A.; Ness, A. Effects of alloying elements on the
heat treatment of steel. In Steel Heat Treatment Handbook,
2nd Ed.; CRC: New York, 2007.
3. Callister, W.D. Jr. Materials Science and Engineering, An
Introduction, 8th Ed.; John Wiley & Sons, Inc.: New York,
4. Sinha, A.K. Physical Metallurgy Handbook; McGraw-Hill:
New York, 2003.
5. Rayson, H.W. Constitution and Properties of Steels; Pick-
ering, F.B., Ed.; VCH: Weinheim, 1992, 583–640.
6. Hosford, W.F. Materials for Engineers; Cambridge Uni-
versity Press: New York, 2008.
8 10 12 7. Hosford, W.F. Iron and Steel; Cambridge University Press:
New York, 2012.
8. Smallman, R.E.; Ngan, A.H.W. Physical Metallurgy and
Advanced Materials; Elsevier: Burlington, 2007.
9. Honeycombe, R.; Bhadeshia, H.K.D.H. Steels, Microstruc-
ture and Properties, 2nd Ed.; Edward Arnold: London,
U.K., 1995.
10. Bhadeshia, H.K.D.H. Bainite in Steel; Cambridge Univer-
sity Press: New York, 2001.
11. Hansen, M. Constitution of the Binary Alloys; McGraw-
Hill: New York, 1958.
12. Bain, E.C.; Paxton, H.W. Alloying Elements in Steel; ASM:
Materials Park, OH, 1966.
13. Schick, H.L. Thermodynamics of Certain Refractory Com-
pounds; Academic Press: New York, 1966.
14. Irving and Pickering, J. Iron Steel Inst. 1960, 194, 137.
15. Steven, W.; Haynes, A.G.J. The Temperature of Formation
of Martensite and Bainite in Low-Alloy Steels, Iron Steel
Inst. 1956, 183, 349.
16. Mehl, R.F. The physics of hardenability, the mechanism
and the rate of decomposition of austenite. In Symposium
on Hardenability of Alloy Steels; ASM: Materials Park,
Carbon–Iron—Carburized
OH, 1938; 40.
17. Geller, Yu. Tool Steels; Mir Publishers: Moscow, 1978.
18. Vinograd, M.I.; Gromova, G.P. Inclusions in Alloy Steels
and Alloys, Metallurgiya, Moscow, 1972.
19. Zimmerman, R.; Gunter, K. Metallurgy and Materials Sci-
ence Handbook, Metallurgiya, Moscow, 1982.
20. Geller, Yu. Tool Steels, 3rd Ed.; Metallurgizdat: Moscow,
1968.
21. Shukyurov, R.I.; Kachanov, N.N.; Mamedov, Z.G.
MITOM, 1973, No.2. 68–69.
22. Bain, E.C.; Paxton, H.W. Alloying Elements in Steel,
2nd Ed.; ASM: Materials Park, OH, 1966.
23. Vogel, R.; Martin, E. Ueber das Ternäre System Eisen-
Kohlenstoff-Vanadin. Archiv für das Eisenhüttenwesen
1930–1931, 4, 487.
24. Takedo, S. Metallographic Investigation of the Ternary
Alloys of the Iron-Tungsten-Carbon System; Technical
Publication: Tôhoku, 1930; Vol. 9.
25. Glover, S.G.; Smith, T.B. Stabilization of austenite. In
Mechanism of Phase Transformation in Metals. Institute
of Metals: London, 1956; 268.
 516
26. Naylor, J.D.; Cook, W.T. Heat Treated Engineering Steels;
ASM: Materials Park, OH, 1967.
27. Hall, A.M. Nickel in Iron and Steel; John Wiley & Sons,
Inc.: New York, 1954.
28. Case, S.L. and Kent R. van Horn; Titanium in Iron and
Steel; John Wiley & Sons: New York, 1955.
30. Grossman, M.A.; Asimow, A.; Urban, S.F. Hardenability,
its relation to quenching, and some quantitative data. In
Hardenability of Alloy Steels; ASM: Materials Park, OH,
1939.
Downloaded by [Cornell University] at 21:59 02 October 2016
Carbon–Iron—Carburized
Carbon—Iron Alloys: Alloying Elements’ Effect on Tempering
31. Brooks, C.R. Heat Treatment of Ferrous Alloys; Hemi-
sphere Publishing Corporation: Washington, D.C., 1979.
32. Edelman, I.; Ivanova, O.; Ivantsov, R.; Stepanov, S.;
Zaikovskiy, V. Heat treatment stimulation of the magnetic
nanoparticles formation in borate glasses doped with tran-
sition elements. In Heat Treatment: Theory, Techniques
and Applications; Bonami, G.J., Ed.; Nova Science Pub-
lishers, Inc.: New York, 2010.
33. McMahon, C.J. Jr. Intergranular fracture in steels, Mater.
Sci. Eng. 1976, 25, 233.