THE HEAT TREAT DOCTOR

Alloy Carbides

he subject of carbide formation in steels

has intrigued The Doctor ever since
he first peered into a microscope and
observed them (Fig. 1). It is also a very
important subject for the heat treater to better
understand. Carbides can be our friend or our
enemy. Lets learn more.

DANIEL H. HERRING
The HERRING GROUP, Inc.
630-834-3017
dherring@heat-treat-doctor.com

Carbide Formation
In simplest terms, alloying elements in steels can
be divided into two groups: those that do not form
carbides (e.g., Al, Co, Cu, N, Ni and Si) and those
that do (e.g., Mn, Cr, W, Mo, V, Zr, Nb, Ta and
Ti). This latter group is arranged in accordance
with their affinity for carbon.
The periodic table of elements (Fig. 2) tells
us these carbide formers fall to the left of iron.
Unstable carbides, those that will dissociate
on heating, can be found at the far left end of
each row, while the elements closest to iron
form extremely stable carbides that dissociate
at temperatures much higher than the critical
temperatures for steel.[1]
Carbide formation in steels is typically limited
to a few carbide types (Table 1). Here M represents
the carbon-forming elements in steel. The types,
combinations and amount of alloying elements
present complicate carbide formation. For example,
in a Cr-Mn steel, the carbide (Cr,Mn,Fe)23C forms
in lieu of a Cr23C carbide.[1]
The stability of the carbides is highly
dependent on the presence of other alloying

Fig. 1. Finely dispersed alloy carbides in a matrix of tempered martensite. Vacuumhardened and high-pressure gas-quenched 52100 steel (3,900X).
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elements in the steel. For example, while

manganese is a (very) weak carbide former, it is a
relatively potent carbide stabilizer. Remember, all
carbide formers are also nitride formers.
Some alloying elements (e.g., Ni, Co, Al) cause
graphitization of cementite (iron carbide) and
for this reason are not typically added to highcarbon steels in any appreciable amount unless to
counteract a strong carbide former.
In addition to forming carbides, alloying
elements influence ferrite and pearlite interaction,
martensite and bainite transformation, retained
austenite and quenching (by influencing the alloy
transformation diagram).
Carburized Steels[3]
In general, finely dispersed carbides are not
considered to be detrimental to carburized alloy
steels. Small spheroidal carbides or incidental
carbides observed in many high-carbon martensite
structures are considered routine. However, grainboundary carbides, massive carbides that occur on
edges and corners, network carbides and carbide
necklaces are deemed detrimental to mechanical
properties and should be avoided.
The number of carbides present in lowtemperature-tempered carburized alloy steels
is typically less than 10%. While carbides are
harder than the surrounding matrix (martensite/
austenite), they do not have an appreciable effect
on Rockwell (macro) hardness at this percentage.
Carbides are known to enhance wear resistance.
It has also been reported that contact loading
of certain types of gears (at very high contact
pressures away from the fatigue limit) may be
enhanced, but grain-boundary and network
carbides are known to be detrimental to bending
fatigue and should be avoided.
Steps many heat treaters and design engineers
have found useful in minimizing carbide
formation during carburizing include:
Use of fine-grained steels (to reduce the
amount of carbon deposited at the grain
boundaries) or elements that pin the grain
boundaries to avoid excessive grain growth.
Limiting of the furnace-atmosphere carbon
potential. For example, running at a carbon
potential in excess of the limit of saturation

THE HEAT TREAT DOCTOR

of carbon in austenite (Acm) can create

carbides during carburizing. Processes using
these techniques must have ways to avoid
carbide formation.
Use of a constant carbon potential (e.g.,
0.80%) throughout the carburizing cycle (as
opposed to a boost/diffuse cycle).
Avoidance of excessively long, slow
cooling (i.e., drop temperature) steps in
the carburizing process (to avoid network
carbides).
Subcritical annealing after carburizing and
slow cooling prior to reheat and quench.
Avoidance of geometry effects such as sharp
corners or radii. Edge round where possible.
Limiting the reheat cycle temperature to
avoid grain growth, excessive distortion and
retained austenite.

IV B

VB

VI B

VII B

VIII B

VIII B

VIII B

IB

TITANIUM

VANADIUM

CHROMIUM

MANGANESE

IRON

COBALT

NICKEL

COPPER

23

24

25

26

27

28

29

30

47,87

50,94

52,00

54,94

55,85

58,93

58,69

63,55

65,39

MOLYBDENUM

TECHNETIUM

Ti

ZIRCONIUM

41

91,22

92,91

Zr

HAFNIUM

Cr

NIOBIUM

40

Nb

Mn

42

Mo

TANTALUM

TUNGSTEN

RUTHENIUM

Co

RHODIUM

Ni

Cu

PALLADIUM

SILVER

Zn

CADMIUM

43

44

45

46

47

48

(98,91)

101,1

102,9

106,4

107,9

112,4

Tc

95,94

Fe

RHENIUM

Ru

OSMIUM

Rh

IRIDIUM

Pd

Ag

PLATINUM

GOLD

Cd

MERCURY

72

73

74

75

76

77

78

79

80

178,5

180,9

183,9

186,2

190,2

192,2

195,1

197,0

200,6

Hf

Ta

Re

Os

Ir

Pt

Au

Hg

Fig. 2. Partial periodic table of the elements[2]

Table 1. Carbide formation in steels[1]
Group-I carbides

Examples

Group-II carbides

Examples

M3C

Fe3C, Mn3C

MC

WC, VC, TiC, NbC, ZrC

M23C6

Cr23C6

M 2C

Mo2C, W2C, Ta2C

M7C3

Cr7C3

M6C

Fe3Mo3C, Fe3W3C

Tool Steels[7]
Alloying to create large amounts of carbides is a major
difference between low-alloy steels and tool steels. Tool-steel
carbides have been discussed previously,[8] but the focus here
is on the relative hardness of the various carbides. Tool steels
contain carbon, anywhere from about 0.5% to over 2%. Tool
steel with 0.5% carbon will harden into the 60 HRC range
during heat treatment. Therefore, any excess carbon will
combine with other elements to form carbide particles. These
carbide particles are extremely small and constitute from less
than 5% to over 20% of the total volume of the microstructure.
The actual hardness of individual carbide particles depends on
their chemical composition, but, in general, chromium carbides
are 65-70 HRC, molybdenum and tungsten carbides are in the
range of 75 HRC, and vanadium carbides are in the range of
80-85 HRC.
The amount and type of carbide present in a particular grade
of steel is largely responsible for differences in wear resistance
(for the same relative hardness, tool steels with greater amounts
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ZINC

22

Tempering[6]
Tempering of alloy steels differs from that of low-carbon
steels in that the presence of retained austenite and strong
carbide-forming elements results in the precipitation of finely
dispersed alloy carbides (often referred to as temper carbides) at
temperatures greater than about 500C (930F). These markedly
contribute to the hardness of alloy steels. The hardness of
martensite in alloy steels initially decreases as the tempering
temperature is increased, but then carbon supersaturation is
relieved by the precipitation of carbides (iron carbides at low
temperature, alloy carbides at higher tempering temperatures
where substitutional alloying allows diffusion to take place) and
reaches a maximum between 500-700C (930-1300F).

16

II B

of carbides or carbides of a higher hardness will show better

resistance to wear). Large volume fractions of carbides optimize
hardness and wear resistance, but there is a trade-off with hot
forming, heat treatment and machinability. Very high amounts
of carbide particles present in a material (such as in tungsten
carbide) can lead to problems in grinding and lower toughness.
Summary
Alloy carbides play a significant role in both the microstructure
and resultant mechanical properties of alloy steels. For this
reason the heat treater must pay particular attention to them,
know when and why they are being formed, and if they will be
helpful or harmful to the end-use application of the product.
References
1. Steel Heat Treatment Handbook: Metallurgy and Technologies,
2nd Edition, George E. Totten (Ed.), Chapter 4: Effects of
Alloying Elements on the Heat Treatment of Steel, A. V.,
Sverdlin and A. R. Ness, pp. 172-174
2. Periodic Table of the Elements, Catalog No. WLS-18806-10,
Sargent-Welch, VWR International, 2004
3. Parrish, Geoffrey, Carburizing: Microstructure and Properties,
ASM International, 1999
4. Key-To-Metals (steel.keytometals.com)
5. Maalekian, Mehran, The Effects of Alloying Elements on Steels
(I), Technische Universitat Graz, 2007
6. Sharma, Romesh C., Principles of Heat Treatment of Steels, New
Age International (P) Limited, 1996
7. Selection of Tool & Die Steels, Crucible Industries (www.
crucibleservice.com)
8. Herring, Daniel H., Tool Steel Carbides, Industrial Heating,
January 2013
9. Roberts, G. A., R. Kennedy and G. Krauss, Tool Steels, 5th
Edition, ASM International, 1998