Alloy Carbides
Alloy Carbides
Alloy Carbides
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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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
Examples
Group-II carbides
Examples
M3C
Fe3C, Mn3C
MC
M23C6
Cr23C6
M 2C
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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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).
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II B