2.

3 Carburizing: A Method of Case Hardening of Steel

MMA Bepari, Bangladesh University of Engineering and Technology, Dhaka, Bangladesh
r 2017 Elsevier Inc. All rights reserved.

2.3.1 Introduction 73
2.3.2 Methods of Carburization 73
2.3.2.1 Solid or Pack Carburization 73
2.3.2.1.1 Carburizing process 73
2.3.2.1.2 Chemical reactions 74
2.3.2.1.3 Decarburization 74
2.3.2.1.4 Advantages 75
2.3.2.1.5 Disadvantages 76
2.3.2.2 Liquid Carburization 76
2.3.2.2.1 Carburizing Process 76
2.3.2.2.1.1 Low temperature baths 76
2.3.2.2.1.2 High temperature baths 77
2.3.2.2.2 Advantages 77
2.3.2.2.3 Disadvantages 77
2.3.2.2.4 Safety precautions 77
2.3.2.3 Gas Carburization 78
2.3.2.3.1 Carburizing process 78
2.3.2.3.2 Carburizing reactions 78
2.3.2.3.3 Atmospheric conditions for gas carburization 78
2.3.2.3.4 Carrier gases 79
2.3.2.3.5 Carbon potential 79
2.3.2.3.6 Advantages 79
2.3.2.3.7 Disadvantages 79
2.3.2.3.8 Safety measures for gas carburization 79
2.3.2.4 Vacuum Carburizing 80
2.3.2.4.1 Carburizing process 80
2.3.2.4.2 Control of carbon supply and case depth 80
2.3.2.4.3 Advantages 80
2.3.2.4.4 Disadvantages 80
2.3.2.5 Plasma Carburizing 80
2.3.2.5.1 Carburizing process 80
2.3.2.5.2 Control of carbon supply and case depth 81
2.3.2.5.3 Advantages 81
2.3.3 Theory of Carburization 81
2.3.3.1 Fick’s Laws of Diffusion 81
2.3.3.2 The Equilibrium State for Chemical Reaction 82
2.3.3.3 Controlling Factors of Carburization 82
2.3.3.3.1 The flow of carbon in iron 82
2.3.3.3.2 Flow of carbon from the supply source 85
2.3.4 Heat Treatment after Carburizing and Properties of Carburized Parts 86
2.3.4.1 Single Hardening without Core Refinement 87
2.3.4.2 Single Hardening with Core Refinement 87
2.3.4.3 Double Hardening 88
2.3.4.4 Direct Quench Technique 89
2.3.4.5 Quenchants for Carburized Steels 89
2.3.4.6 Heat Treatment of Gas-Carburized Steels 90
2.3.4.7 Subzero Treatment 90
2.3.5 Microstructures of Carburized Steels 90
2.3.5.1 Martensite 90
2.3.5.1.1 How martensite forms 90
2.3.5.1.2 Martensite morphologies 91
2.3.5.1.3 Effect of tempering 92

Comprehensive Materials Finishing, Volume 2 doi:10.1016/B978-0-12-803581-8.09187-6 71

72 Carburizing: A Method of Case Hardening of Steel

2.3.5.1.4 Role of transition carbides 92

2.3.5.2 Austenite 92
2.3.5.2.1 Characteristic features of austenite 92
2.3.5.2.2 Effect of austenite composition 93
2.3.5.2.3 Excessive retained austenite 93
2.3.5.2.3.1 Effect on properties 93
2.3.5.2.3.2 Major cause 93
2.3.5.2.4 Reducing retained austenite 94
2.3.6 Carburization of Alloy Steels 94
2.3.6.1 Carburization of Low Alloy Steels 94
2.3.6.1.1 Carburization of chromium–nickel steel 94
2.3.6.1.2 Carburization of molybdenum–nickel steel 94
2.3.6.2 Carburization of Microalloyed Steels 97
2.3.6.2.1 Carburization of vanadium-microalloyed steel 97
2.3.6.2.2 Carburization of niobium-microalloyed steel 98
2.3.6.3 Low Temperature Carburization of Austenitic Stainless Steel 99
2.3.6.3.1 Introduction 99
2.3.6.3.2 Activation 99
2.3.6.3.3 Processing temperature ranges 100
2.3.6.3.4 Carburizing atmosphere 101
2.3.6.3.5 Microstructure of the low temperature carburized layer 101
2.3.6.4 Carburization of Tool Steels 101
2.3.6.4.1 Carburization of hot working tool steel 101
2.3.6.4.2 Carburization of cold working tool steel 102
2.3.6.4.3 Carburization of shock resisting tool steel 102
2.3.6.5 Carburization of Mold Steel 102
2.3.7 Problems during Carburization and their Remedy 102
2.3.7.1 Nonuniform Carburizing 103
2.3.7.1.1 Prevention 103
2.3.7.2 Uneven Case Depth 103
2.3.7.2.1 Prevention 103
2.3.7.3 Insufficient Case Depth 103
2.3.7.3.1 Prevention 103
2.3.7.4 Low Hardness 103
2.3.7.4.1 Higher case depth 103
2.3.7.4.2 Prevention 103
2.3.7.4.3 Retained austenite 103
2.3.7.4.4 Prevention 103
2.3.7.4.5 Decarburization 103
2.3.7.4.6 Prevention 103
2.3.7.5 Sooting 103
2.3.7.5.1 Prevention 103
2.3.7.6 Distortion 104
2.3.7.6.1 Release of internal stresses 104
2.3.7.6.2 Prevention 104
2.3.7.6.3 Drastic quenching 104
2.3.7.6.4 Prevention 104
2.3.7.6.5 High temperature hardening 104
2.3.7.6.6 Prevention 104
2.3.7.6.7 Rehardening 104
2.3.7.6.8 Prevention 104
2.3.7.6.9 Uneven heating 104
2.3.7.6.10 Prevention 104
2.3.7.7 Soft Spots 104
2.3.7.7.1 Prevention 104
2.3.7.8 Cracking and Exfoliation 104
2.3.7.8.1 Prevention 104
 Carburizing: A Method of Case Hardening of Steel 73

2.3.7.9 Grinding Cracks 105

2.3.7.9.1 Prevention 105
2.3.8 Recommended Processing Sequence for Carburized Components 105
References 105

2.3.1 Introduction 2.3.2 Methods of Carburization

The service condition of many machine parts of steel such as There are three general methods of carburization depending
gears, shafts, cams, pinions, and piston pins demands very on the carburizing medium.
hard and wear-resistant surface but with tough and shock-
1. Solid or pack carburization – solid medium.
resistant core. Such a combination of properties is not usually
2. Liquid carburization – liquid medium.
possible from the commercial steels. A low carbon steel con-
3. Gas carburization – gas medium.
taining carbon 0.10–0.30% is sufficiently tough while a high
carbon steel containing carbon up to 1.00% possesses ade- Two other specialized methods are plasma carburization
quate hardness. By suitable heat treatment the high carbon and vacuum carburization.
steel can be made very hard while low carbon steel will
develop sufficient toughness. A machine part requiring hard
2.3.2.1 Solid or Pack Carburization
surface but tough core will require a combination of high
carbon surface and low carbon core which is developed by 2.3.2.1.1 Carburizing process
heat treatment only. In solid or pack carburization process parts to be carburized
Carburizing is the most satisfactory and widely used are charged in a heat resisting metallic box with a carburizing
method of surface hardening of low carbon steel. It is a mixture (Figure 2). The solid carburizing mixture is of the
process by which the carbon content of the surface of steel is following proportions:
increased. Since the objective of surface hardening is to
obtain a hard, wear-resistant surface called case with a tough Hard wood charcoal 53–55 parts
interior called core, the first consideration is the selection of Sized coke 30–32 parts
low carbon (usually r0.20%) steel. It is then subjected to Barium carbonate 10–12 parts
carburization to an extent of eutectoid–hypereutectoid com- Calcium carbonate 3–5 parts
position and by subsequent heat treatment to the desired Sodium carbonate 2–3 parts
hardness.
Carburizing is the addition of carbon to the surface of low
carbon steels at a temperature between 850 and 950 1C. At this In the preparation of the above carburizing mixture,
temperature stable austenite structure has higher solubility of molasses is commonly used as binder. The carbonates are used
carbon which is diffused from the surrounding carburizing as energizers. They are added to the charcoal to accelerate the
environment. Hardening is accomplished when the high car- carburizing process.
bon surface layer is quenched to form martensite. This pro- Workpieces, which are to be pack carburized, are first
duces a high carbon martensite case with good wear and cleaned of dirt, scale, and rust. They are then placed in a box.
fatigue resisting properties while the low carbon martensite Welded heat resisting steel boxes are generally employed. The
core gives high toughness and shock resisting properties. A
Schematic representation of carburizing process is shown in
Figure 1. Cover Test bar

Lute

Work pieces
Heat resisting metallic box
Carburizing mixture

Figure 2 Packing of workpieces (low carbon steel parts) in a box for

Figure 1 Schematic representation of carburizing process. carburizing.1
74 Carburizing: A Method of Case Hardening of Steel
boxes are usually in rectangular or cylindrical form. It is
advisable to employ cylindrical boxes or pots. Packing the
work is accomplished by first covering the bottom of the box
with a 40–45 mm layer of carburizer (Figure 2). The work-
pieces to be carburized are placed on this layer with spaces of
20–25 mm between them and the box walls. Then they are
covered with a dense layer of carburizer, 20–25 mm thick,
which is rammed before laying the next row of workpieces.
The upper row is covered with a layer of carburizer 40–50 mm
thick. The box is closed with a cover whose edges are luted
with fireclay or with mixture of clay and talc with water glass.
Packed box is placed in the furnace.
The carburizing compound is in form of coarse particles or
lumps, so that when the cover is sealed on the box, sufficient
air will be trapped to form carbon monoxide. The box is then
heated to the proper temperature (about 900–925 1C) for a
required period of time (usually 3–5 h) and cool slowly in the
furnace. The box is then withdrawn from the furnace and
workpieces are taken out from the box.
The holding time at the carburizing temperature depends
on the specified depth of carburized case. The deeper the case
required, the longer the holding time should be at the car-
burizing temperature. The required holding times for various
depths of carburized case are given in Table 1.1
At carburizing temperature the steel consists of austenite.
Carburizing is concerned with the solid solution of carbon in
austenite. The limits of carbon content of this phase depend
on the temperature and composition of the steel. The max-
imum amount of carbon that can be dissolved in austenite at
the carburizing temperature is indicated on the iron–iron
carbide equilibrium diagram at the Acm line (Figure 3).
Therefore very quickly a surface layer of high carbon (about
1.2%) is built up. Since the core is of low carbon content, the
carbon atoms trying to reach equilibrium will begin to diffuse
inward. The rate of diffusion of carbon in austenite at a given
temperature is dependent upon the diffusion coefficient and
carbon concentration gradient. After the diffusion has taken
place for the required amount of time dependent upon the
case depth desired, the part is cooled in the furnace and
examined microscopically. The carbon gradient will be visible
in the gradual change of the structure. At the surface is
hypereutectoid zone consisting of pearlite with a white
cementite network, followed by the eutectoid zone of only
pearlite and finally hypoeutectoid zone of ferrite and pearlite,
with amount of ferrite increasing until the core is reached. This
is illustrated in the Figure 4. Figure 5 shows carbon
Table 1 Relationship between case depth and holding time
(carburizing temperature 930 1C)
Case depth (mm) Holding time (hour)
0.4–0.7 4.5–5.5
0.6–0.9 5.5–6.5
0.8–1.2 6.2–10.0
1.0–1.4 8.0–11.5
1.4–1.8 11.5–16
1.5–1.9 13–18
1.6–2.0 14–19
1.8–2.2 16–22
concentration gradient in the carburized steel with 0.08 in.
total case.
2.3.2.1.2 Chemical reactions
There is always air present in the carburizing box, even when it
is filled with carburizer. At the carburizing temperature, the
oxygen in the air reacts with the carbon in the carburizer to
produce carbon dioxide gas. This carbon dioxide further reacts
with carbon in the carburizer to produce carbon monoxide.
C þ O2 -CO2 ½I
CO2 þ C-CO ½II
This carbon monoxide is the carrier of carbon and when comes
in contact with austenitic iron, iron carbide is formed, which is
dissolved in austenite.
Fe þ CO-½CFe ðC dissolves in austeniteÞ þ CO2 ½III
Energizers (like BaCO3, CaCO3, and NaCO3) in the car-
burizing mixture decompose at the carburizing temperature to
produce oxides and CO2 as follows:
BaCO3 -BaO þ CO2
CaCO3 -CaO þ CO2
Na2 CO3 -NaO þ CO2
This ensures enough supply of CO2 for the reaction [II] to
continue, and hence enough supply of CO for the reaction
[III]. The reactions cycle will be repeated.
At the initial stage of carburization, the maximum satura-
tion limit of carbon (about 1.2%C) at the surface of the steel is
reached. Then carbon begins to diffuse to the interior as shown
in Figure 6. The diffusion of carbon depends on the diffusion
coefficient D ¼ D0 eQ/RT, where Q is the activation energy, R is
gas constant, and T temperature in degree kelvin. As D
increases, depth of penetration of carbon or case depth
increases.
The relation of carburizing time and temperature to case
depth is shown in Figure 7. The higher the temperature
and longer the period of carburization, the greater is the
case depth.
2.3.2.1.3 Decarburization
The carburization equation given previously,
Fe þ CO-½CFe ðC dissolves in austeniteÞ þ CO2
is reversible and may proceed to the left, removing
carbon from the surface layer if the steel is heated in an
atmosphere containing carbon dioxide (CO2). This is called
decarburization.
Other possible decarburization reactions are:
Fe3 C þ H2 O-Fe þ CO þ H2
Fe3 C þ O2 -Fe þ CO2
 Carburizing: A Method of Case Hardening of Steel 75

Figure 3 Portion of Iron–Iron Carbide equilibrium diagram.

Figure 4 Microstructure of pack carburized and furnace cooled low carbon steel showing different zones from case (right) to core
(left),  400.

Decarburization is a problem primarily with high carbon • Special furnaces are not required to heat the carburizing
steel and tool steel. boxes.
• The soft case produced by slow cooling from the carbur-
2.3.2.1.4 Advantages izing temperature permit additional machining prior to
• Pack carburization is economical and advantageous for hardening.
small machine parts. • It does not require a controlled atmosphere furnace.
76 Carburizing: A Method of Case Hardening of Steel
Figure 5 Carbon concentration gradient in a carburized steel with
0.08 in. total case.
C
C
0.2% C
C
1.2% C
Figure 6 Flow of carbon from high carbon surface to the interior.
• Carburizing compounds give good support to parts, help-
ing to prevent sagging at high temperatures.
2.3.2.1.5 Disadvantages
• Larger and complicated machine parts cannot be carbur-
ized effectively.
• There are some limitations in handling larger and com-
plicated machine parts.
• Packed carburized machine parts cannot be hardened
directly from the carburizing temperature.
• The box containing the charge when heated gets oxidized
and warrants frequent replacement.
• Uniform case depth cannot be obtained in pack
carburization.
• The preparation of judicious mixture is a skilled job and is
time consuming.
2.3.2.2 Liquid Carburization
2.3.2.2.1 Carburizing Process
The liquid carburization is used for parts requiring thin car-
burized case. The liquid carburization is suitably practiced for
complex machine parts and is carried out by heating them in a
liquid bath.
In liquid carburizing, workpieces to be carburized are
immersed in molten salt baths maintained at carburizing
temperatures as shown in Figure 8. These baths contain
sodium cyanide as a carburizing agent. Liquid carburizing
Figure 7 The relation of time and temperature to case depth.2
Low carbon
steel
Cyanide bath
Figure 8 Liquid carburization in cyanide bath.
baths can be divided into two categories: (1) low temperature
baths and (2) high temperature baths.
They not only differ with respect to temperatures of car-
burizing, but the compositions of these baths and the
mechanisms (chemistry) of carburizing are also different.
Table 2 gives compositions of these baths. Recently some non-
cyaniding liquid baths have also been developed.
2.3.2.2.1.1 Low temperature baths
These are normally operated at 850–900 1C and are best suited
for producing shallow case depths (B0.075–0.75 mm). Typi-
cal composition of low temperature carburizing baths is given
in Table 2.
Chemistry of carburizing in low temperature baths is rather
complex. The main reactions involved are as follow:
2NaCN-Na2 CN2 þ C ðCynamide shiftÞ ½IV
and either
NaCN þ O2 -2NaNCO ðCyanate formationÞ
or
NaCN þ CO2 -NaNCO þ CO ðCyanate formationÞ ½V
The cyanate (NaNCO) thus produced, further reacts to give:
NaNCO þ C-NaCN þ CO ½VI
 Carburizing: A Method of Case Hardening of Steel 77

Table 2 Compositions of liquid carburizing baths (in wt%) Table 3 Sodium cyanide content in liquid carburizing bath at
different operating temperature
Constituent Low temperature High temperature
baths baths Temperature (1C) Sodium Cyanide (%)

Sodium cyanide 10–23 6–16 Maximum Preferred Minimum

Barium chloride – 30–55
Salts of alkaline 0–10 0–10 815 23 18 14
earths 840 20 16 12
Potassium chlorides 0–25 0–20 870 18 14 11
Sodium chlorides 20–40 0–20 900 16 12 10
Sodium carbonate 40 max. 30 max. 925 14 10 8
Other accelerators 0–5 0–2 955 12 8 6
Sodium cyanate 1.0 max. 0.5 max.
Density 1760 kg m3 2000 kg m3
(at 1173 K) (at 1198 K) content, through which the carbon activity of the bath can be
controlled to some extent. Table 3 gives preferred operating
cyanide content at different temperatures. Lower end of the
4NaNCO þ 2O2 -2Na2 CO3 þ 2CO þ 4N ½VII cyanide content range, at a given temperature, would normally
produce a hypoeutectoid case, whereas, a hypereutectoid case
and
is obtained with the cyanide content near the upper limit.
4NaNCO þ 4CO2 -2Na2 CO3 þ 6CO þ 4N ½VIII Reactions [VII] and [VIII] show that, there is also nascent
nitrogen present in the carburizing baths to some extent. This
CO and C produced by above reactions react with Fe at the nitrogen is also absorbed at the surface of steel and diffuses
steel surface to enrich it with carbon as, inwards. However, at cyanide concentrations of carburizing
baths, nitrogen activity is relatively low and hence only very
2CO þ Fe-CðFeÞ þ CO2 ½IX little nitrogen diffuses into the steel. Activity of nitrogen is
higher at higher end of the cyanide content range at a given
and
temperature.
C þ ðFeÞ-CðFeÞ ½X
2.3.2.2.2 Advantages
Reactions [VII] and [VIII] deplete the activity of the bath and
lead to an eventual loss of carburization potential, unless • Complicated machine parts can be carburized.
suitable replenishment is done. • Uniform case depth can be obtained.
• Less distortion and cracking in hardening.
2.3.2.2.1.2 High temperature baths • High output even from a relatively small furnace due to
These are normally operated at 900–950 1C. Typical compo- rapid rate of heat transfer.
sition of high temperature baths is given in Table 2. High • Labor costs are reduced, since the operation of the process
temperature baths are used for producing deeper case depths, is simple.
in the range of 0.5–3.0 mm. Apart from cyanide, these baths • Surface decarburization is eliminated.
contain a major amount of barium chloride. • Time of carburization is reduced compared to pack
In liquid carburization the carburizing reaction depends carburization.
primarily on the sodium cyanide, activated by the presence of
alkaline earth salt-usually barium (or calcium) chlorides. The 2.3.2.2.3 Disadvantages
salts (chloride) react with the cyanide to form a cyanide of
alkaline earth metal, which then reacts with iron to form Fe3C. • Materials cyanide solution and fumes coming up from the
Although reaction given above for low temperature baths both are poisonous.
occur here also to some degree, the principle reactions in high • Great care required in disposal of cyanide bearing salts.
temperature baths are: • Necessary of removing the salt from the work by special
means, such as hot water spray washing, acid dip, etc.
2NaCN þ BaCl2 2 2NaCl þ BaðCNÞ2 ðbarium cyanideÞ ½XI • There is a danger of explosion if moisture is introduced into
the salt.
2NaCN þ CaCl2 2 2NaCl þ CaðCNÞ2 ðcalcium cyanideÞ ½XII • Separate storage required for keeping the salts under lock
and key.
BaðCNÞ2 þ Fe-½CFe þ BaCN2 ðbarium cyanamideÞ ½XIII • Exhaust system is required.
• High cost of the carburizing salt.
CaðCNÞ2 þ Fe-½CFe þ CaCN2 ðcalcium cyanamideÞ ½XIV
2.3.2.2.4 Safety precautions
Carbon content of the case can be controlled by the cyanide Sodium cyanide is a very poisonous substance and requires
content of the bath. Low temperature bath operates at higher great care in its handling and storage. At all stages of the use
cyanide content than high temperature bath. Both high as well of sodium cyanide, care must be taken to prevent any
as low temperature baths can be operated with varying cyanide body contact so that no cyanide can enter the blood stream
78 Carburizing: A Method of Case Hardening of Steel

(e.g., via cuts). Adequate protective clothing must be worn. compounds (gas), may be considered independently. The
Well-designed eye shields or goggles and well-fitting helmets interface reactions3,4 for common carbon compounds may be
are essentials in order to protect eyes and head. written:

CH4 ðgÞ þ 3FeðsteelÞ2 ½CFeðin austeniteÞ þ 2H2 ðgÞ ½XV

2.3.2.3 Gas Carburization
2.3.2.3.1 Carburizing process
In gas carburization, the carbon of the furnace atmosphere is
in the form of gaseous hydrocarbon compounds such as
methane, ethane, propane, and butane or carbon monoxide.
The principal source of carbon in gas carburizing is methane,
which is present in manufactured and in natural gas. Gas
carburizing is carried out at 900–950 1C and a case depth of up
to about 0.4 mm may be obtained after 1 h heating at 900 1C.
A case depth of up to 1 mm is commonly produced.
The low carbon (r0.2%C) steel parts are placed in the
carburizing chamber. The air inside the carburizing chamber is
then driven out by introducing hydrocarbon gas or carbon
monoxide gas. The carburizing chamber is then heated to the
temperature (900–925 1C) in the furnace and a continuous gas
flow is maintained. A typical gas carburizing process is shown
in Figure 9.
At this temperature and environment the low carbon steel
part is heated for 2–3 h. At the end of the holding period the
temperature of the furnace is reduced to 840–870 1C in order
to decrease the grain size. The carburized part is then with-
drawn from the chamber and quenched directly in water or
oil. As a result the high carbon surface layer transforms into a
hard wear-resistant case.
Quenching produces martensite microstructure with high
residual stress inside the machine parts. This residual stress is
undesirable because it causes cracking and distortion. In order
to remove the residual stress, the machine part is tempered at a
temperature of 150–180 1C immediately after quenching.
2.3.2.3.2 Carburizing reactions
The reaction involving the actual transfer of carbon occurs at
the steel surface (interface) and the reactants, which are carbon
C2 H6 ðgÞ þ 9FeðsteelÞ2 ½CFeðin austeniteÞ þ 4H2 ðgÞ ½XVI
C3 H8 ðgÞ þ 9FeðsteelÞ2 ½CFeðin austeniteÞ þ 4H2 ðgÞ ½XVII
2COðgÞ þ 3FeðsteelÞ2 ½CFeðin austeniteÞ þ CO2 ðgÞ ½XVIII
Reactions that occur for the same compounds, away from the
interface (i.e., the reactions for the deposition of carbon)3,4 are
as follows:
CH4 ðgÞ2 2H2 ðgÞ þ Cðsolid carbonÞ ½XIX
C2 H6 ðgÞ2 3H2 ðgÞ þ Cðsolid carbonÞ ½XX
C3 H8 ðgÞ2 3H2 ðgÞ þ Cðsolid carbonÞ ½XXI
2COðgÞ2 2H2 ðgÞ þ Cðsolid carbonÞ ½XXII
After the required period of carburization the parts are either
cooled in the furnace or quenched directly from the furnace.
If water vapor is present in the gas it will act as a dec-
arburizing agent, removing carbon from steel by the reaction3:
Fe3 C þ H2 O-Fe þ COðgÞ þ H2 ðgÞ ½XXIII
2.3.2.3.3 Atmospheric conditions for gas carburization
Usually the volume of the chamber of gas carburizing furnace
is small and it is sealed, which ensure small volume of gas
requirement for each shift. For a pit furnace having a working
chamber 64 cm in diameter and 90–120 cm deep, the com-
monly used gas flow rate is 63–118 cm3 s1.5 The rate at which
the furnace atmosphere responds to changes in inlet gas
composition depends on the mean residence time of the

Furnace
Pilot flame

CH4
Carburizing
Chamber

Fire Clay boat Temp: 900-925°C

Low
Carbon Steel
part
Figure 9 Gas carburizing process.

atmospheric gases in the furnace. The mean residence time
(tres) of the gas in the furnace is,6
tres ¼ V  Ta =F  Tf ½1
where V is the chamber volume, Tf is the absolute temperature,
and F is the flow rate of gas measured at ambient temperature
Ta. Residence time may be from 2 to 15 min.6 For times of this
order the reaction in the furnace chamber are fast enough so
that equilibrium gas composition are approached closely for
the usual carburizing temperatures.
For natural gas as carburizing medium the possible con-
stituents of the gas carburizing atmosphere are CO, CO2, H2,
H2O, CH4, and C2H6 gases. For uniformity of carburizing the
above gases have to be well circulated within the chamber and
the parts being carburized must be well spaced to get contact
of the carburizing gases. A positive pressure in the furnace
should be maintained for effective carburization rate and to
prevent infiltration of air within the chamber. For gas carbur-
izing a positive furnace pressure of about 12–37 Pa is satis-
factory6 and it is controlled by adjusting the gas flow rate.
2.3.2.3.4 Carrier gases
In gas carburizing, it is found that the amount of carbon avail-
able is more than what is required for absorption. This excess
carbon precipitates as a heavy soot and deposits on the com-
ponent surface as well as on the walls of the furnace. Hence, in
gas carburizing, it is necessary that the hydrocarbon gases used
are diluted with carrier gas to avoid the formation of heavy soot.
Carburizing agent (hydrocarbon gas) is diluted by a carrier
gas before it enters the carburizing furnace. The carrier gas itself
is normally made by controlled burning of CH4, or some other
hydrocarbon gas. Most commonly used carrier gas is endo-
thermic base, obtained by controlled burning of CH4 in air,
with air-to-gas ratio of 2:5, to give:
CH4 þ O2 ðairÞ-2CO þ 4H2 ½XXIV
Endothermic carrier gas, then, contains the remaining
nitrogen from air, CO, and H2 as by-products of above reac-
tion and small amounts of CO2 and H2O that may form
during the production of carrier gas. Composition of the car-
rier gas is 39–40% N2, 20–21% CO, 38–39% H2 and small
amount of CH4, CO2, and H2O (all in vol.%). Sometimes,
commercially pure nitrogen is also used as a carrier gas. Ratio
of hydrocarbon gas (carburizing agent) to carrier gas in a
carburizing gas mixture could vary from about 1:8 to 1:30,
depending upon the desired surface carbon content, tem-
perature of carburizing, and other considerations.
2.3.2.3.5 Carbon potential
The carbon potential in a furnace atmosphere at a specified
temperature is defined as the carbon content in pure iron that
is in thermodynamic equilibrium with the atmosphere. The
carbon potential of the furnace atmosphere must be greater
than the carbon potential of the surface of the workpiece in
order for carburizing to occur. It is the difference in carbon
potential that provides the driving force for carbon transfer to
the parts. In most systems, the addition of a hydrocarbon gas
such as methane is used for the control of carbon potential.
Carburizing: A Method of Case Hardening of Steel 79
The gases CO and CH4 are carburizing, whilst H2, H2O,
and CO2 are decarburizing agents. In order to control the
carbon availability of the atmosphere, i.e., the carbon poten-
tial, a hydrocarbon gas is used to enrich the carrier gas, by
reducing the H2O (dew point) according to the reaction:
CH4 þ H2 O-CO þ 3H2 ½XXV
and by reducing the CO2 according to the reaction:
CH4 þ CO2 -2CO þ 2H2 ½XXVI
as well as the following carburizing reaction takes place:
CH4 -CFe þ 2H2 ½XXVII
in addition to reaction [XXVII], the other main carburizing
reactions in a CO–CO2–H2–H2O–CH4 atmosphere are:
CO þ H2 -CFe þ H2 O ½XXVIII
2CO-CFe þ CO2 ½XXIX
(in the gas reactions described CFe is the available carbon,
from the atmosphere, for diffusion into the steel surface).
Reactions [XXVIII] and [XXIX] are considered the main
equilibrium reactions for the basic method of carbon transfer
into the steel surface. The assumption is that the carburizing is
taking place as a direct result of the CO content in the
atmosphere.
2.3.2.3.6 Advantages
• The complicated machine parts can easily be carburized by
the gas.
• Uniform case depth can be obtained by the gas carburizing
compared to that by pack carburizing.
• Time–temperature cycles can be determined accurately for
close control of the case depth.
• Composition of the carburizing gas can be varied to pro-
vide a close control of the carbon content of the cases.
• It is cheaper than pack carburization.
• Hardening by direct quenching from the carburizing tem-
perature is possible in gas carburizing.
• The rate of penetration of carbon is more in gas carburizing
as compared to pack carburization.
• Less time is required to attain the carburizing temperature,
since there is no need to heat the boxes as in pack
carburization.
2.3.2.3.7 Disadvantages
• A gas generator is required to produce carrier gas.
• Partial carburizing cannot be performed which is possible
in liquid carburizing.
2.3.2.3.8 Safety measures for gas carburization
The outlet gas from the chamber is very toxic and highly
inflammable whether it is mixed or unmixed with air. For this,
a safety program is essential to avoid the risks of the operation
especially for the personnel under work. As a safety measure,
all the gas discharged from the furnace has to be burned to
80 Carburizing: A Method of Case Hardening of Steel

ensure that poisonous carbon monoxide has been converted

into carbon dioxide. Therefore, a pilot flame has to be main-
tained until carburizing gas flow is continued. For safety
measure, it is convenient to have a source of inert gas, such as
nitrogen for purging the chamber after completion of the
process.

2.3.2.4 Vacuum Carburizing

2.3.2.4.1 Carburizing process
Vacuum carburizing refers to carburizing of steel components
in vacuum furnaces with the introduction of controlled
amounts of carburizing gaseous mixture, usually a mixture of
nitrogen and hydrocarbon gases (normally CH4 or C2H8), at
relatively low pressure. Heating steel components in vacuum
furnaces provide excellent oxidation and decarburization
resistance. A vacuum furnace may be backfilled with a car-
burizing gas mixture after the load has been heated to the
Figure 10 Carbon concentration profiles after (1) boost stage and (2)
desired carburizing temperature usually 900–1050 1C.
diffusion stage, in a two-step vacuum carburizing of AISI-1022 steel at
Vacuum furnaces are specifically suited for high temperature 1040 1C.7
carburizing. Carburizing gas mixture containing oxygen com-
pounds are not generally used in vacuum carburizing, as CO steps depend on the desired surface carbon content and depth
and H2O react with the traditional vacuum furnace materials, of carburizing, and are empirically determined.
such as graphite and molybdenum. Hydrocarbons present in
the backfilled carburizing gas mixtures crack at the surface of
2.3.2.4.3 Advantages
steel and provide carbon to the steel surface.
• Fast carbon transfer.
CH4 -2H2 þ CðFeÞ ½XXX
• No surface oxidation.
• Good case depth uniformity.
or • Integration into manufacturing lines.

4C2 H8 -4H2 þ 2CðFeÞ ½XXXI

Carbons produced by these cracking reactions are highly
reactive and is easily absorbed at the surface of steel. As a result
of cracking of hydrocarbons, the gas mixture in the furnace
consists of N2, CH4 (or C2H8), and H2. Such atmosphere has
tendency to produce soot.
2.3.2.4.2 Control of carbon supply and case depth
With no chemical equilibrium available as a control para-
meter, the carburizing process during vacuum carburizing is
controlled by controlling the process variables, i.e., the partial
pressure of hydrocarbon gas in the backfilled gas mixture, and
the temperature and the time of carburizing. Shallow cases,
that are formed in less than 20–30 min, can be obtained by
time control only, i.e., fixed amount of hydrocarbon gas is
introduced and carburization is carried out for a pre-
determined time. For deeper cases and to allow for more
accurate surface carbon control, a two-step process consisting
of a boost period and a diffusion period is used. During the
boost period, sufficient hydrocarbon gas is introduced to
obtain saturated carbon level without undue sooting of the
furnace or components. Subsequently, the furnace is evacuated
of all gases and diffusion is allowed to occur. Under vacuum
heating, during the diffusion period, decarburization at surface
does not occur. The existing carbon at the surface is redis-
tributed, lowering the surface carbon and increasing the depth
of carburizing. Figure 10 shows typical results obtained by a
two-step process. The relative durations of boost and diffusion
• Small consumption of carburizing gas.
• No formation of furnace atmosphere.
• High carburizing temperatures possible.
2.3.2.4.4 Disadvantages
• Higher initial capital equipment cost than atmosphere
carburizing equipment.
• Empirical process control, which requires processing loads
to determine optimal settings or fine tune simulator.
• Formation of soot and tar, which occur due to the type,
pressure, and quantity of hydrocarbon gas introduced.
2.3.2.5 Plasma Carburizing
2.3.2.5.1 Carburizing process
In plasma carburizing partial heating of parts and their car-
burization is carried out in a plasma of low-pressure ionized
gases. This method is also known as ‘glow discharge’ carbur-
izing. The component to be carburized works as cathode of
glow discharge, with a suitable d.c voltage impressed between
the cathode and anode to support a stable glow as well as to
act as carburizing agent. An atmosphere of hydrocarbon gas
(like CH4) at a proper pressure is provided as a conducting
atmosphere. Figure 11 schematically shows a plasma carbur-
ization chamber.
The chamber is evacuated and then backfilled with a
hydrocarbon gas at reduced pressure, generally in the range of
0.1–2.7 kPa. A continuous flow of gas at reduced pressure
is maintained during the carburization (boost) cycle. High

Figure 11 Schematic illustration of plasma carburizing setup.8
voltage (500–1000 V) is applied to strike the plasma in a
methane atmosphere of B2.7 kPa. Under these conditions, a
thin plasma completely envelops the workpiece and closely
follows its contours, even if the surface is quite irregular.
Methane is dissociated within this thin plasma envelope and a
high carbon potential is established at the workpiece surface,
even though the total pressure in the furnace is relatively low.
The plasma consists of ionized gases and electrons. Posi-
tively charged ions of the type CHi þ n (i¼ 0–3) accelerate
toward the cathode (workpiece) and introduce carbon at the
surface, whereas electrons accelerate to the anode. In the pro-
cess, both anode and cathode also get heated. However, heating
the workpiece in plasma process in not sufficient to heat it up to
the carburizing temperatures of 900–1050 1C. Thus to keep the
workpiece at appropriate carburizing temperature an auxiliary
induction or radiation heating source (Figure 11) is used.
2.3.2.5.2 Control of carbon supply and case depth
Rate of carburization in plasma carburizing is higher com-
pared to vacuum or conventional gas carburization. Within the
glow discharge gaseous molecules, some chemical reactions
may occur, which would not occur under normal thermo-
dynamic equilibrium condition. The electrons in the plasma
atmosphere help to break chemical bonds and thereby dis-
sociate methane to provide necessary carbon at the surface.
Hydrogen generated by dissociation of CH4 and ion bom-
bardment of the surface may also dissociate surface oxides,
and thus remove potential barrier to quick introduction of
carbon at the surface. These factors accelerate uniform intro-
duction of carbon and the attainment of saturation level of
carbon at the surface. Like vacuum carburizing, plasma car-
burizing is normally carried out in two steps. In the first step,
carbon is introduced at the surface by methane plasma and the
second step is carried out by further heating the workpiece in
vacuum to decrease surface carbon to the desired level and to
Carburizing: A Method of Case Hardening of Steel 81
Figure 12 Carbon concentration profiles in AISI-1018 steel, plasma
carburized at 1050 1C (a) after plasma carburizing for 10 min; (b) after
additional diffusion period of 30 min.8
increase the case depth by diffusion processes. As the second
step is carried out in vacuum, no decarburization at the surface
occurs, only redistribution of carbon by diffusion takes place.
Figure 12 shows carbon profiles obtained in AISI-1018 steel in
plasma carburizing for 10 min at 1050 1C followed by a dif-
fusion period of 30 min at the same temperature.
2.3.2.5.3 Advantages
• Consumption of gases in plasma carburizing is much less
compared to conventional gas carburizing.
• No oxidation takes place at grain boundaries, and the fin-
ished surface is clean and glossy.
• Uniform carburized layer is obtained, no sooting is encountered.
• Carburizing of high concentration and the one into the
hard-to-carburized materials such as stainless steel and
sintered metals can easily be carburized.
• Due to fast carburizing rate and low temperature/short time
treatment, no grain growth is observed and residual strain
is very little.
• This is a pollution-free and energy-saving processing.
2.3.3 Theory of Carburization
The carburization of steel may be explained on the basis of two
fundamental concepts. The first is diffusion, influenced by the
properties of the iron, and concerned with the movement of
carbon in the iron itself; the second deals with the source sup-
plying the carbon, and with the transfer of carbon to the surface.
These two general concepts may be described briefly:
2.3.3.1 Fick’s Laws of Diffusion
Fick's first law3: it describes diffusion under equilibrium con-
ditions and is stated mathematically by:
dc1
J1 ¼ D1 ½2
dx
82 Carburizing: A Method of Case Hardening of Steel
Where D1 is the diffusion coefficient and J1 is the resulting flux
gradient.
Fick’s second law3: it expresses the nonequilibrium condi-
tion of diffusion where the concentration, at a point, changes
with respect to time.


dc d dc1
¼ D1 ½3
dt dx dx
Carburizing is a nonequilibrium process, i.e., the gaseous
constituents of the atmosphere are not fully in equilibrium
with one another and the atmosphere is not in equilibrium
with the steel being carburized.
The value of the diffusion coefficient is critical in any cal-
culation dealing with carburizing or any other diffusion pro-
cess. The diffusion coefficient D is defined by:
D ¼ D0 eQ=RT ½4
where D0 and Q are experimentally determined constants. Q is
the heat of diffusion (activation energy, i.e., the energy
required for one atom to jump to a new position in the lat-
tice); R is the gas constant; and T is the absolute temperature.
The greater is the value of Q, the smaller is the value of D at a
given temperature and hence the slower is the rate of diffusion.
The diffusion coefficient which describes the diffusion of
carbon in austenite varies somewhat with carbon content. The
following expression, according to Tibbetts,9 is a good fit to
the experimental data.
D ¼ 0:47 expð1:6CÞexpfð3700026600CÞ=RTgcm2 s1
½5
where, C is the carbon concentration in weight percent and T is
the temperature in degrees Kelvin.
2.3.3.2 The Equilibrium State for Chemical Reaction
The equilibrium state3 for chemical reactions may be repre-
sented by numerical constants, Kp, derived from the general
expression,
A natural gas, capable of supplying carbon to the metal. The
logKp ¼ B ½6
T
where Kp is termed as the ‘equilibrium constant,’ which is
derived from the values for the concentrations of the reactants
and products of a chemical reaction. The subscript p denotes
the dependency of the chemical reaction on pressure. T is the
absolute temperature at which the reaction takes place. A and
B are constants derived for the particular reaction.
2.3.3.3 Controlling Factors of Carburization
Instead of being developed in a formal way from the basic
principles, the mechanism of carburization may be analyzed
from the view point of carbon flow, by stating the controlling
factors.3 These factors may be divided for discussion into two
distinct classifications:
1. Factors that control the of carbon in iron.
2. Factors that influence the transfer of carbon to the iron
surface.
The mechanism may by explained as follows:
2.3.3.3.1 The flow of carbon in iron
Iron when heated in presence of carbon makes a solid solu-
tion. A solid solution may be described to be a solution of two
or more components as solute and solvent sharing their atoms
in their initial cells in the solid state. In other words a solution
may be defined as any phase of which the composition may
vary continuously within certain limits. Carburizing is con-
cerned with the solid solution of carbon in austenite. The
limits of carbon content of this phase depend on the tem-
perature. The solid solution of carbon in gamma iron is an
interstitial type of solid solution. As is evident from the iron
and iron–carbide thermal equilibrium diagram (Figure 13), at
temperature below about 910 1C (1183 K), pure iron occurs as
a body-centered cubic (bcc) structure. Above 910 1C (1183 K)
there is a temperature range in which iron has a face-centered
cubic (fcc) structure. In fcc lattice, a relatively large unoccupied
‘hole’ exists in the center of the unit cell.10 Carbon being an
extremely small atom can move into this hole to produce a
solid solution of iron and carbon as shown in Figure 14. When
iron has a bcc structure at lower temperatures, the interstices
between the iron atoms become much smaller and conse-
quently the solubility of carbon in bcc iron is relatively small.
The penetration of carbon into the iron forming steel will
depend upon the temperature, the time at temperature and the
carburizing agent. Since the solubility of carbon in steel is the
greatest above the Ac3 temperature, carburization takes place
most readily above this temperature. Furthermore, the higher
the temperature, the greater the rate of carbon penetration,
since the rate of diffusion is greater. It is customary to select a
temperature about 50 1C above the Ac3 point. The carburizing
temperature is an important factor and is usually maintained
within 900–925 1C. The depth of carbon penetration depends
mostly upon the holding time.
Figure 15(a) shows the carburizing procedure in which a
low carbon iron (carbon-free iron) is held for several hours at
a high temperature in contact with an atmosphere, such as
initial carbon content of the iron plate is zero at all distances
from the surfaces. As the carbon atoms go into solution at the
surface of iron, they are free to diffuse further into the plate.
The maximum concentration of carbon atoms in iron at
925 1C can be used from the iron–carbon diagram, and is
about 1.3%C.11 The carburizing atmosphere can build up this
carbon concentration at the surface almost immediately, so
that the carbon penetration curve shortly after the beginning of
carburizing is of the form shown in Figure 15(b). The carbon
penetration source that is produced by carburizing for a
number of hours at a given temperature (925 1C in this case) is
shown in Figure 15(c).
The rate of flow of carbon in austenite depends on values
for the diffusion coefficient and characteristics of the con-
centration gradient. The diffusion coefficient is in turn a
function of temperature and carbon concentration. The diffu-
sion of carbon proceeds from the higher concentration,
developed from the supply source, to the lower concentration

Figure 13 Iron and iron–carbide equilibrium diagram.
of the core when the concentration limits are maintained
consistently, the form of the gradient may be predicted for any
given and constant temperature of operation.3
The general form of the carbon gradient is influenced only
by the range of concentration from surface to the core. For a
given temperature, the rate of diffusion increases with
increasing carbon concentration. For common carburizing
steels and practice, the surface concentration limits are from
1.0 to 1.3%C with core concentration usually from 0.12 to
0.25%C.3 For its attainment, the standard carbon gradient
obviously requires a constant temperature of operation and a
sufficient supply of carbon to the steel surfaces.
Carburizing: A Method of Case Hardening of Steel 83
The case depth for a carburized machine parts may be
considered to be the extent of carbon concentration which on
heat treatment provides the desired uniform mechanical prop-
erties. The case depth for carburized steel is a function of process
temperature and time. It has already been mentioned that the
higher the temperature the greater will be the rate of carbon
diffusion and thus deeper will be the case depth. Experiment
shows that 40% more5 will be the rate of diffusion by 50 1C rise
of carburizing temperature, say from 875 to 925 1C.
For consistent results in carburizing, it is important that
the temperature be uniform. Uniformity in various locations
throughout the work load depends on the furnace design,
84 Carburizing: A Method of Case Hardening of Steel
load density, gas recirculation, and heating rate. For a given
density of load the difference in temperature between the
outer and inner portions of the load may be high at car-
burizing temperatures, because the outside of the load is
heated primarily by radiation and the rate of heating is rapid
to reach to carburizing temperature. For better control of
temperature, the thermocouple should be placed as close as
possible to the work.
F. E. Harris5 has developed a formula for the effect of time
and temperature on case depth for normal carburizing:
pffiffi
31:6 t
Case depth ¼ 6700
10 T
Figure 14 Interstitial solid solution (carbon in face-centered cubic
iron).10
Figure 15 The diffusion of carbon in iron during carburizing. (a) Schematic representation of the procedure used in carburizing an iron plate. (b)
Carbon penetration curve near the beginning of the carburizing process, and (c) after 10 h.11
where case depth is in inches: t is time at temperature, in
hours: and T is the absolute temperature, in degree Rankine.
For a specific carburizing temperature, the relationship
becomes simply:
pffiffi
Case depth ¼ K t
pffiffi
¼ 0:025ptffiffi for 925 1C
¼ 0:021ptffiffi for 900 1C
¼ 0:018 t for 875 1C
When carburizing is purposely controlled to produce
surface carbon concentrations somewhat less than saturated
austenite, the case depth will be slightly less than the Harris
equation shown above. The case depth determined by the
equation is total case depth. For case depths in the range
of 0.040–0.070 in the case depth corresponds to a point on
the carbon gradient where the carbon concentration is about
0.07%C higher than the carbon content of the core.5
In addition to the time at carburizing temperature several
hours may be required for bringing the work to operating
temperature. For work quenched directly from the carburizer,
the cycle may be further lengthened to allow time for the work
to cool from carburizing temperature to a quenching tem-
perature of perhaps 840 1C. Although some diffusion of car-
bon from case to core occurs during this time, diffusion is
slower than it would be at the carburizing temperature. This
period may be used deliberately as a moderate diffusion per-
iod to lower the carbon concentration at the surface by
 Carburizing: A Method of Case Hardening of Steel 85

maintaining an atmosphere of low carbon potential in contact

with the work during this time.5
F. E. Harris5 has also developed a method for calculating
the carburizing time and diffusion time to produce a carbur-
ized case of predetermined depth and carbon concentration at
the surface:

2
C  Ci
Carburizing time ¼ Total time
C0  Ci
and

Diffusion time ¼ Total time  carburizing time

Figure 16 Grain boundaries. Note the area of disorder at the
boundary.
Where total time in hours, C is the final desired surface carbon
concentration, C0 is the surface carbon concentration at the
end of carburizing cycle, and Ci is the concentration of carbon
at the core. Effect of carburizing time and temperature on case
depth obtained in gas carburizing is shown in Figure 7.
Diffusion coefficient varies with the nature of the solute
atoms, with the nature of the solid structure and with changes
in temperature. Higher temperatures provide higher diffusion
coefficients, because the atoms have higher thermal energies
and therefore, greater probabilities of being activated over the
energy barrier. Carbon has a higher diffusion coefficient in Figure 17 Point defects: interstitialcy.
iron because the carbon atom is small one. Atoms have higher
diffusion coefficients in bcc iron than in fcc iron because the
former has a lower atomic packing factor.10
The diffusion proceeds more rapidly along the grain
boundaries because this is a zone of crystal imperfections.10 At
the grain boundaries between two adjacent grains there is a
transition zone which is not aligned with either grains as
shown in Figure 16. The mismatch of the orientation of adja-
cent grains produce a less efficient packing of the atoms along
the boundary. Thus the atoms along the boundary have a
higher energy than those within the grains. This higher energy
Energy

of the boundary atoms is important for the nucleation of

polymorphic phase changes and the lower atomic packing
along the boundary favors atomic diffusion.
Other crystal imperfections namely point defects facilitate
atomic diffusion more rapidly. Interstitials is the most pro-
minent point defect which favors diffusion of carbon in iron
and steel. It arises when an extra atom is ledged within a crystal
structure particularly if the atomic packing factor is low. Such
an imperfection produces atomic distortion as shown in
Figure 17, unless the interstitial atom is smaller than the rest of
the atoms in the crystal.
The interstitial mechanism moves atoms among the
neighboring atoms of the crystal structure shown in Figure 18.
The interstitial atom of Figure 18 has an equal probability
of moving in the six coordinate directions. If the atoms are to
change locations, the ‘energy ridges’ of Figure 18 must be
overcome. The energy required to overcome them is called the
activation energy of diffusion. With interstitial diffusion,
energy is required to force the atom into closer contact with
neighboring atoms as it moves among them. The activation
energy varies with a number of factors. For example, a small
atom has a lower activation energy than a larger atom or a
molecule. Likewise, interstitial movements require more
energy than vacancy movements.10
←Diffusion path→
Figure 18 Atom movements: interstitial mechanism.
2.3.3.3.2 Flow of carbon from the supply source
The primary function of carburizing mediums is to furnish an
adequate supply of carbon to the steel surface. The transfer of
carbon from the source of supply to the steel is involved with
reactions occurring at this surface. The carburizing agent
responsible for the actual transfer of carbon is a carbon com-
pound. The extent to which various carbon compounds may
supply carbon is related to the conditions that determine the
equilibrium with the surface carbon of the steel. The equili-
brium composition of the reactants and products is a function
of temperature and also of the carbon concentration at the
surface.
Low carbon steels when heated to the carburizing tem-
perature, will be completely transformed into austenite. At the
carburizing temperature austenitic iron is capable of holding
86 Carburizing: A Method of Case Hardening of Steel
in solid solution an amount of carbon approaching the
saturation limit of 1.7%. When a source of carbon, such as
carbon monoxide is brought into contact with the steel in this
condition, there will be a transfer of carbon from the gas to the
steel. There is a difference of opinion12 as to the exact form of
the carbon.
Some feel that there is an interaction of the carbon mon-
oxide and the iron to form iron carbides, which are then
absorbed by the steel, others feel that the carbon being
brought to the surface of the metal as carbon monoxide will,
in the presence of austenite, break down to form atomic car-
bon, which will diffuse as such in the iron.
In pack carburization the carburizing compound is in rea-
lity the gas producer. In other words, the carbon monoxide is
the result of the reaction between the carbonaceous com-
pound and the oxygen from the air entrapped with the com-
pound particles. The CO thus formed will give up its carbon to
the iron according to the following equations:
2CO þ 3Fe⇌2CO2 þ ½CFe ½XXXII
Without a further supply of CO this reaction between CO,
CO2, and austenite would soon reach equilibrium and car-
burizing would stop. Herty12 states the CO:CO2 ratio must be
above 24 for this reaction [XXXII] to proceed and also that the
rate of penetration must be about 0.01–0.02 mm h1.
Since at carburizing temperature, there is always a large
amount of incandescent carbon present, the CO2 will be
constantly reduced, so that there will be a continuous supply
of CO according to the reaction:
2CO2 þ C⇌2CO ½XXXIII
This cycle continues to repeat itself, and the process of
carburizing will continue as long as the proper temperatures
are maintained and the CO:CO2 is kept high enough. In this
case the carbon will be absorbed, the concentration of carbon
will be built up at the surface and will then move inward
according to the simple laws of diffusion of heat or dissolved
substances, i.e., from a region of high concentration to one of
lower concentration as stated earlier. The carburizing phase of
case hardening is, thus, one of absorption at the surface plus
inward migration.
Since the usual carburizing compounds have incorporated
in them one or more of the carbonates of alkaline or alkaline
earth metals, it is generally considered that they may react
according to the following equation:
MxCO3 þ heat-MxO þ CO2 ½XXXIV
The M is any metal of the alkaline or alkaline earth group.
The CO2 formed will react with hot carbonaceous packing, as
in reaction [XXXIII], and will increase the concentration of
available CO.
It is also believed that the carbonate reacts with the hot
carbon as:
MxCO3 þ C-MxO þ 2CO ½XXXV
and that the oxide thus formed will act as a catalyst between
the reaction of the CO and the iron.
In gas carburizing, the carbon of the furnace atmosphere is
in the form of gaseous hydrocarbon compounds such as
methane, ethane, propane, and butane or carbon monoxide.
The principal source of carbon in gas carburizing is methane
which is present in manufactured and in natural gas.
The reactions involving the actual transfer of carbon occur
at the steel surface (interface) and the reactants, which are
carbon compounds, may be considered independently. The
interface reactions3,4 for common carbon compounds may be
written as:
CH4 ðgÞ þ 3FeðsteelÞ⇌½CFeðin austeniteÞ þ 2H2 ðgÞ ½XXXVI
C2 H6 ðgÞ þ 9FeðsteelÞ⇌3½CFeðin austeniteÞ þ 4H2 ðgÞ ½XXXVII
C3 H8 ðgÞ þ 9FeðsteelÞ⇌3½CFeðin austeniteÞ þ 4H2 ðgÞ ½XXXVIII
2COðgÞ þ 3FeðsteelÞ⇌½CFeðin austeniteÞ þ CO2 ðgÞ ½XXXIX
Considering the reactions that occur for the same com-
pounds, away from the interface, the reactions for deposition
of carbon3,4 are expressed as:
CH4 ðgÞ-2H2 ðgÞ þ CðSolid carbonÞ ½XXXX
C2 H6 ðgÞ-3H2 ðgÞ þ 2CðSolid carbonÞ ½XXXXI
C3 H8 ðgÞ-4H2 ðgÞ þ 3CðSolid carbonÞ ½XXXXII
2COðgÞ-CO2 ðgÞ þ CðSolid carbonÞ ½XXXXIII
The reactions [XXXVI] and [XXXIX] are definitely reversible
reactions at carburizing temperature. Pure CO2 would dec-
arburize steel to form CO by reversing reaction [XXXIX] and
pure H2 would decarburize steel by forming CH4, the reverse
of reaction [XXXVI]. If water vapor is present in the gas it will
act as a decarburizing agent, removing carbon from steel by
the reaction,3,4
H2 OðgÞ þ Fe3 Cðin austeniteÞ⇌3FeðsteelÞ þ H2 ðgÞ þ COðgÞ
½XXXXIV
2.3.4 Heat Treatment after Carburizing and
Properties of Carburized Parts
The purpose of carburization is to develop hard, wear-resistant
surface, and a tough core in some moving machine parts.
Carburization mainly provides the concentration of carbon on
the surface to a case depth of about 1.25–1.50 mm. The case of
carburized parts is eutectoid or hypereutectoid steel and the
core is a hypoeutectoid steel of initial composition containing
from 0.1 to 0.2% carbon. The mechanical properties of the
machine part will be obviously different for the case and the
core due to differential concentration of carbon and may not
be sufficient enough to respond to the desired properties
wanted from the carburized machine part. Figure 19 represents
the equilibrium microstructure of a carburized machine part
which is furnace cooled after carburizing.

Figure 19 Microstructure of carburized and furnace cooled machine parts (  100). High carbon case at the left, low carbon core at the right.2
Figure 20 Heat treatment cycle without core refinement of carburized steel.
Hence the carburized machine parts are heat-treated to get
higher mechanical properties namely hardness at the surface
and toughness at the core.
2.3.4.1 Single Hardening without Core Refinement
Parts which are pack carburized, are first allowed to cool in the
box, and then heated to a temperature necessary for hardening.
After heating them just above Ac1 temperature (750–780 1C),
they are quenched in water, oil, or salt bath. In quenching
from such a temperature, the outer zone will be hardened and
the core will be partially refined. This avoids overheating of
surface layer and results in reduced distortion. Therefore,
this method is more suitable for treatment of complex
shaped parts.
This method can also be adopted for parts that are car-
burized in salt bath, whose case depth exceeds 0.5 mm with
0.8–1.0% carbon potential. If the parts are quenched directly
from the carburizing bath, it may lead to lower surface
hardness due to presence of retained austenite resulting from
higher surface carbon. Quenching from a low temperature
results a higher hardness. The amount of retained austenite
may be reduced further by subzero treatment. After
quenching, the part is tempered at a low temperature of
150–180 1C to relieve stress. The heat treatment cycle is
shown in Figure 20.
Carburizing: A Method of Case Hardening of Steel 87
2.3.4.2 Single Hardening with Core Refinement
In this method, after carburizing the components are cooled
slowly to room temperature. They are then reheated to a
higher temperature (880–900 1C) for core refinement. Parts
quenched from this temperature possess a higher impact and
tensile strength. This method is widely used for automobile
gears, and the resulting product has a case which secures more
support from the hardened core, specially required for heavy
duty services. A further advantage is the minimized distortion,
since only one quenching treatment is used. The treatment is
best adopted for fine-grained steels. If used on steels posses-
sing marked hardening tendencies, the high quenching tem-
perature favors the retention of austenite due to the presence
of a relatively high proportion of alloying elements. This may
result in some reduction in case hardness. Retention of aus-
tenite is undesirable, and it can be reduced by suitable subzero
treatment. After quenching, the part is tempered at a low
temperature of 150–180 1C to relieve stress. The heat treat-
ment cycle is shown in Figure 21.
Single hardening with core refinement is being increasingly
preferred over other methods. It is true that the grain of the
surface layer is somewhat coarse, but this is quite often
accepted in view of the fact that the mechanical properties of
the core are equal to those produced by a double-hardening
operation.
88 Carburizing: A Method of Case Hardening of Steel
Figure 21 Heat treatment cycle with core refinement of carburized steel.
Figure 22 Heat treatment cycle for double-hardening (double heat treatment) process of a carburized steel part.
2.3.4.3 Double Hardening
Parts of carbon steel requiring high mechanical properties, are
usually subject to double hardening, followed by tempering,
after the carburizing process. The following considerations
made double hardening a necessary procedure in these cases.
After carburizing, the work may be considered to consist
of two layers: an outer layer, which is a eutectoid or hyper-
eutectoid steels and requires a hardening temperature of
750–780 1C (above point Ac1), and a core which is a
hypoeutectoid steel of initial composition containing from
0.1 to 0.25%C and requiring grain refinement by heating
above point Ac3 (for the core), i.e., 880–900 1C. Thus to
improve structure of the core and to impart optimum
properties to the surface layers, a single heating to one
temperature will evidently be insufficient. Therefore, the first
hardening is conducted at temperature of 880–900 1C to
improve the core structure of the work which has been
overheated in carburization. This heating will also dissolve
the cementite network which will not reappearing in
quenching. The second hardening operation is conducted at
750–780 1C to eliminate the effects of overheating and to
impart a high hardness to the carburized case. A schematic
representation of the double heat treatment procedure is
shown in Figure 22. Heat treatment is completed by tem-
pering at 150–180 1C. The variation of hardness and
toughness properties in relation to carbon contents from
surface to the core of the double heat-treated carburized steel
are shown in Figure 23.
The chief disadvantages of this heat treatment are the
complexity of the procedure, excessive warping of the work,
and the possibility of oxidation and decarburization. For these
reasons, single hardening at 820–850 1C is extensively used at
present for inherently fine-grained carbon steels and alloy

steels. Such procedure will refine the grain in both core and
case and, at the same time, warping and decarburization will
be considerably reduced.
2.3.4.4 Direct Quench Technique
In direct quenching method, the components are hardened by
quenching directly from the carburizing temperature. This
method can be employed when the components are carbur-
ized by using molten liquid or a gaseous medium. Quenching
can be done in water, oil, or in a martempering bath,
depending on the type of steel used. For minimum distortion,
Figure 23 Variation of hardness and toughness from surface to the
core of the double heat-treated carburized steel.
Figure 24 Heat treatment cycle for direct quenching of carburized steel.
Carburizing: A Method of Case Hardening of Steel 89
quenching in a martempering bath may be adopted, followed
by air cooling. After water, oil, or martempering bath
quenching, the components are tempered at a low temperature
of 150–180 1C to relieve stress and hence to minimize cracking
and distortion. For this reason direct hardening generally
results in the smallest dimensional changes of the compo-
nents. Figure 24 shows the direct quenching method.
Quenching directly from the carburizing temperature
results in the hardening of both case and core. However,
quenching directly from the carburizing temperature may
leave retained austenite; when high alloy content steels are
treated to minimize the retained austenite this technique is not
suitable. In steels of high alloy content, it is the usual practice
to control the carbon of the case to a somewhat lower level
than in low alloy and plain carbon steels.
Such procedure will refine the grain in both core and case
and, at the same time, warping and decarburization will be
considerably reduced. But for coarse-grained structure at the
case and the core, and high proportion of retained austenite is
found at the case. Therefore, direct quenching for the furnace is
only used when the work is made of an inherently fine-grained
steel and where best properties are not required.
2.3.4.5 Quenchants for Carburized Steels
The carburized parts are hardened by quenching into a cer-
tain medium known as quenchant. The cooling rate for
hardening is controlled by selection of proper quenching
medium. There are numerous quenchants such as brine, tap
water, salts, soluble oil and water solutions, oil and air, etc. If
the part is to be used as heat-treated condition without any
finishing operation to control dimensional accuracy mar-
quenching can be used. In marquenching the part is quen-
ched into molten salts or hot oil keeping the quenchants
temperature above the Ms temperature of the case, but below
the Ms temperature of the core. Consequently, the core
transforms while parts are in the quenchant, to a mixed
microstructure of martensite, bainite, and ferrite. The case
90 Carburizing: A Method of Case Hardening of Steel
transforms to martensite while the parts are cooling in air
after leaving the quenchant.
2.3.4.6 Heat Treatment of Gas-Carburized Steels
Direct quenching is applied to gas-carburized parts at the end
of carburization. The steel is precooled to 840–860 1C in the
carburizing chamber (Figure 25) with the carburizing medium
and then quenched in water or oil.
The surface layer, after heat treatment, will have a mar-
tensite structure with excess carbides. In cases of quenching
direct from the carburizing furnace, the heating temperature
of the core will be in the vicinity of Ac3. In low carbon steels,
austenite cannot be supercooled to the martensite point in
quenching from this temperature and the core will have a
ferrite and bainite structure. After heating austenite in alloy
steels to a temperature close to point Acm, it can easily be
supercooled, without decomposition, to the martensite
point. This core will acquire a low carbon martensite struc-
ture possessing high strength and ample toughness. After
quenching, subzero treatment is done in liquid nitrogen to
transform the retained austenite into martensite. Finally the
part is tempered at a low temperature of 150–180 1C to
relieve stress.
The microstructure of the carburized case of a low carbon
steel after hardening is shown in Figure 26. The normal hard-
ness at the surface of carburized case is usually within the
range of RC 59–64.
2.3.4.7 Subzero Treatment
When alloy steels are subjected to single hardening treatment,
a large amount of retained austenite will be found in the
carburized case. This sharply reduces its hardness. Retained
austenite may be eliminated by a subzero treatment which
transforms mostly into martensite, thereby substantially
increasing the hardness.
Figure 25 Carburizing cycle of gas carburized steel.
2.3.5 Microstructures of Carburized Steels
2.3.5.1 Martensite
The microstructures of hardened carburized steels consist of
high carbon martensite at the surface and low carbon mar-
tensite in the core. High carbon martensite is gradually
replaced by martensite of lower carbon content with increasing
distance from the surface. Lightly tempered martensite is the
dominant microstructural constituent of properly carburized
steel. However, the martensite changes in morphology,
amount, and properties as a function of distance from the
surface. Other case microstructural constituents may also be
present and may significantly affect the performance of car-
burized parts. These other microstructural features include
retained austenite, carbides of various origins, sizes and
morphologies; inclusions; prior austenite grain boundaries
embrittled by phosphorus segregation; microcracks; and pro-
cessing-induced surface oxides. Superimposed on the case
microstructures are compressive residual stresses produced
during quenching. Core microstructures, depending on hard-
enability, may consist of tempered martensite, bainite, or fer-
rite and pearlite.
2.3.5.1.1 How martensite forms
Under slow or moderate cooling rate the carbon atoms are
able to diffuse out of the austenite structure. The iron atoms
then move slightly to become bcc structure. This austenite to
ferrite transformation is a diffusion-controlled process. This
transformation takes place by a process of nucleation and
growth and is time dependent. With still further increase in
cooling rate, insufficient time is allowed for carbon to diffuse
out of solution and although some movement of iron atoms
take place, structure cannot become bcc while the carbon atom
is trapped in solution. The resultant microstructure is called
martensite. It is formed from austenite by a diffusion-less shear
transformation and quenching has the important function of
providing cooling rates rapid enough to suppress competitive
diffusion-controlled transformations of austenite. Martensite

Figure 26 Structure of carburized case of low carbon steel after hardening. (a) normal martensitic microstructure,  250 and (b) with an
increased amount of retained austenite,  500.1
is a supersaturated solid solution of carbon trapped in body
center tetragonal (bct) structure. Two dimensions of the unit
cell are equal, but the third is slightly expanded due to trapped
carbon.
During carburization carbon is introduced into austenite
typically at a temperature of around 925 1C. After carburiza-
tion, martensite is produced by quenching. This martensite is
reheated or tempered at low temperature (150–180 1C) to
produce low temperature tempered (LTT) martensite. This LTT
martensite is the primary component of carburized micro-
structure that gives the desired properties to carburized steel.
Carburizing is applied to low carbon steels containing
typically 0.2 wt%C. The process introduces carbon to the sur-
face of the steel, and the carbon diffuses into the low carbon
interior. Depending on atmosphere control and carburizing
temperature and time, surface carbon contents of 0.8% or
more and carbon gradients over a range of distances, or case
depths, into the steel are produced. The carbon gradients have
a profound influence on martensitic transformation, mor-
phology and properties. The temperature at which martensite
begins to form during the quench is designated as the mar-
tensite start temperature, Ms. As carbon content increases, Ms
decreases.
2.3.5.1.2 Martensite morphologies
The martensite crystals that form at low Ms temperature have a
three-dimensional plate geometry, and hence are called plate
martensite. Figure 27 is a micrograph of martensite in the high
carbon case of a carburized low carbon Ni steel. Adjacent
plates of martensite are nonparallel, and the appearance of the
Carburizing: A Method of Case Hardening of Steel 91
microstructure under the light microscope is that of a zigzag
array of needles or acicular shapes. The needlelike shapes are
in fact cross sections of martensite plates. The plates etch dark
after tempering and are surrounded by white-appearing
retained austenite. The amount of martensite that forms is
determined only by the amount of cooling below Ms; there-
fore, the lower the Ms, the smaller the amount of martensite
and the larger the amount of retained austenite after cooling to
room temperature.
In contrast to high carbon regions, the martensite that
forms in austenite of medium or low carbon content assumes
a completely different morphology. The martensite crystals
appear to have a lath or board-shaped geometry – the crystals
are relatively thin and flat with one long dimension and
adjacent crystals form parallel to each other in stacks or
packets. Figure 28 is a micrograph of martensite in the low
carbon core of a carburized steel.
The high Ms temperature of low carbon austenite provides
a much wider temperature range over which martensite can
form during quenching, and therefore there is little or no
retained austenite in low carbon lath martensites cooled to
room temperature. With increasing carbon content, the
amount of retained austenite in lath martensitic micro-
structures increases, but the austenite is retained as thin films
between the laths and is not resolvable in the light microscope.
The carbon gradients introduced into austenite by carburiz-
ing result, after quenching, in a gradient of martensitic micro-
structure, ranging from plate martensite morphologies with
large amounts of retained austenite to lath martensitic micro-
structures with essentially no retained austenite (Figure 29).
92 Carburizing: A Method of Case Hardening of Steel

Figure 28 Lath martensite microstructure in the core of a gas-

carburized low carbon steel. Light photomicrograph, nital,  300.
Figure 27 Plate martensite microstructure in the case of a gas-
carburized low carbon Ni steel. The ‘needles’ are cross sections of
plates. Retained austenite appears white. Light photomicrograph,
nital,  500.

These gradients in microstructure are related directly to the

hardness and strength gradients produced by carburizing.
Although features resolvable in the light microscope influence
hardness (especially retained austenite, which coexists with plate
martensite in the case region), it is the carbon-dependent fine
structure of LTT martensite crystals that primarily determines the
strength gradients in carburized steels.

2.3.5.1.3 Effect of tempering

When the as-quenched martensite is tempered at low tem-
peratures, very fine carbides precipitate to relieve the carbon
supersaturation. Low tempering temperatures of 150–180 1C
ensure that the precipitated carbides remain fine. In addition,
the retained austenite remains stable at these low tempera-
tures. Consequently, the only microstructural changes pro-
duced by tempering occur on a very fine scale within the
martensite plates. Figure 29 Percent retained austenite as function of carbon content.
The carbides are not cementite, which forms on tempering Vertical lines show carbon ranges in which lath and plate martensites
at higher temperatures, but are transition carbides. These are found in Fe–C alloys.13
transition carbides have been designated either epsilon car-
bides or eta carbides, depending on small differences in their
crystal structures and diffraction patterns. High densities of
tempering lowers the hardness of as-quenched martensite
dislocations, produced by the deformations that accompany
because of the relief of carbon supersaturation and stress relief,
martensitic and subsequent tempering transformations, are
but increases toughness.
also associated with the transition carbides.

2.3.5.1.4 Role of transition carbides 2.3.5.2 Austenite

The higher the carbon content of the martensite, the higher the
density of the clusters of transition carbides after tempering.
These carbide arrays, and the associated dislocation sub-
structures, make deformation by slip or dislocation motion
difficult. As a result, the hardness and strength of LTT
martensite increases with increasing carbon content. This
is illustrated in Figure 30. The figure shows the hardness of
as-quenched martensitic microstructures, and LTT martensitic
microstructures tempered between 150 and 180 1C. The
hardness increase is almost linear up to 0.8%C. At higher
carbon contents, the rate of hardness increase falls because
of larger amounts of retained austenite. Low temperature
Although LTT martensite dominates strengthening in the case
regions of carburized steels, case microstructures are actually
composites of LTT martensite and retained austenite.
Depending on the amount of retained austenite and the
loading conditions in service, the austenite may either degrade
or enhance performance of the part.
2.3.5.2.1 Characteristic features of austenite
Austenite is essential to the manufacture of carburized steels. It
has a high solubility for the carbon introduced into steel by
high temperature exposure to carburizing atmospheres. On
quenching, the high carbon austenite transforms into high

carbon martensite. This high carbon martensite on tempering,
produces high-strength tempered martensite. This high-
strength tempered martensite is the backbone of carburized
steels.
The parent austenite phase influences the microstructure of
carburized steels in several ways. Most important, the chemical
composition of the austenite, directly determines Ms tem-
perature and the amount of austenite retained after quenching
to room temperature.
Also, the grain structure of the parent austenite affects the
martensitic microstructure after quenching, because austenite
grain size limits the size of martensite crystals. Thus, fine-
grained austenite results in fine distributions of martensite
plates and improved mechanical properties.
For this reason, most carburizing grade are aluminum-kil-
led, fine-grain steels. Small amounts of aluminum are added
during melting and dissolve in austenite during subsequent
high temperature bar rolling or forging. At lower temperatures
(about 900 1C), where carburizing is typically performed, the
solubility of aluminum in austenite is low, and the aluminum
combines with nitrogen to form aluminum nitrides. These fine
aluminum nitride particles restrict grain growth during car-
burizing. At higher carburizing temperature the aluminum
nitride particles are coarser and because of higher solubility,
are present in lower densities, resulting in coarser austenite
grain sizes.
2.3.5.2.2 Effect of austenite composition
Martensite transformation start temperature Ms is a function of
chemical composition of austenite. The relation between Ms
and chemical composition is given by the following empirical
equation15:
Ms ð1CÞ ¼ 539  423C  30:4Mn  12:1Cr  17:7Ni  7:5Mo ½7
Figure 30 Hardness as a function of carbon content for as-quenched
martensite and LTT martensite tempered between 150 and 180 1C.
Case martensitic microstructures have similar hardness gradients, with
maximum and minimum values determined by surface and core
carbon contents, respectively.14
Carburizing: A Method of Case Hardening of Steel 93
where the element amounts are in weight percent. The above
equation shows very strong dependence of Ms on carbon
content and lesser dependence of Ms on the alloying elements
manganese, chromium, nickel, and molybdenum, which are
often added to improve hardenability. When the Ms tem-
perature is calculated from the composition of a steel of uni-
form carbon content, or at a point in a carburized case, the
amount of martensite that forms on cooling to a given quench
temperature, Tq, can be estimated from16:
fm ¼ 1  expð0:011 DTÞ ½8
where fm is the volume fraction of martensite, and DT is the
undercooling below Ms(DT ¼ Ms  Tq).
Figure 31 shows martensite and retained austenite in the
case of a carburized microalloyed steel containing small
amounts of niobium. The martensite plates appear dark and
the retained austenite appears white between the martensite
crystals.
2.3.5.2.3 Excessive retained austenite
2.3.5.2.3.1 Effect on properties
Too much retained austenite, B40 vol.% or more, may be
detrimental to the performance of carburized steels in several
ways. Most important, because austenite is of much lower
strength than tempered martensite, the hardness, wear resis-
tance, and fatigue resistance of a carburized part may be
reduced. Also, high retained austenite content may reduce
surface compressive residual stresses and accordingly, con-
tribute to a decrease in fatigue resistance.
2.3.5.2.3.2 Major cause
A very high carbon content is the major cause for excessive
retained austenite. Equations [7] and [8] show that Ms and the
Figure 31 Tempered martensite (black) and retained austenite
(white) in the case of a carburized Nb-microalloyed steel. Light
photomicrograph, nital,  300.
94 Carburizing: A Method of Case Hardening of Steel
amounts of martensite formed on cooling are very sensitive to
carbon content. If carburizing temperatures are high and if the
austenite is allowed to become saturated with carbon, then
large amounts of retained austenite can be expected.
However, excessive austenite may be retained even in
boost-diffuse carburizing in regions of a part where surfaces
meet at included angles of 901 or less. At such corners, carbon
diffuses in from the carburizing atmosphere from two surface,
but the high carbon content that results has only a limited area
through which to diffuse into the interior of the part. The
result is that carbon concentration at the corner remains high
throughout the diffusion step. Excessive retained austenite at
the corner of a gas-carburized low carbon steel specimen is
shown in Figure 32(a). Figure 32(b) shows that surface hardness
at the corner is considerably lower than that of the plane
surface with its more moderate amount of retained austenite.
Massive carbides may also be present at corners because of the
high carbon concentration.
2.3.5.2.4 Reducing retained austenite
In steels directly quenched after carburizing, excessive retained
austenite may be reduced by several methods, such as temper-
ing, refrigeration, or subzero treatment. Process selection
depends on the desired performance level of the carburized part.
2.3.6 Carburization of Alloy Steels
2.3.6.1 Carburization of Low Alloy Steels
Low carbon steel is usually used for carburization because
of its excellent toughness. For high duty applications alloy
steels are also carburized for additional properties of both
the case and the core. In alloy steels, the alloying elements
remain in the form of various carbide and nitride precipitates.
To take precipitates into the solution higher temperature is
required. For this reason, comparatively a higher carburization
temperature is usually selected for alloy steels. Low carbon
steels containing nickel, chromium, manganese, vanadium,
molybdenum, etc. singly or in combination usually have
sufficient hardenability. From these steels maximum case
hardness can be attained by oil quenching and desired core
(a)
Figure 32 (a) Excessive retained austenite at the corner of a speicmen of low carbon steel. Light photomicrograph, nital,  500. (b) Schematic
representation of variation of hardness as a function of distance from a specimen corner or a specimen surface in the same steel.
properties up to a tensile strength of 1380 MPa is obtainable
with suitable toughness by proper selection of the steel
composition.
2.3.6.1.1 Carburization of chromium–nickel steel
Chromium increases the case depth of the carburized steels
while nickel decreases it (Figure 33(a)). Chromium (as Cr3C)
and nickel refine the austenite grain size of the carburized case
but nickel is more effective than chromium in inhibiting the
austenite grain growth (Figure 33(b)). Both chromium and
nickel promote the formation of retained austenite but chro-
mium is more effective than nickel in promoting the forma-
tion of retained austenite in the case of carburized and
hardened steels.17
Microhardness measurements have shown that chromium
in solution and as Cr3C increase and nickel in solution
decreases the hardness of the case while both of them increase
the core hardness although chromium is more effective than
nickel as far as core hardness is concerned (Figure 34).
The hardenability increases with the increase of austenite
grain size and with the extent of carbon penetration in the case
of carburized steels. Nickel and chromium reduce the tough-
ness of the core of low carbon steels in the carburized and
hardened condition. Chromium is more detrimental to
toughness than nickel.18
2.3.6.1.2 Carburization of molybdenum–nickel steel
Both molybdenum and nickel in steel increase the carburized
case depth. Nickel is more effective than molybdenum in
increasing the case depth. The combined effect of molybde-
num and nickel is much greater than that of either molybde-
num or nickel alone in increasing case depth (Figure 35(a)).
The undissolved particles of Mo2C refine the austenite grain
size of the carburized case. Nickel in solution does not have any
effect in restricting grain growth of austenite. But the presence of
nickel enhances the austenite grain size refining effect of
molybdenum steel in the carburized case (Figure 35(b)).
Under identical conditions, molybdenum and nickel
enhance the formation of retained austenite in the case of
carburized and hardened steels but nickel is more effective
than molybdenum in enhancing the formation of retained
austenite. In the presence of molybdenum this enhancing
Hardness
Plane surface
Corner
Case depth
(b)
 Carburizing: A Method of Case Hardening of Steel 95

Figure 33 (a) Variation of effective case depth with carburizing time at 950 1C in steels 1–4 and (b) variation of prior austenite grain size with
carburizing time at 950 1C in the case of steels 1–4.17

Figure 34 Microhardness profiles of steels 1–4 carburized at 950 1C for 1 h, quenched in 10% brine and tempered at 160 1C.18

effect of nickel is increased as shown in Figure 36. Subzero
treatment substantially reduces the retained austenite content
in the hardened cases of all the steels. Molybdenum and nickel
both sluggish the retained austenite transformation to mar-
tensite during subzero treatment. Molybdenum is more
effective than nickel in sluggishing the transformation of
retained austenite to martensite. In the presence of nickel this
sluggishing effect of molybdenum reduces.20
Molybdenum improves and nickel reduces the maximum
case hardness and wear resistance of low carbon steels in the
carburized and hardened condition. The presence of nickel
decreases the effect of molybdenum in the increment of max-
imum case hardness. Molybdenum and nickel both increase the
core hardness but molybdenum is more effective than nickel.
Molybdenum with nickel is more effective in increasing the core
hardness than molybdenum without nickel (Figure 37(a)).
Subzero treatment increases the surface hardness and
maximum hardness of the carburized low carbon steels in the
hardened and tempered condition (Figure 37(b)). The max-
imum surface hardness values of the carburized, hardened,
96 Carburizing: A Method of Case Hardening of Steel

Figure 35 (a) Variation of effective case depth with carburizing time of steels 1–4 carburized at 950 1C and (b) variation of prior austenite grain
size with carburizing time of the case of steels 1–4 carburized at 950 1C.19

1. Plain C steel
2. Mo steel
3. Mo-Ni steel
4. Ni steel

Steel1 Steel 2

Steel3 Steel 4
Figure 36 Optical micrographs showing the microstructures in the case of steels 1–4 carburized at 950 1C for 4 h, quenched in 10% brine and
tempered at 160 1C,  300.20

and tempered plain carbon, molybdenum and nickel steels are
always lower than those of subzero treatment ones (Figure 37).
Molybdenum improves and nickel reduces the wear resistance
of the carburized case of low carbon steel. Subzero treatment
improves the wear resistance of the carburized, hardened, and
tempered cases of low carbon steels containing molybdenum
and nickel alone and in combination. Molybdenum and
nickel both reduce the toughness of the core in the carburized
and hardened condition. Nickel is more detrimental to
toughness than molybdenum. The combined effect of
molybdenum and nickel is greater than that of either molyb-
denum or nickel alone in reducing toughness.20
 Carburizing: A Method of Case Hardening of Steel 97

Figure 37 (a) Microhardness profiles of steels 1–4 carburized at 950 1C for 1 h, quenched in 10% brine and tempered at 160 1C and
(b) microhardness profiles of steels 1–4 carburized at 950 1C for 1 h,quenched in 10% brine, subzero treated in liquid nitrogen and tempered
at 160 1C.20

Figure 38 (a) Variation of effective case depth with carburizing time at 950 1C in steels 6–10, and (b) variation of prior austenite grain size with
carburizing time at 950 1C in case of steels 6–10.21

2.3.6.2 Carburization of Microalloyed Steels
2.3.6.2.1 Carburization of vanadium-microalloyed steel
Microalloying elements such as vanadium with or without
nitrogen and aluminum with nitrogen reduce the case depth of
the carburized steels. Vanadium without nitrogen is more
effective than vanadium with nitrogen in reducing the case
depth while aluminum with nitrogen is the most effective of
all in reducing the case depth (Figure 38(a)).
The undissolved particles of vanadium carbide (VC),
vanadium carbonitride, (V(C,N)) and aluminum nitride (AIN)
all refine the austenite grain size of the carburized case, but
V(C,N) is much more effective than VC; AIN is the most
effective in inhibiting the grain growth of austenite in the case
of carburized steels (Figure 38(b)). Vanadium without nitrogen
does not have any effect in the formation of retained austenite
while vanadium with nitrogen promotes the formation of
retained austenite in the carburized case. Aluminum is the
most effective in promoting the formation of retained auste-
nite in the case of carburized steels (Figure 39).
The undissolved particles of VC and V(C,N) increase the
case and core hardness while AIN reduces the case and core
98 Carburizing: A Method of Case Hardening of Steel
Figure 39 Optical micrographs showing the microstructures of steels 6–10 carburized at 950 1C for 4 h quenched in 10% brine and tempered at
160 1C,  280.22
hardness. V(C,N) is more effective than VC in raising the
hardness of the case and core. Vanadium alone and combi-
nation with nitrogen increase the case and core hardness
(Figure 40) while vanadium alone reduces the toughness, and
vanadium with nitrogen improves toughness.22
2.3.6.2.2 Carburization of niobium-microalloyed steel
Niobium with or without nitrogen decreases the case depth of
the carburized steels. Niobium with nitrogen is more effective
than niobium without nitrogen in reducing the case depth
(Figure 41(a)). Both the undissolved particles of niobium car-
bide (NbC) and niobium carbonitride (Nb(C,N)) refine the
austenite grain size of the carburized case, but Nb(C,N) is
much more effective than NbC in restricting the austenite grain
growth Figure 41(b).
Under identical conditions, niobium alone and in combina-
tion with nitrogen decrease the formation of retained austenite in
the carburized and hardened steels. Niobium with nitrogen is
more effective than niobium in reducing the austenite retention
(Figure 42). Subzero treatment substantially reduces the retained
austenite content in the hardened cases of all the steels.24
Niobium improves the surface hardness and maximum
hardness of the case and core hardness of low carbon steels
in the carburized and hardened conditions (Figure 43(a)).
It also improves wear resistance of the carburized and
hardened low carbon steel. Niobium in combination with
nitrogen causes further improvement in hardness and wear
resistance. Subzero treatment again causes further improve-
ment in the case and core hardness of these carburized steels
(Figure 43(b)).
Both the NbC and Nb(C,N) particles are detrimental to the
toughness of the core of low carbon steels in the carburized
and hardened condition, but Nb(C,N) precipitates are less
harmful than NbC precipitates.24
 Carburizing: A Method of Case Hardening of Steel 99

Figure 40 Microhardness profiles of steels 6–10 carburized at 950 1C for 1 h, quenched in 10% brine and tempered at 160 1C.22

Figure 41 (a) Variation of effective case depth with carburizing time of steels 1–3 carburized at 950 1C and (b) variation of prior austenite grain
size with carburizing time of the case of steels 1–3 carburized at 950 1C.23

2.3.6.3 Low Temperature Carburization of Austenitic
Stainless Steel
2.3.6.3.1 Introduction
Low temperature carburization is a gaseous carburization
process performed at atmospheric pressure, at temperatures
where the kinetics of substitutional diffusion are very slow.
Low temperature (350–550 1C) carburization hardens the sur-
face of austenitic stainless steels through the diffusion of
interstitial carbon, without the formation of carbides. The sur-
face must be activated, by modification and removal of the
naturally occurring chromia (chromium oxide) layer, for the
diffusion process to work. The process results in a hardened
diffusional case on the surface, typically 20–35 mm thick, with
carbon content at the surface in excess of 10 at% and near-
surface hardness of about HV 1200 (over 70 HRC). The case
remains austenitic and retains its ductility.
2.3.6.3.2 Activation
Stainless steels and other chromium-containing alloys obtain
their ‘stainless’ characteristic from the chromium-rich oxide
that forms on the exposed surface. This oxide layer forms when
a fresh surface is exposed to an oxygen containing medium,
such as air, and will form after very short time exposures. The
chromia layer on the surface of stainless steel constitutes a
100 Carburizing: A Method of Case Hardening of Steel

Figure 42 Optical micrographs showing the microstructures in the case of steels 1–3 carburized at 950 1C for 4 h, quenched in 10% brine and
tempered at 160 1C,  300.24

Figure 43 (a) Microhardness profiles of steels 1–3 carburized at 950 1C for 1 h, quenched in 10% brine and tempered at 160 1C. (b) Microhardness
profiles of steels 1–3 carburized at 950 1C for 1 h, quenched in 10% brine, subzero treated in liquid nitrogen and tempered at 160 1C.24

major barrier to low temperature carburization because it
prevents the inward diffusion of carbon. In order to diffuse the
carbon atoms into the stainless steel from the surface, the
chromium oxide layer must be removed, or at least modified
to become carbon-transparent. This step generally is known as
surface activation or depassivation.
Several methods have been developed25–29 that eliminate
the inhibiting effects of the oxide and activate the surface for
efficient transport of carbon from a conventional carburizing
atmosphere into the stainless steel matrix. Some processes,
such as plasma or liquid sodium treatments, readily activate a
passive stainless steel surface by removing the oxide by sput-
tering. In commercial production processing, activation can be
achieved by exposing the furnace load to a halide-containing
gas mixture such as nitrogen trifluoride or hydrogen chloride
and nitrogen at atmospheric pressure. Hydrochloric acid is
effective as an activating gas for a wide range of chromium-
containing corrosion-resistant austenitic alloys, including
stainless steels.
2.3.6.3.3 Processing temperature ranges
Low temperature carburization has a limited temperature
processing range, usually 350–550 1C. At the lower processing
temperature, the process becomes very slow and less eco-
nomically feasible. Lower temperatures mean longer times
for the same case thickness. At the upper end, it becomes
increasingly difficult to avoid the formation of carbides, which
depend in part on the thermally assisted mobility of
substitutional alloying elements, such as chromium, in the
iron matrix. Traditionally, carburization is carried out at
high temperature to maximize the solubility and the rate
of interstitial solute diffusion. On cooling to room tempera-
ture, however, a major part of the solute atoms will preci-
pitate as carbide phases. Figure 44 shows the appropriate

time–temperature–transformation (TTT) diagram for the heat
treatment of an austenitic stainless steel with conventional
carbon contents.30 After high temperature carburization
(T4950 1C), precipitation of carbides can be avoided only by
extremely high cooling rates (path A). Furthermore, it is easy
to exceed the solubility limit at these temperatures and form
carbides during the carburization process itself. At the cooling
rates typical of industrial processes, however, the path will
cross the carbide ‘nose’ and precipitation will occur (path B).
Carburization at low temperatures proved capable of hard-
ening the surface of austenitic stainless steel without forming
phases that would deplete the matrix of chromium, and
thereby degrade corrosion resistance. In this process, the for-
mation of carbides is kinetically suppressed (path C). This
results in an extremely high carbon supersaturation, in fact far
higher than can be achieved by high temperature carburization.
At moderate temperatures, substitutional solutes such
as chromium and nickel diffuse much more slowly in auste-
nitic steels than do interstitial solutes such as carbon. At
450–500 1C, the diffusivity of chromium is on the order
of 10–21 m2 s1,31 whereas the carbon diffusivity at this
temperature is in the range 1016–1017 m2 s1.32–34 This
factor of 104–105 differences in diffusion coefficients enables
homogeneous carburization in austenitic stainless steels (and
other fcc alloys) under conditions where the formation of
chromium-rich carbides is suppressed by insufficient diffusion
kinetics for substitutional solutes. In other words, carburiza-
tion is possible below the nose of the carbide curve on the TTT
diagram shown in Figure 44.
2.3.6.3.4 Carburizing atmosphere
Several carburizing gas species will impart carbon to the active
surface, with varying levels of efficiency at the processing
temperatures required for low temperature carburization.
These include acetylene and carbon monoxide, among others.
A side effect of the high carbon potential needed for processing
can be the generation of soot, which then has to be removed
after processing using standard aqueous cleaning methods.
2.3.6.3.5 Microstructure of the low temperature
carburized layer
The low temperature carburized layer is a diffusion gradient
of carbon in solid solution in the austenite matrix. The struc-
ture of the case has been shown to be expanded austenite.
The lattice parameter of the austenite expands from 0.360 to
Figure 44 Time–temperature–transformation (TTT) diagram of
carbide formation in austenitic stainless steels.30
Carburizing: A Method of Case Hardening of Steel 101
0.372 nm after treatment.35 However, there is no phase
transformation and the layer does not represent a new phase.
Expanded austenite is formed when large amounts of either
nitrogen or carbon (or both) are dissolved in the surface of
an austenitic stainless steel, forming a supersaturated solid
solution without the precipitation of chromium-containing
nitrides or carbides.
2.3.6.4 Carburization of Tool Steels
Carburization may be employed to retard abrasive and adhe-
sive wear in tool steels with satisfactory case depth and
improving hardenability and toughness. Different types of tool
steels require relevant carburization technique.
2.3.6.4.1 Carburization of hot working tool steel
Hot working tool steels generally require a combination of
high temperature strength (i.e., hot hardness and temper
resistance), wear resistance, and toughness. In addition, heat
check resistance is also required for applications involving
thermal cycling.36 To obtain desired properties gas carburizing
can be employed to extensively increase case hardness by
diffusion of carbon into the surface of a component. It is
conducted at a temperature generally over 900 1C, followed by
quenching and tempering operations. A typical gas carburizing
cycle is depicted in Figure 45.
After normal stress relieving annealing treatment, carbur-
ization is carried out at around 930 1C followed by quenching
in oil bath from 830 to 180 1C. Tempering is conducted at
200 1C for 2 h immediately after quenching. After carburizing,
the surface layer is saturated with carbon to a eutectoid or
moderately hypereutectoid content. The microstructure of hot
working tool steels after quenching consists of high carbon
martensite and some amount of carbides (i.e., Fe3C, M7C3,
and M23C6).
The determining factors for gas-carburized tool steels include
microstructure, grain size, morphology and quantity of car-
bides, chemical compositions, hardness, and internal oxidation
including retained austenite. The effect of retained austenite
(softer phase) content has two different schools of thought. The
transformation of retained austenite to martensite act to
increase the yield stress under compression but reduce viscosity,
which is favorable for friction coefficient.37 The presence of
retained austenite, under the effect of the compressive stresses,
resulting from abrasion contact, can harden under the effect of
Figure 45 Gas carburizing cycle for hot working tool steels.36
102 Carburizing: A Method of Case Hardening of Steel
induced work hardening, i.e., strain accommodation resulting
an improvement in terms of friction.38,39 In addition, during
abrasive test the strain accommodation induces ability of
retained austenite to evolve into martensite.40
2.3.6.4.2 Carburization of cold working tool steel
Cold work tool steels are designed for operation under the
conditions of dry friction. Carburization is carried out on cold
work tool steels to modify the surface layer for substantially
increasing its abrasive wear resistance thereby increasing the
quality of manufactured tools.41
Cold work tool steel introduces substantial changes to the
surface layer as a result of changes of the carbide phase and the
matrix. The carbide phase is responsible for the properties of
surface layer. The initial microstructure of cold work tool steel
consists of different degree of refinement of ledeburite carbides
and dissolved dispersion and spheroidization of dispersion
carbides.
After carburizing, the main carbides present in the structure
are of M3C and M7C types with Fe, Cr, V, and Mo in their
composition. Tempering causes carbides of M3C, M7C3, and
M23C6 types to precipitate from the oversaturated martensite
solution with the carbides of types M23C6 occurring only at a
temperature above 550 1C (823 K). The microstructure of
matrix phase consists of a complex of austenite, martensite,
and tempered martensite.
2.3.6.4.3 Carburization of shock resisting tool steel
To address repetitive impact stresses shock-resistant tool steels
are employed. The specific properties to consider are good
fracture toughness performance but with low-to-medium wear
resistance.42,43 To improve the surface hardness of shock
resisting tool steel the vacuum carburizing surface hardening
method can be adopted to obtain high surface carbon content
and hardness.44 The tool steels are generally preheated at
650–700 1C for 30 min carburized at 950 1C for 30 min under
a low-pressure acetylene atmosphere followed by a rapid
quench in nitrogen gas. The carburized and quenched speci-
mens are tempered at around 300–600 1C.
As carburizing is carried out at high austenitizing tem-
perature, alloying elements are easily dissolved in the solid
solution resulting drop in Ms temperature. The microstructure
corresponds to twin martensitic structure and retained auste-
nite within the matrix. After tempering, the microstructure
consists of needle-shaped tempered martensite inside cemen-
tite network.
During tempering, alloying elements, especially Cr, Mo,
and V, combined with the high carbon content supplied by the
carburizing to form a number of carbides of different sizes and
compositions, which strongly influenced the toughness and
strength of the steel. Carbide precipitation results in high
surface hardness when tool steels are tempered. A typical
highest fracture toughness of 80 MPa m1/2 can be obtained
for tools steels tempered at 600 1C.
2.3.6.5 Carburization of Mold Steel
The molds made from low carbon steels (P2, P3, P4, P5, P6) in
which cavities are formed by hubbing are always carburized
before hardening and tempering, and molds made from P20
steel, with its higher carbon content, are frequently carburized
when used for plastic molding. It is extremely important that
the surfaces of parts to be carburized be as clean as possible,
because foreign matter on surfaces may lead to nonuniform
carburizing, which in turn leads to polishing difficulties.
Carburizing is a well-established heat-treating technology
and can be accomplished by gas carburizing, pack carburizing
in solid carbon-containing compounds, liquid carburizing in
salt baths, vacuum carburizing, and plasma or ion carburizing.
Carburizing temperatures may range from 870 to 995 1C, with
carburizing times ranging between 2 and 24 h depending on
the desired case depth.
All the low carbon hubbing grades and P20 are typically
cooled in air or in the pack after carburizing and are therefore
reheated for hardening. Reheating for hardening at tempera-
tures below Acm produces a dispersion of small carbide par-
ticles and a fine austenite grain size. This structure then
transforms on quenching to a fine martensitic microstructure
of high hardness and low susceptibility to intergranular
cracking.45 The carbide particles retained on austenitizing are
incorporated into the martensitic structure, and the retained
austenite content of reheated and hardened case micro-
structures is low.
Mold steels with higher hardenability, such as P4, can be
hardened by air cooling directly after carburizing, but the
retained austenite content may be high and the hardened
microstructure will be susceptible to intergranular crack-
ing.45,46 The retained austenite content can be reduced by
refrigeration at subzero temperatures, but reheating, as noted
above, may more effectively lower retained austenite and
increase hardness.
Austenitizing, quenching, and solution treating of type P21
mold steel are usually done by the tool steel manufacturer.
Therefore, the only heat treatment required after machining is
relatively low temperature aging between 510 and 540 1C for
20–24 h. No surface protection is necessary during the aging
treatment. Type P21 can be simultaneously nitrided and aged
in one operation. Once P21 steel is nitrided, it is very difficult
to resoften or remove the nitrided case.
Tempering of mold steels requires no special precautions.
For plastics molding, a surface hardness near 60 HRC is
advantageous for polish ability and wear resistance, while
molds for die casting of low-melting alloys are operated satis-
factorily at a hardness of about 50 HRC or lower. To ensure
structural stability and hardness retention during operation, a
tempering temperature close to maximum operating tempera-
ture of the mold is desirable, though not always mandatory.
2.3.7 Problems during Carburization and their
Remedy
There are a number of problems usually encountered in the
carburizing process. The most commonly encountered pro-
blems are:
1. Nonuniform carburizing
2. Uneven case depth
3. Insufficient case depth
 Carburizing: A Method of Case Hardening of Steel 103

4. Low hardness carburization. Higher carbon content lowers the MS and Mf

5. Sooting temperatures during quenching. Lower Ms and Mf tempera-
6. Distortion tures enhance the formation of retained austenite which is
7. Soft spots responsible for low hardness of the carburized case.
8. Cracking and exfoliation
9. Grinding cracks. 2.3.7.4.2 Prevention
This problem may be overcome by subjecting the components
The above problems are discussed as follows:
to a single quench treatment. That is after cooling from car-
burizing temperature, the components are heated above the
2.3.7.1 Nonuniform Carburizing critical temperature (800–830 1C), followed by quenching.
This is due to improper cleaning of components before car-
burizing. If the components are dirty, with a greasy work 2.3.7.4.3 Retained austenite
surface or an oxidized surface, it will lead to nonuniform Retained austenite occurs mostly in high alloy steels. The
carburizing. presence of carbon and alloying elements in steels prevent the
transformation of austenite to martensite during quenching.
2.3.7.1.1 Prevention This untransformed austenite is called the retained austenite.
The components are thoroughly cleaned before carburizing, The retained austenite is soft, and hence contributes toward
either by degreasing, or sand blasting, or acid cleaning. lowering the overall hardness of the components.

2.3.7.2 Uneven Case Depth
In pack carburizing, the uneven case depth may be due to an
improper packing or an uneven heating of the container. In gas
carburizing, if the free flow of gas all around the surface is
prevented, some parts of the components will not be in con-
tact with the gas long enough to be carburized.
2.3.7.2.1 Prevention
2.3.7.4.4 Prevention
This situation generally is avoided in gas carburizing by
adopting a two-step process: the first step introduces a high
surface carbon content (41 wt%), while the second is per-
formed at a lower carbon potential, which lowers the surface
carbon content by permitting carbon introduced in the first
stage to diffuse deeper into the steel. This process is often
referred to as boost-diffuse carburizing and if properly con-
trolled, results in reasonable levels of retained austenite.

1. Thorough mixing of the carburizer. 2.3.7.4.5 Decarburization

2. Use of a solution of carbonate and molasses as a binder in
the manufacture of the carburizer.
3. Uniform heat soaking of the container.
4. In gas carburizing, a powerful circulating fan together with
a suitable baffle system should be used to have a uniform
distribution of the gas around the charge.
2.3.7.3 Insufficient Case Depth
Insufficient case depth may be due to the low temperature
employed during carburizing. Insufficient case depth may also
be due to a weak solid carburizer or an insufficient gas feed in
gas carburizing.
In pack carburizing, the decarburization may occur due to
slow cooling rate. As a result carbon content of the surface
deceases. During quenching, low carbon martensite is formed
in the lower carbon surface. This low carbon martensite will
cause low hardness in the carburized layer. Decarburization
may also occur due to the moisture present in the carburizing
mixture.
2.3.7.4.6 Prevention
Carburizing should be repeated at a normal temperature for a
short time, followed by cooling of the container in air at a
faster rate. The carburizing mixture should be dried in order to
make it free from moisture.

2.3.7.3.1 Prevention
1. Carburizing should be repeated with the usual carburizer at
a normal temperature between 900 and 930 1C.
2. In gas carburizing, required case depth can be obtained by
using a strong carburizer and sufficient feeding of gas.
2.3.7.5 Sooting
Sooting in gas carburizing spoils the appearance of the work
and also interferes with carburizing. Sooting is due to an
excessive amount of gas being fed into the furnace, resulting in
a free-carbon deposit on the components and in the furnace.

2.3.7.4 Low Hardness

The common causes of low hardness are mainly due to a
higher case depth, presence of retained austenites and
decarburization.
2.3.7.4.1 Higher case depth
Higher case depth is produced when the surface of the steel is
enriched by higher carbon content (B1.2–1.4% carbon) on
2.3.7.5.1 Prevention
This may be minimized, or prevented, by controlling the car-
burizing atmosphere, so that the rate of carbon supply to the
steel surface does not exceed the rate at which it can be
absorbed. Various methods can be adopted, but the use of
either a diluted hydrocarbon mixture under controlled flow
conditions, or a mixture of gases which will mutually react to
give an atmosphere in equilibrium, is generally satisfactory.
104 Carburizing: A Method of Case Hardening of Steel
2.3.7.6 Distortion
A certain amount of dimensional alteration usually takes place
due to the change in microstructure when a part is quenched.
The distortion may occur during hardening due to the fol-
lowing reasons:
2.3.7.6.1 Release of internal stresses
Stresses can be caused in steel by carrying out rolling, forging
or machining operations before hardening. It is these stresses
that will be released during heating to the hardening tem-
perature and cause heavy distortion after hardening.
2.3.7.6.2 Prevention
It is best to release stresses due to rolling or forging by
annealing or normalizing before machining.
2.3.7.6.3 Drastic quenching
Distortion may take place due to drastic quenching; the extent
depends on the shape of components. Long, slender parts or
parts with abrupt and considerable changes of section will
always warp to a certain extent after the steel is quenched from
the hardening bath.
2.3.7.6.4 Prevention
Distortion will be more if the components are water-quen-
ched, and may be reduced by quenching in oil (60 1C). Fur-
ther, it may be reduced by quenching in a warm bath
maintained at 180–200 1C, and subsequently cooling in air.
2.3.7.6.5 High temperature hardening
When case-hardened mild steel parts of fair size, with only a
superficial case, are water-quenched from approximately
900 1C, there is a decided tendency for warpage and
expansion.
2.3.7.6.6 Prevention
Distortion may be reduced by hardening from a low (780 1C)
or a medium hardening temperature (800–830 1C).
2.3.7.6.7 Rehardening
Sometimes repeated hardening will lead to abnormal dimen-
sional changes in the component, leading to rejection of the
component itself.
2.3.7.6.8 Prevention
It is necessary to counter-check the furnace temperature before
hardening.
2.3.7.6.9 Uneven heating
Uneven heating is a cause of distortion. It is more common in
the ‘box’ carburizing process, where the portion of the com-
ponent nearest to the wall of the box gets heated well before
the central parts get heated. Also, long shafts which have to be
laid horizontally, undergo distortion as the carburizing com-
pound underneath them gets consolidated, resulting in
unevenness. Such parts can be hung vertically by using a
proper fixture.
2.3.7.6.10 Prevention
The carburizing treatment of such components should be done
either by liquid carburizing or gas carburizing to reduce dis-
tortion to a minimum.
2.3.7.7 Soft Spots
The causes of soft spots are as follows:
1. The presence of dirt patches or scale on the surface will
hinder, or entirely prevent, the penetration of carbon. This
may result in soft spots.
2. Unevenness of carburizing may be another cause for soft
sports. This is more common in pack carburizing, if the
compounds are not properly mixed before packing.
3. Soft sports may also result because of the insufficient time
allowed for the center of the pack to attain and remain at
the required temperature for a sufficiently long time during
carburizing. Even though carburization may have taken
place, it may be very thin in some places, and a subsequent
grinding may expose the soft core.
4. Another cause for softness may be the development of an
excessively high temperature under the grinding wheel.
5. Use of an insufficient quenching media, too warm a con-
dition of quenching media, or improper agitation of the
quenchant may also cause soft spots in the case of a heavy
charge.
2.3.7.7.1 Prevention
1. Cleaning the components thoroughly before carburizing.
2. Proper mixing and packing of compounds.
3. Avoiding repeated use of used compounds.
4. Using proper coolant during grinding.
5. Control of temperature of quenching media.
2.3.7.8 Cracking and Exfoliation
Cracking and exfoliation occur on the carburized component
due to the supersaturation of the case with carbon, leading to
the formation of a carbide network. This phenomenon takes
place because of too slow heating to the carburizing tem-
perature (mainly in pack carburizing) with a high carbon
potential.
In pack carburizing, if the concentration of the carburizing
compound is higher, the austenite is supersaturated with car-
bon, leading to precipitation at the austenite grain boundaries,
when the components are subjected to slow cooling from the
carburizing temperature. This structure causes brittleness and
is responsible for the development of cracking and exfoliation.
2.3.7.8.1 Prevention
1. Maintain appropriate carbon potential in the carrier gas
during heating.
2. In pack carburizing, a low activator may be preferred.
3. A faster rate of cooling may be adopted after carburizing.
4. Single or double hardening with case refinement may be
adopted during heat treatment.
 Carburizing: A Method of Case Hardening of Steel 105

2.3.7.9 Grinding Cracks 2. Clark, D. S.; Varney, W. R. Physical Metallurgy for Engineers; 2nd ed.; D. Van
Nostrand Company, Inc.: New York, NY, 1962; pp. 150, 253–255.
The supersaturated case has a greater tendency to crack during 3. Harris, F. E. The Mechanism of Carburization. In The Metal Handbook, 1948
grinding than a eutectoid case. Even a perfect case can crack if an ed.; The American Society for Metal: Cleveland, OH, 1948; pp. 678–680.
unsuitable wheel, without proper dressing, is used. The process of 4. Leighou, R. B. Chemistry of Engineering Materials; 4th ed.; McGraw-Hill Book
grinding heavy cuts or insufficient coolant may also cause cracks. Company, Inc.: New York, NY; London, 1942; pp. 342–345.
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2. Proper dressing. London, 1979; p. 69.
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Depending on the type of the component to be manufactured, Co.: New Delhi, 1967; pp. 406–407.
the following processing sequences may be adopted47: 12. Teichert, E. J.; Metallography and Heat Treatment of Steel, Vol. 3, 2nd ed.;
McGraw-Hill Book Company, Inc.: New York, NY and London, 1944;
A. Small and medium size components: pp. 343–345.
1. forge 13. Stickels, C. A.; Carburizing, Friction, Lubrication, and Wear Technology, ASM
Handbook, Vol 18; ASM International: Metals Park, OH, 1992; pp. 873–877.
2. normalize
14. Grange, R. A.; Hribal, C. R.; Porten, L. F. Hardness of Tempered Martensite in
3. anneal Carbon and Low-Alloy Steels. Metall. Trans. A 1977, 8, 1775–1785.
4. pre-machine 15. Andrews, K. W. Empirical Formulae for the Calculation of Some Transformation
5. carburize and harden Temperatures. J. Iron Steel Inst. 1965, 203, 721–727.
6. temper 16. Koistinen, D. P.; Marburger, R. E. A General Equation Prescribing the Extent of
the Austenite–Martensite Transformation in Pure Iron–Carbon Alloys and Plain
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