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Special Edition.
Linde Gas
Furnace Atmospheres No. 1
Gas Carburizing and Carbonitriding
Preface
This booklet is part of a series on heat treatment, brazing and soldering
process application technology and expertise available from Linde Gas.
The booklet focuses on the use of furnace atmospheres; however, a brief
introduction to each process is also provided. In addition to this work on
carburizing & carbonitriding, the series includes:
Annealing & Hardening
Nitriding and Nitrocarburizing
Sub-zero Treatment of Steels
Brazing of Metals
Soldering of Printed Circuit Boards
Table of contents
I. Introduction
4
II.
A.
B.
C.
7
7
7
9
Properties of Carburized and Carbonitrided Steels
Case Hardness and Carbon/Nitrogen Surface Concentration
Case and Carburizing Depths
Core Hardness
III. Steels for Carburizing and Carbonitriding
10
IV.
A.
B.
C.
D.
E.
F.
G.
H.
Interaction between Furnace Atmosphere and Steel
Carbon Transfer from Gas to Surface
Nitrogen Transfer
Atmosphere Carbon Activity
Atmosphere Carbon Potential
Carbon Concentration Profile Control
Internal Oxidation
Hydrogen Pick Up
Surface Passivation
11
11
13
14
14
15
16
17
17
V.
A.
B.
C.
Carburizing Atmospheres
Endogas
Nitrogen/Methanol Atmospheres
50 %CO/50 %H2 Atmosphere
18
18
18
19
VI. Description of a Nitrogen/Methanol System21
A. Media Storage and Supply
21
B. Distribution to Furnace
22
C. Intake into Furnace
22
D. On-site Nitrogen Generation
22
E. Atmosphere Control
22
VII.Results23
A. Productivity and Reproducibility
23
B. Safety
23
C. Economy
23
VIII. References24
IX. Appendices25
A. Appendix 1: Dew point – carbon potential tables for
nitrogen/methanol atmospheres
26
B. Appendix 2: CO2 – carbon potential tables for
nitrogen/methanol atmospheres
29
C. Appendix 3: Oxygen probe mV - carbon potential tables for
nitrogen/methanol atmospheres
32
D. Appendix 4: Selection of European and
American Safety Standards
35
Introduction
I. Introduction
The purpose of this booklet is to provide an introduction to carburizing and carbonitriding processes. Sections I-III contain a brief
introduction to the processes, the properties obtained and the steels
used. The remaining sections, IV-VII, deal with the properties and
functions of the furnace atmospheres used for these processes.
The highest hardness of a steel is obtained when its carbon content
is high, around 0.8 weight % C (Figure 1). Steels with such high carbon content are hard, but also brittle, and therefore cannot be used
in machine parts such as gears, sleeves and shafts that are exposed
to dynamic bending and tensile stresses during operation. A carbon
content as high as 1% C also makes the steel difficult to machine by
cutting operations such as turning or drilling. These shortcomings
can be eliminated by using a low carbon content steel to machine a
part to its final form and dimensions prior to carburizing and hardening. The low carbon content in the steel ensures good machinability
before carburizing. After carburizing and quenching the part will have
a hard case but a softer core that will assure wear and fatigue resistance. The martensitic case attains a hardness corresponding to its
carbon content, as is shown in Figure 1. The case is typically 0.1–1.5
mm (0.004- 0.060 inches) thick. The core of the part maintains its
low carbon concentration and corresponding lower hardness.
In this booklet we use the term carburizing for a heat treatment process carried out at a temperature where the steel is austenitic, typically in the temperature range 820-950 °C (1510-1740 °F), and which
requires a controlled furnace atmosphere at slight overpressure that
transfers carbon from the atmosphere to the steel surface. Similarly,
the term carbonitriding is used where the aim is to transfer both carbon and nitrogen to the steel surface. The terms carburizing and carbonitriding are normally understood to include hardening, and thus
quenching, as the final step. In this step the carburized or carbonitrided case transforms to a hard martensite microstructure constituent.
The term of case hardening is sometimes alternatively used to more
clearly describe the fact that the process includes the hardening step.
The process cycle shown in Figure 2 also includes tempering, which is
required to ensure ductility by eliminating internal micro stresses and
by somewhat reducing the hardness. After cooling before tempering
there is usually a washing step to remove the quench oil that is used
in the cooling step.
1000
Carburizing
900
800
700
Temp, °C
65
800
500
400
300
60
Tempering
200
600
50
500
400
40
300
30
200
20
10
0
Hardness, HRC
Hardness Vickers
700
Cooling
600
68
900
100
0
0
2
4
6
8
10
12
Time, h
Figure 2: Gas carburizing cycle including the quenching and tempering steps
100
0
0.2
0.4
0.6
0.8
Weight-% C
1.0
1.2
Figure 1: Hardness as a function of carbon content in hardened steel. The shaded area shows the scatter effect of the retained austenite and alloy content of
steel [1].
A carburizing atmosphere must be able to transfer carbon – and
also nitrogen in the case of carbonitriding – to the steel surface to
provide the required surface hardness. To meet hardness tolerance
requirements this transfer must result in closely controlled carbon
or nitrogen concentrations in the steel surface. The carbon concentration, as indicated in Figure 3, can be controlled by the ratio
(vol% CO)2/(vol% CO2) in the furnace atmosphere. The atmosphere
nitrogen activity, which plays an important role in carbonitriding,
Introduction
Gas
Gas/surface
Metal
can be controlled by the ratio vol% NH3 / Vol %H23/2. Expressions for
the atmosphere oxygen and hydrogen activities are also shown in
Figure 3, although they are not of primary interest, but they are related to the oxidation risk for alloying elements and to hydrogen pick
up respectively.
N2
O2
CH4
CO
H
O
H2 O
NH3
CO2
N
C
H2
C 3 H8
2
Carbon activity
Oxygen activity
Nitrogen activity
Hydrogen activity
PCO
PCO2
PCO2
PCO
PNH3
3/2
PH2
or
PCO · PH2
PH O
or
2
or
PH2O
or
PN
or
PH2
PCO
PO2
PO2
2
P
H2
Figure 3: Schematic illustration of atmosphere/metal interaction and
expressions for proportionality between atmosphere composition and carbon
and nitrogen activities. P is the partial pressure, which at atmospheric pressure
is equal to vol% divided by 100.
The procedure in carburizing is as follows. Ready-machined parts
that are to be carburized, for instance gears, are placed in baskets or
mounted (hung) on some type of fixture, see Figure 4c. The basket
(fixture) is loaded into a furnace, which typically is at a temperature
of 820-880 °C (1508-1616 °F) for carbonitriding and 900-950 °C
(1652-1742 °F) for gas carburizing. When the charge has reached
carburizing temperature, the effective transfer of carbon from gas
to steel surface begins. Carburizing is allowed to proceed until the
desired depth of penetration is reached, see Figure 9. The charge is
then moved from the heating chamber to a gas tight cooling chamber
integrated into the furnace. There the load is rapidly quenched in a
quench oil bath. After cooling, the charge normally undergoes washing and tempering. The quenching process is important both in order
to achieve the correct hardness and also to minimize distortions. Sub
zero treatment is sometimes used as a post process after carburizing
and quenching to increase hardness. The principles for quenching
and sub zero treatment are briefly described in references [2] and
[3] and are not described further in this booklet. Dimension-adjusting grinding is normally required before the parts are completely
finished.
a
Oil burn out and
preoxide
Heating
Diffuse
Carburize
b
Quench
tank
Wash
Tempering
b
Figure 4:a) Example of a sealed quench furnace line and charging equipment (left)
and cross section of a sealed quench furnace showing the heat chamber and the
integrated oil quench bath (right) (Courtesy of Ipsen International GmbH.)
c
b) Layout of a continuous carburizing line with the pusher furnace in the center.
c) Example of load.
Introduction
The sealed quench batch furnace shown in Figure 4a is commonly
used within the metalworking industry. In the automotive industry
mostly continuous pusher-type furnaces are used that are more suitable for mass production of parts (see Figure 4b). Conveyor-belt
furnaces, shaker-hearth furnaces or rotary-retort furnaces are used
for small parts, such as screws. Cylindrical batch retort furnaces are
commonly used when long parts are to be gas carburized.
The process of carbonitriding is principally performed in the same
way as carburizing, only with the difference that both carbon and
nitrogen are transferred from the gas to the steel surface. Nitrogen
acts in the same way as carbon to increase the hardness of the hardened steel.
Carburizing and carbonitriding are carried out on parts subjected to
high fatigue stresses or wear, such as parts for transmissions, car
engines, roller and ball bearings, rock drill parts, etc. The automotive
industries and their sub-suppliers are key examples of industries that
have carburizing and carbonitriding as steps in their manufacturing
processes.
Low pressure carburizing – commonly called vacuum carburizing – is
not described in this booklet; however, a detailed description is given
in reference [4]. Pack carburizing and liquid drip feed carburizing are
rarely used alternatives that are not described in this booklet.
After carburizing quenching is mostly carried out using mineral oils.
An alternative, mainly used in vacuum carburizing, is gas quenching.
There have also been initiatives to apply gas quenching to atmospheric pressure carburizing. For further information on gas quenching
the reader is referred to references [2] and [4].
Properties of Carburized and Carbonitrided Steels
II. Properties of Carburized and Carbonitrided Steels
The gas-carburized (carbonitrided) part can be said to consist of a
composite material, where the carburized surface is hard but the
unaffected core is softer and ductile. Compressive residual stresses
are formed in the surface layer upon quenching from the carburizing temperature. The combination of high hardness and compressive
stresses (Figure 5) results in high fatigue strength, wear resistance,
and toughness.
steels obtain an intermediate surface hardness. (See paragraph IV. D
for the relation between carbon concentration and carbon potential.)
Major alloy elements Carbon concentration, %C Surface hardness, HV
Residual
Hardstress
ness
2
N/mm %C HV
Ni (1-4%) 1.5%Cr, 2%Ni, 0.2%Mo
1.5%Mn, 0.004%B
Mn, Cr
Mo, Cr
0.60-0.75
0.65-0.70
0.85
0.70
1.0
620-670
840
815
840
940
1.0 1000
–100
–200
–300
–400
0.9
900
0.8
800
0.7
700
0.6
600
0.5
500
0.4
400
0.3
300
0.2
200
0.1
100
Hardness
The maximum surface hardness after carbonitriding depends on both
the carbon and nitrogen surface concentrations. These concentrations
are typically in the range 0.6-0.9 %C and 0.2-0.4 %N. An approximate
guideline is that martensite with the same total concentration of the
interstitial elements carbon and nitrogen has about the same hardness, irrespective of the relative proportions of the elements carbon
and nitrogen.
Carbon content
Residual stress
0
0.1
0.3
0.5
0.7
0.9
1.1 Depth, mm
Figure 5:Typical hardness, carbon content and residual stress gradients after
carburizing, quenching and tempering
A. Case Hardness and Carbon/Nitrogen Surface Concentration
Maximum hardness for unalloyed steels is obtained when the carbon
concentration is about 0.8%C, as was shown in Figure 1. Above that
carbon concentration the hardness decreases as the result of an increased amount of retained austenite. The hardness curve therefore
often exhibits a drop in hardness close to the surface, where the
carbon concentration is highest. Carbon, nitrogen and almost all alloying elements lower the Ms-temperature (see reference [2] for the
definition of Ms temperature). This leads to a retained austenite concentration gradient that increases towards the surface after carburizing and quenching. To compensate for this effect, the surface carbon
concentration after carburizing that provides maximum surface hardness has to be lowered as the alloy content of the steel increases.
Carbide forming elements, such as chromium and molybdenum, can
counteract this effect and raise the surface carbon concentration that
provides maximum hardness. This is because the formation of carbides leads to a lowered carbon concentration in the austenite, although the average carbon concentration is high. Table 1 gives some
examples of the relation between maximum hardness and carbon
concentration for different types of steels. Mo-alloyed steels obtain
the highest surface hardness and Ni-alloyed steels the lowest. Mn-Cr
B. Case and Carburizing Depths
According to European standards [6], the case depth is abbreviated
to CHD (case hardened depth) and defined as the depth from the surface to the point where the hardness is 550HV, as shown in Figure 6.
Sometimes a hardness other than 550HV is used to define the case
depth.
HV
0
Table 1. Surface carbon concentration for maximum surface
hardness for some types of case hardening steels [5]
550
CHD
Depth from surface, mm
Figure 6: Definition of case depth [6]
The attained case depth depends not only on carburizing depth, but
also on the hardening temperature, the quench rate, the hardenability of the steel and the dimensions of the part. This is illustrated in
the schematic CCT diagrams in Figure 7. The hyperbolic temperature/
time-dependent parts of the transformation curves depict the transformation from austenite to ferrite/pearlite. For a high hardenability
steel these curves are located far to the right in the diagram, ensuring that the cooling curves do not cross the ferrite/pearlite transfor-
Properties of Carburized and Carbonitrided Steels
mation curve. Hardenability increases not only with base steel alloy
content but also with increased carbon and nitrogen concentrations.
The carburized or carbonitrided case therefore has higher hardenability than the base steel. Some examples of how different parameters
will affect hardenability are described in relation to Figure 7 in the
following.
In Figure 7a the cooling curves for both “surface” and “center” cross
the transformation line for the base steel, the core. This means that
the core will transform to ferrite/pearlite upon cooling from hardening temperature. If the cooling curves are related to the “case”
instead, it can be seen that the cooling line for the surface passes
to the left of the ferrite/pearlite transformation curve. Thus the
“surface” cooling line first crosses the Ms (case) line, meaning that
the austenite will transform to martensite, as is the intention in case
hardening.
Temperature, °C
The hardenability of steel number 1 in Figure 7b is too low to result
in martensite transformation even for the carburized case. As shown
in Figure 7c carbonitriding is a method for achieving high enough
hardenability to form a martensitic case. (The “surface” cooling line
Core
Carburized case
Ms (core)
passes to the left of the carbonitrided transformation curve.) Carbonitriding is a way to make water-quench steels become oilhardening
steels.
Figure 7d schematically shows the effect of part dimensions on cooling rate. The bigger the dimensions, the slower the cooling rate.
Therefore there is a certain maximum diameter for a certain steel
grade that can be hardened to form a martensitic case. When a martensitic case is formed the case depth will decrease with increasing
diameter, as shown in Figure 8.
Carburizing depth is not standardized but is nevertheless used in
practice, and is defined as the depth from the surface to the point
corresponding to a specified carbon concentration. As a guideline,
the case depth (CHD) for common steels and part dimensions is approximately equal to the carburizing depth to the point where the
carbon concentration is about 0.35%C (cf. Figure 1). The carburizing
depth depends on treatment time and temperature. With prolonged
carburizing time carbon can diffuse to a greater depth into the steel.
Increasing the temperature increases the rate of diffusion and thus
increases the carburizing depth. This is illustrated in Figure 9.
Temperature, °C
Ms (case)
Steel no 1
Low hardenability
Steel no 2
High hardenability
Ms (core)
Ms (case)
Surface
Core
Surface
Time
Time
Carburized case
Carbonitrided case
Ms (core)
b. Two steels with different case hardenabilities
Temperature, °C
a. Same steel but different core and carburized
case hardenability
Temperature, °C
Core
Ms (case)
Ms (case)
Surface
Core
Time
c. Case hardenability after carburizing and carbonitriding respectively
Figure 7:The relation between the cooling rate of the surface and of the center
to the hardenability of the carburized case and unaffected core.
a. The hardenability of the carburized case, resulting in martensite formation, is
higher than for the non-carburized core that transforms to pearlite.
b. Upon hardening, the case of steel number 2 will transform to martensite,
Small diameter
Large diameter
Time
d. For the same quench severity the cooling rate
decreases with increased part dimensions
whereas the case of steel number 1 will be pearlitic.
c. The carbonitrided case will transform to martensite, whereas the carburized
case will transform to pearlite.
d. The small diameter cools faster, resulting in a martensitic case, whereas the
larger diameter will have a pearlitic case.
Properties of Carburized and Carbonitrided Steels
0.9
900
0.8
800
Depth to 0.3 %C, mm
0.7
Hardness, HV
700
600
1030°C (1886°F)
0.6
0.5
980°C (1796°F)
0.4
930°C (1706°F)
0.3
880°C (1616°F)
0.2
500
0.1
10
400
Diameter, mm 145
300
0
0.2
0.4
0.6
100
0
50
0.8
1.0
1.2
1.4
Depth below the surface, mm
1.6
0
0.2
0.4
0.6
0.8
1.0
Time, hours
1.2
1.4
a. Carburizing depth for a carburizing time of 0-1.6 hours
1.8
mm
3.5
Figure 8: An example of how case depth depends on dimensions [7]
1030°C
(1886°F)
3.0
2.5
Depth to 0.3 %C, mm
Carbonitriding often yields carburizing depths that are somewhat
greater than for pure carburizing. It is an effect caused by the interaction with respect to diffusivity between carbon and nitrogen
The proper case depth requirements are determined by the surface
load, wear conditions, and static and bending fatigue stresses that
the finished part will be subjected to in its service life. A limiting factor is the cost of the required process time, which, as Figure 9 shows,
increases in a parabolic manner as carburizing depth increases. Some
guidelines for case depth specifications are given in Table 2.
Distortion after carburizing and quenching normally results in the
part dimensions not meeting the specified tolerances. The carburizing depth must therefore be high enough to attain the final specified
case or carburizing depth after grinding. Grinding allowance is typically of the order of 0.1-0.2 mm.
C. Core Hardness
Core hardness is not affected by the carburizing process itself but depends only on the type of steel and its carbon content, hardenability,
part dimensions and quenching severity. The best fatigue resistance
both for gears and parts subjected to bending fatigue is obtained
with a core hardness in the range 400-450HV [5].
980°C
(1796°F)
930°C
(1706°F)
2.0
880°C
(1616°F)
1.5
1.0
0.5
0
0
5
10
15
20
Time, hours
25
30
Figure 9: Approximate relationship between temperature, time and carburizing
depth to 0.3%C: Curves are calculated for the following conditions; steel 16MnCr5,
carbon potential 0.8 %C, atmosphere 40% nitrogen/60 % cracked methanol. No
account is taken of heating up time or time for atmosphere conditioning.
There is an interdependence between case and core as regards residual stresses. The amplitude of the compressive residual stresses in
the case is lowered as core strength increases.
Case depth
Remark
Stress
Parts subjected to surface fatigue
1
2
3
1. Shallow case
2. Optimum case
3. Deep case
The case depth shall be deep enough to avoid failure initiated below the surface.
Fatigue strenth
Potential
fallure zone
Applied stress
Distance from surface
Gear
Thin parts
Parts subjected to surface loads
35
b. Carburizing depth for a carburizing time of 0-25 hours
Table 2. Simple rules for selection of case depth
Type of part
1.6
CHD = 0.15 to 0.20 times the gear module
CHD < 0.2 × thickness
CHD = 3 to 4 times the depth to maximum stress
For optimum fatigue life
To prevent through-hardening
10
Steels for Carburizing and Carbonitriding
III.Steels for Carburizing and Carbonitriding
Some rare applications require carburizing of high alloy steels. The
term excess carburizing is used when such steels are carburized to
surface carbon concentrations as high as 2-3%C. The aim is not just
to produce a martensitic case but also to form high concentrations
of carbides and of retained austenite, which has been shown to improve contact fatigue life, as illustrated in Figure 10.
4000
3000
2000
4
L10 LIFE (× 10 )
When selecting the steel type, the first requirement is that the alloy
and carbon concentration meet the requirements for the resulting
core hardness after austenitizing, quenching and tempering. For
specific core hardness requirements this means that, as the dimensions of the treated parts increase, the required alloy content will
also increase. The hardenability of a case hardening steel must be
sufficiently good to result in a martensitic surface case to the required depth. Case hardening steels must therefore contain a certain
amount of alloying elements. A further requirement is that steels for
carburizing should be fine grain treated. This means that the steel
should contain an alloy element, usually aluminum, that creates fine
precipitates. These precipitates act as barriers to grain growth up to a
certain maximum temperature, typically about 950 °C (1742 °F). Examples of some standardized carburizing steels are given in Table 3.
1000
800
600
Carbonitriding can be applied to low cost, low alloy steels. The combination of adding nitrogen as well as carbon to the case increases
the case hardenability sufficiently to result in a martensitic case that
would not be possible with pure carburizing. A few examples of steel
types suitable for carbonitriding are given in Table 4.
400
10
20
30
40
Retained austenite (%)
50
Figure 10: Contact fatigue life of excess carburized steels [8]
Table 3. Composition of selected steel types that can be carburized and hardened
European steel
designation
USA Chemical composition
ASTM steel
designation
%C
%Mn
16MnCr5
5117
16MnCrS5
5117
20MnCr5
5120/5120H
20MnCr S5
5120/5120H
18CrMo4
4118/4118H
18CrMoS4
5120/5120H
16NiCr4
8620
16NiCrS4
20NiCrMoS2-2
8620/8620H
17NiCrMo6-4
17NiCrMoS6-4
AISI 4317
0.14-0.19
0.14-0.19
0.17-0.22
0.17-0.22
0.15-0.21
0.15-0.21
0.13-0.19
0.13-0.19
0.17-0.23
0.14-0.20
0.14-0.20
1.00-1.30
1.00-1.30
1.10-1.40
1.10-1.40
0.60-0.90
0.60-0.90
0.70-1.00
0.70-1.00
0.65-0.95
0.60-0.90
0.60-0.90
%S
%Cr
%Mo
<0.035
0.020-0.040
<[0.035
0.020-0.040
<0.035
0.020-0.040
<0.035
0.020-0.040
0.020-0.040
<0.035
0.020-0.040
0.80-1.10
0.80-1.10
1.00-1.30
1.00-1.30
0.90-1.20
0.15-0.25
0.90-1.20
0.15-0.25
0.60-1.00
0.60-1.00
0.35-0.70
0.15-0.25
0.80-1.10
0.15-0.25
0.80-1.10
0.15-0.25
Table 4. Composition of some steel types that can be carbonitrided
Steel type
Steel for cold-rolled strip
Free-cutting steels
General constructional steel
% C
0.07
max 0.14
max 0.14
0.12-0.18
0.12-0.18
max 0.20
% Si
max 0.30
max 0.05
max 0.05
0.18-0.40
0.10-0.40
max 0.5
% Mn
0.25-0.45
0.90-1.30
0.90-1.30
0.80-1.20
0.80-1.20
(1.0-1.6)
% P
max 0.030
max 0.11
max 0.11
max 0.06
max 0.06
max 0.05
% S
max 0.040
0.24-0.35
0.24-0.35
0.15-0.25
0.15-0.25
max 0.05
% Pb
0.15-0.35
0.15-0.35
0.15-0.35
-
%Ni
0.80-1.10
0.80-1.10
0.40-0.70
1.20-1.50
1.20-1.50
60
Interaction between Furnace Atmosphere and Steel
IV.Interaction between
Furnace Atmosphere and Steel
The primary function of the furnace atmosphere is to supply the
needed carbon – and nitrogen in carbonitriding – and to provide the
right surface carbon content – and surface nitrogen content – in carburized (or carbonitrided) parts. The atmosphere must have a composition that meets these needs and that can eliminate (buffer) the
disturbances caused when air enters the furnace via an open door or
a leakage. To control the surface carbon content, it must be possible
to control the composition of the gas. This is done with a separate
enriching gas, a hydrocarbon, usually propane or methane. In order
to achieve an even heat treatment result, both temperature and gas
composition must remain the same throughout the volume of the
charge. This is achieved by forced gas circulation by means of a fan.
For the sake of safety, the supplied gas flow should create a positive pressure in the furnace in order to prevent air ingress. To ensure
safety it must also be possible to purge a combustible gas out of the
furnace in the event of insufficient furnace temperature, a power
failure or insufficient furnace pressure.
In summary the functions of the furnace atmosphere are to:
– Supply the necessary carbon (and nitrogen)
– Provide the right carbon (and nitrogen) content
– Buffer from disturbances
– Purge
– Give uniform results
– Maintain a positive pressure
– Permit safety purging
A. Carbon Transfer from Gas to Surface
Possible carbon transfer reactions are
components [9]. The slowest carburizing reaction is from
methane, with a rate that is only about 1% of the rate of
carburizing from CO+H2.
In the above reaction, carbon monoxide (CO) and hydrogen
(H2) react so that carbon (C) is deposited on the steel surface and water vapor (H2O) is formed. The furnace atmosphere must contain enough carbon monoxide and hydrogen
to allow the carburizing process to proceed in a uniform and
reproducible fashion. The supply of fresh gas must compensate for the consumption of CO and H2. A higher gas flow
is required in cases where the furnace charge area is high,
resulting in a high rate of carbon transfer from gas to surface. In the initial part of a carburizing cycle, there is also a
high carbon transfer rate, which may be compensated for by
increasing the gas supply.
According to the fundamental principles of chemistry, the
equilibrium condition for the carburizing reaction 1 is described by an equilibrium constant expressed by:
where PH2O etc. is the partial pressure of the respective gas
species. At atmospheric pressure that pressure is obtained
from an atmosphere concentration value expressed in vol%
divided by 100. The value of K1 is dependent on the temperature and can be calculated from the relationship:
2CO → C+CO2
CH4 → C + 2H2
CO+H2 → C+H2O
1.
It has been shown that the last of these reactions, illustrated in
Figure 11, is by far the fastest and is therefore the rate-determining reaction in carburizing atmospheres with CO and H2 as major gas
CO + H2
C + H2O
C
H2
H2O
Figure 11: Schematic illustration of the carburizing process
log K1 = –7.494 + 7130/T
where T is the absolute temperature in Kelvin. ac is termed
carbon activity and is a measure of the “carbon content” of
the gas. We see that ac can be calculated if K1 and the gas
composition are known.
When the carbon activity of the gas, acg, is greater than that
of the steel surface, acs, there is a driving force to transfer
carbon as expressed by the following equation:
CO
K1 = (ac · PH2O)/(PCO · PH2)
dm/dt = k · (acg – as) or dm/dt = k’ · (ccg – ccs)
where:
m designates mass, c concentration per unit volume, t time,
dm/dt expresses a carbon flow in units of kg/cm2 · s or
mol/m2 · s, and k or k’ is a reaction rate constant dependent on temperature and gas composition in accordance
11
12
Interaction between Furnace Atmosphere and Steel
g
g
ac ( c c )
with Figure 12. (Sometimes the notation b is used instead of k’). The
maximum value for k´ is obtained in a gas mixture with equal parts
of CO (carbon monoxide) and H2 (hydrogen), illustrated at the point
marked CARBOQUICK®‚ in Figure 12. Section V explains how to make
use of this.
3.5
C
acs
k' – CARBOQUICK®
Boundary condition
g
s
dm
dc
= k' . ( c c – cc ) = – D .
dt
dx
2.5
k' – 100%
methanol
–7
2
k' × 10 , mol/m s
C
dc
dx
3.0
2.0
Nitrogen + equal parts
of CO and H2
Figure 13: Carbon flux and activities (concentrations) at the gas/steel interface.
Nitrogen + methanol
k' – 60/40 N2/MeOH
1.5
1.0
0.5
0
(ccs )
0
10
20
30
40
50
60
70
80
90
100
Volume % N2
Figure 12: Carbon mass transfer rate coefficient in two types of atmospheres
at 930°C (1742°F) and carbon potential 0.8wt%C as a function of nitrogen dilution. The upper curve shows k’ for an atmosphere with equal concentrations
of CO and H2 and the lower curve k’ for dissociated methanol. k’ calculated
from data in reference [10].
The gradient dc/dx has its highest value at the beginning of the
cycle when carbon has only diffused to a thin depth. This results in a
high driving force for carbon flux by diffusion into the steel. The rate
of the carbon transfer from gas to surface will therefore initially be
the limiting step. At the start of a carburizing cycle, the term (ccg – ccs)
has its highest value, and accordingly the driving force for carbon
transfer from gas to steel has its highest value. The surface carbon
concentration ccs will increase with increasing carburizing time. The
driving force for carbon transfer, (ccg – ccs), will thus decrease. The
carbon concentration gradient, dc/dx, will decrease concurrently as
carbon diffuses into the steel. In conclusion, these limitations will
lead to a continuous reduction of carbon flux into the steel as shown
in Figure 14. About 60 minutes into the carburizing cycle the carbon
flux in the example shown in Figure 14 is reduced to about 20 % of
the initial rate.
Fick’s first law expresses the carbon flux from the surface into the
steel:
5 ·10 –4
dm/dt = – D × dc/dx
where D is the temperature dependent diffusion coefficient for carbon, see Table 5 (not taken into account that the diffusion coefficient
increases with increased carbon and nitrogen concentrations [11]).
Table 5 Typical values of the diffusion coefficient for carbon
and nitrogen in austenite expressed as D = Do × exp – Q/RT
(R = 8.314 J/mol × K) ; D {900°C (1652°F)} is calculated as
example.
2
2
Do , m /s
Q , kJ/mol
D(900°C) m /s
Carbon
Nitrogen
11 × 10–6
20 × 10–6
129
145
20 × 10–12
  7 × 10–12
Since mass balance must exist between carbon flux by transfer
from the gas to the steel surface and by diffusion from the surface
to steel interior, the following boundary condition applies at the
steel surface:
k’ · (ccg – ccs) = – D · dc/dx
as illustrated in Figure 13.
Carbon flux mol/m2s
Rapid carbon transfer controlled
by transfer from gas to surface
4 ·10 –4
3 ·10 –4
Slow transfer
controlled by diffusion
2 ·10 –4
1 ·10 –4
0
0
50
100
150
200
Carburizing time, min
250
300·10 2
Figure 14: Carbon flux as a function of the carburizing time at 930°C (1706°F) in
a 20%CO/40%H2 atmosphere with a carbon potential of 0.8%C.
From the expression for carbon transfer it follows that there are two
fundamentally different ways to increase the rate of carbon transfer.
Firstly, the difference (acg – acs) or (ccg – ccs) can be made as large as
possible. This means maximizing acg. The upper limit is given by
acg = 1, which is the limit for the formation of free carbon or soot.
Another upper limit is given by the fact that the carbon activity must
not exceed the value that corresponds to carbide formation in the
steel. This principle is used in what is called “boost carburizing” or
Interaction between Furnace Atmosphere and Steel
two-stage carburizing (see Figure 18). Secondly, the reaction rate
constant k’ can be maximized. k’ reaches its highest value when the
product PCO · PH2 is greatest, i.e. for an atmosphere with equal parts
of carbon monoxide and hydrogen (See Figure 25).
Both the rate of diffusion and the rate of transfer of carbon from gas
to the steel surface increase exponentially as temperature increases.
Increasing the temperature is therefore one way to shorten the carburizing time, as was shown in Figure 9.
Gas composition and gas flow can be adjusted to obtain the best
economy and fastest carburization. During the phase when the transfer of carbon from gas to surface is rate-determining, the carbon
activity of the gas should be as high as possible, and the product
PCO · PH2 should be maximized.
B. Nitrogen Transfer
Ammonia, NH3 , is added to the furnace atmosphere as the source of
nitrogen in the carbonitriding process. The transfer of nitrogen from
the gas to the steel surface takes place via the reaction illustrated in
Figure 15.
According to this equation it is possible in principle to control the
nitrogen activity by analyzing the NH3 (residual) and the H2 content
of the furnace gas. However, there is no reliable analyzing technique
for closed loop nitrogen atmosphere potential control. The common
practice is instead to add ammonia of the order 1-10 vol% to the inlet
gas stream. Most of the ammonia is dissociated on entering the hot
furnace. Remaining residual ammonia concentrations available for
active nitriding are typically in the range 50-200ppm. An example of
the relation between ammonia addition and the resulting nitrogen
surface concentration is shown in Figure 16. The curves in Figure 16
were established empirically and are valid only for the furnace for
which the analysis was conducted. The reason is that the degree
of ammonia decomposition depends on the catalyzing effect of the
interior surfaces of walls, load baskets, radiant tubes etc. Metallic
surfaces on radiant elements, for instance, catalyze the ammonia
decomposition to a higher degree than ceramic surfaces. The residual
ammonia content, which determines the resulting nitrogen concentration in the steel, will therefore be different for different furnaces,
although the ratio of ammonia addition in the inlet gas stream is the
same. It is therefore necessary to experimentally establish a curve
such as the one in Figure 16 as a guideline for each furnace or furnace type.
2N + 3H2
N
H2
NH3
Figure 15: Schematic illustration of the nitriding process
0.8
0.5
870°C (1598°F)
0.4
900°C (1652°F)
0.3
930°C (1706°F)
0.2
0
0
2
4
6
8
10
12
14
16
18
20
Volume % NH3 in inlet
2 NH3 → N2 + 3H2
It is only the portion that does not decompose – called residual ammonia or NH3 (residual) – that is the active component for nitriding
expressed by the reaction
0.6
0.1
However, most of the supplied ammonia does not actively cause
nitriding, but decomposes into hydrogen and nitrogen in accordance
with the reaction
840°C (1544°F)
0.7
Surface nitrogen concentration, wt% N
2NH3
13
Figure 16: Relation between ratio of ammonia in the inlet gas and resulting
surface nitrogen concentration at four temperatures. The relations are valid only
for the small laboratory furnace for which the analysis was conducted. Industrial
size furnaces require markedly higher ammonia additions than shown here [12].
NH3 (residual) → N + ³/²H2
The same type of equation as given in Figure 13 for the carbon flux
is valid for the rate of nitriding. There is, however, limited data on the
nitriding rate constant k’ and additionally a lack of means to control
the atmosphere nitrogen activity. Therefore it is not possible to calculate reliable results for the rate of nitriding.
The %N-NH3 curves in Figure 16 are approximately linear for low NH3
additions but progress in a parabolic arc to reach a constant maximum nitrogen concentration level above a certain ratio of ammonia
in the inlet gas. The reason is that over a certain nitrogen concentration denitriding is initiated according to the reaction
Similarly to the case of carbon transfer, it is possible to express an
equilibrium constant for the nitriding reaction illustrated in Figure 15
with the expression
/
K4 = (aN × PH³ ²)/PNH (residual)
2
3
2N → N2
During denitriding atomic nitrogen that is dissolved in the steel will
diffuse to weak points such as slag inclusions or grain boundaries
in the steel microstructure and form gaseous nitrogen. The resulting
14
Interaction between Furnace Atmosphere and Steel
equilibrium nitrogen gas pressure is so high that voids and porosities
can form. These porosities will form at lower nitrogen concentrations
when the temperature is increased. This is the reason why the experimentally determined nitrogen concentration decreases as temperature increases, as shown in Figure 16. The 930°C data indicates that
in extreme cases the denitriding may even become higher than the
nitriding rate.
PCH (eq), where PCH (exp) is the actual empirically measured atmos4
4
phere methane concentration, and PCH (eq) is the equilibrium meth4
ane concentration. The actual methane concentration, PCH (exp),
4
is always higher than the equilibrium concentration, PCH (eq). The
4
reason for this is the high stability of the methane molecule, which
means that the reaction
C. Atmosphere Carbon Activity
According to the preceding paragraph, the carbon activity of the furnace atmosphere can be calculated from:
ac = (K1 · PCO · PH )/PH
2
does not reach equilibrium. The carbon activity expressed by
ac = K4 × PCH (exp)/PH 2
4
2
is therefore higher than the equilibrium carbon activity, for instance
based on the equilibrium
2O
The equation is valid under conditions of equilibrium, i.e. the state the
system would assume if it was left undisturbed for an infinite length
of time. Practical experience shows that the assumption of equilibrium
in the gas phase is reasonable for normal carburizing conditions. It is
therefore possible to control the gas composition to the desired carbon activity if the value of the equilibrium constant K1 is known. From
the expression above, we see that the carbon activity can be controlled if PCO , PH and PH O can be controlled. This is the basis for dew
2
2
point analysis (a certain value of PH O corresponds to a certain dew
2
point) for the carbon activity control.
Atmosphere carbon potential is nowadays preferably controlled by
oxygen probe or CO2 infrared gas analysis. This is based on the assumption of gas equilibrium in the water gas reaction
CH4 → C + 2H2
CO + H2O = CO2 + H2
This in turn leads to the assumption that equilibrium also exists for the
carbon-transferring reactions:
2
2CO = C + CO2
with the equilibrium constant K2 =ac · PCO /P CO
CO = C + ½ O2
with the equilibrium constant K3 =ac · PO ½/PCO
2 CO + H2 = C + H2O
The carburizing rate for the methane reaction increases with increased methane concentration. For high methane concentrations
this means that the actual carburizing power will be higher than
predicted by the carbon potential gained from oxygen probe, dew
point or CO2 analysis. The deviation will be highest for CO2 control
and smallest for dew point control. The average carbon potential will
increase as the ratio PCH (exp)/ PCH (eq) increases, as will the scatter
4
4
in attained surface carbon concentration.
To achieve a high quality atmosphere carbon potential control, it is
thus important to keep the ratio PCH (exp)/ PCH (eq) as close as pos4
4
sible to unity. A rule of thumb as a minimum quality requirement is to
assure that the condition
PCH (exp)/ PCH (eq) <10
4
4
is fulfilled. This can be controlled by analyzing the atmosphere
CH4(exp) concentration and by calculating the equilibrium CH4(eq)
concentration.
2
We can therefore express the carbon activities in the furnace gas in
the following alternative ways:
ac = K2 · P2CO /PCO
ac = K3 · PCO / P½O
2
2
D. Atmosphere Carbon Potential
In practice, the concept of “carbon potential” is used instead of carbon activity. The carbon potential of a furnace atmosphere is equal to
the carbon content that pure iron would have in equilibrium with the
gas. The relationship between carbon activity ac and carbon potential
Cp may be expressed by the following equation:
From this it is evident that the carbon activity of the gas can be controlled by controlling the CO2 content or the O2 content, provided that
PCO is known. CO2 control with an infrared (IR) gas analyzer and O2
control with an oxygen probe are practical ways to do this. See also
the tables in the Appendices.
For carbonitriding atmospheres, accurate carbon activity control
should take into account the effect of dilution on the gas composition
caused by the addition of ammonia.
The accuracy of the carbon potential control depends on how close
or how far the atmosphere composition is from equilibrium. The deviation from equilibrium may be expressed by the ratio PCH (exp)/
4
ac = γ ° × xC /(1 – 2 xC)
where xC is the carbon mole fraction that is calculated from Cp and γ °
is a temperature dependent constant expressed by [13]
γ ° = exp {[5115.9+8339,9 · xC /(1-xC)]/T –1.9096}
A graphical presentation of the relation carbon activity – carbon potential is shown in Figure 17. The carbon activity in an atmosphere
should not exceed ac = 1, which is the carbon activity of solid graphite. Over that value soot will form as indicated in the figure.
To calculate the relation between the carbon content in low-alloy
case hardening steels, C, and the carbon potential, Cp , the following
Interaction between Furnace Atmosphere and Steel
1.2
1.1
800°C
(1472°F)
aC = 1 –> Soot
15
regression formulae developed by Gunnarsson [14] and others
[15-16] may be used .
900°C
(1652°F)
1.0
log CP/C = 0.055 · (%Si) – 0.013 · (%Mn) – 0.040 · (%Cr) + 0.014 ·
(%Ni) – 0.013 · (%Mo) – 0.013 · (%Al) – 0.104 · (%V) – 0.009 · (%Cu)
– 0.013 · (%W) + 0.009 · (%Co)
0.9
Carbon activity, aC
0.8
1000°C
(1832°F)
0.7
E. Carbon Concentration Profile Control
Different forms of the carbon concentration profile can be achieved
by varying the carbon potential of the gas during the carburizing
cycle. The two main characteristic carbon concentration curve forms
that can be attained are shown in Table 6. Single stage carburizing
uses one constant carbon potential throughout the carburizing cycle
and results in a carbon concentration gradient with the concave curvature shown in the upper part of the table. Boost carburizing uses
a high carbon potential for most of the cycle time, but at the end of
the cycle the carbon potential is lowered to meet hardness requirements. The resulting carbon concentration curve close to the surface
is convex, as shown in the lower part of the table. As indicated in the
“benefits” column, there are certain advantages of each of these two
types of carburizing cycles.
0.6
0.5
0.4
0.3
Cp = Soot
0.2
0.1
0
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Carbon potential, wt% C
Figure 17: Relationship between carbon activity and carbon potential (= carbon
content in pure iron) at different temperatures.
Table 6. Carbon profile characteristics
Carburizing cycle
Type of carbon profile
Benefits
Single stage
0,8
Temperature
0,6
w%C
Residual stress
distribution that
is optimised for
certain fatigue
properties.
Carbon potential
0,4
0,2
0
Time
0
0,2
0,4
0,6
1,0
1,2
1,4
1,6
Depth, mm
Boost
0,8
Temperature
0,6
Minimized
carburizing time
Grinding allowance
Wear resistance
w%C
Carbon potential
0,8
0,4
0,2
0
Time
0
0,2
0,4
0,6
0,8
1,0
Depth, mm
1,2
1,4
1,6
16
Interaction between Furnace Atmosphere and Steel
Figure 18a shows the calculated carbon concentration profiles for
two cycles with the same carburizing time and temperature, but
where one run as a “single stage” and the other as a “two stage”
“boost” cycle. The boost cycle results in a carburizing depth of
about 1.1mm, whereas the single stage cycle results in a depth of
about 0.9mm, a difference of 0.2mm. Figure 18b shows two carbon
concentration profiles with equal depths but different curve forms
due to the fact that one cycle was run as a 206-minute single stage
and the other as a 146-minute boost cycle.
should be used in the first part of the carburizing cycle. This gives the
fastest carbon transfer. There are two upper limits that the carbon
potential must not exceed. First, the carbon potential must not exceed the limit for the creation of soot. Secondly, for parts subjected
to impact or bending fatigue, the carbon potential must not result
in grain boundary cementite formation in the steel. These two limits
are numerically close to each other, with the soot limit being slightly
higher, as shown in Figure 19. To ensure best results, the atmosphere
carbon potential should not exceed the carbide limit.
If high productivity is preferred, then a “boost” carburizing recipe
should be used. The highest possible atmosphere carbon potential
Figure 19 shows that both the carbide and soot limit increase with
increased temperature. Increased temperature can therefore shorten
the carburizing time not only because of the increased diffusion rate,
illustrated in Figure 9, but also because a higher carbon potential can
be applied, as illustrated in Figure 17.
0.8
During the second part of a boost carburizing cycle the carbon
potential should be lowered to ensure a final surface carbon
concentration with optimum properties and to prevent an excessive
amount of retained austenite.
Two stage
wt%C
0.6
Single stage
1.80
0.4
0
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Depth, mm
a. Equal carburizing time
Carbon potential, wt% C
1.60
0.2
1.40
Soot limit
1.20
Carbide limit
1.00
0.80
0.60
0.8
700
Two stage
wt%C
800
900
1000
1100
Temperature, °C
0.6
Figure 19: Cementite (lower curve) and soot limits as a function of temperature. Cementite limit is calculated for the steel 16MnCr5
0.4
Single stage
0.2
0
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Depth, mm
b. Equal carburizing deth
Figure 18: Calculated carbon concentration profiles for “single-stage” and
“two-stage” carburizing processes at 930°C (1706 °F) with:
a) identical total carburizing time, 5 hours, and
b) identical carburizing depth of 0.7 mm.
With constant time there is an increase in depth from 0.87 to 1.10 mm, i.e.
an increase of 26%. With identical carburizing depths the time decreases
from 206 to 146 minutes, i.e. a decrease of 29%.
“Single-stage process” = constant carbon potential.
“Two-stage process” = high carbon potential for the first three hours and low
carbon potential for the last hour. (Cycles are idealized and do not include
time for ramps for heating and carbon potential change)
F. Internal Oxidation
The oxygen partial pressure in a carburizing atmosphere is typically
of the order of 10–20atm. This low oxygen partial pressure means
that the atmosphere is reducing with respect to iron oxide (FeO)
that has an equilibrium oxygen partial pressure of the order 10–16
atm at normal carburizing temperatures. However, oxides of alloying
elements such as Mn, Si and Cr have equilibrium oxygen partial
pressures of the order 10–24 to 10–30 atm, which are thus much lower
than the oxygen partial pressure of the carburizing atmosphere.
These elements can therefore be selectively oxidized during
carburizing. Selective oxidation is normally seen as grain boundary
oxidation but also as selective oxidation within the grains, see Figure
20. The selective oxidation depletes the matrix composition with
respect to alloy content, leading to lower hardenability. Thus the
outermost surface of carburized steels sometimes contain a pearlitic
non-martensitic structure, see Figure 20b.
Interaction between Furnace Atmosphere and Steel
a
The negative effects of internal oxidation on hardenability can be
compensated for by ensuring that the hardenability of the steel is
sufficient to result in full martensite transformation even after loss of
hardenability from oxidized alloying elements. Another possibility is
to compensate for the hardenability drop by adding nitrogen to the
steel surface as a last step in the carburizing process. This is achieved
by adding ammonia as in carbonitriding but only for a short time, of
the order of 10 minutes, at the end of the carburizing cycle.
b
Figure 20: Grain-boundary oxidation as viewed on
a) a polished un-etched surface and
b) an etched surface exhibiting pearlite in the surface zone of internal
oxidation [17].
Vacuum carburizing completely prevents internal oxidation, as outlined in more detail in reference [4].
Additional uncontrolled oxidation may occur after furnace door openings when loading and unloading takes place. This is a risk especially
during heating. Internal oxides may be the starting points for crack
initiation. The formation of surface pearlite results in a tensile residual stress at the surface. Therefore internal oxidation has a detrimental
effect on fatigue resistance, as illustrated in Figure 21
110
Ni – Cr – Mo
Cr – Mo
Cr
Fatigue limit (kg/mm2)
100
17
G. Hydrogen Pick Up
Some of the hydrogen in the carburizing atmosphere is transferred in
atomic form into the surface layer of the carburized steel. Hydrogen
solubility increases with increased temperature. Upon quenching, the
amount of dissolved hydrogen after carburizing remains in the surface layer, resulting in a supersaturated hydrogen concentration. In
some cases this leads to embrittlement, especially for high strength
steels and for thick case depths. Upon tempering, hydrogen will
leave the surface, but to ensure efficient removal the tempering time
or the tempering temperature has to be increased.
The nitrogen/methanol atmosphere technique is a method that offers the possibility to end the carburizing process with a nitrogen
purge to remove hydrogen (and other active gas species) from the
furnace atmosphere and thereby making the hydrogen to diffuse out
of the steel.
90
80
70
0
5
10
15
H. Surface Passivation
Carburizing can sometimes be blocked because a passive layer is
formed at the surface, which prevents or decelerates carbon transfer.
The passivation is often local, which leads to some surface areas not
being carburized. This may lead to what is called white spots. The
reason for passivation is not completely understood, but suggested
causes are thin adherent oxide layers or adhered substances left over
from operations such as turning or washing before carburizing.
Inernal oxidation depth (µm)
Figure 21: Effect of internal oxidation on the fatigue limit [18]
The surface can be activated to eliminate the passivation effect
by pre-oxidation at a temperature of about 650 °C (1202 °F) or by
pre-phosphating.
18
Carburizing Atmospheres
V. Carburizing Atmospheres
C3H8 + 7.2 air → 5.7 N2 + 3CO + 4H2
CH4 + 2.4 air → 1.9 N2 + CO + 2H2
The mixing and combustion of fuel and air takes place in special endothermic gas generators. See reference [2] for a description of the
endogas generator.
B. Nitrogen/Methanol Atmospheres
Introducing nitrogen and methanol directly into the furnace chamber
is a common way of creating the furnace atmosphere. Upon entering
the furnace, methanol cracks to form carbon monoxide and hydrogen
in accordance with the following reaction:
CH3OH → CO + 2H2
As shown in Figure 22, complete cracking of methanol into CO and H2
only occurs if the temperature is above 700-800°C (1292-1472°F),
H2
30
CO
20
O
H2
40
4
A. Endogas
A carburizing atmosphere can be achieved by means of incomplete
combustion of propane or methane with air in accordance with one
of the reactions:
The cracking of methanol into CO and H2 requires energy. This energy
is taken from the area surrounding the point of methanol injection.
There must therefore be sufficient heat flux towards the injection
point to ensure proper dissociation.
CH
To control the atmosphere carbon potential an “enriching gas” is
also needed. The enriching gas is a hydrocarbon, such as propane or
methane, for increasing the carbon potential. Sometimes air is added
to decrease the carbon potential. For carbonitriding, ammonia is additionally required.
which is why methanol should not be introduced into a furnace at a
lower temperature.
vol. %
There are a number of possible options to produce an atmosphere for
carburizing. Naturally, the atmosphere must have a carbon source,
which could be carbon monoxide, a hydrocarbon, an alcohol or any
other liquid carbon source. To obtain a high quality controllable carbon atmosphere, the options are limited to atmospheres that contain
carbon monoxide and hydrogen in order to result in carburizing according to the illustration in Figure 11. In addition a certain part of
the atmosphere often consists of nitrogen, which acts as a carrier
for the active gases. Nitrogen also dilutes the concentrations of the
active and flammable gases to minimize flames and the risk of soot
deposits. Nitrogen also ensures safety. The combination of N2+CO+H2
is often called the “carrier gas”. Endogas and nitrogen/methanol are
the two main options for carrier gas supply, which is briefly described
in the following two sections. The fastest carburizing is achieved in
an atmosphere consisting of equal parts of carbon monoxide and
hydrogen, as was described in section IV.A. One method of producing
an atmosphere of this kind is described in section C below.
C
10
CO2
0
400
500
600
700
800
900 1000
°C
Figure 22: Resulting gas composition upon cracking of methanol in an atmosphere containing 40 % nitrogen and 60 % cracked methanol.
For every liter of methanol that is added, approximately 1.7m3 of
gas is formed, consisting of one part CO and two parts H2. Different
gas compositions are obtained by varying the mixing ratio between
nitrogen and methanol. Compared with endothermic gas, the nitrogen/methanol system offers the advantage that both the gas flow
and the gas composition can be adjusted to particular needs at any
time. This is illustrated for purging (conditioning) and for atmosphere
disturbance from door openings in Figures 23-24.
A high gas flow is desirable in the following cases:
– At the beginning of a cycle when the furnace is originally airfilled or has been contaminated with air after a door opening. The
higher the gas flow is, the faster the correct gas composition will
be obtained.
– When carbon demand is great, i.e. at the beginning of a process
or in cases with a large charge surface area.
Carburizing Atmospheres
Low gas flow can be used in the following cases:
– When the furnace is empty.
– When the carbon demand is low, i.e. at the end of a process or in
cases with a small charge surface area.
Impurity O2 , CO2 , etc. %
The need to vary the gas composition parallels to some extent the
need to vary flow. A high proportion of methanol, i.e. active portion
19
CO + H2 , is required at the beginning of a cycle when carbon demand
is high. High nitrogen content can be used when the furnace is empty during purging and when carbon demand is low.
To allow the benefits of flow and composition flexibility to be exploited to the full, a more advanced flow control system is required
than is customary for endothermic gas. Continuous flow control with
mass flow meters and motorized valves is the most advanced type of
system. Fixed flow combined with solenoid valves is another possibility. Even being able to adjust the gas flows manually is a considerable advantage.
Low flow
C. 50%CO/50%H2 Atmosphere
In accordance with section IV.A, the fastest carbon transfer is
achieved in an atmosphere consisting of equal parts of CO and H2.
It is technically feasible to create an oxidizing reaction of a hydrocarbon that leads to a ratio of 1:1 between CO and H2 by oxidizing methane with CO2 according to the reaction
High flow
Time
CH4 + CO2 → 2CO + 2H2
Figure 23: Purging of a furnace with inert gas.
Generating a reaction gas atmosphere with an optimum k´ value in
this way is more expensive than generating endothermic or nitrogen/methanol atmospheres. One reason for this is that the reaction
between CH4 and CO2 to form CO and H2 is extremely endothermic
and therefore requires energy. It is therefore only worthwhile using
gases of this kind if it is possible to achieve either cost cuts due to
increased productivity or improvements in quality. The absolute time
saving increases with increased carburizing depth, but the possible
percentage reduction in carburizing time is particularly significant
for low carburizing depths, see Figure 25. For a carburizing depth of
0.1 mm the time saving is close to 20%, but falls to about 5% for
1 mm depth. As seen in Figure 25, the absolute time saving effect in
minutes is greater at lower carburizing temperatures. These benefits
are best utilized in carburizing small components (such as bolts or
Gas flow
Door open
Time
Figure 24: The gas flow can be adjusted to demand
20
35
18
30
880°C
(1616°F)
16
14
Time reduction, %
Time reduction, min
25
930°C
(1706°F)
20
15
980°C
(1796°F)
10
12
10
8
6
4
5
0
2
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Carburizing depth to 0.3%C, mm
Figure 25: a. Calculated time saving in minutes as a function of carburizing depth
and temperature when comparing carburizing in atmospheres containing 50%CO/
50%H2 (CARBOQUICK®) to 20%CO/40%H2 (40%N2-60% cracked methanol).
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Carburizing depth to 0.3%C, mm
b. Approximate relative time saving in % as a function of carburizing depth.
(The calculation was conducted for an atmosphere with 0.8%C carbon potential.
Heating up time and atmosphere conditioning time were neglected).
20
Carburizing Atmospheres
machine components) and thin-walled sheet metal parts to low
carburizing depths in continuous furnaces such as belt furnaces.
1.4
1.2
Atmospheres that only contain CO, H2 and traces of CO2 , H2O and CH4
also have the advantages of improved heat transfer. The heating-up
speed in a chamber furnace was shown to be approximately 4.5 °C/
min for endothermic gas and 5.8 °C/min for the CARBOQUICK®
atmosphere with the same charge load and dimensions. It appears
that the improved emission behavior of the CO contents has a positive effect in that it shortens the heating period and improves heat
conduction due to the increased hydrogen contents.
CARBOQUICK®
Endogas
1.0
wt% C
The results of a production test carried out in order to evaluate the
difference in carburizing rate when using three carburizing atmospheres – CARBOQUICK®, endogas from methane, and direct feed of
natural gas and air (the Ipsen SUPERCARB process) – is shown in Figure 26. For all three atmospheres the carburizing parameters were
the same, temperature 940 °C (1724 °F), carburizing time 180 min.,
and carbon potential 1.2 %C. The result with CARBOQUICK® reveals
a significant increase in the carburizing depth.
0.76 mm
0.9 mm
0.8
Subercarb
0.6
0.4
C = 0.35%
0.2
0.025
0.1
0.3
0.5
0.7
Carburizing depth, mm
Figure 26: Comparison of carburizing depths [19]
0.9
1.1
Description of a Nitrogen/Methanol System
21
VI.Description of a Nitrogen/Methanol System
A nitrogen/methanol system for heat treatment is set up by media
storage, flow control and distribution to furnaces, intake into furnace
and atmosphere control as shown in Figure 27. Assurance of safety is
an important part that has to be integrated into the system.
Liquid methanol
Actual value
Furnace
Temp
Setpoint value
Actual
value
% °C
Setpoint
value
Automatic
Liquid
nitrogen
Propane
Air
Vaporizer
Pump
Methanol tank
Figure 27: Nitrogen/methanol system
A. Media Storage and Supply
The nitrogen is usually stored in liquefied form in a vacuum-insulated
tank. (See description in reference [2]).
Methanol is stored in tanks of varying size depending on the rate
of consumption. Small consumers fill their tanks from barrels, while
large consumers fill them from road tankers. An example of a methanol tank installation is shown in Figure 28.
Figure 28: Methanol tank installation. The liquid nitrogen tank is seen
in the background
22
Description of a Nitrogen/Methanol System
For propane and ammonia, small consumers use cylinders or cylinder bundles and large consumers use tanks. Propane and ammonia
liquefy at relatively low pressures. These “gases” are therefore also
stored in liquid form.
Local safety directives have to be obeyed for all installations.
B. Distribution to Furnace
The nitrogen leaves the storage tank at a medium pressure set on
the tank or cylinders. Inside the industrial premises, the pressure is
reduced before the gas reaches the furnaces.
Methanol is introduced into the piping system by means of a pump.
Propane and ammonia are transported by the pressure in the storage
vessels.
C. Intake into Furnace
The gaseous components in nitrogen-based systems are introduced
in the same way as gas from other systems, i.e. to ensure optimum
mixing and circulation. However, for methanol, which is introduced in
liquid form a special technique is required, which uses lances in order to ensure good vaporizing and cracking regardless of the type of
furnace, location of intake, or whether a fan is used etc. (Figure 29).
D. On-site Nitrogen Generation
One alternative for nitrogen supply is what is called on-site generation of nitrogen. There are primarily three on-site generation methods: 1) Cryogenic on-site generator, 2) membrane or 3) a PSA (Pressure Swing Adsorption) unit. These supply methods are explained in
reference [2].
Especially membrane generators may be an advantageous alternative
compared to high purity liquid nitrogen. Membrane nitrogen typically
has a concentration level of the order of 0.5-2-vol% of the impurity
oxygen. The cost for nitrogen is lowered with an increased concentration level of the impurity oxygen. A carburizing atmosphere typically has 60 vol% of the reducing species CO and H2. A consequence
of these high concentrations is that the oxygen in the membrane
nitrogen stream is reduced, for instance in the reaction
H2+ ½O2 → H2O
CO2 + CO
Figure 29: Examples of methanol injection lancses
thereby eliminating the risk of oxidation. Studies have shown that an
oxygen concentration level of the order of 0.5 -1.0 vol% in the membrane nitrogen stream does not increase the risk of internal oxidation
[20]. However, as the nitrogen should be available for purging in
safety situations the preferred maximum oxygen concentration level
is 0.5vol%.
E. Atmosphere Control
Atmosphere control can be automatic, semiautomatic or manual. In
100% automatic control the flows of different media are automatically adjusted to ensure that the set points for the atmosphere carbon potential and composition are maintained. This is achieved by
connecting gas sampling, gas analysis and flow control to the control
cabinet that contains the required software algorithms, analyzers and
controllers as shown for the example of a nitrogen/methanol system
for a pusher furnace in Figure 30. (This system has the option of injecting water at the end of the furnace in order to lower the carbon
potential and was made for development with results described in
reference [21]).
As a safety precaution, all media except nitrogen should have safety
shut-off devices. The most common method is to allow all additions
only to be made above a given temperature. The additions should
also be stopped at a given minimum flow or nitrogen pressure.
Oxygen Probe CO
CARBOFLEX® cabinet
Gas sampling system
Zone 1
Zone 2
Zone 3
Zone 4
Oil
Gas-/Methanol inlets
Nitrogen/Methanol/C3H8 / Air
Nitrogen/Water
Figure 30: Example of a closed loop atmosphere
control system including atmosphere flow control,
gas sampling, gas analysis and control cabinet.
Results
23
VII.Results
When the results achieved with nitrogen-based systems are evaluated, four beneficial factors in particular stand out:
Productivity
Reproducibility
Safety
Economy
A. Productivity and Reproducibility
The nitrogen gas technique often paves the way to higher production in existing plants. The simplicity and reliability of the gas supply
system reduces production disruptions. Fast atmosphere conditioning
reduces start up time. This feature may be enforced by the use of a
low nitrogen flow during non-production time such as during weekends. This flexibility – in that each medium is controlled separately –
permits variations during the course of the process, especially during
carburizing, so that a shorter process time is achieved. As shown for
instance in Figures 18 and 26, there are ways to drastically reduce
carburizing times by using boost processes or the CARBOQUICK®
technique.
The availability of nitrogen makes it possible to prevent the charge
from being ruined as a result of power failures and the like.
A nitrogen based atmosphere system permits a uniform composition
of the atmosphere in a furnace. Uniformity in turn means fewer rejections and makes it possible to work with closer tolerances on surface
carbon content, hardness and case depth. A closed loop atmosphere
control system helps to ensure close tolerances in the resulting case
depths and surface carbon concentrations.
B. Safety
As methanol is supplied in a separate line from the storage to the
furnace, there is no transport of combustible and toxic gas, as is the
case, for instance, with endogas. Only when methanol is injected into
the furnace are carbon monoxide and hydrogen formed. Compared
with endogas supply the risk of leakages that may form poisonous or
explosive gas mixtures is therefore eliminated.
The availability of the safe and inert nitrogen gas makes it possible
to ensure safety purging in connection with rapid temperature drops,
oil fires etc. Generally, the inert properties of the nitrogen should be
used for protection wherever possible.
N2 flow
–
–
–
–
Quenching
Time
Figure 31: Temporary increase of nitrogen flow at the moment of quenching to
counteract negative pressure which could draw air into the furnace.
C. Economy
All of the factors mentioned above contribute towards good overall
economy. In evaluating the influence of the gas system on the economy of the process, two factors in particular can be pointed out:
– For nitrogen-based gas systems, the fixed cost is a small percentage of the total cost. Due to the low investment required, low
maintenance costs, low material costs and low electricity costs
etc., the quantity of gas consumed is the main cost. This in turn
means that it pays to adjust consumption to the actual need. It has
been shown to be possible to reduce the gas flow by up to 30 %.
Moreover, less gas is consumed at the start, and very small flows
can be used when the furnace is empty. In this way, the total gas
saving can be even higher, in some cases up to 50 %.
– With nitrogen-based systems, the productivity of the process can
often be enhanced in a number of ways. Firstly, its higher operational reliability permits high capacity utilization. Secondly, the
quality of the gas ensures uniform and high yields. Thirdly, the
composition of the gas can be controlled to minimize the process
time. Lastly, both labor and furnace production time can be saved
due to the fact that the start-up time after weekend interruptions
and production stoppages is reduced.
The size of the savings that stand to be made varies between different furnaces and processes.
24
References
VIIIReferences
Author:
Torsten Holm
1. Krauss G., Steels heat treatment and processing principles, ASM Int.,
Materials Park, 1989
2. Andersson R., Holm T., Wiberg S., Furnace Atmospheres No. 2, Neutral
Hardening and Annealing, Linde Gas Special Edition, 43487467 1105 1.1 au,
Munich, 2005
3. Sub-zero Treatment of Steels, Linde Gas Special Edition, 43490875 0104-1.1
au, Munich, 2004
4. Vacuum carburizing and gas quenching, Linde Gas Special Edition,
forthcoming
5. Holm T., Material properties of carburized and carbonitrided steels,
IVF 73625, Stockholm, 1973
6. European standard EN ISO 2639, Determination and verification of the depth
of carburized and hardened cases.
7. Thelning K. E., Steel and its Heat Treatment, Butterworths, London, 1975
8. Furumura K., Murakami Y., Tsutomu A., NSK, Motion and control, no 1, 1996
9. Grabke H. J., Härterei-Technische Mitteilungen, Vol 45, 1990
10. Collin R., Gunnarsson S., Thulin D., Iron Steel Inst., Vol 20, 1972
11. Ågren J., Scripta Metall, Vol 20, 1986
12. Holm T., unpublished work
13. Ågren J., private communication
14. Gunnarsson S., Härterei-Technische Mitteilungen, Vol 33, 1967
15. Neumann F., Person B., Härterei-Technische Mitteilungen, Vol 33, 1968
16. Uhrenius B., Scand. Journ. Met., vol 6, 1977
17. Randelius M., Haglund S., Thuvander A., Gas carburizing and vacuum
carburizing and the case hardening steels Ovako 255 and 16MnCr5 – evaluation of distortion and fatigue properties, Report no IM-2003-546, Swedish
Institute for Metals Research, Stockholm, 2003
18. Namiki K., Isokawa K., Trans. IS13, Vol 26, 1968
19. Jurmann A., Härterei-Technische Mitteilungen, Vol 54, No 1, 1999
20. Laumen C., Åström A., Jonsson S., Härterei Techn. Mitt. Vol 54, No 1, 1999
21. Holm T., Arvidsson L., Thors T., IFHT Heat Treatment Congress, Florens, 1998
Appendices
IX Appendices
A. Appendix 1: Dew point – carbon potential tables for nitrogen/methanol atmospheres
Table 7a: Dew point (°C) for different carbon potentials in an atmosphere
consisting of 100 % cracked methanol and 0 % nitrogen.
Table 7b: Dew point (°C) for different carbon potentials in an atmosphere
consisting of 60 % cracked methanol and 40 % nitrogen.
Table 7c: Dew point (°C) for different carbon potentials in an atmosphere
consisting of 20 % cracked methanol and 80 % nitrogen.
B. Appendix 2: CO2 – carbon potential tables for nitrogen/methanol atmospheres
Table 8a: CO2 content (vol-%) for different carbon potentials in an atmosphere
consisting of 100 % cracked methanol and 0 % nitrogen.
Table 8b: CO2 content (vol-%) for different carbon potentials in an atmosphere
consisting of 60 % cracked methanol and 40 % nitrogen.
Table 8c: CO2 content (vol-%) for different carbon potentials in an atmosphere
consisting of 20 % cracked methanol and 80 % nitrogen.
C. Appendix 3: Oxygen probe mV - carbon potential tables for nitrogen/methanol atmospheres
Table 9a: Output signal from an oxygen probe (mV) for different carbon potentials in an atmosphere
consisting of 100 % cracked methanol and 0 % nitrogen.
Table 9b: Output signal from an oxygen probe (mV) for different carbon potentials in an atmosphere
consisting of 60 % cracked methanol and 40 % nitrogen.
Table 9c: Output signal from an oxygen probe (mV) for different carbon potentials in an atmosphere
consisting of 20 % cracked methanol and 80 % nitrogen.
25
26
Appendices
A. Appendix 1:
Dew point – carbon potential
tables for nitrogen/methanol
atmospheres
Table 7a
Appendices
Table 7b
27
28
Appendices
Table 7c
Appendices
B. Appendix 2:
CO2 – carbon potential
tables for nitrogen/methanol
atmospheres
Table 8a
29
30
Table 8b
Appendices
Appendices
Table 8c
31
32
Appendices
C. Appendix 3:
Oxygen probe mV – carbon
potential tables for nitrogen/
methanol atmospheres
Table 9a
Appendices
Table 9b
33
34
Table 9c
Appendices
Appendices
35
D. Appendix 4:
Selection of European and American Safety Standards
The European Committee for Standardization, CEN, issues its standards in English, French and German. The CEN members translate the
standards into their own languages. In addition to the European
Standards, EN, there are national standards and safety regulations
that have to be taken into account. The CEN homepage is at www.
cenorm.be, from where links are given to national standards authorities.
In the USA the National Fire Protection Association (NFPA) maintains
the main safety standard for heat treatment. In addition standards
and regulations are issued by the U.S. Occupational Safety and
Health Administration (OSHA), and by insurance underwriters. The
Compressed Gas Association (CGA) maintains standards for gases.
National Electrical Codes and local requirements of states and communities will also apply. NFPA standards can be ordered on-line at
www.nfpa.org
The standards given below are a selection of existing standards; for
a full listing of standards the reader is advised to obtain the information from the standardization authorities
Selected European safety standards related to carburizing and carbonitriding
EN-746-1, 1997:
Industrial thermoprocessing equipment - Part 1:
Common safety requirements for industrial thermoprocessing equipment.
EN-746-2, 1997:
Industrial thermoprocessing equipment - Part 2:
Safety requirements for combustion and fuel handling systems.
EN-746-3, 1997:
Industrial thermoprocessing equipment - Part 3:
Safety requirements for the generation and use of atmosphere gases.
EIGA: IGC Doc 17/85
Liquid nitrogen and liquid argon storage installations at user’s premises
Selected American safety standards related to carburizing and carbonitriding
NFPA 86
Standard for Ovens and Furnaces, 2003 Edition
CGA P-18
Standard for Bulk Inert Gas Systems at Consumer Sites
CGA G-2.1, 1999
Safety Requirements for the Storage and Handling of Anhydrous Ammonia
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