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Thermochemical diffusion processes like carburizing, nitriding and
boronizing play an important part in modern manufacturing
technologies. They exist in many varieties depending on the type of
diffusing element used and the respective process procedure. The
most important industrial heat treatment process is case hardening,
which consists of the thermochemical diffusion process of carburizing
or its variation, carbonitriding, followed by a subsequent quench. The
latest developments of using different gaseous carburizing agents
and increasing the carburizing temperature are one main area of this
paper. The other area is the evolvement of nitriding and especially the
ferritic nitrocarburizing process by improved process control and
newly developed process variations using carbon, nitrogen and
oxygen as diffusing elements in various process steps. Also,
boronizing and special thermochemical processes for stainless
steels are discussed.
In thermochemical diffusion processes, elements like carbon,
nitrogen or boron are diffused into metal surfaces in order to enhance
the surface properties and the strength or all-metal components.
In modern heat treatment furnaces, the diffused elements usually
originate from gases reacting at high temperatures with the all-metal
surfaces. This can be a pure thermal and chemical reaction as a
consequence of the thermal dissociation of the gases. An increase of
the reaction velocity can be achieved in utilizing an electric field in
order to ionize the reaction gas (plasma) resulting in largely
increased mass transfer.
The industrial thermochemical diffusion processes existing today are
known as carburizing, nitriding and boronizing. Though they have
existed for many decades, they have evolved with time into more
precisely controlled and reliable processes as part of the total
manufacturing process of metal, especially steel components.
In the last few years, a number of new developments and
improvements in different areas have helped to increase the
importance of diffusion processes, leading to all-metal components
with higher endurance capability.
1. Carburizing
The dominating carburizing technology today is the gaseous
carburizing process which uses endothermic gas, carrier gas and a
hydrocarbon gas, such as natural gas, propane, LPG or others, as
enrichment gas for achieving high carbon potentials. Also, methanol
diluted with nitrogen can be fed into the furnace, which at elevated
temperatures creates a carrier gas inside the furnace similar to
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endothermic gas.
The most economical gassing process is the direct feed of a fuel
(hydrocarbon gas) plus an oxidizing gas (air, carbon dioxide or water)
into the furnace and creating a CO- and H2- containing carburizing
atmosphere inside the furnace [1].
Figure 1 Comparison of gas consumption v alues f or a pusher
Certain requirements like sufficiently high furnace temperatures,
strong gas circulation or furnace muffle, need to exist in the furnace
for a successful utilization of this in-situ gassing technique called
Supercarb [2]. Therefore, years ago, this process was limited to
batch furnaces like pit furnaces and sealed quench furnaces. In the
meantime, the Supercarb process is used also in all types of
continuous furnaces like mesh-belt furnaces, rotary hearth furnaces
and, in the last four years, specially adapted pusher furnaces [3]. The
savings in gas consumption using Supercarb can be very high, as the
example of a pusher furnace in figure 1 shows.
1.1 Low-Pressure Carburizing
Even more process gas can be saved when hydrocarbon gases,
totally without an oxidizing gas, are directly introduced into
carburizing furnaces. In this case, the carbon transfer is a direct
result of the decomposition of the hydrocarbon into free carbon and
hydrogen. Because of the high carbon availability of hydrocarbon
gases, such a process only works with a high dilution of the
hydrocarbon gases or a utilization of the hydrocarbon gases at low
pressures. The last version is the well-known low-pressure
carburizing process.
In the eighties and nineties, the main hydrocarbon gas used for low-
pressure carburizing was propane, despite its inherent deficiencies of
furnace sooting and non-uniform carburizing [4, 5].
Figure 2 Mean carbon f lux v alues (g/m2h) f or dif f erent carburizing processes
In the last five years, the hydrocarbon gas acetylene has taken the
dominant role in low-pressure carburizing. Acetylene has an average
of 10% more carbon transferred compared to propane, increased
carburizing capability, especially on complicated work piece
geometries, and does not show any soot formation if run at a
pressure below 10 mBar [5,6]. This gives acetylene extraordinary
carburizing power.
The main advantages of low-pressure carburizing are the increased
mass transfer resulting in reduced process times, improved layer
uniformity, no internal oxidation, increased stress resistance and
better surface quality (in connection with gas quenching) [7].
1.2 Low-Pressure Carbonitriding
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Until recently, a deficiency still existed, and this was the inability to
do a carbonitriding process at low pressure.
With plasma carburizing, it has been possible for about 30 years to
carbonitride using methane or propane in the boost phases and
nitrogen gas in the diffuse phases [8]. This procedure is not possible
with low-pressure carburizing, as nitrogen gas starts to dissociate
thermally only above 1832F (1000C).
Figure 3 Cy cle f or low-pressure carbonitriding
Lately, however, a method was developed using ammonia at low
pressures in the diffuse phases, or in most cases in the last diffuse
phase, in order to transfer nitrogen next to carbon into the steel
surface (Fig. 3).
Figure 4 Carbon and nitrogen prof iles of a steel 30CrMo4 af ter low-pressure carbonitriding at
880C
Figure 5 Carbon and nitrogen prof iles of a steel 15CrNi6 af ter low-pressure carbonitriding at
930C/820C
Adjusting the time and temperature ratio of the ammonia utilization
against the acetylene utilization allows for the production of defined
carbon and nitrogen surface contents. In this way, relatively low
surface nitrogen contents (e.g., 0.3 wt.-%, as in Fig. 4) or very high
surface nitrogen contents (e.g., 0.7 wt.-%, as in Fig. 5) can be
produced [9].
The advantage of carbonitriding versus carburizing is that a
carburized microstructure with an increased content of nitrogen has a
higher temperature resistance, an increased hardenability, improved
wear resistance and, in some instances, a higher load carrying
capability [10].
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Figure 6 Inf luence of temperature and carbon potential on carburizing depth and cy cle duration
1.3 High-Temperature Carburizing
Another trend in the last few years is the increased utilization of
higher carburizing temperatures with the main goal to reduce cycle
times and, thus, save costs. Fig. 6 shows curves of carburizing
depths versus carburizing times for four different carburizing
temperatures of 1616F, 1706F, 1796F and 1922F (880C, 930C,
980C and 1050C) for gaseous carburizing in endothermic gas and
different carbon potentials. In this diagram, the time saving for
different carburizing depths in using higher carburizing temperatures
can be seen. For example, a carburizing depth of 1.2 mm, the
holding time on temperature can be reduced from 400 minutes to 220
minutes to 115 minutes by increasing the carburizing time (on
temperature) from 1706F to 1796F and further to 1922F (930C,
980C and 1050C, respectively).
Figure 7 Industrial applications of high-temperature Carburizing f urnaces
Naturally, the utilization of higher carburizing temperatures of above
1832F (1000C) can also be done with low pressure carburizing, as
can be seen in Fig. 2. Vacuum furnaces for low-pressure carburizing
are even more adapt for higher temperatures because the material
used for the furnace lining and the furnace heating elements is
usually graphite, which has very high temperature resistance. But
also atmosphere furnaces for gas carburizing are today increasingly
used for high-temperature carburizing, as the table in Fig. 7 shows.
Thus, even in sealed quench furnaces, temperatures of 1859F and
1868F (1015C and 1020C) are used today industrially, and also
pusher furnaces have gone up to 1796F (980C) [11].
This is due to the increased use of newly developed silicon carbide
materials for hearth, muffles and especially radiant tubes.
The main problems remaining with high temperature carburizing is
the grain growth of existing case hardening steels and the reduced
lifetime of grids and baskets.
2. Nitriding
2.1 Control of the Nitriding Potential
The state of the art of nitriding in ammonia or diluted ammonia gas is
to control the nitriding potential. The nitriding potential is defined as:
KN = p(NH3)
p(H2
3/2
)
This definition is a direct consequence of the ammonia dissociation
reaction:
NH3 [N] + 3/2 H2
By choosing the respective nitriding potential, nitrogen-rich
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compound layers of the s-nitride, nitrogen-poor compound layers of
the -nitride as well as totally compound- layer-free nitrided surfaces
can be produced.
The so-called Lehrer diagram also gives good guidelines for industrial
steels and what type of compound layer to expect for the respective
nitriding potentials controlled in the furnaces [12].
For controlling the nitriding potential, it is necessary to measure
either the ammonia content or the hydrogen content of the
atmosphere. This can be done with infrared or other gas analyzers.
The state of the art is, however, to measure the nitriding potential
continuously online directly inside the furnace with a hydrogen
sensor called HydroNit [13]. This sensor, the scheme of which is
shown in Fig. 8, is capable of directly measuring the partial pressure
of hydrogen inside the nitriding furnace using a measuring tube of a
special material capable of being permeable only to hydrogen gas.
Figure 8 Principle of the Hy droNit-Sensor
2.2 Ferritic Nitrocarburizing
In ferritic nitrocarburizing, both nitrogen and carbon are transferred
into the steel surface to produce a nitrogen and carbon containing ?-
compound layer.
The gas used for this process, therefore, is a mixture of ammonia
gas and a carbon carrying gas. Standard industrially-used gases are
a mixture of ammonia and endothermic gas (50:50) or a mixture
consisting of ammonia plus CO2 (5%) and nitrogen gas (45%) [14,
15].
In these gas mixtures, the nitrogen transfer depends on the ammonia
dissociation just like in nitriding. The carbon transfer is caused by the
CO-hydrogen reaction:
CO + H2 [C] + H2O
with gases with high CO-content (endothermic gas) delivering much
more carbon than those with low CO-content (CO2).
Figure 9 Chemical composition of ?-compound lay er produced by dif f erent nitriding and
carburizing potentials [16].
The main problem with the nitrocarburizing atmospheres produced by
these two gas mixtures is that the carbon content and the nitrogen
content in the compound layer cannot be adjusted independently of
each other. The carbon transfer increases with higher hydrogen
content, which at the same time, however, lowers the nitriding
potential. Thus, automatically compound layers produced in ferritic
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nitrocarburizing with the two gas mixtures mentioned above will have
a low carbon content if a high nitrogen content is produced, and vice
versa (Fig. 9) [16].
With a new method developed in the last few years, it is possible to
produce ?-compound layers in ferritic nitrocarburizing which have at
the same time a high nitrogen content as well as a high carbon
content. J. Wnning had already in 1977 shown that the strongest
carbon transferring gases in nitrocarburizing next to endothermic gas
are hydrocarbon gases, and especially propane [17].
Figure 10 Special two-step FNC cy cle resulting in ?-lay ers with large nitrogen and carbon
content
The new method developed [18] splits the nitrocarburizing cycle in
two parts with the first part run in ammonia plus CO2 and nitrogen in
order to produce a high nitrogen content in the compound layer. The
second part is run in a gas mixture consisting of ammonia and
propane (plus nitrogen) (Fig. 10).
2.3 Ferritic Oxi-Nitrocarburizing
Oxi-nitriding has also been known since the 1970's and was noted for
faster surface reactions and higher nitrogen transfer [19]. It never
gained much importance, as in pure classical nitriding in ammonia
gas the growth of the compound layer was already sufficiently fast,
and the goal in those days was more to restrict its thickness than to
improve it.
With the short time cycles of ferritic nitrocarburizing and the problem
with sometimes bothered surface reactions due to passive oxide
layers on the surface of the steel components, the importance of the
utilization of oxygen in a first part of an fnc cycle was noticed about
three years ago [20].
This led to the development of the ferritic oxi-nitrocarburizing process
with air being added to the nitriding atmosphere inside the furnace
during the last part of the heating cycle and the first part of the
nitrocarburizing cycle. H.-J. Spies examined this effect and found,
that high oxidizing potentials are needed in order to transform the
passive oxide layer into a nitrogen permeable layer of iron oxide [21].
Figure 11 Structure and hardness prof ile of an oxi-nitrocarburized austenitic stainless steel
X5CrNi 18-10 (DIN 1.4301)
The ferritic oxi-nitrocarburizing treatment is favorably used for higher
alloyed materials (e.g., hot and cold working tool steels and also
especially stainless steels), as the example of the steel X5CrNi 18-
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10 (DIN 1.4301) in Fig. 11 demonstrates.
3. Special Processes for Stainless Steels
Stainless steels, if treated with normal nitriding or carburizing
processes, lose most of their corrosion resistance due to the
formation of chromium nitrides or carbides.
By the development of new low-temperature or high-temperature
processes, this deficiency can be overcome.
3.1 Plasma-Carburizing of Austenitic Steels
Figure 12 Microstructure of the steel X2CrNiMo 18-14-3(DIN 1.4435) af ter plasma-carburizing
at 662F (350C) [22]
Lowering the carburizing temperature to values, which prohibit the
formation of chromium carbides (Cr23C6) (i.e., to temperatures below
752F [400C]), can produce a thin shallow surface layer
supersaturated with carbon with a large hardness increase and
basically no loss of corrosion resistance.
Fig. 12 shows as an example the microstructure of the steel
X2CrNiMo 18-14-3 (DIN 1.4435) after plasma carburizing for 96 hours
at 662F (350C), having produced a carburized layer of 25 ?m
thickness with a hardness of approx. 1150 HV and a carbon content
of approximately 3 wt.-% [22]. Because of the low temperature, there
are hardly any dimensional changes involved with this process.
Figure 13 Microstructure of the steel 314L af ter plasma-nitriding at 752F (400C) [23]
The formation of the chromium nitrides CrN and Cr2N can be avoided
by nitriding at temperatures below 878F (470C) leading to a shallow
(10-30 ?m) nitrogen super-saturated diffusion layer of high hardness
(approximately 1100 HV) [23].
The structure of such a layer produced on the steel 314L after
plasma-nitriding at 752F (400C) is shown in Fig.13 [23]. This
process is used in different areas of food processing equipment,
chemical industry, nuclear power plants, etc.
3.3 Solution Nitriding
The low-temperature processes of plasma-carburizing and
plasmanitriding have the disadvantage that the thickness of the
diffusion layers produced are extremely shallow, in economical times
reaching not much above 20 JTM.
A new developed process is able to overcome this deficiency and to
produce hardened layers on stainless steels with thicknesses of up
to 1 and even 2 mm without any loss of corrosion resistance.
This process uses the capability of stainless steels to dissolve
nitrogen at temperatures above 1832F (1000C) to a large extent
without formation of chromium nitrides.
This process was developed theoretically and in the laboratory by
Professor H. Berns [24]. The industrialization of the solution nitriding
technology SolNit

was done in a joint co-operation between


Professor Berns, Ipsen International and H"rterei Gerster AG,
Switzerland [25, 26].
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4. Boronizing
In boronizing, boron atoms diffuse into the surface of steels and form
compound layers of FeB and Fe2B of appreciable thickness (50-200
?m).
The industrial utilization of boronizing is mainly done with boron
containing pastes or granules [27] with limited importance because of
the labour intensive procedure of paste application and removal.
Gas boronizing and plasma boronizing promised to be much cleaner
and more economical processes. Their industrial utilization, however,
is almost non-existent due to the poisonous character of the gaseous
donor media, like diborane, borontrichloride or boron-trifluoride.
Because of this, a development project was started a few years ago
at the Institut fr Werkstofftechnologie Bremen (IWT) to develop a
novel boronizing process using harmless boron containing
precursors. Successful results were achieved using trimethylborate
B(OCH3)3 and exciting it with a plasma. Fig. 14 shows a typical
Fe2B-layer produced by plasma-boronizing in an argon-hydrogen-
trimethylborate gas mixture at 1832F (1000C) for 16 hours at 1
mBar [28]. More lately, the also harmless precursor triethylboran
B(C2H5)3 proved to be an excellent boron source as well [29]. Thus,
it can be expected that these plasma-boronizing processes, using
precursors, will soon develop into full-fledged industrial processes.
5. Innovative Equipment for Thermochemical Diffusion
Processes
In the past, thermochemical diffusion processes were carried out in
batch furnaces (pit, bell or chamber) or stepped respectively
continuous furnaces with limited process and quenching flexibility.
In the last few years, an innovative cell concept of furnaces
integrating atmosphere, vacuum (low pressure) and plasma
processes into one heat treatment line and leaving each load the
choice for quenching in oil, water, polymer or gases, was developed
[30]. Fig. 15 shows such a multiple cell system called mult-i-cell,
where a type of shuttle system called Vac-Mobil

(a travelling vacuum
furnace in itself) transfers the load from cell to cell, until a whole heat
treatment sequence (e.g., preheating, austenitizing, quenching,
tempering, nitriding (gas or plasma) and cooling) is finished.
At the end of the heat treatment sequence, the load has passed
through a plurality of furnace cells (six in the example mentioned
above) without ever having been in contact with air and without any
necessity of the subsequent load to pass through the same cells or
same sequence. Thus, an ultimate flexible heat treatment installation
is now available for high-quality industrial manufacturing of all-metal
components.
6. Conclusions
The examples mentioned above of carburizing, carbonitriding, ferritic
nitrocarburizing and boronizing represent only a limited amount of the
development work on thermochemical diffusion processes of the last
few years. They prove, however, that thermo-chemical diffusion
processes are clearly on the advance. Only due to their increased
capabilities, the development of higher stressed motor engine
components, car suspension parts, drive shafts and gear
components is made possible, frequently in conjunction with a
respective wear resistant or low-friction surface coating produced in
pvd-installations [31].
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Nayak A. Experiences in using the Ipsen Supercarb Process for
Case-Hardening of Automobile Components in a Pusher Furnace.
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Gr"fen W. Low-Pressure Carbonitriding using Acetylene and
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