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Metal Science and Heat Treatment

Vol. 46, Nos. 7 8, 2004

UDC 621.785.532

LOW-TEMPERATURE SALT BATH NITRIDING OF STEELS


K. Funatani1
Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 7, pp. 12 17, July, 2004.
Nitriding technology has gone a long way, from the old gas nitriding to the relatively recently developed
plasma nitriding. The latter has replaced the process of soft nitriding in the automotive industry based on
nitrocarburizing in cyanide salt baths. It seemed that the high toxicity of the initially used compositions for
soft nitriding (Tufftride or Tenifer) should have eliminated salt baths from the industry. However, they are still
rather widely used. The replacement of old compositions by nontoxic ones has solved fundamental problems
of environment protection. Low-temperature nitriding technology also advanced considerably. Salt bath
nitriding is a very active process, more intense than that of gas nitriding and nitrocarburizing including the
processes of plasma nitriding. The reactivity of the nitriding medium and the final efficiency of the process
with allowance for the cost of the equipment have to be taken into account. An additional advantage of salt
bath nitriding is the possibility of treatment of stainless maraging steels.
The present work is devoted to comparison of the processes of treatment in a nontoxic salt bath and in a gas
medium and discussion of the advantages of nitriding in nontoxic salt baths.

process control technology in 1975. Nitriding in salt baths


was replaced by gas nitriding for virtually all the parts, and
only some items, like exhaust valves, were still treated in salt
baths but at subsidiary plants.
Though less than half of the earlier used baths for soft
nitriding based on cyanides are still in operation, there is a
tendency for using cyanate baths, which solves virtually all
of the environmental problems.
The development of a low-temperature process is a recent advancement in slat bath technology. Low-temperature
treatment of aluminum extrusion dies and of other forming
dies at 480C is acquiring a wide use and ensures enhanced
wear resistance without deterioration of hardness even in repeated nitriding. In addition, low-temperature nitriding reduces the distortion of shafts and crankshafts for automotive
applications.
One more advantage of salt bath nitriding is the possibility of control of the chemical composition of the bath and of
lowering the operating temperature by changing the chemical composition, which promises wider and more effective
use of salt bath treatment including the nitriding of stainless
and maraging steels.

INTRODUCTION
As distinct from the long-used process of gas nitriding,
which yields a layer of Fe2N nitrides on the surface [1], the
Tenifer-Tufftride process, also known as soft nitriding [2],
yields a tough and wear-resistant layer. It has been widely
used in the automotive industry since BMW started to use
salt bath nitriding for treating crankshafts and other parts.
The diffusion layer lying under the layer of chemical compounds exhibited high wear and seizure properties and enhanced fatigue resistance. The Toyota Motor Company
started the production of automobile parts in 1963 and installed the worlds largest automated salt bath nitriding lines
in the engine components plant. However, the requirements
on environment protection made the company replace the
treatment of engine parts in cyanide baths by soft nitriding in
a gas medium. However, salt bath nitriding was still used for
treating parts fabricated from special steels, the gas nitriding
of which gave unsatisfactory results.
The problems of toxicity of cyanide baths were solved by
creating nontoxic cyanate-bearing baths in 1970 [3, 4]. Difficulties with the nontoxic baths arose in connection with control of the nitriding capacity, and in many cases the
nitrocarburizing was performed by the method of soft
nitriding in continuous gas carburizing furnaces. In order to
improve the process of soft gas nitriding, Toyota pursued
the goal of creating a compound layer with equivalent chemical composition and final properties and installed a novel
1

COMPOSITION OF SALT BATHS


Cyanide-Base Salt Baths
Tenifer salt baths contained a high percentage of potassium and sodium cyanides, which are very toxic materials.

IMST Institute, Nagoya, Japan.

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0026-0673/04/0708-0277 2004 Springer Science+Business Media, Inc.

278

K. Funatani

TABLE 1. Nitriding Methods, Materials, and Characteristics of Diffusion Layer


Method

Tufftride TF1

Thickness of com- Thickness of difpound layer, mm fusion layer, mm

Temperature, K

Steel

853

1015

e, 13

800

1045

e, 13

780

34Cr4

480

The same

[2, 3]


843

X210Cr12

e, 10

1015

e, 12

780

843

SCM435

e, 8

171

Soft nitriding in gas medium

843

SS2250

g, e(?)

353

[7]

Soft nitriding in gas medium

793

38CrMoAl

g, e : (5)

78 97

[8]

40Cr

g, e : (4)

63 80

Gas nitriding

773

SAE9254

49

[9]

793 (pulsed)
793 (DC)

722M24

(e, g : 5)
12 h

72

[10]

100
110
46
100
200

[11]

+ 0.1Y

()
()
()
()
()

+ 0.1Ce
SKD61

()

215

e : 1.5

150

Tufftride NS1

Plasma nitriding
Plasma nitriding

Reference

833
813
793
823
823
823

Low-temperature salt bath


nitriding (Palsonite)

753

En40B
En19
Nirtaps
36CrMo

160

SCM435

e : 4 + (CrN)

106

753

e:4

141

843

200

843

During the process the cyanides are oxidized due to aeration,


and nearly half of them are converted to cyanates.
Oxygen-saturated cyanates are active compounds and react with the surface of a steel part forming e- and g-nitrides
in salt bath nitriding at 570C. This layer of compounds is
not as brittle as Fe2N (x), and its formation is used effectively
for raising the wear and seizure resistances. Nitrogen also
diffuses into the layers lying below the layer of chemical
compounds and contributes into the growth in fatigue resistance. This double effect of nitrogen made the process very
popular starting from the 1960s [2].
However, the process in such baths had one more disadvantage, i.e., it was hard to control the chemical composition
of the bath. In addition, the subsequent neutralization of the
waste salt and the disposal of the rinse water were hazardous
for the environment. The ecological problems due to the use
of toxic compositions hindered the development of the process, and in many cases it was replaced by gas nitriding.

[6]

[12]

[6]
[6]

plified control of the process with the help of the developed


regenerator. Nitriding in new salt baths reduced the treatment
cost by 30% as compared to the process in the old cyanide-base baths.
However, the chemical activity of cyanate-base baths
was more difficult to control. For this reason some time
passed before the new technology employing cyanate-base
baths was installed in heat treatment plants.
Low-temperature treatment below 480C was set up by
Nihon Parkerizing in 1973 for nitriding dies for hot deformation and extrusion [5]. The process temperature of 480C
made it possible to prevent a decrease in the hardness during
the treatment process. Low-temperature nitriding of extrusion dies was repeated without deterioration of the hardness.
Further studies of this group of tools made it possible to
lower the temperature to 430 440C and widened the use of
nitriding in active salt baths.
Reactivity of Salt Baths and Diffusion Rate

Cyanate-Base Salt Baths


The necessity for novel chemical compositions providing
the same nitriding capacity resulted in a successful solution,
i.e., creation of cyanate-base baths bearing no cyanide [3, 4].
The new compositions reduced the problems of salt collection for controlling its reactivity to a minimum and sim-

The reactivity of salt baths combined with their high heat


capacity and direct contact with the steel surface create better
possibilities for nitrogen penetration than in gas nitriding.
This especially concerns cases where the gas process is conducted at reduced pressure and requires additional measures
for improving the reactivity.

Low-Temperature Salt Bath Nitriding of Steels

279

Such treatment is recommended for steels TABLE 2. Results of Nitriding of Stainless and Tool Steels
with a high content of alloying elements,
Thickness Treatment time,
Method
Temperachromium in particular, which form a protecSteel
of diffusion layer thickness, Reference
of treatment
ture, K
and phases
layer, mm/h
tive oxide film on the surface and delay the
beginning of nitrogen diffusion. The process Gas nitriding
773
304
22.37
20 h
[13]
is accelerated by acid etching, shot blasting,
803
26.85
20 h
or cathode ion sputtering. The energy of
843
34.68
20 h
plasma, ionization, and some other treatment
873
36.91
20 h
techniques, for example nitriding with the use
Plasma nitriding
803
SKD61
51.96
[14]
3 h 100 mm
of radicals, can raise the reactivity.
853
NCF601(60Ni) 10.4 (2.9) 3 h (CrN)
[15]
The data on the earlier developed Tuff- Gas nitriding
SUH35
56.6
0.5
h

49
mm
tride process stimulated its wide use at plants
NCF47W
21.2
2 h 25 mm
engaged in mechanical treatment of car parts
843
304
730
1 h CrN,
[16]
and in shipbuilding. Today, the parameters ob- Tufftride (TF)
g (C + N)
tained by the DEGUSSA Company in the development of the Durferrit process have be843
402J2
50
1h
come a goal to be reached in other nitriding
843
SKD61
84.9 (5 7)
processes. However, in order to raise the effi- Palsonite
753
304
169.7
[16]
2 h CrN, e,
ciency of nitriding and reduce its cost, it is
g (N)
necessary to consider the problems connected
753
402J2
35.4
2h
with the chemical efficiency of processes con- Gas nitriding
703
304
(3)
1h
[17]
ducted in salt baths without hazard to ecology.
833
304
(40)
1h
The diffusion rate in nitriding depends on
the amount of alloying elements, especially
chromium. It can be seen from Table 1 that
that nitriding at a temperature below 480C is very effective
the thickness of the diffusion layer depends on the type of the
for dies used in hot deformation is an even more important
alloying elements. However, the main characteristic of nitrofeature. In addition, the procedure of formation of hardened
gen diffusion in carbon steels C15 and C45 is its rate. The
layer can be repeated up to ten times without impairing the
diffusion rates in a- and g-phases and in e and g compounds
hardness.
differ, but the nitrogen potential is the highest in salt bath
We have already mentioned that nitriding is used for
treatment. As follows from Tables 1 and 2, in this case the fitreating some automotive parts (crankshafts, camshafts, and
nal result is obtained in the shortest time.
various retainers). Such parts as valve springs in high-perforComparing the duration of the treatment as a function of
mance engines should possess an especially high heat resisdiffusion rate for various variants of nitriding (see Table 1)
tance due to operation at a high temperature [9, 18, 19]. Niwe will see that processes occurring in salt baths are pretrogen is a very effective element for raising the high-temferred. Even at the lowest temperature (about 400C) a salt
perature strength, especially for high-performance parts and
bath provides the highest nitriding activity and minimum dutools.
ration of treatment.
It is important that nitrided stainless steels do not lose
It cannot be doubted that safety and preservation of the
their
corrosion resistance in operation. Parts used in the food
ambient are very important, but modern processes in baths
industry
and biotechnology should also combine high corrowith cyanates do not yield toxic emissions, and a nitriding
sion
resistance
with wear resistance and hardness [20].
plant today is free of waste water.
APPLICATIONS
As compared to the original Tufftride process, the temperature range of nitrocarburizing in salt baths has widened
considerably, which makes it possible to treat parts from automotive valves to tiny pieces for electronics and interdigital
transistors. The opinion on the environmental hazard of traditional cyanide-bearing baths has stimulated the use of various gas nitriding processes including reduced-pressure
nitriding.
Processes conducted at a lower temperature than that
used in the traditional Tufftride process and in soft gas
nitriding have the advantage of minimum distortion. The fact

ADVANCED PROCESSES
Gas Nitriding
The efficiency of nitriding is controlled by the nitrogen
potential Np, which is affected by the conditions arising on
the surface of the treated material. The final state of the surface and the chemical composition of the material considerably influence the reactivity of the surface. This primarily
concerns chromium-bearing materials that have a coat of
chromium oxides on the surface, which hinders the interaction with nitrogen-bearing gases. For this reason many researchers have studied various methods for increasing the

280

surface reactivity, such as shot blasting, oxidizing, or treatment with chlorine- or fluorine-bearing substances.
Nitriding at reduced pressure with ionization and without
it has some use, but such processes take more time than
plasma nitriding. On the contrary, enhanced-pressure nitriding promotes a certain increase in the nitrogen potential and
is applied at an industrial scale.
In any case, the addition of carbon increases the surface
reactivity and results in the formation of e-carbonitride, and a
carbon-bearing saturating medium can accelerate the reactions.
Specialists in nitriding argue on the interrelation between
the formation of the layer of chemical compounds and its
properties and the presence or absence of carbon. The general term nitriding applied to any process of the kind
should be differentiated into nitriding as such, carbonitriding, and nitro-oxinitriding because each of the processes is characterized by specific duration and by resulting
properties.
Plasma Nitriding
Plasma can accelerate the reactions by increasing the energy of nitrogen ions and additionally activating them as a result of cathode sputtering. The traditional ionization processes have been improved by the development of methods
of plasma nitriding with a through case (TC) or active screen
(AS) that raise the efficiency and quality of the process.
Plasma nitriding is ecologically safe, and various kinds of installations use the process primarily in Europe [10]. Plasma
nitriding has the advantage that it is easy to stop the process,
in contrast to gas nitriding and especially to salt bath
nitriding.
The requirements that commercial processes should be
performed at reduced temperature, yield durable products,
and be low-cost are becoming obligatory. In this connection,
processes ensuring a hardened layer at medium and low temperatures, like nitrocarburizing and nitriding, have become
especially attractive.
Salt Bath Nitriding and Carbonitriding
Cyanate salt baths have the same or an even higher nitrogen potential, and the developed method for controlling the
composition of baths eliminates virtually any disadvantage
of the process. The high reactivity of salt baths based on cyanates is preserved even when the quality of the salt worsens,
and modern regeneration techniques are quite economical.
Cooling after nitriding in an AS140 salt bath is used for
dissociation of CN, and finishing oxidizing of the surface
is performed for raising the corrosion resistance due to formation of an oxide layer.
Low-Temperature Nitriding and Carbonitriding
Low-temperature processes have become possible due to
appropriate choice of the chemical composition and ad-

K. Funatani

vanced methods of chemical control. Diffusion of carbon or


nitrogen in plasma nitriding ensures formation of a hardened
layer at a low temperature.
Nitriding without formation of a layer of chemical compounds is effective for chromium-alloyed stainless steels and
can also be recommended for improving the properties of
spring and maraging steels. It seems that the use of such process for treatment of such steels will be widened.
CONCLUSIONS
1. Gas nitriding and nitrocarburizing, including plasmaassisted processes, are progressive methods, and their further
study and advancement should raise the productivity. Successful realization of gas and plasma nitriding depends on
appropriate measurement of the composition of the atmosphere and of the temperature.
2. Plasma nitriding presents practical interest but requires solution of the problems of reduction of the cost of the
equipment and of increasing the efficiency.
3. Salt bath nitriding is more expedient for many grades
of steel than gas nitriding, including the plasma-assisted
methods.
4. The use of cyanate salt baths has solved environmental
problems due to the elimination of the operations of waste
and water disposal; such baths preserve high reactivity in
nitriding and carbonitriding.
5. Nitriding in salt baths at a temperature below 480C
yields a thin hardened layer without formation of a layer of
chemical compounds.
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