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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
277
0026-0673/04/0708-0277 2004 Springer Science+Business Media, Inc.
278
K. Funatani
Tufftride TF1
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
843
SS2250
g, e(?)
353
[7]
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
753
En40B
En19
Nirtaps
36CrMo
160
SCM435
e : 4 + (CrN)
106
753
e:4
141
843
200
843
[6]
[12]
[6]
[6]
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
281
16. K. Shinkawa, Y. Yuneyama, M. Higashi, and E. Eiraku, Characteristics of low temperature salt bath, JSHT Conf., No. 2,
57 58 (1999).
17. K. Gemma, R. Saitoh, and M. Kawakami, Behavior of nitrided
layer formed in SUS304 austenitic stainless steel, J. JSHT,
37(2), 100 110 (1997).
18. F. Yoshikawa, Application of low-temperature cyaniding for
automotive valve springs, J. JSAE, 19(4), 274 281 (1963).
19. F. Yoshikawa and T. Deguchi, Improvement of characteristics
of spring made of oil tempered Si Cr steel wire by low temperature cyaniding, J. JSAE, 21(10), 1025 1029 (1967).
20. T. Bell and K. Akamatsu (eds.), Stainless Steel 2000. Thermochemical Surface Engineering of Stainless Steels.