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Use of a probe to control low-pressure nitriding treatments

Conference Paper · June 2017

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 Use of a probe to control low-pressure nitriding treatments

Philippe JACQUET1,2,a* , Marc DEVIENNE 3,b, Aude GOKELAERE1,c,

Nicolas DURET1,d
1 Université de Lyon, ECAM Lyon, INSA-Lyon, LabECAM, F-69005 Lyon, France

2 LaBoMaP, Arts et Métiers ParisTech, 71250 Cluny, France

3 BMI Fours Industriels, 38070 Saint-Quentin-Fallavier, France

a
[email protected], b [email protected]
c
[email protected], d [email protected]

Keywords: KN, low-pressure nitriding, sensor, continuus control, steel

Abstract:

In nitriding processes, the link between cycle parameters and the resulting microstructures is
studied for many years [1]. In this work, a 42CrMo4 steel grade is nitrided by means of a low-
pressure process. The furnace is equipped with a probe which continuously measures the
nitriding potential KN of the atmosphere.

During the first experiments, the probe is used in a control mode to highlight the influence of
several parameters such as the temperature, the surface of the load inside the furnace, gas
pressure and gas flow. These first results bring some qualitative conclusions about the
influence of these parameters on the nitriding potential.

During the second set of experiments, the probe is used in a regulation mode to achieve some
specific microstructures (with or without compound layer). The influence alloying elements
and the low-pressure is discussed compared to the traditional Lehrer diagram which is
established for pure iron nitrided at atmospheric pressure. In this case, quantitative results are
obtained and will help to develop specific cycles for specific steel grades so as to achieve the
required specifications thanks to a low-pressure nitriding treatment.

Although the use of a probe has been developed for a few years in nitriding at atmospheric
pressure [2, 3], to our knowledge, this is the first time that such a tool is used for low-pressure
nitriding processes.
1. Introduction

Nitriding treatments are applied to mechanical steel parts for many years and the benefits are
numerous: enhancement of fatigue limit thanks to compressive surface residual stresses, better
corrosion resistance, improvement friction coefficient,…Whatever the process is, an accurate
control of the nitriding potential, KN, is necessary to obtain the desired metallurgical
components and the required mechanical properties [1-2]. For liquid processes the KN is
determined by a chemical analysis of the salt bath whereas for gaseous processes a
thermodynamic control of the atmospheres is necessary. Among gaseous processes, some low
pressure treatments exist, most of them are plasma assisted (the first known is from 1932 [3])
and those without plasma assistance are more recent (one of the first patents is from 1995 [4]).
This process is interesting for its reduced gas consumption [5]. Some probes have been
developed for atmospheric nitriding treatments [2, 6, 7] some years ago but, up to now, none
has been tested at low pressure. For the process which is presented in this paper, the
depression is maintained by a vacuum pump unit while the injection of the nitriding gas (pure
NH3 or a mixture with H2) is controlled by mass flow meters. The nitriding temperatures are
standard: between 400 and 600°C. The principle of the probe used in this work has been
previously described in the literature [8].

2. Influence of parameters on KN
2.1. Theory

The nitriding reaction is given by equation (1):

1 3
𝑁𝐻3 ⬄ 2 𝑁2 + 2 𝐻2 (1)

The constant of this reaction may be expressed by equation (2):

G0
𝑅
𝐾 = 𝑒− 𝑅𝑇 (2)

Or equation (3)
𝑃𝑁𝐻3
𝐾𝑁 = 1/2 3/2 (3)
𝑃𝑁2 .𝑃𝐻2

If  is the degree dissociation of ammonia in reaction (1), in case of nitriding with a mixture
H2/NH3, equation (3) becomes (see reference [1]):
(1−𝛼)𝑥𝑁𝐻3 .(1+𝑥𝑁𝐻3 .𝛼)1/2 −1/2
𝐾𝑁 = 3𝛼 3/2 . 𝑃𝑡𝑜𝑡 (4)
(𝑥𝐻2 + .𝑥𝑁𝐻3 )
2

Where Ptot is the total pressure and xi the mole fraction of i.

In case of nitriding with pure ammonia, equation (4) becomes:

1 −1⁄
(1−𝛼)(1+𝛼) ⁄2 2
𝐾𝑁 = 3 3⁄ . 𝑃𝑡𝑜𝑡 (5)
𝛼 2
2
Thanks to the thermodynamic data given in table 3, entropy, enthalpy and free enthalpy for
reaction (1) can be calculated:

H0R = 1.5x H0fH2 +0.5xH0fN2 - H0fNH3 = -(-45 900) = 45 900 J.mol-1.

SoR = 1.5xS0H2 + 0.5xS0N2 - S0NH3 = 1.5x130.6+0.5x191.5-192.7 = 98.95 J.mol-1.
G0R= H0R - T SoR = 45 900 – 98.95xT.

N2(g) H2(g) NH3(g)

H0f -1
(kJ.mol ) 0 0 -45.9
S (J.mol-1.K-1)
o
191.5 130.6 192.7
Table 3: Thermodynamic data for reaction (1)

According to equation (2), K is superior to zero if temperatures are higher than 191°C, which
means that reaction (1) evolves from left to right with ammonia dissociation and possible
nitriding.

20
18
16 KN 1 bar 100%NH3
14
12 KN 1 bar 50%NH3 - 50%H2
KN

10
KN 1 bar 80%NH3 - 20%H2
8
6
KN 400 mbar 100%NH3
4
2
0
0 0,2 0,4 0,6 0,8 1
Ammonia dissociation

Figure 1: Nitriding potential plotted against degree of dissociation of ammonia

According to figure 1 the following conclusions appear:

 If ammonia is diluted in a mixture, its degree of dissociation is increasing and the

nitriding potential is decreasing.
 If the total pressure is decreasing, the nitriding potential is increasing.
 From equation (2), if the temperature is increasing, the degree of dissociation is
increasing, so the nitriding potential is decreasing.

Additional conclusions are described in the literature:

 The higher is the surface of the load inside the furnace, the higher is the degree of
dissociation, so the lower is the nitriding potential [1].
  The higher is the flow of the ingoing nitriding gas in the furnace, the higher is the
nitriding potential [9].

2.2. Experimental

The steel grade used in this study is 42CrMo4 and its analysis is given in Table 1. The
specimens are disks (10 mm depth, 45 mm in diameter). Before nitriding, the samples were
quenched in oil and tempered at 600°C, the corresponding hardness is around 350 HV30.

C Cr Mo S Mn P Si Ni V
0,45 1,14 0,2 0,04 0,91 0,06 0,26 0,05 0,01
Table1: composition of 42CrMo4 steel measured by spark spectrometry

The nitriding gas is ammonia (NH3), the nitriding temperature is 540°C, the pressure during
nitriding sequence is 300 mbar and some sheets of iron with variable surfaces (from 1 to 9 m2)
are placed inside the furnace. The flow of ingoing nitriding gas is also a varying parameter.
The basic nitriding cycle is presented in Table 2.

Sequence Duration Temperature °C Pressure Atmosphere

Pumping 5 min room vacuum -
Heating 2h 450°C variable -
Nitriding 6h 540°C 300 mbar NH3
Cooling 40 min room 1 bar N2
Table 2: Basic nitriding cycle

For these first experiments, some of the furnace parameters are fixed: temperature, total
pressure, nature of the nitriding gas (100% NH3) ; the probe is working on a lecture mode,
which describes the evolution of the nitriding potential versus the time.

S 5S
10S
KN (a.U.)
KN (a.u.)

Q (l/min) 3xQ (l/min)

5xQ (l/min)
52 102 152 202 252 302 352 402
0 200 400 600
Time (min) Time (min)
Figure 2: Influence of the gas flow on the Figure 3: Influence of the surface load on the
nitriding potential. nitriding potential.

For the experiments presented on figure 2, the surface of the load inside the furnace for each
of the three experiments were the same and the sheets of iron have been changed for each
experiments; the value of the ingoing nitriding gas flow varied from one to five and it clearly
appears that the nitriding potential is increasing with the flow, this evolution was also noted
by [9]. For the results presented on figure 3, the flow of the ingoing nitriding gas flow was
constant for the three experiments whereas, S which represents the surface of the load inside
the furnace varied from one to ten. The conclusions are in agreement with [1].

3. Nitriding cycles with KN regulation

For this second set of experiments, the fixed parameters were, temperature, nature of nitriding
gas (100% NH3), total pressure (300 mbar), surface of iron sheets inside the furnace and
nitriding potential; the probe is working on a regulation mode, which means that once the
furnace is fulfilled with the nitriding atmosphere at the set pressure, the mass flowmeter is
adjusting the flow of the ingoing gas to keep the set nitriding potential. On the example shown
on figure 4, we can observe that the ammonia flow is increasing to keep the set value for the
nitriding potential, KN = 0,2 in this case. The high values for KN just before the nitriding
period at 540°C corresponds to a calibration sequence of the probe.

Ammonia Flow

Temperature 540°C

Pressure (300 mbar)

Nitriding Potential 0,2

0 100 200 300 400 500 600

Time (min)

Figure 4: Nitriding cycle with KN=0,2

Four nitriding potential were tested: KN = 0,2; 0,3; 1 and 2. These values were chosen
according to the Lehrer diagram; at this temperature (540°C), iron nitriding lead to different
results: no compound layer for KN = 0,2, apparition of ’ phase for 0,3 < KN < 1 and
apparition of  phase for KN > 2.
For each case, some samples, as described in paragraph 2.2 were placed in the furnace and
analyzed. They were cut, polished and etched with Nital reagent to check the microstructures.
The resulting micrograhs (SEM views) are presented on figure 5.

A martensitic structure is observed and despite the fact that no compound layer was expected
for KN = 0,2, the results are not surprising: an increasing depth is observed when increasing
the nitriding potential.

KN = 0,2 KN = 0,3
Compound layer’s thickness = 4,50,4µm Compound layer’s thickness = 5,30,7µm

KN = 1 KN = 2
Compound layer’s thickness = 13,71µm Compound layer’s thickness = 16,80,4µm

Figure 5: Evolution of the compound layers’ thicknesses for various KN

Concerning the case depth, some microhardness profile measurements were realized;
approximately 700 HV0,3 is obtained on the surface and case depth of 0,25µm is reached.
These results are similar to those obtained by Cavaliere [10]. Series 1 to 3 correspond to three
profiles on the same sample. Figure 6 presents the hardness profile only for KN=0,2 but the
three other cycles, results are similar. This result indicates that the diffusion rate does not
depend on the nitriding potential if the atmosphere is rich enough with nitrogen.
 800

700
Série1
600 Série2
Hardness HV 0,3

500 Série3

400

300

200

100

0
0 0,1 0,2 0,3 0,4 0,5
Depth (mm)

Figure 6: Hardness profile for KN = 0,2

Concerning the nature of the surface compound layers, some XRD patterns with a cobalt
source (=1,789Ǻ, 25KV and 25mA in our experimental conditions) have been done. They
are presented on figure 7.

'(111)
(11-1)
'(020)

(110) (-1-12)
Kn = 2
a.u.

Kn = 1

Fe(101) Kn = 0,3

Kn = 0,2

40 45 50 55 60 65 70
Angle 2 q

Figure 7: XRD patterns; nitriding cycles with various KN.

For the two finest compound layers obtained with KN=0,2 and KN=0,3, the peak (101) of iron
is still observed, which is in good accordance with the penetration depth of X-Rays, superior
at approximately 6µm with these experimental conditions. Concerning the two observed
phases,  and ’, they are presents for the four studied nitriding potential but if the ratio
between peak (11-1) and ’(111) is calculated, it clearly appears that the higher the nitriding
potential is, the richer with the  phase the compound layer is.

4. Conclusion

In this work, a probe has been set up inside a nitriding vacuum furnace.

In the first part of this study, the probe has been used in its lecture mode. It was shown that
the recorded nitriding potential evolves as expected by the theory.

KN decreases when:

 the load’s surface inside the furnace increases,

 the total pressure increases,
 the temperature increases,
 the flow of the ingoing nitriding gas decreases.

In the second part of this work, the probe has been used in its regulation mode: a value for the
KN is set up and the furnace automatically adapts the flow of the ingoing nitriding gas to keep
the KN value constant. Four values for KN were tested from 0,2 to 2, and the metallurgical
results for 42CrMo4 steel were not exactly as expected according to the Lehrer diagram. The
differences are due to the fact that this reference diagram was not established for alloyed
steels but for pure iron and for nitriding with a 1 bar total pressure. The influence of alloying
elements was already shown for salt bath nitriding [11] which means that frontiers for each
phase on Lehrer diagram evolve with additional elements and probably with the total
pressure.

5. References:

[1] E. J. Mittemeijer and M. A. J. Somers, Thermodynamics, kinetics, and process control of

nitriding. Proceedings of the tenth congress of the IFHT, Brighton, England, pp. 83-117,
1999.

[2] H.J. Spies, H. Le Thien and H.B. Biermann, Nitriding and carbonitriding of Steels –
Controlled nitriding. Metal Science and Heat Treatment, Vol. 46, n°7-8, pp272-276, 2004.

[3] Practical Nitriding and Ferritic Nitrocarburizing. ASM International 2003.

[4] J.P. Souchard, Procédé pour la nitruration à basse pression d’une pièce métallique et four
pour la mise en œuvre dudit procédé. Brevet WO 1995029269A, 2 Novembre 1995.
 [5] Małdziński, L., and J. Tacikowski. "ZeroFlow gas nitriding of steels." Thermochemical
Surface Engineering of Steels Improving Materials Performance, Woodhead Publishing
Series in Metals and Surface Engineering, Elsevier 62 (2015): 459-483.

[6] Dalke Anke, Nitropuls, a new technology of sensor controlled gas nitriding potential.
European Conference on Heat Treatment 2016, 11-13 May 2016, Brevnov Monastery,
Prague, Czech Republic.

[7] Jing, H., Wang, X., & Liu, W. (2009). Application of advanced nitriding expert system [J].
Heat Treatment of Metals, 3, 026.

[8] Crevoiserat, O, Beguin, C, Contrôle des processus de nitruration et de nitrocarburation

gazeuses avec la sonde Datanit, Berichtsband ATTT-AWT-SVW-VWT-Tagung, 2002, p331-
339.

[9] Akhtar, S. S., Arif, A. F. M., & Yilbas, B. S. (2010). Evaluation of gas nitriding process
with in-process variation of nitriding potential for AISI H13 tool steel. The International
Journal of Advanced Manufacturing Technology, 47(5-8), 687-698.
[10] Cavaliere, P., A. Perrone, and A. Silvello. "Multi-objective optimization of steel
nitriding." Engineering Science and Technology, an International Journal 19.1 (2016): 292-
312.

[11] Jacquet, P., J. B. Coudert, and P. Lourdin. "How different steel grades react to a salt bath
nitrocarburizing and post-oxidation process: Influence of alloying elements." Surface and
Coatings Technology 205.16 (2011): 4064-4067.

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