2. At the beginning of the nitriding process (0.

5 h) all phases corresponding to the

Fe--N phase diagram are observed in Armco iron and the steels tested. With increasing holding times at nitriding temperature there are no changes in the phase composition but the distortion of the crystal lattice, manifest in line broadening, increases.
3. The periodicity of changes in the stress and hardness of the nitrided case in the
process of formation was established, and therefore the results of nitriding may also depend
on the time at which it ceases.
LITERATURE CITED
i.
2.
3.
4.
5.

6.
7.

8.

A . V . Belotskii, V. G. Permyakov, and I. M. Samsonyuk, "Nature of the hardness of

nitrided steel," Fiz. Met. Metalloved., 26, No. 5, 942 (1968).
G . F . Kosolapov and O. N. Sidunova, Electron Microscopic Analysis of the Nitrided Layer
[in Russian], VINITI, Moscow (1957), M-57-178/12.
Yu. M. Lakhtin and Ya. D. Kogan, Nitriding of Steel [in Russian], Mashinostroenie,
Moscow (1976).
V . D . Yakhnina and V. V. Nikitin, "Hardness of the nitrided layer," Metalloved. Term.
Obrab. Met., No. 2, 28 (1975).
A . P . Gulyaev, V. V. Nikitin, and V. I. Konoval'tsev, "Change in the hardness of the
nitrided layer in the process of saturation," in: Chemicothermal Treatment of Metals
and Alloys (Reports of the Fourth All-Union Scientific Conference on Chemicothermal
Treatment of Metals and Alloys) [in Russian], Minsk (1981), p. 246.
G . F . Kosolapov and S. A. Gerasimov, "Structure of ~ phase in the nitrided layer on
steels 38KhMYuA and iKhl3," Metalloved. Term. Obrab. Met., No. 5, 71 (1973).
A . V . Belotskii, V. G. Permyakov, and I. M. Samsonyuk, "Some characteristics of the
structure of ~ iron nitride," in: Metal Physics [in Russian], No. 38, Naukova Dumka,
Kiev (1971), p. 73.
Ya. B. Fridman, Mechanical Properties of Metals [in Russian], Part 2, Mashinostroenie,
Moscow (1974).

NITRIDING OF STEEL PARTS FOR MACHINE CONSTRUCTION

IN AN ENDOTHERMIC ATMOSPHERE
A. N. Utkina, Yu. Yu. Cherkis,
M. N. Kozlova, and V. L. Kozlov

UDC 621.785.533

The life of parts that were hardened by methods of chemical heat treatment (casehardening and nitriding) is chiefly determined by the structure, the phase composition, the thickness of the case, by the concentration of carbon in the case, etc. The large variety of complexly alloyed heat-resisting steels used, the variety of design features of the parts, of
the operating conditions and their long service life require constant improvement of the
methods of chemical heat treatment [1-3].
The present work involved the investigation of nitriding of heat-resistant steel 20Kh3MVFA in an endothermic atmosphere with additions of natural gas and ammonia, and for comparison, casehardening in pyrobenzol. We determined bending and contact endurance after diffusion saturation, heat resistance, the phase composition [4], and the structure with optical
and electron microscopes.
Nitriding of the specimens was carried out in the following regimes:
i. Saturation at 870 I0C for 6 h in an endothermic atmosphere with an addition of 3%
natural gas and 4% ammonia.
2. Saturation at 900C f o r 6 h in anendothermic atmospherewithanaddition of 6% natural
gas and 4% ammonia.

Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 4, pp. 34-36,

April, 1982.

270

0026-0673/82/0304-0270507.50

1982 Plenum Publishing Corporation

z~

Is

~.

i ,,\

o,.
0,81

0,6

~6~(

t13

0,~,
~29

o,t 32 as

a* 4s 4s ~7 t~8

emm

N
~t

g2

Fig. 1

gs

0,5 h, mm

/l#

Fig. 2

Fig. i. Change of carbon and nitrogen concentration and of microhardness across the thickness of the diffusion layer (h is the distance from the surface).
The numbers next to the curves indicate
the regime.
Fig. 2. Carbon content of the martensite in a nitrided layer (h
is the distance from the surface).
The numbers next to the curves
indicate the regime.
3. Saturation at 900 I 0 C
natural gas and 6% ammonia.

for 6 h in an endothermic

atmosphere with an addition of 9%

4. Saturation at 950C f o r 2 h i n e n d o g a s w i t h a n
addition of 12% natural gas and 4% ammonia, lowering the temperature to 900C, holding for 5 h in endogas with an addition of
6% natural gas and 4% ammonia.
With all regimes the atmosphere in the furnace was exchanged 6 times.
The subsequent heat treatment was:
quenching in oil at the nitriding temperature, cold
treatment at--70eC for2 h, tempering a t 2 5 0 C for 3h. For comparison, one batch of specimens
was h e a t - t r e a t e d b y the standard technology (regime 5): c a r b u r i z i n g a t 930C for 6-8 h, high
tempering at 6500C for 4 h, quenching in oil at 900C, cold treatment at -70C for 2 h, low
tempering at 250-300~C for 3 h.
The tests were carried out with specimens on which 50-200 ~m had been ground away or
which were polished after chemical heat treatment.
The change of carbon and nitrogen concentration and of microhardness across the thickness of the diffusion layer is shown in Fig.
i.
TABLE i
Type of mechanical
treatment after CHT

% C*

% N*

ttRC*

Polishing
Grinding to a depth of
100

~IYl

Polishing

Grindinc to a depth of
100-15~

/Jrn

Polishinc

Grinding to a depth of
]00-15@ gnl
Grinding to a depth of
5 0 ~]]

Grinding to a depth of
1,50 ~11

Grinding to a depth of
200

Thiclmess of
layer, mm

c~
$

atN"K10-6= cycles,2300
MPa

x , 1

O, 13

61 - - 6 2

0,9

1 0

0,13

61--62

0,8

760

8,2

1 26

0,35

62--64

0,9--0,95

930

30

I I

0,28

61--62

0,8--0,85

840

5,0

2, 1

o, 1

63-64

1, i

760

28

2,0

0,1

60--60,5

1,0

760

5,0

2,2

0,21

63--64

1,25

920

30

1,85

0,2

62--63

1,I5

920

30

--

61--62

1,0--1,1

860

22--24

1,3--1,4

*On the surface of the specimen after mechanical

--

--

treatment.

271

TABLE 2

Distance from
surface of
=
specimen, mm E ~N
<e.
0 -- 0 , 0 2 0
0,020--0,075
0 , 0 7 5 -- 0 , 1 2 0
0,120 -- 0,170
0,170--0,210
0,210 -- 0,255

36,3
35,0
26,2
22,4
2l ,2
15,7

Phase composition

Fe~C;M~ (CN); MN; Cr,N

Ms (CN); MN; M,~C,

M, (CN); MN
FeaC; Cr~Cs
Fe~C;
CrTCa
F%C; Cr,C,

Note. Nitriding was carried

out by regime 4.
It follows from the presented data (Table i) that after nitriding by the single-stage
regime 2, the specimens retain their good bending and contact endurance only after polishing.
When they are ground to a depth of 100-150 ~m, their bending and contact endurance are substantially impaired.
Specimens treated by the two-stage regime 4 have maximum contact and
bending endurance when ground to a depth of 50 or 150 ~m: N ~ 3 0 . 1 0 6 cycles,,o-1 =920 MPa.
These characteristics are considerably poorer in specimens treated by the standard technology
(regime 5): N > ( 2 2 - 2 4 ) . I 0 6 cycles and o-i =860 MPa.
The high level of contact endurance of specimens after nitriding by the two-stage
regime 4 can be explained by the data of phase analysis:
there is a layer of nitride and
carbonitride phases on the working surfaces (Table 2). By phase analysis of the nitrided
layer it was established that the excess phases are cementite and vanadium carbide. At a
distance of 260 ~m from the surface, the carbide M7C3 based on trigonal chromium carbide
CrTC~ is found in the layer; at a distance of 350 ~m it is carbide M23C6 based on the cubic
chromium carbide Cr2aC6.
The excess phases contain 67-33% Cr, 56-46% Mo. 50-34% V. At a
distance of 200-300 ~m from the surface, the layer contains 18.7-13.1% carbide phases.
During the nitriding process, the finely dispersed complexly alloyed nitride phase MN
based on chromium nitride CrN forms in the surface and near-surface zones of the diffusion
layer together with complexly alloyed carbonitride M3(CN) (Table 3). After nitriding by
the single-stage regime 2, we find the carbide M7C3 in the layer; the amount of excess segregation phases is ~21-16%.
After nitriding by the two-stage regime 4, the layer contains a
more complex finely dispersednitridephase M2N based on chromium nitride Cr2N (Table 3).
The layer then contains 36.3-15.7% excess phases.
Thus the presence of complex hardening
phases in the nitrided layer ensured that a higher level of contact and fatigue endurance
was obtained than in a casehardened layer.
The hardening phases, situated along the grain
boundaries, have a blocking effect on the slip in plastic deformation.
It was established that roller-shaped specimens after nitriding by various regimes
contain much more carbon in solid solution than specimens after casehardening.
The maximum
carbon content of the cementite of a nitrided layer after the two-stage process is 1.2 times
that of a casehardened layer: 0.45% (Fig. 2).
~le carbon content of the solid solution of the nitrided layer, which was higher than
the carbon content of the casehardened layer, as well as the additional alloying of the solid
solution with nitrogen increased the contact endurance.
The lowering of the contact endurance of the rollers as a result of grinding of the surface layer by ~I00 ~m after singlestage nitriding (regime 2) occurred as a result of the removal of the saturated carbonitride
zone ~120 ~m thick by grinding.
The amount of excess phases decreased from 21.1 to 16-10.4%,
and their alloying also decreased. When the nitriding process was prolonged, the thickness
of the layer increased from 0.9 to 1.3 mm. As against casehardening and single-stage nitriding, after nitriding by the two-stage regime the thickness of the saturated carbonitride
zone increased to ~300 ~m, and it contained a large amount of complexly alloyed excess phases.
Yet the high level of contact endurance (N >30.106 cycles) was maintained after the layer was
ground to a depth of 150 Dm. The contact endurance of nitrided specimens is 30% greater than
of casehardened specimens. An analogous regularity was obtained with specimens subjected to
bending endurance tests (see Table i).
Microfractographic investigations showed that the considerable length of the phase
interfaces and the high local ductility of the diffusion layer also enhanced the bending and

272

TABLE 3
Distance
from surface, mm

Phase composition

Content of alloying elements

in the nitrided Iarer, %

Amount of
phases, %

It

Cr

Mo

17,0 I 2,
17.0
2, 2
12.8 [ 1,8
8,2
1,

0,18
0,18
0,16
0,13

0,31
0.33
0,29
0,20

0,53
0.52
0,41
0,34

0,14
0,16
0,13
O, 12

8,0 [ 1,3
8,1
0,92

0,14
0,13

0,21
O, 23

0,35
0.31

0.12
0,14

Fe

v [Z o ~ ' ~

0 -- 0.06
0 , 0 6 - - 0.120
0 , 1 2 0 - 0,180
0,180--0,240

19.6/21,1
M3C; VC/M3C; MN; CrTC~ 219,6/21,0
0,7/16,0
18,7/10,4

0,240 -- 0,280
0.280 -- 0,340

MTCs; MsC; VC/MN;

CraGs

13,1/10,4
13,1/I0,0

Note.
The numerator contains the phase composition and amount
of phases in the carburized layer; the denominator gives the
same for the nitrided layer.
contact endurance of the nitrided specimens.
During the nitriding process the alloying elements of steel (chromium, molybdenum, tungsten, vanadium) dissolved in the carbonitride
Ma(CN) and increased its stability.
In a layer up to 250 ~m thick, 82-52% Cr, 92-36% Mo,
70-58% W, and ~76% V are bound into carbonitrides.
One of the principal elements determining the composition of the excess phases is chromium.
The chromium content of these phases
in the casehardened layer is 9.2-10.0%, in the nitrided layer in the single-stage process
8.9-10.4%, in the two-step process 5.5-9.8%.
In the casehardened layer, chromium is distributed among the carbides M3C, M7C3, and M23C6; in the nitrided layer chromium takes part in
the formation of many phases because in this case also the carbonitride phases Ma(CN) and
the nitride phases MN and M2N form in addition to the carbide phases.
The third element
taking part in the formation of excess phases is vanadium.
In the nitrided layer the vanadium content is higher than in the casehardened layer.
In nitriding by the two-stage regime,
the layer at a distance of 150 ~m from the surface contains 2.6-3.8% V, by the single-stage
regime it contains 2.5% V. The nitrided layer contains ~2.0% W, the casehardened layer contains up to 0.6% W (relative to the sum of excess phases).
In the casehardened layer we
encounter vanadium carbide, in the nitrided layer vanadium and tungsten do not form separate
phases but are contained in the complex carbide and nitride phases type MC and MN. T~e
nitrogen content of the excess phases in single-stage nitriding at a distance of 350 ~m
from the surface is 4.5-2.6%, with the two-stage regime it is 3.5% (relative to the total
amount of phases).
~ m s nitriding by the two-stage regime increases the contact and bending endurance and
operating reliability of machine parts.
CONCLUSION
To ensure the required characteristics of the diffusion layer in heat-resistant steels,
it is recommended to subject them to two-stage nitriding: saturation at 950C for 2 h in endogas with an addition of 12% natural ~as and 4% ammonia, lowering the temperature to 900C,
holding for 5 h in endogas with an addition of 6% natural gas and 4% ammonia; exchange of
gas 6 times.
LITERATURE CITED

1.
2.
3.
.

B. Prenos11, Nitriding [Russian translation], Mashinostroenie, Moscow (1969).

R. P. Shubin and M. L. Grinberg, Nitriding of Machine Parts [in Russian], Mashinostroenie, Moscow (1975).
A. T. Kalinin and A. Ya. Novikova, "Optimum degree of saturation with carbon and nitrogen in nitriding," Metalloved. Term. Obrab. Met., No. i0, 2 (1965).
N. F. Lashko, F. M. Zaslavskaya, and M. N. Kozlova, Methods of Physicochemical Analysis
of Steels and Alloys [in Russian], Metallurgizdat, Moscow (1970).

273