Metal Science and Heat Treatment Vol. 46, Nos.

1 – 2, 2004

THE 3rd LAKHTIN READINGS

UDC 620.18:620.17:669-155.3

NEW IDEAS ON THE MECHANISM OF STRUCTURE FORMATION

IN NITRIDED STEELS

S. A. Gerasimov,1 A. V. Zhikharev,1 E. V. Berezina,1 G. I. Zubarev,1 and V. A. Pryanichnikov1

Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 1, pp. 13 – 17, January, 2004.

The main laws of formation of structure and properties of nitrided structural steels are studied depending on
their composition, parameters of preliminary heat treatment, and nitriding modes. New factors controlling the
structure and operational properties based on new concepts of the mechanism of formation of nitride particles
in the nitriding process are determined.

INTRODUCTION Despite the obviousness of the advantages of nitriding

Interest in the process of low-temperature saturation of
iron alloys with nitrogen, i.e., nitriding, has grown substan-
tially in the last 10 – 15 years. This topic has become very
popular at international forums of heat treatment specialists.
The traditional high-temperature methods of carburizing and
nitrocarburizing are frequently replaced by nitriding for nu-
merous articles of the machine building industry.
The enhanced interest in the problem of nitriding is ex-
plainable by the unique combination of properties provided
in steel parts by low-temperature saturation of their surface
with nitrogen. The properties are the wear resistance, seizure
resistance, corrosion strength, fatigue resistance, and heat re-
sistance, i.e., properties that at an insufficient level are a
cause of about 90% failures of machines.
The most important distinctive features of nitrided parts
are low deformation and warping. The low-temperature
treatment does not cause phase transformations in steel in
contrast to nitrocarburizing and carburizing. In addition, the
hardening provided by nitriding is not connected with forma-
tion of martensitic structure in the surface layer. Therefore,
the local growth in the temperature to about 600°C in places
of contact of joints under friction does not cause local soften-
ing of the diffusion layer, whereas the martensite of carbu-
rized or nitrocarburized layers decomposes under such heat-
ing (even a short-term one), and the earlier attained harden-
ing disappears.
1 dard heat treatment modes, i.e., quenching from 950°C and
N. É. Bauman Moscow State Technical University, Moscow,
Russia.
with respect to other methods of surface hardening, its use
has been limited for a long time because of the laboriousness
of the process and the brittleness and small thickness of the
nitrided layer accompanied by low contact fatigue resistance.
The absence of appropriate data on the structure of
nitrided steels, on the complex processes that occur during
nitriding, on the role of structural factors in the formation of
important operational properties of nitrided parts, i.e., wear
resistance, contact endurance, and bending strength, is an-
other hindering factor that lowers the reliability and service
life of nitrided parts.
The majority of researchers studying the process of
nitriding used to devote most of their attention to technologi-
cal aspects and ignore structure formation. However, the spe-
cial features of structure formation of the nitrided layer and
the matrix are responsible for the serviceability of machine
parts and, consequently, the choice of the steel and the meth-
ods for their preliminary treatment and nitriding.
METHODS OF STUDY
We studied commercial steels of pearlitic and martensitic
classes (of type 38Kh2MYuA, 16Kh2N3MFBAYu-Sh, etc.)
and model carbonless iron alloys bearing 1 and 4 at.% Cr.
Saturation with nitrogen was performed in installations for
ion and furnace nitriding at 500 – 600°C with a hold of 30 h.
The preliminary heat treatment was performed in stan-
2-h tempering at 620°C for steel 38Kh2MYuA and quench-

13
0026-0673/04/0102-0013 © 2004 Plenum Publishing Corporation
14
ing from 930°C and 2-h tempering at 590°C for steel
16Kh2N3MFBAYu-Sh.
When studying the dependence of the structure and pro-
perties of nitrided layer on the modes of preliminary treat-
ment we performed quenching (tq = 950°C) and annealing
(ta = 950°C) of specimens with subsequent tempering
(or heating) in a range of 500 – 700°C at a 50°C step for 2
and 10 h.
In our studies we used the method of electron micros-
copy of thin foils and x-ray diffraction and Auger spectro-
scopic analyses.
RESULTS AND DISCUSSION
The structure of the nitrided layer on alloy steels forms
by the same mechanism as on pure iron and carbon steels.
The difference consists in the fact that in addition to iron, ni-
trogen interacts with some alloying elements forming special
submicroscopic nitrides during the nitriding, which are indis-
cernible by metallographic analysis but increase the etching
susceptibility of the diffusion layer as compared to nonni-
trided steel. These nitrides are detectable only with the help
of an electron microscope [1, 2]. A layer consisting of iron
nitrides is formed on the surface of nitrided steels, which
looks light and almost structureless when observed in an
etched microscopic specimen under a light microscope.
Three types of nitride particles differing in the type of
structure, size, shape, and interaction with the crystal lattice
of the matrix have been detected in nitrided steels depending
on the chemical composition, defects of the crystal structure
of the matrix, the temperature-and-time parameters of pre-
liminary heat treatment, and the nitriding mode [2].
1. Nitride nuclei in which the atoms occupy the same
places as in the initial solid solution, i.e., the nitrogen atoms
occupy the octahedral pores of the b.c.c. lattice of the matrix,
and the atoms of the alloying element substitute some of the
iron atoms. The dissolved substitutional and interstitial atoms
are arranged at random in the initial cluster, which should be
fully coherent to the matrix. In this case the redistribution of
alloying elements is not accompanied by restructuring of the
old structure but rather occurs with distortion of the lattice of
the matrix around lamellar zones. This explains the appear-
ance of continuous diffusion tension lines over the á100ñ di-
rections of the matrix lattice on microscopic electron diffrac-
tion patterns.
2. Multilayer complexes of nitride phase with a thickness
of 2 – 5 nm have a crystal lattice of the NaCl type with period
a = 0.412 nm. Due to the great difference in the interfacial
distances in the b.c.c. matrix and in the nitride phase the for-
mation of such a multilayer nucleus disturbs the coherence
over the edges of the lamellas. The coherence of the matrix
lattices and of the nitride over the (100) face is still preserved.
3. Nitride particles 7 – 10 nm in size with disturbed co-
herence of the nitride lattices and of the matrix. The nitrides
S. A. Gerasimov et al.
are accumulated in the form of thin lamellar segregations ar-
ranged at a small angle to each other.
The size and distribution density of the nitride phase are
affected by the chemical composition of the steel, the defects
of the crystal structure of the matrix, and the modes of pre-
liminary heat treatment and nitriding. In the nitrided layer of
low-alloy heat-resistant steels of martensitic class the parti-
cles formed on defects are commonly incoherent to the lat-
tice of the matrix and promote fixation of high dislocation
density in the martensite.
The nitrided layer of martensitic steels like
16Kh2N3MFBAYu-Sh and 16Kh3NMVFB-Sh subjected to
quenching and high-temperature tempering at 580°C simul-
taneously bears coherent (matrix) nitride nuclei and coarser
incoherent equiaxial nitride particles 4 – 5 nm in size, which
are positioned on defects of the crystal structure.
The presence of dispersed nitride particles in the nitrided
layer intensifies the deformation of the crystal lattice of the
matrix, which is reflected in the physical broadening of the
interference lines of the crystal lattice of the solid solution.
The maximum microdeformation corresponds to the maxi-
mum hardness of the layer. The incoherent nitride particles
formed on defects (in steels of martensitic class) are respon-
sible for the considerably lower (by a factor of 1.5) level of
microdeformation relative to coherent particles.
The size of the nitride particles is also affected by the na-
ture of the alloying element and its amount. For example,
chromium nitride nuclei form in the Fe – 1 at.% Cr alloy
nitrided for 35 h at 540°C, whereas incoherent equiaxed par-
ticles 4 – 6 nm in size form in the Fe – 4 at.% Cr alloy.
Nickel affects both the size and the uniformity of distri-
bution of nitride particles of alloying elements. Increase in
the nickel content in chromium-nickel steels results in a
more uniform distribution of nitride particles over the vo-
lume of a grain; their size decreases and the distribution den-
sity increases. For example, the nitride particles formed in
nickel-free or low-nickel steels are 15 – 20 nm in size,
whereas the size of nitrides formed in steel bearing about
3 at.% Ni is 7 – 10 nm; in this case the chains of nitride parti-
cles observed in nickel-free steels on grain and subgrain
boundaries are absent. The influence of nickel on the pro-
cesses of formation of dispersed particles of nitrides of the
alloying elements in nitriding is similar to its effect on the
processes of formation of carbides in high-temperature tem-
pering [3].
As a rule, the main task of preliminary heat treatment in
practical nitriding of pearlitic and martensitic steels is to pro-
vide an optimum combination of mechanical properties in
the core of the parts and machinability of the latter. The prob-
lem is solved by hardening and high-temperature tempering.
However, preliminary treatment is required not only for for-
mation of the appropriate structure and properties of the core,
but also for providing the specified size of nitride
segregations, which is largely dependent on the temperature
and time parameters of the preliminary heat treatment.
New Ideas on the Mechanism of Structure Formation in Nitrided Steels 15

HV0.2 d, nm n ´ 10 – 21, HV0.1

m–3
à
700 1
1300 d 4 15

500 2

1200 n 3 10
300

1100 HV0.2 2 5 100

0 0.1 0.2 0.3 0.4 h, mm
HV0.1
1000 1 0 1 b
Init. 500 550 600 th , °C
state
700
Fig. 1. Variation of the hardness of nitrided layer (HV ), size of ni-
trides (d ), and density of their distribution (n ) in steel 38Kh2MYuA 500 2
as a function of the heating temperature (initial condition: annealing
at 950°C for 30 min): )) tn = 2 h; ^) 10 h.
300

d, nm 100
0 0.1 0.2 0.3 0.4 h, mm

Fig. 3. Distribution of the microhardness over the thickness of

2
6 nitrided layer in alloy Fe – 4% Cr after treatment by different re-
gimes (h is the distance from the surface): 1 ) hardening from 950°C
1
in water + tempering at 500°C + nitriding at 500°C for 30 h;
4 2 ) hardening from 950°C in water + tempering at 600°C + nitriding
at 500°C for 30 h; a) 2-h tempering; b ) 10-h tempering.
2
0 0.2 0.4 0.6 h, mm

Fig. 2. Variation of the size of nitrides over the thickness of nitrided

layer after different kinds of preliminary heat treatment (h is the dis-
tance from the surface): 1 ) annealing at 950°C + heating to 550°C
for 10 h + nitriding at 500°C for 30 h; 2 ) hardening from 940°C +
tempering at 600°C for 2 h + nitriding at 550°C for 50 h.
Many studies have been devoted to the effect of prelimi-
nary heat treatment on the structure and properties of nitrided
parts, and different authors understand the effect in different
manners.
It has been established that as the heating temperature is
increased to 500 – 550°C, the hardness of the nitrided layer
decreases at any hold time both for steel 38Kh2MYuA and
for the model alloy Fe – 4% Cr, and the size of the nitride
particles increases (Fig. 1). Upon further growth in the tem-
perature the hardness begins to increase monotonically, and
the size of the nitride particles decreases. Thus, in order to
obtain larger and incoherent nitride particles the heating tem-
perature should not exceed 500 – 550°C [4].
It can be seen from Fig. 2 that as the distance from the
surface increases, the size of the nitride particles in nitrided
steel 38Kh2MYuA preliminary treated by the standard re-
gime increases monotonically. After a preliminary heat treat-
ment consisting of hardening from 950°C + heating to
500 – 550°C with 10-h hold the size of the nitride segre-
gations does not change in the entire layer. Such treatment
provides larger and incoherent nitride particles on the surface
and in the layer, which decreases the level of microdefor-
mation of the crystal lattice of the solid solution. For the
Fe – 4% Cr alloy the increase in the tempering temperature
produces a more uniform distribution of the hardness over
the thickness of the hardened layer (Fig. 3).
The increase in the size of nitrides in the nitrided layer
due to changes in the mode of preliminary tempering can be
explained by the formation of nitrides on segregations of al-
loying elements formed in the solid solution in the process of
preliminary tempering. In subsequent nitriding they become
sites of generation of nitrides. Formation of such segrega-
tions in high-chromium steels at 500 – 600°C has been
proved earlier. The fact that they were not detected in alloys
bearing less than 10% Cr is explainable by the insufficient
sensitivity of the neutron diffraction method used in [5].
The service properties of nitrided steels, especially the
fatigue characteristics, depend considerably not only on the
intragrain structure, but also on the structural, phase, and
chemical compositions of the near-boundary regions.
The near-boundary regions of former austenite grains in
the nitrided layer of pearlitic and martensitic steels have a
composite structure. Cementite-type carbides and nitrides of
alloying elements are arranged over the boundaries together
with very fine (tenth fractions of a micrometer) ferrite crys-
16
N50 , mln. cycles
55
30
5 have shown that the fine grain boundary crystals of recrystal-
0 1 2 Ni, wt.%
Fig. 4. Effect of the content of nickel on the contact endurance of
experimental steels of martensitic class after 50-h nitriding at 550°C.
tals, which, like the ferrite grains of the matrix, bear dis-
persed particles of nitrides of alloying elements. In a metallo-
graphic study, the grain boundary ferrite segregations have
the form of light unetched veins that are erroneously treated
as a nitride net consisting of g¢-phase particles.
Formation of grain boundary ferrite crystals can be
treated as a result of the beginning of the process of
recrystallization of deformed microvolumes of the matrix
a-phase. This hypothesis is confirmed by the hardening of
the matrix due to formation of nitride particles with a higher
(by about 50%) specific volume than the specific volume of
the a-phase, the temperature and time nitriding parameters,
the equiaxial crystal shape, and the growth of crystals over
the boundaries. The data of electron microscopic and x-ray
diffraction studies give grounds to assume that at a certain
distance from the surface (200 – 300 mm) individual fine nu-
clei of ferrite crystals with equiaxial shape form on grain
boundaries, grow in size, and merge into nonetching light
veins with decrease in distance to the surface of the layer.
Grain boundary ferrite crystals in the form of a net appear
only in steels and alloys bearing nitride-forming elements
and are absent in nitrided iron and carbon steels.
Auger spectroscopic studies of fractures in nitrided layer
of steel 38Kh2MYuA obtained at the temperature of liquid
nitrogen have shown that the concentration of alloying ele-
ments (Al, Cr) in grain boundary regions is 1.5 – 2 times
higher than their mean content in the steel.
Thus, the structure of nitrided steels of pearlitic class is
characterized by nonuniform distribution of alloying ele-
ments, nitride and carbide phases in the layer and carbide
phases in the core, formation of brittle grain boundary ferrite
crystals due to enhanced content of nitride-forming elements
in the latter, and considerable microdeformation of the crys-
tal lattice of the matrix. This explains the high brittleness of
nitrided steels of this class.
Nitrided martensitic steels are characterized by a more
uniform distribution of nitride and carbide particles in the
nitrided layer and of carbide particles in the volume, which is
a consequence of a more defective structure of the steel. The
distribution is the most favorable in steels bearing about 3%
Ni (16Kh2N3MFBAYu-Sh, 18Kh2N4V-Sh, 38KhN3MFA),
S. A. Gerasimov et al.
where lengthy chains of nitride and carbide particles are vir-
tually absent in the layer and carbide chains are absent in the
volume, whereas the nitrided layer of nickel-free steels
(20Kh3MVF-Sh) and low-nickel steels (16Kh3NMVFB-Sh,
etc.) bears grain boundary segregations of nitrides and
cementite in the layer and of cementite in the volume in the
form of discontinuous chains. The results of an Auger spec-
troscopic analysis of the surface of fractures in nitrided layer
lized ferrite in nickel-bearing steels (16Kh3N4MFBAYu-Sh)
are considerably enriched with nickel (its content is 3 – 5
times higher than the mean nickel content in the steel) and
depleted of nitrogen and chromium [5].
It has been established that the structures of nitrided
layer corresponding to maximum hardness and maximum
wear resistance differ. Maximum wear resistance corre-
sponds to formation of incoherent nitride particles in the
layer, which are responsible for the high hardness at a lower
level of microdeformation of the matrix lattice as compared
to coherent particles.
Maximum contact endurance, like wear resistance, is at-
tained upon formation of incoherent nitride particles respon-
sible for the minimum level of microdeformation of the crys-
tal lattice of the matrix and the hardness of the layer suffi-
cient for resisting the plastic deformation under contact
loading.
The higher contact endurance of martensitic steel is en-
sured by the lower level of microdeformation of the crystal
lattice of the matrix, favorable distribution of nitride and car-
bide phases in the layer and of carbide phases in the volume
of the specimens, and enrichment of the grain boundary re-
gions in the nitrided layer with nickel.
As the nickel content in martensitic steel grows to 3%, its
concentration in the near-boundary zones increases to
10 – 15%, which promotes a decrease in the brittleness of the
nitrided layer and, consequently, increases the contact endur-
ance (by about a factor of 8) relative to nickel-free steels
(Fig. 4).
Testing showed that nitrided steels with structure meet-
ing the requirements have the ultimate contact endurance
commensurable with that of carburized steels [6].
CONCLUSIONS
1. Models of structural state of nitrided layer in pearlitic
and martensitic steels are developed depending on their
chemical composition, density of defects of the structure of
the matrix, and temperature and time parameters of prelimi-
nary heat treatment and nitriding. Changes in these parame-
ters cause formation of three types of nitride segregations in
the diffusion layer, which differ in the sizes, shapes, and in-
teraction with the crystal lattice of the matrix. Preliminary
heat treatment is understood as an additional factor for con-
trolling the size of nitride particles and the properties of
nitrided steels.
New Ideas on the Mechanism of Structure Formation in Nitrided Steels
2. Cementite particles, nitrides of alloying elements, and
fine (tenths of micrometer) equiaxial ferrite crystals are lo-
cated in grain boundary regions of nitrided layer of pearlitic
and martensitic steels. The formation of grain boundary fer-
rite crystals is connected with the initial processes of
recrystallization in the deformed matrix around nitride parti-
cles the specific volume of which exceeds considerably the
specific volume of the matrix, which is responsible for its de-
formation.
3. Nickel interferes with the formation of chain nitride
and carbide segregations over grain boundaries in the nitri-
ded layer, which are observed in nickel-free steels. This pro-
motes their uniform distribution between the grain volume
and the boundaries of the former austenite grains.
4. The high brittleness of nitrided steels is connected
with growth in the concentration of alloying elements on the
boundaries of former austenite grains, which leads to an in-
crease in the amount of nitride segregations (38Kh2MYuA).
In nickel-bearing steels (16Kh2N3MFBAYu-Sh) the grain
boundary regions contain an enhanced amount of nickel, the
concentration of which reaches 10 – 15%, whereas the con-
centration of nitrogen is about half, which noticeably de-
creases the embrittlement.
5. Nitrided steels containing dispersed particles of inco-
herent nitrides possess the maximum wear resistance, where-
as the maximum contact endurance corresponds to the same
17
structural parameters and enhanced (to 10 – 15%) nickel
content in grain boundary regions, which interferes with the
formation of segregations of nitride and carbide particles in
these regions of the layer and of chains of carbide particles in
the core.
REFERENCES
1. S. A. Gerasimov, “Progressive method of nitriding,” in: Univer-
sity of Engineering Progress in Machine Building [in Russian],
Mashinostroenie, Moscow (1985), p. 32.
2. S. A. Gerasimov, Scientific Foundations of Advancement of
Nitriding Processes for Structural Alloy Steels for Raising the
Service Properties of Wearing Machine Joints, Author’s Abstract
of Doctoral Thesis [in Russian], Moscow (1997).
3. B. N. Beinisovich, A. L. Geller, and M. É. Natanson, Metallur-
giya, Moscow (1977).
4. S. A. Gerasimov, A. V. Zhiharev, V. A. Golikov, et al., “Effect of
preliminary heat treatment on the structure and properties of
nitrided steels,” Metalloved. Term. Obrab. Met., No. 6, 24 – 25
(2000).
5. E. Z. Vintaikin, V. Yu. Kolontsov, and É. A. Medvedev,
“Low-temperature part of the phase diagram of the Fe – Cr sys-
tem,” Izv. Akad. Nauk SSSR, Metally, No. 4, 169 – 172 (1969).
6. S. A. Gerasimov, V. I. Kutcheryavyi, and S. D. Karpoukhin, and
E. A. Eliseev, “Structure of nitrided steels,” in: Proc. XI Con-
gress of IFHTSE, Florence (1998).