Metal Science and Heat Treatment, Vol. 52, Nos. 11 12, March, 2011 (Russian Original Nos.

. 11 12, November December, 2010)

UDC 669.15-194.55/621.785.532

EFFECT OF THE SIZE OF AUSTENITE GRAINS ON THE CAPACITY

OF LOW-CARBON MARTENSITIC STEEL 12Kh2G2NMFT FOR NITRIDING
O. V. Silina1 and S. S. Yugai1
Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 11, pp. 57 61, November, 2010.

The department of metals science and heat treatment of the Perm State Engineering University actively works
on the problem of dispersion of low-carbon martensitic steels with ultrafine grains and a nanometric size of
the characteristic element of structure. It is shown that the highest efficiency of nitriding of this group of steels
is attained when the formed structure has a high density of phase boundaries and an elevated content of imperfections of the crystal structure.

Key words: low-carbon martensitic steels, refinement of austenite grains, nitriding, structure, properties.

Studies performed in the recent years [1, 2] show that

LCMS are promising structural materials for making welded
constructions and machine parts strengthened by heat and
thermochemical treatment. LCMS possess a high set of mechanical and process characteristics unattained in steels of
other classes. Specific combinations of carbon and alloying
elements provide a high stability of supercooled austenite,
which makes it possible to harden LCMS articles with cross
sections up to 1500 mm in size in air. The low stresses and
the low volume effect permit the use of LCMS in a hardened
state with strength sr of up to 1500 MPa.
The perspectives of the use of LCMS for parts subjected
to nitriding are shown in [3]. It is expedient to nitride LCMS
in a hardened condition (with structure of low-carbon
martensite). This eliminates preliminary heat treatment and
the accompanying additional thermal operations and reduces
the duration of the nitriding. The best results have been obtained for the LCMS complexly alloyed with vanadium and
titanium. However, despite the high operating characteristics
of the hardened layer, nitrided steels including LCMS ones
are inferior to carburized steels where the strength characteristics of the core are concerned. For this reason and due to
the low thickness of the nitrided layer a source of fatigue
fracture lies close to the surface, which lowers the fatigue resistance of the metal.
The results of a study of the effect of grain boundaries on
the diffusion of interstitial impurities allow us to judge on the
effect of the grain size of austenite on the processes of diffusion saturation of low-carbon martensitic steels with nitrogen.

INTRODUCTION
The processibility of structural steels determines the
method of production of parts (the number and succession of
mechanical operations) and the degree of complexity of the
hardening heat treatment for forming the final combination
of the characteristics of mechanical properties and for providing precision of the parts.
Various kinds of heat and thermochemical treatment
(TCT) are used to raise the working capacity of parts serving
under conditions of wear, corrosion, and contact and fatigue
loads.
The main kinds of TCT improving the hardness, wear resistance, and contact endurance are carburizing and nitriding.
Carburized materials are most often low-carbon structural
steels (12KhN3A, 20Kh, etc.) and nitrided materials are preferentially medium-carbon heat treatable steels of type
38Kh2MYuA.
Virtually any nitrided heat-treatable steel is characterized
by low processibility. The great number of preliminary heat
treatment and auxiliary operations, the high hardening temperatures, the large tolerances for mechanical processing,
and the durable nitriding process complicate the production
of parts and increase their cost and probability of rejection.
For this reason, it is important to develop and install new
manufacture-adaptable steels that would simplify considerably the production of parts and lower their cost. A new class
of materials, i.e., low-carbon martensitic steels (LCMS),
meets these requirements.
1

Perm State Engineering University, Perm, Russia (e-mail:

jugaj@do.pstu.ru).

568
0026-0673/11/1112-0568 2011 Springer Science + Business Media, Inc.

Effect of the Size of Austenite Grains on the Capacity of Steel 12Kh2G2NMFT for Nitriding

Since the diffusion of nitrogen atoms primarily occurs

over grain boundaries (high- and low-angle ones) and grain
bodies, we may expect that the structure of surface layers after nitriding should differ.
Thus, it would be interesting and expedient for solving
the task of raising the structural strength of nitrided low-carbon martensitic steels to study the special features of saturation of the surface of steels with nitrogen as a function of the
grain size of the austenite.
In the present work we posed a task to study the effect of
the grain size of austenite on the structure and properties of
nitrided low-carbon martensitic steel 12Kh2G2NMFT.

569

50 mm

50 mm

50 mm

METHODS OF STUDY
We studied an LCMS of grade 12Kh2G2NMFT with the
following chemical composition (in wt.%): 0.13 C, 2.24 Mn,
0.40 Si, 2.39 Cr, 1.38 Ni, 0.45 Mo, 0.10 V, 0.03 Ti.
Steel 12Kh2G2NMFT belongs to the group of LCMS
with elevated strength. The specific combination of carbon
and alloying elements provides a high stability of supercooled austenite and hence a high hardenability. Complex alloying with strong carbide-forming elements (vanadium and
titanium) makes it possible to preserve fine grains after heating and to raise the tempering resistance of the steel.
The initial preforms had the form of a hot-rolled sheet
with a thickness of 6 mm. Specimens for the study were fabricated with a size of 5 10 25 mm and 5 10 55 mm.
The volume and surface heat treatment was performed
under laboratory and industrial conditions.
In order to determine the effect of the grain size of austenite on the capacity of steel 12Kh2G2NMFT for nitriding
we used specimens treated in three modes:
(1 ) hardening from the rolling temperature (hot-rolled
condition);
(2 ) hardening from t = 1200C, t = 40 sec;
(3 ) thermocycling at t = 1030C, t = 20 sec, water cooling, 5 cycles.
Gas furnace nitriding was performed in a hardened state
at 560C, 30 h, in an atmosphere of ammonia diluted with nitrogen (20 30% NH3 ).
After the nitriding we measured the hardness of the surface and of the core of the specimens and determined the
thickness of the nitrided layer and the distribution of microhardness over the thickness of the diffusion zone. In addition,
we evaluated the brittleness of the surface of the nitrided
layer, performed x-ray phase and diffraction analyses, and
determined the characteristics of mechanical properties.
RESULTS AND DISCUSSION
After hardening from the rolling temperature, hardening
from 1200C, and thermocycling the structure of the specimens was represented by low-carbon martensite with grain
size d = 15 mm, d = 70 mm, and d = 2 mm, respectively. In

Fig. 1. Microstructure of the core of low-carbon martensitic steel

12Kh2G2NMFT after treatment by different regimes: a) hot-rolled
condition; b ) hardening from 1200C for 40 min; c) thermocycling
at 1030C, 20 sec, 5 cycles.

hardened condition (modes 1 and 2 ) the structure of the core

of the LCMS is represented by typical lath martensite with a
high dislocation density. The differences concern only the
sizes of the packets and the content of the high- and low-angle boundaries (Fig. 1a and b ). The structure of the core is
represented by a partially preserved substructure of martensite known as block one (Fig. 1c ).
Since any LCMS is nitrided with an initially martensitic
structure, the core acquires the final properties after nitriding
at 560C for 30 h.
A stable micro- and submicrostructure is preserved in
LCMS up to 500 550C. Above 550 600C the strength
characteristics decrease as a result of decrease in the density
of crystal structure defects and cell formation in the a-phase.

570

O. V. Silina and S. S. Yugai

Fig. 2. Microstructure of steel 12Kh2G2NMFT ( 40,000): a) hardening from 1200C, 40 min; b ) hardening + tempering at 560C,
30 h.

The low content of carbon and the complex alloying with

elements hindering the recrystallization processes promote
preservation of the structure of low-carbon martensite up to
high tempering temperatures (Fig. 2).
Table 1 presents the properties of steel 12Kh2G2NMFT
after treatment by the chosen regimes and nitriding.
In the process of nitriding at 560C the hardness of the
metal decreases by about 10 HRC. This may be connected
with segregation of carbides, lowering of the dislocation density, and redistribution of dislocations. The lath structure of
martensite is preserved and provides a high resistance to brittle fracture.
It can be seen from Table 1 that as the size of the austenite grains increases, the impact toughness becomes lower; at
standard (15 mm) and large (70 mm) grain sizes it is twice
lower than in the case of ultrafine grains (2 mm). This may
imply that the LCMS with ultrafine grains are much more
advantageous than the LCMS with grain size d = 15 mm.
Thus, after nitriding of steel 12Kh2G2NMFT the core
preserves a structure of low-carbon martensite, which may
be a sign of a high tempering resistance of the LCMS.
In traditional nitrided steels formation of a nitrided layer
with a nitride net is a result of dominant diffusion of nitrogen
over boundaries of former austenite grains and of the presence of a strong carbide former, i.e., aluminum, which promotes formation of nitrides on the boundary. In steel
12Kh2G2NMFT a net is not formed, because aluminum is

not present in the composition, and the highly defective crystal structure provides a more uniform diffusion of nitrogen.
Nonbrittle layers form on steel 12Kh2NMFT (one scale division according to the VIAM scale).
Since the diffusion of nitrogen atoms develops over
boundaries (high- and low-angle ones) and over the bodies of
grains, we may expect differences in the structure of nitrided
layers after nitriding.
After nitriding of specimens hardened from the temperature of rolling (Fig. 3a ) we observe well manifested division
of the diffusion layer into two parts at a standard grain size
d = 15 mm, i.e., a thin nitride crust (about 15 mm) and a zone
of internal nitriding (ZIN) The ZIN has a homogeneous
structure, because the high degree of defectiveness of the
crystal structure of martensite results in uniform diffusion of
nitrogen from the surface to the core; the nitrides are distributed uniformly over the whole of the volume of the layer.
After nitriding of specimens hardened from 1200C
(Fig. 3b ) at grain size d = 70 mm, the nitride crust is thicker
(about 20 mm) and the diffusion layer is not so deep and homogeneous. Near the nitride crust we observe iron nitrides
(of type Fe4N) that have the form of elongated inclusions
over boundaries of packets and former austenite grains. It
can be assumed that at specific high loads these elongated nitrides can behave as a nitride net in traditional heat-treatable
nitrided steels, break, and play the role of an abrasive, which
lowers the wear resistance of the surface.
After nitriding of specimens subjected to thermocycling
(Fig. 3c ) at grain size d = 2 mm a nitride crust is also present,
but its boundary with the ZIN is more smeared than in the
metal with initially coarse grains. The dark-etching zone near
the crust is a sign of an elevated concentration of nitrogen,
which is responsible for intense formation of nitrides. The
zone of internal nitriding has a homogeneous dispersed
structure. When the thickness of the diffusion layer increases, the concentration of nitrogen decreases and the hardness becomes lower.
We judged on the presence of dispersed nitrides of alloying elements not detected by x-ray diffraction analyses using
published data [4] and indirectly, i.e., by enhanced etching
and high growth in the hardness of the nitrided layer.
The distribution of microhardness over the thickness of
nitrided layer in specimens with different gain sizes is presented in Fig. 4. Table 2 presents the values of surface hardness and the effective thickness of nitrided layers as a func-

TABLE 1. Properties and Structure of the Core of Steel 12Kh2G2NMFT

Core hardness, HRC

Preliminary heat treatment

Size of austenite grains,

mm

prior to
nitriding

after
nitriding

Hardening from the rolling temperature (hot-rolled state)

Hardening at t = 1200C, t = 40 min
Thermocycling at t = 1030C, t = 20 sec, 5 cycles

15
70
2

40
39
40

29
27
27

KCT,
MJ/m2

0.5
0.4
0.9

Effect of the Size of Austenite Grains on the Capacity of Steel 12Kh2G2NMFT for Nitriding

571

HV, kgf/mm2
1200
1000

800

70

600

15

HVeff

400
200

0.1

0.2

0.3

0.4

0.5

0.6

0.1 mm

0.7

0.8

l, mm
Fig. 4. Microhardness distribution in depth of the diffusion layer on
steel specimen 12Kh2G2NMFT with different austenite grain size
(indicated for each curve, mm).

0.1 mm

0.1 mm

Fig. 3. Microstructure of nitrided layers on steel 12Kh2G2NMFT

after different variants of treatment: a) hot-rolled condition; b ) hardening from 1200C, 40 min; c) thermocycling at 1030C, 20 sec,
5 cycles.

tion of the regimes of preliminary (prior to nitriding) heat

treatment.
The distribution of microhardness over the thickness of
the nitrided layer in the steel with grain size d = 15 mm is
smooth and exhibits no marked change. Up to a depth of
about 0.35 mm the hardness of this layer is lower than the
hardness of the layer in the steels with grain sizes d = 70 mm
and d = 2 mm. At a distance of about 25 mm from the surface
the hardness of the metal with fine and coarse grains is
200 HV. This is a result of the difference in the concentration
of nitrogen at this depth due to the higher diffusion over
large-angle boundaries, which causes formation of a high

amount of nitrides strengthening the layer. Nitrides of type

Me4N formed near the nitride crust and nitrides of the alloying elements of the steel with grain size d = 70 mm raise the
hardness of the layer but simultaneously hinder the inflow of
nitrogen atoms into the depth of the metal. As a consequence, the layer is not so homogeneous and deep. However,
when the thickness of the layer increases, the hardness values
are leveled; at a distance of 0.4 mm from the surface the
hardness of the layer of the steel with grain size d = 15 mm
increases.
The maximum microhardness of the surface of diffusion
layer is higher in the steel with grain size d = 2 mm. At a distance of 0.4 mm from the surface the hardness of the layers
in the steels with d = 70 mm and d = 2 mm is virtually the
same.
The highest effective thickness of nitrided layer
(h = 0.5 mm) is exhibited by the LCMS with grain size
d = 15 mm, which is 0.1 mm greater than the thickness of the
layers in the steels with initially coarse and fine grains
(h = 0.4 mm).
Thus, nitriding of LCMS with initially ultrafine and initially coarse grains increases the surface hardness (which
seems to be a result of a higher nitrogen concentration) and
decreases somewhat the effective thickness of the diffusion
layer. However, the metal with initially coarse grains has a
higher brittleness (2 3 divisions of the VIAM scale).

TABLE 2. Properties of Nitrided Layer on Steel 12Kh2G2NMFT

Preliminary heat treatment

Hardening from the rolling temperature (hot-rolled state)

Hardening from t = 1200C,
t = 40 min
Thermocycling at t = 1030C,
t = 20 sec, 5 cycles

Austenite
grain size, mm

HRA

heff , mm

15

82

0.5

70

84

0.4

84

0.4

572

It is known [5] that nitriding of low-carbon martensite

causes growth in the effective thickness of the layer (as compared to traditionally nitrided steels) due to the higher density of crystal structure imperfections and more extended
boundaries of grains and packets. Large-angle boundaries are
more preferable regions for diffusion of nitrogen atoms [6].
When the grain size decreases, the extent of the grain boundaries grows. When the grain size increases, the extent of the
boundaries of former austenite grains decreases but that of
the packet boundaries grows. In the case of fine grains the
density of the grain boundaries is high; when the grains are
coarse, so is the density of the packet boundaries.
It should be noted that dislocation tubes are effective
elements of mass transfer. X-ray diffraction analysis shows
that the dislocation density decreases by an order of magnitude upon formation of coarse or ultrafine grains. This causes
lowering of the rate of diffusion of nitrogen into the depth of
the metal and explains formation of less deep layers.
Thus, the size of the austenite grains affects formation of
diffusion layer in the process of nitrogen saturation.
Nitriding of LCMS with coarse and ultrafine grains causes
decrease in the effective thickness of the layer, but at the
same time increases the surface hardness due to the higher
concentration of nitrogen.
CONCLUSIONS
1. Nitriding of steel 12Kh2G2NMFT yields hard surface
layers as a result of dispersion of the structure of low-carbon
martensite but lowers the thickness of the diffusion layer due
to reduction of the dislocation density.

O. V. Silina and S. S. Yugai

2. A coarse-grained structure in the steel also provides

formation of hard surface layers with elevated brittleness due
to the appearance of acicular nitrides but simultaneously
preserves an elevated impact toughness of the core.
3. An optimum combination of properties on the surface
and in the core of steel 12Kh2G2NMFT is provided by a
structure with a mean size of austenite grains equal to 15 mm;
in the case of such a structure the layers are deeper and the
set of mechanical properties of the core is high.
REFERENCES
1. L. M. Kleiner and A. A. Shatsov, Novel Structural Materials:
Low-Carbon Martensitic and Powder Steels. Applied Metals Science, A Study Aid [in Russian], Perm Gos. Tekh. Univ., Perm
(2004), 142 p.
2. N. N. Mitrokhovich, Yu. N. Simonov, L. M. Kleiner, et al.,
Processibility and Structural Strength of Low-Carbon Steels with
Martensitic Structure [in Russian], A Study Aid, Perm Gos.
Tekh. Univ., Perm (2004), 123 p.
3. L. M. Kleiner, S. A. Kokovyakina, N. N. Mitrokhovich, et al.,
Ecologically Pure Processes for Manufacturing Heat-Hardened
Semiproducts, Preforms, Parts, and Welded Structures [in Russian], A Study Aid, Perm Gos. Tekh. Univ., Perm (2000), 41 p.
4. Yu. M. Lakhtin and Ya. D. Kogan, Nitrided Steels [in Russian],
Mashinostroenie, Moscow (1976), 256 p.
5. S. S. Yugai, L. M. Kleiner, and A. A. Shatsov, Structure
and properties of nitrided low-carbon martensitic steel
12Kh2G2NMFT, Fiz. Met. Metalloved., 99(1), 110 115
(2005).
6. Yu. M. Lakhtin, Ya. D. Kogan, H. J. Spies, and Z. Bmer, The
Theory and Technology of Nitriding [in Russian], Metallurgiya,
Moscow (1991), 320 p.