Metal Science and Heat Treatment

Vol. 47, Nos. 3 4, 2005

UDC 621.785.533

CARBONITRIDING OF LOW- AND MEDIUM-CARBON STEELS

IN FLUIDIZED BED
Al. A. Aliev1
Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 3, pp. 30 33, March, 2005.

Results of a study, development, and commissioning of an ecologically safe process of carbonitriding of lowand medium-carbon steels in fluidized bed with the use of an updated commercial Korund-300 unit are presented.

15L, A12, and 40 using an updated commercial

Korund-300 unit.
A fluidized bed of a catalyst is created in the retort of this
unit (operating zone) with the help of compressed air. Town
gas is fed upon the attainment of the specified temperature
(830 840C), and then ammonia is added. A container with
articles is placed into the retort. After a certain hold the container with the treated parts is quenched in oil or water (depending on the required hardness), and then the parts are
washed and subjected to low-temperature tempering at
180 200C for 1 h and cooled in air. Metallographic analysis is performed for determining the thickness of the layer
and its hardness. If the thickness of the layer and the hardness meet the design requirements, the parts are transported
for assembly. The process of carbonitriding in fluidized bed
is finished.
We cut specimens for the study from carbonitrided parts,
polished them in a Metasinex machine using a set of grinding paper, diamond paste APP-7 and APP-2, and an aqueous
emulsion of powdered chromium oxide.
Polished sections were etched in a 4% alcoholic solution
of nitric acid. The microstructure was studied under a
Neophot-21 microscope at magnifications of times 100
and 400.
The surface hardness of the parts was determined using a
TK-2M Rockwell device in accordance with the GOST
901379 standard for scales C and A and a TKS-1m
Super Rockwell device at a load of 15 N.
The microhardness over the polished section of templates was determined using a PMT-3 device with a diamond
pyramid at a load of 0.98 N according to GOST 1071775.
The heating temperature was measured using TKhA
thermocouples in the retort, TKhK thermocouples (GOST
661684) in the unit for cleaning the gas from sulfur, and

INTRODUCTION
It is known that carbonitriding is a substitute for cyaniding in liquid media. One method of carbonitriding is by
the use of a mixture of carbon- and nitrogen-bearing gases
(propane-butane or natural gas and ammonia) for surface
hardening of low- and medium-carbon and low-alloy steels.
A recently developed process consists in carbonitriding
of steel parts in fluidized bed of a catalyst (aluminumnickel-molybdenum). Under simultaneous diffusion of carbon and nitrogen, maximum concentration of nitrogen in a
surface layer up to 0.4 mm thick on steel parts is ensured in
1.5 2 h depending on the gas used and temperature of the
process.
Carbonitriding in fluidized bed has the following advantages over other kinds of TCT:
ecological purity of the process;
relatively low temperature of the process (820
840C);
1.5 2 times shorter duration of the process;
reduced probability of formation of a light nitride
crust at nitrogen concentration below 0.4%.
The aim of the present work consisted in developing an
ecologically safe process for carbonitriding of low- and medium-carbon steels in fluidized bed with the use of updated
commercial equipment.
METHODS OF STUDY
We studied magneto (ignition system of automotive engines) parts and starters from steels of grades 08kp, 10kp, 15,
1

Research and Experimentation Institute for Automotive Electronics and Electrical Equipment (FGUP NIIAE), Moscow, Russia.

107
0026-0673/05/0304-0107 2005 Plenum Publishing Corporation

108

Al. A. Aliev
D, mm
0.4
880
860
840

0.3

820
0.2

0.1

0.5

1.0

1.5

2.0

t, h

Fig. 1. Effect of the hold time and temperature on the thickness of

carbonitrided layer in steel 08kp.

secondary equipment, i.e., millivoltmeters Shch4500 for

1100C and Shch4541 for 600C (GOST 973686).
The heating agents were catalysts, i.e., aluminumnickel-magnesium fine spherical particles ( 0.4 1.0 mm)
of grade A (TU6-68-11991) in the retort and GIAP-10
(TU113-03-200286) in the unit for cleaning the gas from
sulfur.
The carbon-bearing gas was town gas of the following
composition: 88.739% methane, 5.365% ethane, 1.300%
propane, 0.176% butane, 0.03% pentane, 0.438% carbon dioxide (CO2 ), 1.75% nitrogen (no oxygen and mechanical
mixtures), and liquid commercial ammonia (GOST 622182).
In order to decrease the number of tests and save power
in the determination of optimum parameters of carbonitriding we based ourselves on the values of the parameters
of the process of carburizing of parts of automotive electrical
equipment (AEE) in fluidized bed obtained earlier for updated commercial Korund-300 installation and corrected
these data (flow rate of town gas 2.75 nm3/h, pressure of
town gas 0.82 105 Pa, air/gas ratio 2.75, and pressure of
compressed air 3.2 105 Pa).
To these parameters we added ammonia flow rate of
1.5 nm3/h (according to the reading of a rotameter) at a pressure of (0.8 1.0) 105 Pa.
We carbonitrided magneto weights (PM302A-6052)
from steel 08kp at a temperature of 820 880C with an interval of 20C.
RESULTS AND DISCUSSION
Analyzing the results of our study (Fig. 1) we established
that the increase in the heating temperature was accompanied
by acceleration of formation of the diffusion layer. For example, after 1-h hold at 820C the thickness of the layer was

0.11 mm, whereas at 880C it was 0.24 mm. When the hold
time was increased to 2 h, the thickness of the layer grew to
0.38 mm. It should be noted that with growth in the temperature to 880C the intensity of saturation of the surface of the
parts with carbon increased and that with nitrogen decreased;
in the range of 820 840C the picture was the opposite.
The intensity of formation of the diffusion layer depends
not only on the heating temperature and the hold time, but
also on the composition of the carbon-bearing gas used. For
example, the formation of a layer with specified thickness of
0.3 mm on the same AEE parts fabricated from the same
grade of steel in fluidized bed in the same mode takes 1 h
with the use of propane-butane and 2 h with the use of town
gas. This seems to be connected with the content of methane
in the gas used and its reactivity, which is confirmed by the
data of [2, 3]. It is shown in these works that methane is a
less reactive fuel gas. The temperature of its steady combustion in fluidized bed is 50 100C higher than that of propane-butane, and the efficiency of the reaction is lower. As in
burning of propane-butane at an air flow rate coefficient
a 1 an equilibrium composition, i.e., absence of chemical
underburning, is attainable only at high temperatures. However, growth in the process temperature to 880C can lead to
a reduction in the nitrogen content and growth in the carbon
content in the diffusion layer. In order to avoid this and obtain an optimum content of nitrogen and carbon in the surface layer of treated parts, we should determine the optimum
temperature range of the process. Experiments show that the
best temperature range for carbonitriding of low- and medium-carbon steels is 830 840C.
We studied the distribution of the concentration of nitrogen and carbon over the thickness of the carbonitrided layer
on specimens 10 mm in diameter and 40 mm long fabricated
from steel 08kp and treated in the following mode: heating to
830 840C, hold for 1.5 h (from the moment of loading of
the specimens), and cooling in air. The carbon concentration
was determined with the help of a Spectrolab spectroscope
(Germany) and the nitrogen concentration was determined
by layer-after-layer removal of chips and their chemical
analysis.
Analysis of the obtained results (Fig. 2) shows that the
concentration of nitrogen on the surface of a part is 0.38%.
At a depth of 0.08 mm it attains maximum values (0.4%) and
then decreases markedly, attaining 0.17% at a depth of
0.27 mm. With growth in the distance from the surface the
concentration of nitrogen decreases progressively and
reaches 0.01% at a depth of the diffusion layer of 0.45 mm.
The carbon concentration over the thickness of the diffusion layer varies similarly to that of nitrogen. At a thickness
of the layer up to 0.08 mm it is 0.52 0.53%, and at a thickness of 0.25 mm it is 0.45%; then it decreases progressively
and attains 0.25% at a depth of 0.35 mm. With further increase in the thickness of the layer it attains 0.08%.
We analyzed the microstructure of the diffusion layer on
a magneto weight from steel 08kp and on a magneto bushing

Carbonitriding of Low- and Medium-Carbon Steels in Fluidized Bed

109

; N, %

HV100

0.6

900

0.5
0.4

800

700

0.3

600

0.2

500

0.1

400

0.1

0.2

0.3

0.4

300

0.5 h, mm

200

Fig. 2. Distribution of nitrogen and carbon concentration over the

thickness of carbonitrided layer on a magneto weight from steel
08kp (h is the distance from the surface).

from steel 15 (the thickness of the diffusion layer on steel

08kp was 0.29 mm and that on steel 15 was 0.3 mm) and
found no light nitride crust on the surface of the polished sections. The microstructure of the diffusion layer was chiefly
represented by martensite, a fine dispersed carbonitride
phase, and retained austenite.
Analysis of the distribution of microhardness over the
thickness of the diffusion layer on a magneto weight from
steel 08kp and on a drive from steel 10kp treated by carbonitriding in fluidized bed at 830 840C with a hold of 1.5 h
(from the moment of loading), water hardening, tempering at
180 200C with 1-h hold, and air cooling showed (Fig. 3)
that steel 08kp was better hardened by carbonitriding than
steel 10kp. The maximum microhardness was detected on
the surface, where the concentrations of nitrogen and carbon
were the highest independently of the grade of the steel. With
growth in the thickness of the layer the microhardness decreased smoothly and corresponded to the level of the core
hardness obtained after hardening.
The variation of the concentration of nitrogen and carbon
correlated with the distribution of the microhardness.

100
0

0.1

0.2

0.3

0.4

0.5 h, mm

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

carbonitrided layer on magneto parts: a weight from steel 08kp (1 )
and a driver from steel 10kp (2 ) (h is the distance from the surface).

We used the results of our study for developing a process

with optimum parameters for carbonitriding steel parts in
fluidized bed on an updated Korund-300 unit, namely:
heating temperature 830 840C;
hold time 1.5 2 h (depends on the thickness of the
layer and on the mass of the charge);
flow rate of natural (town) gas 2.75 nm3/h;
pressure of natural (town) gas 0.82 105 Pa;
air-to-gas ratio 2.75;
flow rate of ammonia 0.5 1.5 nm3/h;
pressure of ammonia 0.08 0.10 MPa;
pressure of compressed air 0.32 MPa.
The results of our study of carbonitriding in fluidized
bed of a commercial batch of AEE parts in updated
Korund-300 equipment are presented in Table 1.
Comparison of the results obtained in the processes of
fluidized bed carbonitriding and carburizing for the same
AEE parts with the same thickness of the layer shows that
the hardness of carbonitrided parts is 3 4 HRC higher than

TABLE 1. Results of Carbonitriding of AEE Steel Parts in Fluidized Bed in Updated Korund-300 Unit
Design requirements
Name of part and number of drawing

Magneto weight (PM302A-6052)

Magneto drive (PM302A-6002)
Starter pole screw (ST221-8105)
Magneto underframe (PM302A-6070)
Magneto bushing (MS22-8111A)
Magneto casing (MS149-8101)
Magneto pin (MS-8011)

Steel

08kp
08kp
10kp
A12
15
15L
40

After carbonitriding in fluidized bed

layer thickness, hardness (HRC ), layer thickness, hardness (HRC ),

mm
at least
mm
at least

0.2 0.3
0.2 0.3
0.2 0.3
0.2 0.3
0.2 0.25
0.15 0.25
0.15 0.25

57
58
59
58
59
50
58

0.3
0.25 0.3
0.35
0.25 0.3
0.3
0.3
0.3 0.35

59
59
60
60
60
59
62

110

Al. A. Aliev
HRC

62

60

58

08kp

10kp

56
54
52

40

Fig. 4. Surface hardness at diffusion layer with a thickness of

0.30 0.35 mm on AEE parts from different steels after carburizing (1 ) and carbonitriding (2 ) in fluidized bed.

the maximum permissible concentration standardized by

GOST 12.1.005.88.
CONCLUSIONS
1. An ecologically safe process of carbonitriding of lowand medium-carbon steels in fluidized bed has been developed and installed with the use of updated Korund-300
equipment.
2. In the case of the use of propane-butane in the process
of fluidized bed carbonitriding the rate of formation of diffusion layer with specified thickness (about 0.30 mm) is twice
higher than in the case of the use of town gas.
3. At 0.4% nitrogen concentration on the surface of
carbonitrided parts there is no light nitride crust on the surface of the parts.
REFERENCES

that of carburized parts due to the presence of nitrogen on the

surface (Fig. 4). It is obvious that carbonitriding is more advantageous than carburizing.
A sanitary inspection has made an independent check of
the process and of operating TCT equipment with fluidized
bed. It established that the concentration of harmful substances emitted by the operating unit was twice lower than

1. Al. A. Aliev, Updating of equipment for thermochemical treatment of steel parts in fluidized bed, Metalloved. Term. Obrab.
Met., No. 12, 40 43 (2004).
2. A. P. Baskakov, Heating and Cooling of Metals in Fluidized Bed
[in Russian], Metallurgiya, Moscow (1974).
3. S. S. Zabrodskii and N. V. Antonishin, Inzh.-Fiz. Zh., No. 2,
10 15 (1962).