Metal Science and Heat Treatment

Vol. 52, Nos. 9 10, 2010

UDC 621.785.533

ADVANCEMENT OF THE PROCESS OF CARBONITRIDING

S. G. Tsikh,1 V. I. Grishin,2 A. V. Supov,2 V. N. Lisitskii,1 and Yu. A. Glebova1
Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 9, pp. 7 12, September, 2010.

Low-temperature processes of surface hardening in molten salts (carbonitriding, Tenifer-QPQ, etc.) are considered. Results of tests of these processes are compared with those of galvanic (chromizing, nickelizing, etc.)
processes. The equipment for and examples of commercial use of processes of liquid carbonitriding are presented.

Key words: carbonitriding, oxidizing, grinding, polishing, wear resistance, corrosion resistance.

INTRODUCTION

RESULTS AND DISCUSSION

The task of improving the operating properties of metallic materials in modern mechanical engineering is closely related with development of new processes of surface hardening of parts produced from them.
One such process has been designed by professor
D. A. Prokoshkin at the Bauman Moscow State Technical
University and is known as liquid carbonitriding. The method
of liquid carbonitriding essentially consists in subjecting machine parts from structural, stainless, heat-resistant tool, and
high-speed steels to heating in molten salts based on potassium cyanate and carbonate at 540 600C with a hold for
5 40 min for cutting tools or for 1 6 h for machine parts
and dies depending on the required thickness of the hardened
layer.
Liquid carbonitriding is used for raising wear resistance
and fatigue resistance. In combination with oxidizing it is
used for raising corrosion strength. In many cases liquid
carbonitriding is an alternative to surface hardening, galvanic
chromizing, carburizing, nitrocarburizing, etc.
Prokoshkins composition of the melt for liquid carbonitriding (75 85% KCNO + 15 25% K2CO3 ) [1] has been
accepted with some alterations by some foreign producers.
Specifically, the Durferrit Company (Germany), which is a
world leader in the field of liquid processes of surface engineering, actively exploits the Tenifer technology (a virtually full counterpart of the Russian process of liquid carbonitriding) all over the world [2].

Liquid carbonitriding yields a hardened layer consisting

of several zones on the surface of the steel (Fig. 1). The external layer is represented by e-carbonitride of type Fe3(N, C);
then goes a zone of g-phase of type Fe4(N, C), under which
we find a diffusion (heterophase) layer consisting of a solid
solution of carbon and nitrogen in iron with inclusions of
carbonitride phases, the hardness of which exceeds considerably the hardness of the core.
The concentration of nitrogen and carbon in the carbonitride layer decreases markedly upon growth in the distance
from the surface. It should be noted that the process of
carbonitriding develops according to the laws of nitriding,
i.e., of the two elements (nitrogen and carbon) capable to saturate the metal nitrogen diffuses into the surface layer dominantly and forms nitrogen-base phases. In the thin surface

1
2

Fe; C; N, wt.%
100
90
80
70
60
50
40
30
20
10
0

NPO TsNIITMaSh Joint-Stock Company, Moscow, Russia

(e-mail: termohim@bk.ru).
N. . Bauman Moscow State Technical University, Moscow,
Russia.

Fe
e
N

Fe
possible location
of N

Porous
zone

g
C
10

20

30

40

50 h, mm

Fig. 1. Structure of steel 40Kh and distribution of nitrogen, carbon

and iron in the hardened layer after liquid carbonitriding at 580C,
1.5 h (h is the distance from the surface).

408
0026-0673/10/0910-0408 2010 Springer Science + Business Media, Inc.

Advancement of the Process of Carbonitriding

carbonate (CO23 ) + regenerator cyanate (CNO ).

Control and timely regeneration of the melt ensure quality hardened layers.
In order to provide corrosion properties in carbonitrided
parts it is recommended to perform oxidizing in a nitrite-alkaline melt at 350 400C or in an aqueous solution at
130 150C.
The method of liquid carbonitriding followed by oxidizing has been called a NOK-process (low-temperature oxycarbonitriding) [3].
In addition to giving corrosion properties to the treated
parts oxycarbonitriding promotes complete removal of the
remnants of cyanides, which guarantees their absence in industrial waste and hence in the sewage system.
The main reactions that occur in the molten salts during
oxidizing can be represented in the following form:
(1) detoxication reactions
cyanide (CN ) + nitrate (NO-3 ) carbonate (CO23 ) +

nitrite (NO-2 );

cyanate (CN ) + nitrate (NO-3 ) carbonate (CO23 )+

nitrite (NO-2 );
(2) oxidation of the carbonitride layer
iron nitride (FexN) + nitrate (NO-3 ) magnetite (Fe3O4) +

nitrite (NO-2 );
(3) regeneration of the pool
nitrite (NO-2 ) + oxygen (O2 ) nitrate (NO-3 ).
Thus, the reactions occurring during the hold of the parts
in a nitrite-alkaline melt ensure decomposition of the cyanides, cyanates, and nitrites into base nontoxic substances.
It should be noted that carbonitriding worsens the roughness of the surface from Rz = 1.6 to Rz = 3.2 mm on the average. The roughness of the surface can be restored after oxidizing by various methods of polishing, namely,
rubbing with abrasive paper with grain 360 or finer;
polishing or fine grinding by special polishing discs in
a continuous manner similar to centerless grinding or grinding in automatic lathes;

Tenifer

TF1,
580

xide,
380
420

Polishing

Oxidizing +
cooling

Tenifer

xide,
380
420

Repeated
oxidizing

Air,
350
400

Preliminary
heating

mperature

layer (up to 15 mm) iron is present primarily in a bound condition in the form of carbonitrides distributed in the layer in a
manner typical for diffusion hardening.
It should be noted that in the process of liquid carbonitriding carbonates are accumulated in the pool due to oxidation
of the cyanates, and this lowers considerably the reactivity
and the fluidity of the melt. Regeneration of the pool is a key
moment of the process of liquid carbonitriding at industrial
enterprises. The main components of regenerating compositions are ammonocarbon compounds such as melamine,
melon, and dicyandiamide, which reduce the carbonates to
cyanates.
The reaction of regeneration can be represented schematically as

409

Time

Fig. 2. Scheme of the Tenifer-QPQ process.

sliding grinding in a vibrating vessel (such treatment is

applied primarily to small and sheet parts);
blasting with glass balls 40 70 mm in diameter.
Grinding and polishing may deteriorate the corrosive
properties of the parts and they are subjected to second oxidizing. In Germany such mode of treatment is known as a
TENIFER-QPQ process, which includes carbonitriding, oxidizing, polishing, and oxidizing and is represented schematically in Fig. 2 [2].
In Russia this process is known as NOK-PQ and is a
complete analog of TENIFER-QPQ.
All low-temperature processes of surface hardening developed and used in Russia and abroad are based on the main
principle of oxidation of cyanides and cyanates, which yields
active nitrogen and carbon atoms in the working melt. This
principle has first been implemented in the method of liquid
carbonitriding at the Bauman Moscow State Technical University and then was spread widely all over the world under
different names.
The equipment for conducting the process is presented in
Fig. 3.
Domestic equipment differs from foreign one, specifically, from that produced by the Durferrit Company (Germany) in the degree of automation and in the cost.
In the absence of waste disposal plants the facilities may
be supplemented with an evaporator of industrial waste
(Fig. 3). In this case the process of surface hardening does
not yield liquid waste. The solid waste formed due to the
evaporation meets danger class 3 (for a five-point scale),
which is safe and can be utilized at any ground for industrial
waste.
The properties of parts after carbonitriding depend much
on the degree of alloying of the steel. The higher the content
of nitride-forming elements (Cr, V, Mo, Al, Ti, W, Mn) in the
composition the lower the thickness of the hardened layer
and the higher its hardness (Fig. 4).
Formation of the structure of the diffusion layer is affected by the rate of cooling after the carbonitriding. After
rapid cooling in water nitrogen remains in the solid solution,
i.e., the layer is formed by a diffusion mechanism (formation

410

S. G. Tsikh et al.

Wet cleaning
of outgoing air

Evaporator

Vessel
for collecting
used water

Exhaust
Fresh water

Heating
furnace

Carbonitriding
tank

Oxidizing
tank

Cooling
tank

HV0.1 , kgf/mm2

TABLE 1. Results of Testing of Steel S45 for Corrosion Resistance

in a Medium Containing 3% NaCl + 0.1% H2O2

1200
1000

800

Kinds of surface hardening

1
3

600

TENIFER-QPQ

400

Solid chromizing (hc = 12 mm)

Double chromizing: hc = 20 mm of soft chromium +

hc = 25 mm of hard chromium

200
0

100

Fig. 3. Diagram of the facility for

processes of oxycarbonitriding and
TENIFER-QPQ.

Washing cascade

200

300

400

500

h, mm

Fig. 4. Distribution of hardness over the thickness of hardened

layer of steel and cast iron after carbonitriding at 580C, 3 h (h is the
distance from the surface): 1 ) Cr Ni iron; 2 ) 12Kh18N10T;
3 ) 30KhGSA; 4 ) 40Kh; 5 ) 3Kh2V8; 6 ) 20.

of solid solutions and nitrides) and by a diffusionless (hardening) mechanism, which results in additional hardening of
the layer.
In the case of slow cooling or subsequent tempering a
part of nitrogen can be segregated in the form of veins of iron
nitride in the external part of the diffusion layer on plain
steels. This makes the surface layer virtually nonbrittle.
On high-alloy steels the hardened layer forms by only a
diffusion mechanism and the cooling rate does not virtually
affect the properties of the layer.
The results of a study of corrosion resistance of differently treated test pieces of steels 45 and 38Kh2MYuA in a
5% solution of NaCl (a sea water type) show (Fig. 5) that the
operations of oxidizing and oiling increase the corrosion resistance of plain steel 45 by up to a factor of 4, whereas for

Decrease in the
mass, g/m2,
in 24 h

0.34
7.10

Nickelizing (hc = 20 mm)

7.20
2.90

Triple coating: hc = 37 mm of copper + hc = 45 mm

of nickel + hc = 1.3 mm of chromium

1.45

alloy steel 38Kh2MYuA the effect is somewhat lower (growth

by a factor of 1.5 2).
According to the data of researchers of the Durferrit
Company the corrosion resistance of coatings deposited by
the Tenifer-QPQ process [2] is tens of times higher than after
various variants of chromizing (see Table 1).
The most rigid corrosion test of DIN 50021 is the CASS
one, where the test solution contains additional acetic acid
and copper chloride (5% NaCCl + 0.26 g Cu2Cl2, pH =
3.11 3.3), and the test temperature is 50C. The results of
comparative tests of parts treated by the method of QPQ and
of piston rods treated by solid chromizing with layer thickness of 10 12 and 30 35 mm, respectively, have shown
high efficiency of QPQ coatings in aggressive media.
In the case of long-term testing according to DIN 50905
(part 4) the corrosive medium is a 3% solution of common
salt + 0.1% solution of hydrogen peroxide (H2O2 ) (see Table 1). None of the coatings participating in the test had cor-

Advancement of the Process of Carbonitriding

411

vcr , g/(m2 h)

S, %

0.12

100
90
80
70
60
50
40
30
20
10
0

0.10

6
1
2

0.08
0.06

35

0.04

0.02
0

150

300

450

ttest , h

vcr , g/(m2 h)
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0

1
2
5

1
1
1

1 2 3
24

48

2 3

2 3

2 3

72

ttest , h

96

Fig. 6. Results of corrosion tests of shock strut pistons subjected to

gas nitriding (1 ), galvanic chromizing (2 ), and oxycarbonitriding
(3 ) (S is the area stricken by corrosion).

4 3
150

300

450

ttest , h

Fig. 5. Corrosion resistance of steels 45 (a) and 38Kh2MYuA (b )

after hardening by various methods: 1 ) heat treatment; 2 ) liquid
carbonitriding; 3 ) liquid carbonitriding + oxidizing; 4 ) liquid
carbonitriding + oxidizing + oiling; 5 ) NOK (carbonitriding + oxidizing + polishing + oxidizing); 6 ) liquid carbonitriding + polishing.

ffr

0.4

1
0.3

0.2

2
0.1

rosion characteristics equal to those of the test pieces treated

by the QPQ process.
We performed field tests of shock strut pistons subjected
to oxycarbonitriding (Fig. 6). The oxycarbonitrided coatings
had corrosion characteristics considerably superior to those
of coatings deposited by standard processes (galvanic chromizing, nitriding); long-term field tests have shown full absence of leakage in the parts.
Oxycarbonitrided coatings are very effective for raising
antifriction properties and wear resistance. The nonmetallic
structure of the joining (oxycarbonitride) layer lowers the
friction factor and the susceptibility to fusion with the mating
nonmetallic surface.
Wear tests including field ones have confirmed high
wear resistance of parts and assemblies after liquid oxycarbonitriding as compared to hardened state and to chromized surfaces. In many cases the wear resistance of the
joining (carbonitride) layer is increased additionally due to
an additional oxidizing treatment. For example, the carbonitrided parts of gears, hydraulic units and press molds serve
for a longer time than those subjected to solid chromizing.
When studying wear resistance and antifriction properties it is interesting to determine the friction factor of the external layer. The interaction on the interface, which arises
due to sliding, depends more on the structure, on geometry of
the surface, and on the lubricant than on the hardness of the
rubbing pair.

1
2

0
Galvanic
Hardening +
chromizing, low-temperature
tempering
30 mm

Without
oxidizing

With
oxidizing

QPQ

Tenifer process

Fig. 7. Friction factors ffr of various coatings on a steel of type

40Kh: 1 ) without lubricant; 2 ) with lubricant (oil of type SAE 30).

The Durferrit Company has studied the antifriction properties of various kinds of coating [2]. The tests were performed in an Amsler device for disc specimens. One disc
was immobile and the other rotated in contact with the former at a speed of 200 rpm. The load was 5 30 N in order to
avoid adhesive wear. Both discs had been treated similarly.
The specimen after chromizing, hardening + low-temperature tempering, and a Tenifer process with and without oxidizing had a roughness Rz = 3.2 mm. After the treatment in
the Tenifer-QPQ mode the roughness of the surface of the
specimens was lowered by polishing to Rz = 0.8 mm. In the
mode of dry friction the specimens treated by the Tenifer
method had much lower friction factors than the specimens
with martensite structure or with chromized layer. Oxidizing
raised the friction factor (Fig. 7).
A study of the antifriction properties under conditions of
friction with a lubricant has shown that the specimens treated
by the Tenifer-QPQ method have the lowest friction factor.

412

S. G. Tsikh et al.

It should be taken into account that oxycarbonitriding increases substantially (almost doubles) the fatigue resistance
in contrast, for example, to galvanic chromizing and zincing.
For this reason the technology of liquid oxycarbonitriding and its foreign counterparts find wide use in all
branches of industry, e.g., in power engineering, car making,
food industry, aviation, agricultural machines.
Figure 8 presents examples of successful application of
carbonitrided coatings in Russia and abroad.
CONCLUSIONS
Thus, the process of oxycarbonitriding is a universal
technology for any branch of industry. It is applicable for
hardening parts from any grade of steel, which operate under

Fig. 8. Examples of using oxycarbonitride coatings in car industry (a),

armature engineering upon manufacturing die tooling (b ) and press
mould (c).

conditions of wear including corrosive one. The cost/quality

ratio of the oxycarbonitriding process is the best among the
hardening technologies.
REFERENCES
1. D. A. Prokoshkin, Thermochemical Treatment of Metals:
Carbonitriding [in Russian], Metallurgiya, Mashinostroenie,
Moscow (1984), 240 p.
2. U. Baudis und M. Kreutz, Technologie der Salzschmelzen:
Warmebehandlung, Hartetechnik, Warmeubertragung, Reinugung, Landsberg/Lech: Verl. moderne Industrie (2001), 84 p.
3. A. V. Supov, Creation of the process of carbonitriding, in:
Metal Science. Heat and Thermochemical Treatment of Alloys
[in Russian], Izd. MGTU Im. Baumana, Moscow (2003),
pp. 142 151.