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UDC 621.785.533
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
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].
1
2
Fe; C; N, wt.%
100
90
80
70
60
50
40
30
20
10
0
Fe
e
N
Fe
possible location
of N
Porous
zone
g
C
10
20
30
40
50 h, mm
408
0026-0673/10/0910-0408 2010 Springer Science + Business Media, Inc.
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 );
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
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
1200
1000
800
1
3
600
TENIFER-QPQ
400
200
0
100
Washing cascade
200
300
400
500
h, mm
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
7.20
2.90
1.45
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
4 3
150
300
450
ttest , h
ffr
0.4
1
0.3
0.2
2
0.1
1
2
0
Galvanic
Hardening +
chromizing, low-temperature
tempering
30 mm
Without
oxidizing
With
oxidizing
QPQ
Tenifer process
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