Metal Science and Heat Treatment

Vol. 38, Nos. 9 - 1 0 . 1996

UDC 621.78.062.3

PROTECTIVE PROPERTIES OF A N I T R O G E N A T M O S P H E R E
WITH AN A D M I X T U R E OF NATURAL GAS
Yu. M . B r u n z e r t
Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 9, pp. 6 - 10, September, 1996.
The present difficulties with energy supply in Russia require strict control of consumption of natural gas and
power and observation of environmental restrictions. This necessitates of the development of economically
and environmentally optimum protective atmospheres. For relatively small heat treatment furnaces the use of
nitrogen as a carrier gas can be of some interest. In this case environmentally inexpedient exo- and endogenerators with the corresponding expensive and complex systems for automatic control of the carbon potential
become unnecessary. Foreign experience shows that nitrogen can be used by means of a rather simple
technology that includes an imported cryostat with liquid nitrogen, a line for feeding natural gas, and the
corresponding mixing and proportioning devices. In the present work the possibility of using nitrogen with an
admixture of natural gas as a protective atmosphere for annealing is considered.

Heat treatment of steel with the use of a protective nitrogen atmosphere containing gaseous hydrocarbons is a common practice in some foreign countries [ 1, 2]. Interest in such
an atmosphere appeared in the U.S. in the energy crisis of the
1970s. Nitrogen used as a carrier gas arrived from oxygen
plants, which made unnecessary the construction of gas generators for the production of exogenous gas or nitrogen-hydrogen mixture ( - 4% H 2 ) and the corresponding investment.
These expenses were especially considerable for metallurgical works, where powerful gas-preparing installations required the construction of large centralized separately located
plants. It was very important that nitrogen cartier gas did not
require natural gas for its production and was a secondary or
side product of the production of oxygen plants.
In the present work 2 we determined the optimum amount
of admixture of natural gas in nitrogen. For this purpose, foils
of different steels were held at different temperatures in an atmosphere of pure nitrogen with various proportions of natural
gas in a laboratory muffle furnace with a precombustion
chamber. Foils 0.1 ram thick were produced from steels further subjected to a heat treatment under experimental industrial conditions, namely, structural steels 25KhGSA (0.25%
C, 1.0% Si, 0.9% Mn, i% Cr) and 30KhSNVFA (0.30% C,
up to 1.5% Cr, Si, Ni, W, V), tool steel U8 (0.8% C), and virtually carbon-free commercial iron with an insignificant content of impurity elements. A foil was placed in a special device in the precombustion chamber, then the chamber and the
communicating functional space were blown with pure nitrogen, and an additive of natural gas was introduced. After this
I

the foil in the device was placed in the functional space

heated to the specified temperature. After a 4-h hold the foil
was placed again in the precombustion chamber, where it was
cooled rapidly in the same atmosphere.
An analysis of the experimental results (see Table 1) has
shown that due to the hold at 800C in the atmosphere of pure
nitrogen (98.98%) all steels were decarburized almost completely. A 8 - 9% addition of natural gas made the atmosphere virtually neutral at 750C for carbon-containing steels
and commercial iron, although the carbon content in them in
the initial state was different (from 0 to 0.8%). A decrease in
the amount of natural gas to 4% at this temperature changed
the picture, namely, carbon-containing steels were decarburized intensely. At 800C the addition of 4% natural gas made
the atmosphere neutral for structural steels (0.3% C), but the
steel with 0.8% C was decarburized markedly. An increase to
8 - 9% natural gas hardly decarburized tool steel but caused
some excess carburization of structural steels. At 850C in
the presence of 8 - 9% natural gas the atmosphere was indifferent for structural steels but exerted some decarburizing action on tool steel.
In industrial tests in the Krasnyi Oktyabr' Plant we used a
three-chamber continuous furnace for soft annealing of rolled
sheets (Fig. 1). The need for this work was caused by the absence of any atmosphere other than the investigated one in
the plant for this furnace. In the course of annealing, stacks of
sheets were subjected to a cyclic motion over the roller hearth
with stops and holds in each chamber. Metal was heated in
the furnace with radiating tubes. The furnace had three chambers, namely, one for heating and holding (I), one for holding
and regulated cooling (//), and one for jet cooling by a pro-

I. P. Bardin Central Research Institute of Ferrous Metallurgy, Russia.

370
0026-0673/96/0910-0370$15.00 ID 1997 Plenum Publishing Corporation

Protective Properties of a Nitrogen Atmosphere with an Admixture of Natural Gas

TABLE l
Steel

I
Regime of
annealing of foils

lee,s , vol.%

371

C, %

25GSA
30KhSNVFA
U8

8000C, 4 h

0.018
0.017
0.011

25GSA
30KhSNVFA
U8

800C, 4 h

0.26
0,3 I
0.44

25K.hGSA
30KhSNVFA
Commercial iron
U8

800*C, 4 h

8- 9

0.37
0.49
0.48

25KhGSA
30KhSNVFA
U8

750"C, 4 h

0.017
0.108
0.180

25KhGSA
30KhSNVFA
Commercial iron
U8

750C, 4 h

8- 9

0.25
0.35
0.016

25KhGSA
30KhSNVFA
Commercial iron
U8

850C, 4 h

0.71

0.71
8- 9

0.35
0.35
0.09
0.62

N2

N 2 CH 4

tective atmosphere (nitrogen) to the temperature of the shop

(111). The last chamber was equipped with air-cooled tubes.
Thick sheets of alloyed and carbon structural steels hot-rolled
and pickled (in order to remove the scale) were annealed. After rolling (before annealing) the steel was somewhat decarburized, but the decarburization was within the standard
value for annealed steels. In order to cool the metal at a regulated rate the second chamber was equipped, like the third
one, with air-cooled tubes (in addition to the heating ones).
For all heat-treatable steels the standards and specifications
envisage that the permissible depth of deearburization after
annealing should not exceed 0.20 - 0.25% of the thickness of
the sheet on each side. The requisite softening of the steels
was controlled by the hardness, the strength parameters, and
in some cases (additionally) by the elongation. The carrier
gas was nitrogen with a purity of 99.98% that arrived from
the units for separation of air in the oxygen plant. In addition,
natural gas was fed into the functional space. The flow rate of
the gas in the zones, the composition of the gas in the functional space, and its moisture content were controlled (the latter by the dew point).
When testing nitrogen atmosphere with natural gas admixtures we studied various temperature modes of moderating annealing: complete, incomplete, and subcritical.
Results of experiments with underannealing are presented in Fig. 2 and can be used for determining the optimum
amounts of the natural gas admixture to nitrogen. The annealed metal has the form of thick (6-mm) sheets of high-alloyed structural steel with 0.25% C and up to 1.5% Cr, Si, Ni,

Fig. 1. Diagram of a three-chamber continuous furnace with a roller hearth

and of the inlets for the components of the protective atmosphere and the cir
eulating flows: 1 ) charging gate; 2 ) knuckle; 3 ) heat gate; 4 ) rollers; 5 ) discharging gate; L 11,111) numbers of the furnace chambers.

CH4, voi. %

n~ vol. %

4.0

CO vol. %

/0,

1.

3.ol&
,.oi/,V

1.

I.C ~

0f
4

0.4

l/

Notation: Vo.s) volume fraction o f natural gas, C) content of carbon in the

foil a / ~ annealing.

N2

O. ~

o.2

Vu.s, vol.%

005\
o

td.p ,oc
td.p

-20'

-30

-50

Vn.g,VOI.*/Q

Fig.2. Composition of the furnace atmosphere and dependence of the dew

point ta.p and the decarburization depth hd,xaco in steel 25KhSNVFA on the
volume fraction of natural gas added to an atmosphere of pure nitrogen:x) the
process temperature is 720C; O) 750C; O) 780"C.

W, and V. With increase in the amount of natural gas in the

furnace atmosphere the concentration of active reducing
components (H 2 , CO) increased. For a large content of natural gas it was close to (but still somewhat lower than) the contents of H 2 and CO 2 in an atmosphere of purified and dried
lean exothermic gas. An 8% addition of natural gas had an
almost full effect on decarburization in the process of heat

372

Yu. M. Brunzel'

90o*c

/sh !05,I
900C
b

650C

I
I
I
I
1

4h
H

i l l -~

1_

Fig. 3. Regimes of true annealing: a) annealing with deceleratedcooling;

b) isothermalmmealing;L 11,111)ambers of the furnacechambers.

treatment. With increase in the amount of natural gas the dew

point (tctp ) changed continuously toward decreased moisture
contents. In the presence of more than 8% natural gas carbon
black appeared in the functional space and on the sheets.
We also studied the parameters of a nitrogen atmosphere
with added natural gas in true annealing (Fig. 3), i.e., at temperatures higher than those considered above. We annealed
thick-sheet alloyed structural steel of grade 30KhSNVFA of
martensitic class. The addition of natural gas to the furnace
amounted (on the basis of the previous experiments) to 6 - 8%
of the fed pure nitrogen.
In true annealing by both studied regimes the rolled stock
was not decarburized in the process of heat treatment, and the
hardness and mechanical properties of the metal corresponded to the requirements of the standard.
It should be noted that the temperature of 900C at which
the steel was annealed is a characteristic hardening temperature for many structural steels. The fact that we obtained positive results in preventing decarburization under conditions of
true annealing allows us to conclude that the atmosphere employed can be used successfully for hardening structural
steels.
We conducted a spheroidizing soft annealing of highcarbon steel (0.85% C) in a nitrogen atmosphere with 8%
natural gas by two regimes, namely, (a) a hold at 760 - 740C
and slow cooling (underannealing) and (b) a hold at 720C
(subcriticai isothermal annealing). Both regimes provided the
requisite softening of the steel. It should be noted that the
high-carbon steel with 0.85% C annealed at a low (subcritical)
temperature was characterized by a hardness of 229 - 170 HB
and a decarburization depth within 0 - 0.25% of the thickness

of the sheet, which met the requirements of the specifications.

In addition, the process of spheroidizing annealing was intensified at a low (subcritical) temperature. The duration of the
subcritical annealing was reduced by 50% compared to the
underannealing (10 and 21 h, respectively). Presumably, this
can be explained by the effect of the intensification of the diffusion mobility of carbon discovered in [3, 4] and hence the
intensification of carbide coagulation at a subcritical temperature. It is important that annealing at a lower temperature
increases the service life of the radiating heating tubes.
An analysis of the results obtained has shown that the optimum amount of added natural gas is about 8% of the consumed nitrogen, which imparts protective properties to the atmosphere formed in the furnace in a wide range of annealing
temperatures and carbon concena'ations in the heat-treated
steel. An optimum addition of natural gas creates in the furnace an atmosphere providing a low rate of carbon mass
transfer in the atmosphere-metal system, i.e., creates a viaually indifferent atmosphere. The preparation of such "stabilized" nonequilibrium atmospheres with a low rate of carbon
mass transfer opens up new possibilities in the development
of protective atmospheres.
Such an approach to the preparation of protective atmospheres differs from the conventional methods, for example,
attainment o f an equilibrium carbon potential in the atmosphere. In the case of a kinetically inactive stabilized atmosphere its carbon potential does not have technological value,
because in slow mass transfer of carbon it can be attained
only for hold times exceeding the duration of actual annealing processes.
It can be seen from the data presented that decarburization can be limited only in the case of a low moisture content
in the furnace (t,tp = - 30C or lower). This requires a high
tightness of the furnace space. Since we used a furnace with a
gate opened for charging, the condition of airtightness was
violated periodically.
In the initial "charging" period (Fig. 4) the composition
of the atmosphere in the furnace worsened due to the introduction of oxidizing components together with the charge.
The reccurrence of charging was determined by the duration
of the entire heat treatment. We could trace the kinetics of the
variation of the concentration of the oxidizing components of
the atmosphere (H20, CO 2 ) after charging a stack of metal
sheets with opening up of the gate. It can be seen that td.p
changes from - 40 to - 8C and the concentration of CO 2 increases considerably. Then the protective properties of the atmosphere are recovered due to the arrival of fresh portions of
dry pure nitrogen. In about 2 h the dew point attains the initial
low value; here the regeneration with respect to CO 2 is completed much earlier.
A favorable circumstance in the operation of this untight
furnace was that the time of the heat treatment exceeded the
period of the "conditioning" of the atmosphere after charging
and that the period in which the atmosphere was worsened
coincided with the period of heating the stack. In the general
case, under other heat treatment regimes lasting for a time

Protective Properties of a Nitrogen Atmosphere with an Admixture of Natural Gas

comparable with the time of "conditioning," it would be impossible to eliminate decarburization. It should be noted that
the airtightness of the furnace was disrupted additionally due
to a defect of its structure, namely, burnout of the radiative
tubes. This hampered further industrial experiments. H o w ever, when the airtightness was satisfactory, we annealed a
considerable amount of metal in this furnace without decarburization and obtained a product meeting the requirements
of the standard.
We can conclude that a nitrogen atmosphere with added
natural gas can be used with a reliable result only in furnaces
with an appropriate airtightness (for example, a muffle furnace with preliminary blowing of the functional space together with the charge by pure nitrogen). In continuous furnaces the suggested atmosphere can be used under the condition that the charge is sluiced at the inlet into the furnace.
CONCLUSIONS
1. A nitrogen atmosphere with an 8 vol.% addition of
natural gas protects structural and tool steels from decarburization hi soft annealing (true, under, suberitical) conducted at
720 - 900C.
2. The atmosphere formed in the furnace in heat treatmerit is characterized by a low rate of mass exchange of carbon with the metal and is virtually indifferent from the standpoint of decarburization for steel with a carbon concentration
ranging between 0.2 and 0.8%.
3. The aforementioned atmosphere can be used under the
condition that the moisture content in the functional space of
the furnace is maintained at a low level (the dew point is at
most -30C), which should be provided by the design of the
furnace.
4. The use of a nitrogen atmosphere with added natural
gas does not require generators of protective gas (for exam-

373

CO; CO 2 ; CH 4 ; H2, vol.%

1.5

I.

-20

~ , ~

-30 J
-4~

( ~""0.,.~ IL=..
I

10

15

30

45

60

I
75

90

105

x, rain

Fig. 4. Measuredcompositionof the furnace atmosphere(volumefractions

of the components)after cl~rging steel sheets into the furnace. Beforecharg
ing, the furnace temperaturewas 760C.

pie, exothermic gas); herre the nitrogen from oxygen plants is

quite suitable.

REFERENCES
1. Yu. M. Brunzel', "Controllable atmospheres," in: Results in Science and Technology. Metals Science and Heat Treatment [in
Russian], Vol. 12, VINITI, Moscow (1978), pp. 143 - 181.
2. W. Hewitt, "Nitrogen-based atmospheres - a user's view," Metals
Mater TechnoL, No. 7, 344 -348 (1983).

3. B. G. Sazonov, "Experimental diffusion activity of steel ifi the

state of pretransformation," Metalloved. Term. Obrab. Met.,
No. 7, 13 - 15 (1990).
4. A. P. Gulyaev, "The pretransformation state in iron alloys," in:
7th. lnt. Congr. Heat Treat. Mater. (Moscow, Dec. 11 - 14 ), Vol.
1, Moscow (I 990), pp. 15 - 22.