CONCLUSIONS

i. Being an austenite-forming element, nitrogen (up to 0.36%) hardens austenite into

austenitic-ferritic steels, but significantly reduces the amount of ferrite - from 65 to 35%.
The overall effect of this influence of nitrogen is to reduce the strength properties of the
steels under investigation.
2. A reduction in the amount of a-phase in the structure of dual-phase steels with the
introduction of nitrogen is accompanied by pronounced enrichment of the ferrite with ferriteforming elements, primarily with chromium and molybdenum, and its impoverishment with austeniteforming elements.
This contributes to the formation of o-phase, which leads to embrittlement
of the steel.
LITERATURE CITED
i.
2.

3.

4.
5.
6.
7.

N. V. Korolev, V. V. Ryukhin, and S. A. Gorbunov, Spectral Emission Microanalysis [in

Russian], Mashinostroenie, Leningrad (1971).
N. V. Korolev, G. G. Kolchin, and A. N. Podust, "Apparatus for electrical-discharge spectral
microanalysis and its use," in: Machine Building - A Progressive Technology and High Component Quality [in RussianJ, Tol'yatti (1983), pp. 16-17.
R. Scherer, G. Riedrich, and H. Kessner, "Die wirkung von stickstoff in austenitischen
und austenitisch - ferritischen chrom-nickel-stahlen," Stahl Eisen, 62, No. 17, 347-352
(1942).
A. G. Alton, "An Fe-Cr-Mo-Ni sigma phase," J. Met., 6, No. 8, 904-905 (1954).
H. T. Shirley, "Microstructural characteristics of acid corrosion in 18% Cr, 8-14% Ni,
3% Mo steels," J. Iron Steel Inst., 174, No. 3, 242-249 (1953).
J. J. Gilman, "Hardening of high-chromium steels by sigma-phase formation," Trans. Am.
Soc. Met., 43, 161-192 (1951).
I. Ya. Sokol, Dual-Phase Steels [in Russian], Metallurgiya, Moscow (1974).

SOLUBILITY OF TITANIUM AND NIOBIUM CARBIDES IN

HIGH-CHROMIUM FERRITE
N. A. Gorokhova, V. I. Sarrak,
and S. O. Suvorova

UDC 668.15'26'71:539.67:661.665

Steels alloyed with chromium and aluminum are widely used for high-temperature operations.
The stability of these steels depends heavily on their carbon content [1-3], and deteriorates
as it increases.
Alloying of type Khl5Yu5 steels with such carbide-forming elements as
titanium and niobium leads to the formation of difficult-to-dissolve carbides and nitrides
and to a reduction in the carbon content in the solid solution.
Data on carbon content in the
solid solution of these steels are limited.
The purpose of the present study was to investigate the solubility of titanium and
niobium carbides in type Khl5Yu5 steels.
The chemical composition of the steels investigated
is presented in Table i.
The method of investigating the temperature dependence of internal friction (TDIF) was
used t o d e t e r m i n e the carbon content in the solid solution.
For this purpose, we employed a
"reverse" torsion pendulum-type relaxation unit and wire specimens 0.8 mm in diameter; the
vibration frequency was 1 H z .
All specimens were prequenched in water from 1250C (holding
for 1 h) to produce a similar grain size, and then quenched repeatedly from different temperatures -- from 1350C to 550C (after each 100C).
The TDIF curves of the steels that we investigated, which were prequenched from 1350C in water, are presented in Fig. i. In conformity with the results of a theoretical investigation conducted earlier [4], the maximum
observed on these TDIF curves at 260...380C is the Snoek peak, and is governed by
I. P. Bardin Central Scientific-Research Institute of Ferrous Metallurgy.
Translated
from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 4, pp. 38-40, April, 1986.

276

0026-0673/86/0304-0276512.50

1986 Plenum Publishing Corporation

TABLE i.
Element content,

Melt

Cr

AI [ Ti

Nb

0,03
0,06
0,03

0,04
0,03

15,1
14,6
15,5
14,8

4,9 [
4,6
0~-40
5,5 [ 0,28
5,5
5,5
0736 0,24

17,2

Q-7.IO4

,,

8o!

,i\'
~

.20

100

200

300

~QO~c,%

"

Fig. i. Temperature dependence

of internal friction, obtained
after quenching specimens from
1350C. Melt numbers are indicated near curves
the presence of carbon atoms in the solid solution (high-chromium ferrite); in this case, the
height of this maximum is proportional to the carbon content in the solid solution.
The
presence of nitrogen in the steels investigated did not affect the shape of the TDIF curves,
since virtually all the nitrogen is bonded in difficult-to-dissolve aluminum nitrides or titanium
or niobium carbides, and its content in the solid solution is negligible.
Proceeding from the
solubility product of aluminum nitride [5] for a total A1 content of 5% in the steel, it is
possible to calculate the amount of nitrogen in the solid solution using the following
equation:
7500
log ~'|AI] [NIl= ----T---+ 1,48,

where L is the solubility product,

( I)

and T is the temperature in K.

The nitrogen content in the solid solution is 2.5"10-4% at 1200C.

gen does not affect the shape of the TDIF maximum.

This amount of nitro-

The results of phase analysis conducted on type Khl5Yu5 steels after holding at 780C
for 20 min (cooling in water) are presented below.
Steel

Excess phases

Khl5Yu5
KhI5Yu5T
KhI5Yu5TB

(Fe, Cr)TC s
(Fe, Cr)TCa; TiC, TiN
(Fe, Cr)TCs; (Ti, NB) (C, N)

Carbon-solubility curves, which are plotted for the type Khl5Yu5 steels alloyed with
titanium and niobium and niobium jointly with titanium, are presented in Fig. 2. The introduction of up to 0.47% and 0.28% Ti in the steel with 0.06 and 0.03% C, respectively, leads
to a reduction in carbon solubility as compared with its solubility in the unalloyed steel
to 0.012...0.015% at I150C.
For a combined alloying of 0.36% Ti and 0.24% Nb and
a total carbon content of 0.03% in the steel, the carbon solubility is reduced to 0.03% at
277

./'/

,'.
;pt/.
7100

log L

-I
300

~oo
700

I~

iIi

-2

/e#

-$

6~

7,0

o,07 o,02 o,03 ,o,o~ o,05% Cso.s

Fig. 2.

6,f
Fig.

70#/T,

oK_ 1

3.

Fig. 2. Carbon content in solid solution of steels with

different alloying additives.
Melt numbers are indicated
near curves.
Fig. 3. Temperature dependence of solubility product of
titanium and niobium carbides:
i, 3) data from Tomilin
and Shor [6]; 2, 4) data obtained by authors.
I150C.
It must be considered that according to phase-analysis data, complex titanium and
niobium carbonitrides, the thermodynamic properties of which differ from similar properties
of simple titanium carbides and nitrides, form in steel containing titanium and niobium.
The lowest carbon solubility (approximately 0.0015%) at I150C is characteristic for the
0.03% C steel alloyed with niobium.
It is apparent from the carbon-solubility curves obtained
(Fig. 2) that a reduction in the overall carbon content in tbe steel from 0.06 to 0.03% and
also a certain increase in titanium content shift the solubility curves into the region of
lower carbon concentrations (Fig. 2).
Let us calculate the solubility product of the titanium and niobium carbides contained
in Cr-A1 steels.
It is possible to determine the carbon content from the solubility curve
(Fig. 2), and then calculate the titanium and niobium concentration in the solid solution at
1150, 1250, and 1350C.
The temperature dependence of the solubility product of the titanium
and niobium carbides for steels 2 and 4 is presented in Fig. 3.
For convenience of calculation and comparison of the carbide solubility, the content
of elements is expressed in atom percents.
Data on the solubility of titanium and niobium
carbides in austenite [6] are presented here, however, since there are no data on the solubility of similar carbides in ferrite in the literature.
It is possible on the basis of the data obtained (Fig. 3) to derive equations describing
the temperature dependence of the solubility products.
For the titanium carbide contained
in steel KhI5Yu5T (melt 2) with 0.06% C, for example, the temperature dependence of the
solubility product is as follows:
825O
lpgL[Ti]

[c] =

--

+4,11,

(2)

For the niobium carbide contained in steel KhlSYu5B (melt 5) with 0.03% C, this relationship
is described by the equation
95O0
log LlNbl [C| ------ ~

278

+ 3, 74,

(3 )

According to Narita [7] and Goldschmidt [8], the solubility products of titanium and
niobium carbides in austenite can be described by the following equations:
log LITi ] It] = - - ~

I0 475

+ 5,33

(4)

+ 3,18

(5)

(for steel with 0.1% C and 0.03...0.10% Ti), and

7700

log LINbl [C] ---- - - ~

(for steel containing up to 0.1% C and up to 0.8% Nb).

It should be noted that according to Eqs. (2)-(5), straight lines exist in the region
of difficult-to-dissolve carbides in conformity with the classification presented by Tomilin
and Shor [6].
CONCLUSIONS
I. The introduction of niobium (0.73%) in 0.03% C steel leads to a reduction from
0.034 to 0.003% in carbon solubility at I150C, whereas up to 1.13% C may be contained in the
steel at the temperature indicated without alloying additives. With the introduction of
titanium, the carbon solubility also decreases and amounts to 0.015% at I!50C with a total
carbon content of 0.06% in the steel.
2. The solubility curve is shifted into the region of high carbon concentrations with
increasing total carbon content in the steel alloyed with titanium or niobium.
3. According to results of the computation of the solubility products of titanium and
niobium carbides in high-chromium ferrite in the I150...1350C interval, niobium carbide is
more stable than titanium carbide.
LITERATURE CITED
i.
2.
3.
4.
5.
6.

7.
8.

I. I. Kornilov, Iron Alloys [in Russian], Vol. i, Izd. Akad. Nauk SSSR, Moscow (1945).
E. Gudremon, Special Steels [in Russian], Vol. I, Gosudarstvennoe Nauchno-Tekhnicheskoe
Izd. Literatury po Chernoi i Tsvetnoi Metallurgii, Moscow (1959), pp. 889-899.
A. V. Ryabchenko, A. I. Maksimov, and B. I. Beketov, "Effect of carbon on the heat resistance of steel KhI3YuS," Zashch. Met., 12, No. 4, 465-469 (1976).
I. A. Tomilin, V. I. Sarrak, N. A. Gorokhova, et al., "Nonuniform distribution of carbon
atoms in iron-chromium alloys," Fiz. Met. Metalloved., 56, No. 3, 501-506 (1983).
T. Glagman and F. B. Pickering, "Grain-coarsening of austenite," Iron Steel Inst., 205,
653-664 (1967).
I. A. Tomilin and F. I. Shor, "Carbide and nitride solubility of transition metals in
iron alloys," in: Problems of Metal Science and the Physics of Metals [in Russian],
Metallurgiya, Moscow .(1972), pp. 99-106.
K. Narita, "Studies on elements of small quantities in iron and steel. VII. On titanium
carbide in iron and steel," J. Chem. Soc. Jpn., 80, 266-269 (1959).
H. J. Goldschmidt, Interstitial Alloys, Butterworths (1967).

279