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EFFECT OF AUSTENITIZING TEMPERATURE AND TIME ON THE MATRIX

COMPOSITION AND STRUCTURE IN STEEL OF ABOUT 2%C AND 12%Cr TYPE
WITH THE ADDITIVES OF W AND V

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METAL 2001 15. - 17. 5. 2001, Ostrava, Czech Republic

EFFECT OF AUSTENITIZING TEMPERATURE AND TIME ON THE

MATRIX COMPOSITION AND STRUCTURE IN STEEL OF ABOUT
2%C AND 12%Cr TYPE WITH THE ADDITIVES OF W AND V

Tadeusz Nykiel
Tadeusz Hryniewicz

TECHNICAL UNIVERSITY OF KOSZALIN, Department of Mechanical

Engineering, Racławicka 15-17, PL 75-620 Koszalin, Poland
Abstract
The main purpose of the studies presented in the paper is to establish the effect of temperature
and time of austenitizing on the chemical composition and structure of the NCWV/D3 tool
steel matrix. It was established that due to the dissolution of carbides during austenitizing of
the 2% C and 12% Cr type tool steel the contents of the elements C, Cr, W and V were
increasing with the increase of austenitizing temperature and time to 30 minutes whereas the
extending of time up to 90 minutes did not cause any essential changes in the contents of Cr,
W and V in the matrix. It was found that vanadium was concentrated mainly in the big
primary carbides, and during austenitizing in the temperature range of 900 °C to 1150 °C
through the period of time of 30 minutes the vanadium contents in matrix increased only of
0.041%. As the result of the study of Cr, W and V distributions carried out using an X-ray
microanalyser of the samples of NCWV/D3 steel the hypothesis was formulated that
distribution of tungsten showed some characteristic features.

1. INTRODUCTION
Fundamental research concerning the effect of austenitizing parameters upon the chemical
compositon of matrix of the quenched 2% C and 12% Cr type steels were carried out by Sato
et al. [1], and Głowacki [2]. Also other investigators were involved in these specific study
problems although their studies were performed rather fragmentary [3]. According to Sato et
al., as the result of dissolution of carbides during austenitizing of steels containing 2.25% C
and 12.3% Cr in the temperature range between 850 °C and 1050 °C throughout 1 hour the
chromium content in the matrix increases up to about 5.2% after austenitizing at 1050 °C.
Also the content of carbon in matrix increases from about 0.45% after austenitizing at 850°C
up to 7% at 1050 °C. The characteristic phenomenon is, what results from the plot given by
Sato et al. [1], the increase of Cr and C in matrix vs. austenitizing temperature is close to the
linear. According to Głowacki [1], in NC11 steel of the content of 2.14% C and 11.50% Cr,
the content of chromium in matrix increases steadily with temperature increase up to 6.87%
after austenitizing at 1150 °C during 30 min, whereas the most intensive increase of
chromium content in matrix appears during first 10 min of austenitizing at 950, 1050, and
1150 °C. After 30 minutes of austenitizing in these temperatures some equilibrium state of
austenite-carbides is achieved what means that prolongation of the austenitizing time up to 90
min in practice does not introdice any change in chemical composition of the matrix.

The studies, concerning the effect of austenitizing parameters on the matrix chemical
composition of the quenched steels of about 2% C and 12% Cr type with the additives of
tungsten, molybdenium, and vanadium, were carried out by Berns [4], [5], and with the
additives of tungsten and vanadium by Nykiel and Hryniewicz [6,7]. It results from the
studies that the changes in the content of chromium in matrix vs. austenitizing temperature in

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METAL 2001 15. - 17. 5. 2001, Ostrava, Czech Republic

X210CrW12 and NCWV/D3 steels (the steels of comparable chemical composition) are
qualitatively similar to the changes in steels of 2% C and 12% Cr type without the alloying
additives, whereas the content of vanadium in matrix of the both quenched steels is very low
and only slightly increases with the austenitizing temperature growth. Contradictory results
were obtained concerning the behaviour of tungsten in matrix.

Basic aim of the present studies is the analysis of relationships between the content of
dissolved carbides during austenitizing and the content of chromium, tungsten, and carbon in
the matrix of NCWV/D3 steel. The complex studies to be carried out in this scope will alow
to perform a detailed analysis of adhesion of superhard layers/films coated over the working
surfaces of tools made of about 2% C and 12% Cr type steels as well as hard chromium
coatings covered.

2. MATERIAL AND STUDY METHOD

The studies were carried out for steel of the following chemical composition: 1.95% C,
11.56% Cr, 1.32% W, 0.31% V, 0.05% Mo, 0.27% Si, 0.44% Mn, 0.024% P, and 0.022% S.
Metallographic specimens (φ = 12 mm, l = 16 mm) were prepared mechanically on abrasive
paper of the grit of 100 to 2500 and polished using aqueous Al2O3 suspension. The
specimenns were etched using reagent of composition: 1 g picric acid + 5 cm3 HCl + 10 cm3
C2H5OH. Metallographic micrographs were done using Epityp 2 microscope.
The microhardness tests of the steel matrix under annealed and quenched states were
performed on the transverse and longitudinal cross-sections slightly etched to reveal the
carbide grain boudaries. Microhardness tests were performed by means of PMT-3 and
Hanemann mph 100 microhardness testers using load of 100 N. The average microhardness
was determined based on 15 measurements.
Carbides were isolated electrolytically by means of 5% HCl solution in H2O, at current
density of 10 mA/cm2, isolation time of 18 to 20 hours. The carbides were isolated from the
specimens of φ = 12 mm, l = 60 mm.
The relative content of remaining austenite in the samples of φ 4x40 mm was determined by
means of MAG-74 WAT magnetometer.
The contents of chromium, tungsten, and vanadium in matrix were determined taking
advantage of the matrix electrolytes obtained during carbides isolation. The chromium weight
share was determined by potentiometric method, whereas of tungsten and vanadium – by
photometric method.
NCWV/D3 steel under soft annealing state is characterized by structure composed of primary
carbides as well as secondary carbides of spheroidal shape placed in Cr-W-V ferrite. The
primary carbides are of very differentiated shape. The structure of steel bars, of the diameter φ
13 mm in the transverse and longitudinal cross-sectiones, of the NCWV/D3 steel are
presented in Fig. 1 a, b.

Fig. 1. Structure of NCWV/D3 steel annealed: (a) transverse cross-section, (b) longitudinal
cross-section. Microhardness of Cr-W-V ferrite is 232±10 µHV0.01.

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METAL 2001 15. - 17. 5. 2001, Ostrava, Czech Republic

3. STUDY RESULTS AND DISCUSSION

According to the study results presented in [ ] in the studied steel, apart from the chromium
carbides of M7C3 type, the carbides of M23C7 type occur in very small amount which dissolve
completely in austenite during austenitizing steel at 1050 ºC during 30 minutes time.
During austenitizing steel at 900 °C throughout 30 min, 3.32 % of carbides is dissolved in
austenite, whereas 11.51% of carbides - at 1150 °C and the same austenitizing time (Fig. 2).
In the quenched steel, 21.52% and 13.33% of undissolved carbides remain, respectively, after
austenitizing in these conditions. The contents of undissolved carbides in NCWV/D3 steel for
each austenitizing temperature in the ranges of 900 to 1150 °C and time of 30 min may be
determined from the empirical equation given in [7]. It is known that during dissolution of
carbides in the austenitizing process, the austenite chemical composition is changing and this
affects the sort of martensite obtained, its hardness and the residual austenite in the quenched
steel matrix. The effect of austenitizing temperature at constant time of 30 min on the contents
of structural components and the matrix microhardness of the quenched NCWV/D3 steel is
presented in Fig. 2, whereas in Fig. 3 the effect of austenitizing time in the range of 900 to
1150 °C upon the matrix microhardness is shown.

Fig. 2. Effect of austenitizing temperature during 30 min on: -o- – content of dissolved
carbides in austenite, - - – relative content of retained austenite, -•- – microhardness of the
NCWV/D3 quenched steel matrix

It can be noticed/found from the plots presented that the highest matrix microhardness vs.
austenitizing temperature increase above 1000 °C results from the increase of retained
austenite content in matrix. The obtained results of matrix microhardness are in very good
agreement with the steel microhardness [7]. It is distinctly apparent that the matrix hardness
decides of the steel microhardness in the quenched state and the effect of displaced
undissolved carbides during austenitizing is small. It should be stressed that the measurement
results of the steel matrix microhardness under annealed state and austenitized below 1050 °C
should be treated as approximate only because in not every case the free-of-carbide matrix
areas could be found to fulfill the required conditions for microhardness testing. The structure
of NCWV/D3 quenched steel after austenitizing at 900, 1000, and 1100 °C during 30 min is
presented in Fig. 3 a, b, c.

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METAL 2001 15. - 17. 5. 2001, Ostrava, Czech Republic

Fig. 3. The structure of NCWV/D3 quenched steel after austenitizing during 30 min at: (a)
900 °C, (b) 1000 °C, and (c) 1100 °C

The determinations of matrix chemical compositions, and practically the determination of

matrix electrolytes after their thickening on the way of evaporating H2O and HCl obtained in
the process of electrolytical carbides isolation showed that due to the carbides dissolution
during austenitizing, the content of chromium and tungsten in the matrix of NCWV/D3
quenched steel increases successively with the growth of austenitizing temperature and time
up to 30 min (Fig. 4).

Fig. 4. Effect of austenitizing temperature and time up to 90 min on the contents of Cr, W,
and V in the NCWV/D3 quenched steel matrix

It results from the determination of vanadium by photometric method that its content in the
matrix increases but very slightly, that is from 0.045% after austenitizing at 900 °C up to

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METAL 2001 15. - 17. 5. 2001, Ostrava, Czech Republic

0.086% at1150 °C. The results of chemical analyses show that extention of the austenitizing
time at 900, 1000, 1100, and 1150 °C up to 90 min causes increase in the chromium and
tungsten contents in matrix but on the level of hundredths per cent.

Based on the contents of carbides dissolved in austenite during austenitizing in the

temperature range from 900 to 1150 °C and determination of Cr and W contents in matrix the
analysis was carried out to find out a mathematical relationship between the content of
carbides dissolved in austenite and Cr and W contents in the steel matrix. This analysis was
performed based on the least square method. Calculation data are presented in Table 1, and in
Fig. 5 the obtained regression lines between the content of dissolved carbides during
austenitizing and Cr and W contents in matrix are shown.

Table 1. Calculation data

TA [°C] Xc-da YCr-m YW-m

900 3.32 2.93 0.38

1000 6.22 4.61 0.58
1100 9.24 6.64 0.94
1150 11.51 7.27 1.06

TA – austenitizing temperature
Yc-da – carbides content in dissolved
austenite
YCr-m – chromium content in the
matrix of quenched steel, determined
by potentiometric method of matrix
electrolytes
YW-m – tungsten content in the matrix,
Fig. 5. Regression lines Yc-m between the content of determined by photometric method of
dissolved carbides during austenitizing in the matrix electrolytes
temperature range of 900 to 1150 ºC throughout 30 min
and the content of chromium (-•-) and tungsten (-o-) in
the NCWV/D3 quenched steel matrix
As the result of calculations for the variable system Yc-da–YCr-m the following regression
equation was obtained:

YˆCr − m = 1.196 + 0.55 X W − m (1)

Correlation factor r=0.9906 was obtained at f=n-2=2 freedom degree and it is higher than
r=0.9500 read of R.A. Fisher [8] Tables. That means the correlation level is higher than 0.05,
whereas 95% confidence interval YCr-m for t0.05;2=4.303 is YCr −m = 5.36 ± 0.7315 , and 95%
confidence interval of the slope a=0.32÷0.78.

For the variable system X W − m − YW − m the following equation of regression line was obtained:

YˆW − m = 0.0799 + 0.0872 X W − m (2)

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METAL 2001 15. - 17. 5. 2001, Ostrava, Czech Republic

where: YˆW − m is the content of tungsten in matrix determined based on the regression equation.
Correlation factor between the the content of carbides dissolved in austenite during
austenitizing in the temperature range of 900 to 1150 °C throughout 30 min and the content of
tungsten in the matrix of quenched NCWV/D3 steel is r=1.002 what means the complete/full
correlation.

It is impossible to determine changes of carbon content in matrix of the NCWV/D3 quenched

steel on the basis of matrix electrolytes because during electrolytic carbides isolation the
carbon of matrix completely or partly is sedimented in carbides isolated carbide particles
causing its contamination.

At present the attempts are made to determine the carbon content in matrix based on the
method given by Popowa et al. [9]. There are difficulties experienced during determination of
carbon content in the tool steels matrix by means of the X-ray microanalyser connected with
the determination accuracy. This is why a calculation method was used, assuming occurrence
of M7C3 type carbides only composed of Fe3Cr4C3, to establish changes in carbon content in
matrix of NCWV/D3 quenched steel after austenitizing in the ranges of temperature of 900 to
1150 °C and austenitizing time of 30 min. Stechiometric carbon content in these carbides is
7.95%. Calculation results of carbon content, based on the amount of carbides dissolved
during austenitizing in the matrix of NCWV/D3 quenched steel is presented in Fig. 6.

1.2
Carbon content in matrix, wt%

1.0

0.6

0.2

850 900 1000 1100 1200

Austenitizing temperature, °C

Fig. 6. Effect of austenitizing temperature on the carbon content in the steel matrix: - -
2.25% C, 12.03% Cr acc. to Sato [1], - × - 2.14% C, 11.50% Cr acc. to Głowacki [2]*, - + -
X210CrW12 acc. to Berns [4], - • - NCWV/D3 acc. to the authors’ own studies
4. - carbon contents calculated based on the given carbides contents in the NC11 (2.14%
C and 11.50% Cr) quenched steel

There are also results of calculations of carbon content in NC11 steel matrix (see Fig. 8),
based on the contents of carbides dissolved during austenitizing at 950, 1050, and 1150 °C,
presented by Glowacki in [2], results of C content determination in X210CrW12 steel matrix
after austenitizing at 1050 and 1200 °C during 15 min given by Berns in [4], and the course of
C content changes vs. austenitizing temperature from 850 to 1050 C and 1 hour austenitizing
time in steel of 2.25% C and 12.03% Cr acc. to Sato [1].

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METAL 2001 15. - 17. 5. 2001, Ostrava, Czech Republic

It results from the Fig. 6 that in the NCWV/D3 steel matrix the carbon content increases
almost proportionally to the growth in austenitizing temperature. After austenitizing at 900 °C
throughout 30 min the carbon content in matrix is about 0.35%, at 1000 °C about 0.6%, and at
1150 °C about 1%. The carbon content in the NC11 steel matrix after austenitizing at the
same conditions approaches that content in NCWV/D3 steel. One should stress that the
courses of the changes of carbon content in the matrices of NC11, X120CrW12, NCWV
quenched steels vs. austenitizing temperature are distinctly different from those given by Sato
in the steel of 25% C and 12.03% Cr type.

It was found that like in case of chromium and tungsten, there is almost linear relationship
between the content of carbides dissolved during austenitizing in the ranges of temperature of
900 to 1150 °C throughout 30 min and the content of carbon in matrix of the NCWV/D3
quenched steel. The regression line is presented in Fig. 7. As the result of calculations, the
following regression line was obtained:

Fig. 7. Regression line between the content of carbides dissolved during austenitizing in the
temperature range of 900 to 1150 °C throughout 30 min and carbon content in the matrix of
NCWV/D3 quenched steel:

YC − m = 0.0426 + 0.0986 X c − da (3)

where: YC − m is carbon content in the matrix of NCWV/D3 quenched steel, X c − da is the

content of carbides dissolved during austenitizing.

Thus obtained value of r=0.9233 at s=n-2=4 freedom degrees is higher that the value of
r=0.8114 taken from R.A. Fisher Tables what means that the correlation occurs with the
probability higher than 0.05, whereas 95% confidence interval YCr − m for t0.05;4=2.776, so
YC − m = 0.65 ± 2.776 S Y = 0.65±2.776×0.0787 yielding YC −m = 0.4315 ÷ 0.8685 ;
95% confidence interval of the slope a = 0.0703 ÷ 0.1269 .

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 METAL 2001 15. - 17. 5. 2001, Ostrava, Czech Republic

4. CONCLUSIONS
The studies carried out allowed for formulation the following conclusions:
1. Microhardness of matrix of the NCWV/D3 quenched steel increases
succesively with the austenitizing time growth up to 1000 °C achieving maximum
value of about 858 µHV whereas the increase in austenitizing temperature above 1000
°C results in reversal course of changes in the matrix microhardness. Beside it results
from the measurements of steel and matrix microhardnesses that the present in the
quenched steel undissolved carbides during austenitizing result in an insignificant
effect on the steel macrohardness under quenched state.
2. Austenitizing NCWV/D3 steel in the temperature range of 900 to 1150 °C at
constant time of 30 min, due to carbides dissolution results in successive growth of
contents of chromium, tungsten, and carbon in the quenched steel matrix. After
austenitizing at 900 °C throughout 30 min, the chromium content in matrix equals
2.93% and increases up to 7.27% after austenitizing at 1150 °C, the tungsten content
from 0.38% up to 1.06%, respectively, and carbon from 0.37% up to 1.16%,
respectively, with only slight insignificant increase in vanadium content.
3. The analysis carried out allowed to find the occurrence of a linear correlation
between carbides dissolved in austenite during austenitizing in the temperature range
from 900 to 1150 °C throughout 30 min and the contents of chromium, tungsten, and
carbon in matrix of the NCWV/D3 quenched steel. Changes in the contents of
chromium, tungsten, and carbon Y vs. the amount of dissolved carbides Xda may be
expressed by the following regression equations:
• in case of chromium
YCr − m = 1.196 + 0.55 X da
• for tungsten
YW − m = 0.0799 + 0.0872 X da
• and in case of carbon
YC − m = 0.0425 + 0.0986 X da

LITERATURE
1. SATO, T., HONDA, Y., NISHIZAWA, T., Tetsu To Hagane, 1956, 42, 12, p.1118-1122.
2. GŁOWACKI, Z., PhD Thesis, Politechnika Poznańska, Poznań, 1964.
3. KOWALSKI, W., Prace Instytutu Mechaniki Precyzyjnej, 1966, XIV, 2, 4, s.1-18.
4. BERNS, H., HTM (Härterei-Technische Mitteilungen), 1974, 29, 4, p. 236-247.
5. HABERLING, E., SCHRUFF, I., Thyssen Edelst. Techn. Ber 13 Band, 1987, Heft 1, p.
64-71.
6. NYKIEL, T., PhD Thesis, Politechnika Poznańska, Poznań, 1982.
7. NYKIEL, T., HRYNIEWICZ, T., Effect of Austenitizing Parameters on the Change of
Concentration of Alloying Components and Phase Structure of Tool Steel of Type 2%C
and 12%Cr with Additives of W, Mo, V, Proc. of the 11th Congress of the International
Federation for Heat Treatment and Surface Engineering, Florence, Italy, 19-21 October,
1998, 116, pp.87-96.
8. FISHER R.A., Statistical Methods for Research Workers, London, Oliver & Boyd, 1934
9. POPOWA N.M., RYBINA M.F., Opredelenie svobodnogo i sviazannogo ugleroda v
staliach, Metody Chimičeskogo Analiza, 1950, pp.280-283.

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