15. - 17. 5.

2013, Brno, Czech Republic, EU

EFFECT OF SELENIUM ON METALLOGRAPHIC PURITY AND FORMABILITY

Vladislav KURKA, Jaroslav PINDOR, Zbyněk HUDZIECZEK, Zdeněk ADOLF, Jiří CIENCIALA

MATERIÁLOVÝ A METALURGICKÝ VÝZKUM s.r.o., Pohraniční 693/31, 706 02 Ostrava - Vítkovice, ČR,
vladislav.kurka@mmvyzkum.cz

Abstract
Metallographic purity of steel products is affected by many factors from chemical composition of input raw
materials, their "purity", proper selection of production technology, preparation of production units and
observance of all technical-technological operations to the actual casting and crystallization. This work deals
with the effect of selenium on the final metallographic purity of material after it has been formed by open-die
forging. Selenium was identified in MnS type inclusions, where it caused lower formability of these inclusions
even in the case of a high degree of forging. This work was realized using the “Vacuum and overPressure
Induction Melting furnace” (VPIM) which is constructed within the construction of the "laboratory for
experimental verification of production technology of new materials", the construction of which is
implemented within "Regional Material Technological Research Centre" No.: CZ.1.05/2.1.00/01.0040, or by
research programme No. 6 called "Experimental verification of new technological processes for steel
materials with higher quality parameters“. The laboratory shall be used in MATERIÁLOVÝ
A METALURGICKÝ VÝZKUM s.r.o. for research and development of metallurgical processes in metal melts.
Keywords: purity, selenium, formability, vacuum, 20MnMoNi55

1. INTRODUCTION

MATERIÁLOVÝ A METALURGICKÝ VÝZKUM s.r.o. (hereinafter referred to as MMV) designs production

technologies and implements production of castings and ingots. The cast materials include low and high-
alloy cast iron, low, medium and high-alloy steels (e.g. super duplex steel), and last but not least metal
chrome and nickel based alloys. This work discusses the results and experiences obtained during production
of 20MnMoNi55, particularly the effect of selenium (Se), which modified by its low content MnS inclusions
into unformable state. Inclusions consisting of Mn, S and Se were formed (MnSSe inclusions).

2. GRADE PRODUCTION AT VPIM

20MnMoNi55 grade material was produced on “Vacuum and overPressure Induction Melting furnace”
(VPIM). Following melting, vacuum refining, alloying, and heating up to casting temperature and sample was
taken for chemical analysis see Table 1. Then the caisson was opened and a heated mould assembly V2A
with tundish was inserted. The caisson was closed again, the pressure was lowered to 100Pa and then it
was filled with argon to 100kPa. When 100kPa pressure was reached, melt was cast from the induction
melting furnace into the tundish and from that to the top of the mould assembly.
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Table 1 Standardized chemical composition of material 20MnMoNi55, produced ingot, and verification
analysis of forging
Standard [3] Forging after
20MnMoNi55 Units Furnace
Min. Max. working
C [wht. %] 0.17 0.23 0.19 0.21
Mn [wht. %] 1.20 1.50 1.38 1.36
Si [wht. %] 0.15 0.30 0.24 0.19
Mo [wht. %] 0.40 0.55 0.46 0.46
Ni [wht. %] 0.50 0.80 0.70 0.72
Cr [wht. %] - 0.20 0.16 0.16
Cu [wht. %] - 0.12 0.08 0.083
V [wht. %] - 0.02 <0.001 0.006
Co [wht. %] - 0.03 0.004 <0.003
Al (tot) [wht. %] 0.0100 0.0400 0.017 0.002
Sn [wht. %] - 0.011 0.005 0.004
As* [wht. %] - 0.015 0.003 0.004
Sb [wht. %] - 0.007 0.002 0.003
Se [wht. %] - - - <0.0100
P [wht. %] - 0.012 0.005 <0.005
S [wht. %] - 0.008 0.005 0.006
N (tot) [wht. %] - 0.013 0.003 0.0031
H2 ppm - 1 0.99 0.96
O2 ppm - 20 20 17
*Decreased by customer contrary to standard

3. FORGING EVALUATION

According to [1] and [2] material 20MnMoNi55 is used for boilers and pressure vessels. The actual use of the
material shows that high demands are applied to it in terms of metallographic purity and strength. Table 1
contains presentation of chemical composition of material 20MnMoNi55 and the produced forging. As is
apparent from Table 1, the required chemical composition was achieved.
The cast ingot was formed and worked into a 2900x250x72mm plate. The forging degree is PK=8. Metal
samples were taken from the plate produced in this way to determine metallographic purity, sample No. H5.
As is apparent from the first line Table 2 the permitted content of inclusions was exceeded - evaluated
according to ASTM E45 method A. These were especially heavy inclusions exceeding several times the
permitted values.

Table 2 Maximum content of inclusions evaluated according to ASTM E45 method A

Type A Type B Type C Type D
sulphides aluminates silicates globular oxides
Requirement 2.0 2.0 1.0 1.5
Plate (chemical composition of 0.0 1.0 >5 >5
inclusions not known) H5
Plate (when it was ascertained that it >6 1.5 - 1
was MnS) H4
Samples from the H1 (PK) >6 2.0 - 1.0
plate after another H2 (P) >6 1.0 - 1.0
forging H3 (K) >6 1.5 - 1.0
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Method ASTM E45 method A, which the customer required places inclusions into categories (from sulphides
to globular oxides) according to the shape of the inclusion. Within analysis of formation of large inclusions,
microanalysis of non-metallic particles was carried out and due to the typical EDX spectrum it was
ascertained that those were MnS inclusions see Fig. 1 a Fig. 2. Based on this new information, evaluation
was made anew on the original plate with sample marked H4, which regraded these inclusions from category
D (oxides) to category A (sulphides), viz. Table 2.

Fig. 2 Typical EDX particle spectrum

from Fig. 1

Fig. 1 MnS inclusions in material

20MnMoNi55, in the case of
ordinary inspection

Under normal forming temperatures, MnS inclusions are easily formable and in metallographic analysis they
should have an elongated shape and not circular shape. Therefore, a test was made when three metal
samples were taken from the forged plate (H1, H2 and H3) for further forging, see Fig. 3.

Fig. 3 The places where metal samples (H1, H2 a H3) were taken from the forged and worked
plate

The taken metal samples (Ø 70 mm, length 170 mm) were subjected to the following forging operations at
temperatures 1150-830°C including specification of the degree of forging:
 H1 - upsetting to Ø 99 mm (P1,6), elongation to 43x21x444 mm (K 4,2), where PK = 7.6,
 H2 - upsetting to Ø 99 mm (P1,6),
 H3 - elongation to 43x21x444 mm (K4,2).
When forging was completed, metal samples were taken from each forging and the source plate to
determine micro-purity according to ASTM E45 - method A. Subsequent metallographic analysis confirmed
that these inclusions are unformable, see Table 2. Therefore checking microanalysis of non-metallic particles
was implemented with an extended EDX spectrum. The analysis confirmed that the non-metallic particles in
sample H1 were primarily manganese sulphides. In these sulphide particles, a small amount of selenium was
found, on average ca 5%, see Table 3. Within the inspection, checking microanalysis with an extended EDX
 15. - 17. 5. 2013, Brno, Czech Republic, EU

spectrum was performed which confirmed that the original plate (H4) contained MnSSe inclusions mostly on
the surface of Al2O3, inclusions see Fig. 4.

Table 3 The results of semi-quantitative RTG microanalysis of non-metallic particles in sample H1 (wht. %)
Analysis No. Se S Mn
1. 7.0 26.3 66.7
2. 4.0 21.5 74.5
3. 4.2 21.3 74.5
4. 4.8 21.6 73.6
5. 3.9 21.5 74.6
Arithmetic mean 4.8 22.4 72.8

Fig. 4Obr. 2
MnSSe zv. 1500x
inclusion with EDX spectrum of Al2O3 inclusions with surface formed by MnSSe

Based on ascertained facts, an analysis was carried out of the content of selenium in the whole content of
metal and not only in inclusions see Table 1. Unfortunately, determination of such a small content of
selenium in the whole volume of metal is difficult and it was ascertained that the content was <0.0100%.
However, it was established that even such low content of selenium as this has a significant impact on
morphology of inclusions and their formability.

4. IMPACT OF SELENIUM ON MNS INCLUSIONS

In general, selenium according to [4] with the content from 0.04 to 0.08% affects the character, morphology
and dispersion of non-metallic inclusions. This also has impact on mechanical and technological and
operational properties of steel. Selenium causes globularity of non-metallic inclusions, decreases ductility
and also increases sensitivity to brittle fracture. Due to these properties, selenium affects elimination of
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occurrence of cracks (preventing their spreading) which occur in metallurgic defects. This further lowers the
loss of metal to scrap.
Selenium is a surface active element and as such it affects (improves globularity) on the shape of graphite
particles, e.g. in the case of cast iron. It further decreases the speed of nitrogen absorption into steel, refines
the grain, and minimizes porosity. It improves forming particularly rolling, because when selenium is added
the structure of lattice edge is oriented in parallel with the direction of rolling. Selenium is also added to
materials for the improving workability at higher speeds which is quite important today in the time or primarily
CNC machining centres. [5] and [6]
As selenium has the boiling temperature of 686 °C and unlike sulphur it is characterized by a metal bond, it
is in gaseous form at liquid steel temperature and therefore its solubility in the liquid steel is minimal. Unlike
sulphides, selenium compounds (selenides) are much less stable and therefore are formed mostly in solid
steel on the surface of inclusions.

5. CONCLUSION

The implemented work, literature analysis and tests confirmed that selenium plays a very significant role in
the morphology of inclusions which subsequently affects mechanical, structural properties and especially
formability. Deposition of selenium on MnS inclusion surface completely prevented its forming into standard
elongated shape and caused failing of the material in purity tests.
Ordinary analysis of the content of selenium in steel proved to be difficult in standard production conditions.
Therefore upon finding that MnS inclusion cannot be formed, it is necessary to carry out an extended
checking microanalysis of non-metallic particles with an extended EDX spectrum.

ACKNOWLEDGMENTS

This paper was created in the project No. CZ.1.05/2.1.00/01.0040 " Regional Materials Science and
Technology Centre" within the frame of the operation programme " Research and Development for
Innovations" financed by the Structural Funds and from the state budget of the Czech Republic.

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05/NewsViews_Jan_Mar05.pdf > 09/04/2013, 7:35.
[3] Verlag Stahlschuessel Wegst GmbH. Stahschluessel 2007. Version 5.01.0000.
[4] Metallovedenie i Termicheskaya Obrabotka metallov, č. 10, s. 2-7, říjen, 1979.
[5] Stewart D. Selenium Element Facts. <http://www.chemicool.com/elements/selenium.html> 09/04/2013, 7:35.
[6] Robert H. Aborn. The role of selenium and tellurium in ferrous metals. <http://eprints.nmlindia.org/3160/1/342-
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