DOI 10.

1007/s11015-016-0353-0
Metallurgist, Vol. 60, Nos. 7–8, November, 2016 (Russian Original Nos. 7–8, July–August, 2016)

EFFECT OF NEW TYPES OF NONMETALLIC

INCLUSIONS ON CONTINUOUSLY-CAST BILLETS
AND THE QUALITY OF HIGH-STRENGTH
LOW-ALLOY STEEL ROLLED PRODUCT

I. G. Rodionova, A. I. Zaitsev, A. I. Kovalev, UDC 669.1.017

D. L. Vainshtein, I. V. Lyasotskii,*
D. L. D’yakonov, K. A. Udod,
and M. V. Rodionova

The nature of new types of nonmetallic inclusions (NI) facilitating improvement of a continuously-cast billet
(CCB) and rolled product of high-strength low-alloy steels is studied. Contemporary approaches are
considered for improving hot-rolled product. It is noted that apart from chemical composition and hot
rolling regimes its properties are affected by CCB quality and the degree of different liquation processes.
Results are analyzed for previous studies pointing to the fact that liquation inhomogeneity is suppressed in
the case when in the concluding stage of steel treatment in a ladle and/or during crystallization there is
formation of oxide NI of complex composition, presumably glassy. NI composition, and macro- and
microstructure of CCB whose rolled product has a different level of mechanical properties and an axial
zone with a different degree of structural inhomogeneity, are studied. It is shown that rolled product with a
high level of properties and uniform structure of the axial zone is obtained from a CCB within whose
structure there are compound NI of complex composition containing oxides of silicon, iron, and other
elements, and also dendrite-like precipitates of carbonitrides (carbides).
Keywords: low-alloy steels, continuously-cast billet, rolled product, nonmetallic inclusions, structural
inhomogeneity, liquation, impact strength.

Contemporary areas for improving the quality of hot-rolled product include not only an increase in strength prop-
erties, but also provision of very good toughness and cold resistance indices, resistance to various forms of corrosion break-
down, in particular against hydrogen cracking (HC), and also provision of absence of metal defects including those revealed
by USM methods in a CCB axial zone and rolled product.
The main approaches for improving the level of cold and HC resistance include optimization of the steel chemical
composition, and also hot rolling regime. In addition, more and more data indicate that the properties indicated are affected
by CCB quality and also occurrence of defects revealed by USM methods in the axial zone of rolled product from contempo-
rary high-strength low-alloy steels. It is evident that one of the main reasons for occurrence of all of these problems is CCB
liquation inhomogeneity.
It has been noted in previous work [1, 2] that CCB macrostructure of some melts of steel type K65 was uniform
through the CCB thickness, with the absence (or minimum extent) of a columnar crystal zone. Rolled product prepared from

*
Deceased.

Bardin Central Research Institute of Ferrous Metallurgy (TsNIIchermet), Moscow, Russia; e-mail: igrodi@mail.ru, aizaitsev1@yandex.ru.
Translated from Metallurg, No. 7, pp. 48–53, July, 2016. Original article submitted April 28, 2016.

0026-0894/16/0708-0691 ©2016 Springer Science+Business Media New York 691

 Fig. 1. Axial zone in rolled product of steel melt No. 1 (a) and melt No. 2 (b).

TABLE 1. Test Steel Chemical Composition, wt.%

С Si Mn P S Cr Ni Cu Al N V Ti Nb Mo В Са

0.05– 0.15– 1.60– 0.010– 0.0015– 0.020– 0.015– 0.025– 0.030– 0.0045– 0.002– 0.010– 0.040– 0.002– 0.0003– 0.0015–
0.09 0.30 1.75 0.020 0.0025 0.125 0.260 0.28 0.040 0.0070 0.030 0.025 0.060 0.250 0.0005 0.0025

these CCB has a very high level of impact strength and uniform microstructure throughout the whole thickness. The micro-
structure of steel of these CCB is ferrite-pearlite. In other CCB, rolled product from which exhibited lower impact strength,
within the microstructure zones typical for a CCB were observed including an extensive zone of columnar crystals. The mi-
crostructure of these steels was Widmanstatten ferrite.
It has been noted [2] that a difference in smelting technology and casting CCB with favorable and unfavorable mac-
ro- and microstructure was included in ladle treatment technology. In steel with favorable macro- and microstructure a certain
amount of silicon- and manganese-containing ferroalloys was added in the concluding stages of ladle treatment. A hypothesis
was advanced that with a certain amount of these additions during steel continuous casting there is formation of a liquid oxide
inclusions of complex composition with high (up to 50%) silica content. During steel crystallization, these inclusions are
transferred into a supercooled liquid or glassy state and fill the space between growing crystals.
Possible mechanisms have been considered for the effect of these inclusions on CBB quality, which are presumably
connected with suppression of primary dendrite growth, absorbed at their surface; an increase in number of crystallization
nuclei, and not the rate of primary dendrite growth; suppression of direct crystallization; initiation of volumetric crystalliza-
tion; breakdown of the crystallization front and a reduction in impurity chemical inhomogeneity in an axial zone; a reduction
in intensity of mass and heat transfer during steel crystallization. In addition, they are substrate for deposition of carbonitride
precipitates, which facilitates uniform distribution of these complex formations throughout the volume of metal.
As a result of this, liquation processes are suppressed, and this facilitates an increase in the degree of structural and
chemical inhomogeneity of metal, formation of a favorable macro- and microstructure of CCB metal, and an improvement in
rolled product quality. It is apparent that these proposals require confirmation by studying the morphology of nonmetallic
inclusions (NI) that form during CCB crystallization, and also the structure and properties of rolled product prepared from
CCB with a different content of these inclusions.
The aim of this work is to study the nature of different types of nonmetallic inclusions facilitating improvement of
CCB quality and rolled product of high-strength low-alloy steels type K65.
Research was carried out on the metal of current production from different enterprises, selected from CCB and rolled
product of steel type K65. Steel chemical composition is given in Table 1. Comprehensive study of steel quality included
analysis of CCB macro- and microstructure for different melts, rolled product from which differed with respect to properties
and nature of the microstructure.
Initially, the microstructure was studied for specimens of hot-rolled melt No. 1 and melt No. 2 with the aim of re-
vealing the nature of the axial zone, the presence of axial liquation, and other features of the microstructure (Fig. 1).

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 Fig. 2. Form of nonmetallic inclusions (dendritic shape) in steel No. 1 (a) and their distribution (b).

Fig. 3. Inclusions not bonded in the main carbonitride structure.

Study of the microstructure of specimens of steel No. 1 showed that the rolled product structure through the section
of a specimen is almost uniform, whereas within the structure of rolled product of steel melt No. 2 there was a clearly defined
axial zone, which has accumulations of stringed fine precipitates of bainitic phase. In these strings, or close to them, there
were accumulations of manganese sulfide precipitates and also complex composition carbides and carbonitrides.
The macrostructure of CCB steel of melt No. 1 was uniform throughout the whole slab thickness, with absence or
minimum extent of a columnar crystal zone. The microstructure of steel of these billets was ferrite-pearlite. In a billet from
steel No. 2, the macrostructure had different zones typical for a CCB, including extensive zones of columnar crystals. The
microstructure was Widmanstatten ferrite.
A study of CCB steel melt No. 1 in a JEOL JEM 200CX transmission electron microscope showed presence within
the structure of a considerable amount of nonmetallic inclusions whose main component is carbonitride precipitates contain-
ing titanium and niobium with size in tenths of a micron and having dendritic morphology (Fig. 2a). Inclusions were distrib-
uted quite uniformly without clear accumulations and chains (Fig. 2b).
During foil preparation, specimens were only subjected to electrolytic polishing. With this foil preparation carboni-
tride precipitates enriched with Ti and Nb were hardly thinned and project above a specimen surface. With the aim of reveal-
ing the complex structure of the NI revealed a specimen was additionally given ion polishing. This made it possible to level
out specimen relief and to reveal the structure of dendrite sections close to their center.
In a dark field image in carbonitride reflection a dendrite-like particle is seen with an irregular contrast, and this may be
connected both with variation of particle thickness in its different sections, and also with the block nature and defectiveness of
its structure (Fig. 3). In a dark field image using the field of a microdiffraction picture separated in Fig. 3 by a circle, inclusions
are seen not connected with the main carbonitride structure. These inclusions with a size of ≈20–30 nm due to the small dimen-
sions could not give clear reflections (all the more a network of reflections) in a microdiffraction pattern. It is possible that the
reflection existing in this case is a weak spot at the edge of the circle indicated, corresponding to interplanar distance ≈0.205 nm.
It is impossible to draw certain conclusions about the structure and composition of these inclusions within a dendrite. Nonetheless,
the presence of similar fine inclusions within dendritic particles is confirmed in studying other dendritic particles.

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 Fig. 4. Macrostructure of steel melts No. 3 (a), No. 4 (b), and No. 5 (c).

A study in TEM made it possible to conclude that dendrite-like particles have a complex structure. It is not excepted
that growth of these carbonitride precipitates occurs on particles of another type that give a clear diffraction pattern.
In any case, these particles were revealed in a significant amount only in metal of CCB melt no. 1 with a favorable
macro- and microstructure, from which rolled product was also distinguished by a more uniform microstructure (absence of
a clear axial zone) compared with rolled product from melt No. 2.
Then steel specimens of three more melts were studied, whose rolled product differed in the level of impact strength
(KCU–40). Impact strength of rolled product specimens of steel melt No. 3 was significantly lower than for specimens of rolled
product of melts Nos. 4 and 5. Values of KCU–40 for specimens of steel melts Nos. 4 and 5 were about 300 and 250 J/cm2, re-
spectively, whereas values of KCU–40 for rolled product of steel No. 3 were not above 170 J/cm2. It is seen in a photograph of
the macrostructure of steel melt No. 3 that typical separation of the structural zone predominates, but for steel of melts Nos. 4
and 5 the microstructure is uniform throughout the CCB thickness, and for steel melt No. 4 it is more finely dispersed (Fig. 4).
The microstructure of CCB steel melt No. 3 is represented by coarse grains of Widmanstatten ferrite, decorated with
allotriomorphic ferrite (Fig. 5a). The microstructure of CCB steel melt No. 4 throughout the whole billet cross section is a
ferrite–pearlite mixture (Fig. 5b). The microstructure of CCB steel melt No. 5 (Fig. 5c) consists of polygonal ferrite and grains
of Widmanstatten type, similar in size and uniformly distributed throughout the metal volume.
Phase composition and microinhomogeneity of chemical element distribution in specimens of CCB melts Nos. 3 and
4 was studied by Auger- and x-ray photoelectron spectroscopy (AES, XPES) in an ESCALAB MK2 (VG) electron spectro-
scope with subsequent treatment of spectra by means of a UNIFIT 2007 program [3]. In order to excite the electron spectra in
a XPES monochromatized Al Kα radiation (hν = 1486.6 eV) was used. The energy resolution of the spectrometer was 0.6 eV
in studying Au4F lines in a spectrum from a gold standard. All of the physicotechnical parameters of recording, computer
accumulation, and subsequent treatment of spectra were selected in order to achieve the best energy resolution. Auger micros-
copy was used for studying structural features of phase distribution. These studies were carried out with a primary electron
energy E0 = 1450 eV. Resolution of the images obtained was not less than 256 × 256 pixels at a magnifications up to 10000.
Topographical contrast was nullified by a special collection system and image computer processing. Before study in order to
remove random contamination metallographic microsections were given ion etching in the preparation chamber of the

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 Fig. 5. Steel macrostructure: a) melt No. 3; b) melt No. 4; c) melt No. 5.

Fig. 6. Photoelectronic spectrum of line Nb3d indicating niobium distribution between

solid solution and carbonitride particles (XPES).

spectrometer with an argon pressure of the order of 1·10–4 Pa and an ion beam current of 40 μA for 5 min. This regime made
it possible to remove absorbed impurities from a specimen surface entirely.
Distribution of Nb atoms between solid solution and particles of the Nb1–(x+y)CyNx type were studied (Fig. 6). As
XPES spectrum analysis showed for a doublet of Nb3d lines for specimens of steel melts Nos. 3 and 4, the amount of niobium
bonded into carbonitride, in steel of melt No. 4 it is less by a factor of 2.3 than in a specimen of steel melt No. 3.
Niobium distribution inhomogeneity was established by means of Auger microscopy in two test specimens (Fig. 7).
An axial image is shown in Fig. 7a obtained in a regime of elastically scattered electrons, and an additional image was ob-
tained in characteristic Nb-MNN radiation with kinetic energy of 164 eV. Particles of niobium carbonitride have a light con-
trast in images. In CCB steel melt No 4 (see Fig. 7a), zones enriched with niobium are distributed over grain boundaries,
whereas in CCB steel melt No. 3 no grain boundary enrichment in niobium is observed (see Fig. 7b). In this case, at grain
boundaries there is a significantly smaller amount of carbonitride particles compared with CCB steel melt No. 4. These parti-
cles are distributed within grains.

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 Fig. 7. Distribution of niobium-containing particles in specimens of steel melts No. 4 (a) and No. 3 (b).

Fig. 8. Auger-electron spectrum from particles at a grain boundary of steel melt No. 4 (see Fig. 7a).

Fig. 9. Chemical element distribution in steel melt No. 3: a) image of specimen microstructure
in elastically scattered electrons; b) chemical element distribution along direction I–I.

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 Fig. 10. Auger-electron spectrum from grain boundary region of steel melt No. 3 in an area
enriched in silicon and niobium.

In a spectrum of a particle at a grain boundary (see Fig. 7a) lines for Nb, C, N, Ti, O, Si, and Fe are present (Fig. 8).
These data make it possible to suggest that fine particles form on the basis of niobium and titanium carbonitrides. Alongside
carbonitride particles in these specimens there is formation of complex silicon and iron oxides. By analyzing the intensity and
energy for the stronger characteristic lines of silicon, oxygen, and iron, it is possible to establish the nature of the connection
of these elements with each other and to determine chemical compound stoichiometry [4]. The intensity of silicon, oxygen,
and iron lines, normalized for standard values, comprise 0.7, 1.59, and 10.73, respectively. It is most probable that silicon
participates in forming a complex oxide SiO2·Fe2O3 (fayalite). It is well known that particles of this complex oxide have a
dendrite-like structure. As shown in this study, niobium and titanium carbonitrides form upon them. These results are in good
agreement with data for transmission electron microscopy (see Fig. 2a) and confirm the hypothesis about precipitation of ti-
tanium and niobium carbonitride on a substrate of glassy amorphous complex oxides.
A microscopic image is given in Fig. 9 in elastically scattered electrons for the microstructure of steel melt No. 4 (a),
and the chemical element distribution along directions I–I (b) is shown in Fig. 9a. Light and dark contrast of images in Fig. 9a
forms as a result of different grain crystallographic orientation. At a grain boundary, there is enrichment with niobium, titani-
um, nitrogen, oxygen, and silicon; zones of local enrichment of grain boundary regions with different elements are adjacent
to each other (see Fig. 9b). Oxygen and silicon enrich one grain boundary section, and niobium, titanium, and nitrogen are
alongside the arranged particles.
Analysis of the intensity of characteristic lines in a spectrum for steel No. 3 shows (Fig. 10) that the intensities of
silicon and oxygen lines normalized for standard values are 4.24 and 7.41, and this corresponds to binding of these elements
in SiO2 oxide. Elements Ti, Nb, N, and C form carbonitride (Ti, Nb)CN. In this case, generation of carbonitride particles on
SiO2 particles is not observed.
Conclusion. Thus, a relationship has been established between formation during steel crystallization of submicron
nonmetallic inclusions of a special type and formation of a favorable macro- and microstructure for continuously-cast billets,
reducing the degree of liquation, facilitating formation of a favorable rolled product axial zone, an increase in cold resistance,
and resistance to hydrogen cracking. In steel with the most favorable macro- and microstructures, there is formation of den-
drite-like glassy (amorphous) oxide inclusions of complex composition containing oxides of silicon, iron, and other elements
(fayalite type) on which precipitates of carbonitride (carbides) are deposited. A new type of NI forms during crystallization
and has a favorable effect on the structure of continuously-cast billets, which is in inherited in rolled product.
The work was carried out within the scope of Subsidy Agreement No. 14.624.21.0100 of 10.21.2014. Unique project
identification is REMEFI62414X0010.

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REFERENCES

1. A. I. Zaitsev, I. G. Rodionova, O. V. Baklanova, et al., “New types of nonmetallic inclusions in structural steels and
features of their effect on continuously-cast metal structural state and rolled product properties,” Probl. Chern. Met.
Materialved., No. 4, 65–73 (2014).
2. A. I. Zaitsev, I. G. Rodionova, O. V. Baklanova, et al., “Nonmetallic inclusions and promising principles for improv-
ing steel set of properties and qualitative characteristics,” Metallurg, No. 11, 62–69 (2014).
3. R. Hesse and R. Denecke, UNIFIT 2007, www.uni-leipzig.de/.
4. J. Watts and J. Wolstenholme, An Introduction to Surface Analysis by XPS and AES, Willey, USA (2003).

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