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Nonmetallic Inclusions in Steel – Origin, Estimation, Interpretation

and Control

Conference Paper · July 2016

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Nonmetallic Inclusions in Steel –
Origin, Estimation,
Interpretation and Control
Alexander A. Kazakov
Thixomet Ltd., St. Petersburg, Russia
Peter the Great Saint Petersburg Polytechnic University, St. Petersburg, Russia
 Origin of Nonmetallic Inclusions in Steel
1) Exogenous (ek-ˈsä-jə-nəs) which come from any external sources such as refractories, slag and other.
2) Indigenous which come as the products of chemical reactions during ladle treatment, casting and solidification of steel.

Indigenous inclusions thermal nature

Fragment of phase diagram Fe-C Equilibrium isotherms for «liquid steel-TiN»

Behavior of
figurative point of
steel composition
during NMI
formation:
I, II and III

Primary (∆MI) - under isothermal conditions during ladle treatment when element (Ti) was added above equilibrium concentration (1-2)
Secondary (∆MII) - during cooling of the liquid steel from “steelmaking temperature” (1600oC) to the liquidus temperature (2-3)
Tertiary (∆MIII-1 , ∆MIII-2) - in solidifying steel because of segregation (3-4, 5-6) and due to decreased solubility during cooling (4-5, 6-7)
Quaternary - precipitation in solid steel
Non-metallic Inclusions in Steel – Origin 2
Solubility surface of the components in the liquid steel
Fe-0.12C-Ti-N-O (temperature variation)
instead of simple isotherms in previous slide,
but we still have the same axes: [N]-[Ti].

Dotted lines are iso-oxygen

profiles.

There are coexistences of liquid

steel with:
1. one phase in the areas,
2. two phases on the lines; and
3. three phases at the points.

Depending on steel composition

the different NMIs are formed.

With temperature variation:

1) the overall level of the
oxygen solubility and
position of phase boundaries
change,
2) some phase regions appear
and disappear.

Non-metallic Inclusions in Steel – Origin 3

 Solubility surface of the components in the liquid
steel Fe-0.12C-Ti-N-O (Si, Al, Ce) at 1600oC
Fix the temperature and continue
the analysis by adding into the
steel the different elements.

Each next element will be added,

leaving in steel the elements added
earlier.

Silicon has excluded gas region

and reduced the area of Ti-oxides.

Only 0.03 % of [Al] excludes the

formation of all titanium oxides and
reduces the area of TiCxNyOz.

Only 0.001 % of [Ce] excludes the

formation of any oxygen-containing
NMIs.

+0.5wt.% [Si] +0.03wt.% [Al] +0.001wt.% [Ce]

Non-metallic Inclusions in Steel – Origin 4
 TiN growing in liquid steel (simulation results)

RK

∂C ∂ 2C 2 ∂C ∂C
= D( + ⋅ ) + VNI ⋅
∂τ (∂r ' ) 2
r '+ R(τ ) ∂r ' ∂r '

To use these equilibrium diagrams for interpretation of non-equilibrium steelmaking processes we apply local equilibrium thermodynamics:
the whole non-equilibrium system “steel-NMIs” we divide to the small but still macro volumes, where equilibrium is established.

Simulation results using Fick’s equation are here: inclusions stop to grow when the depletion zones of neighboring inclusions overlap.
So, during only 1 second, concentrations around the growing inclusions reach the equilibrium values. It is many times shorter than the duration of
processing of mass production steel. Therefore, we can use the local equilibrium for simulation of NMI formation in liquid and solidifying steel.

Non-metallic Inclusions in Steel – Origin 5

 Simulation of nonmetallic inclusions formation in liquid and
solidifying steel (on the example TiCxNyOz)
1. Mass conservation law:
How much impurities went away from the liquid,
so much impurities come to the solid and to NMIs:
d (Ci ⋅ S ) = Ci ⋅ γ i ⋅ dS − dM ⋅ yCi ;
2. Thermodynamic equilibrium for “liquid steel -TiCxNyOz” :
KTiС [C]⋅[Ti] + KTiN [N]⋅[Ti] + KTiO [O]⋅[Ti] = 1
A+ B
Nonmetallic inclusions in steel, wt.%: dM =
A = S ⋅ [Ti ] ⋅ (dK TiC ⋅ [C ] + dK TiN ⋅ [ N ] + dK TiO ⋅ [O])
C
B = [Ti ] ⋅ ( K TiC ⋅ [C ] ⋅ (γ Ti + γ C − 2) + K TiN ⋅ [ N ] ⋅ (γ Ti + γ N − 2) + K TiO ⋅ [O ] ⋅ (γ Ti + γ O − 2))
C = K TiC ⋅ ( yTi ⋅ [C ] + [Ti ] ⋅ yC ) + K TiN ⋅ ( yTi ⋅ [ N ] + [Ti ] ⋅ y N ) + KTiO ⋅ ( yTi ⋅ [O] + [Ti ] ⋅ yO )

Where A and B are the contributions into inclusions growth:

of decreasing of solubility (dKTiO , dKTiN , dKTiC)
and segregation of elements (γTi , γO , γN , γC ).
С – takes into account inclusions composition (yTi , yO , yN , yC).

Non-metallic Inclusions in Steel – Origin 6

 Simulation results of non-metallic inclusion formation
in the liquid and solidifying steel

a) 0.5% Ti, 0.3% C, 0.0014% O b) 0.1% Ti, 0.3% C, 0.003% O

Changing a composition of steel (here using Ti), we can learn how the composition and the wt.% of nonmetallic inclusions
change.

So, right now we have complete physico-chemical background to start with the next chapter “interpretation and control”, but
few remarks about an estimation. Non-metallic Inclusions in Steel – Origin 7
 Standards for Quantification of the Non-Metallic Inclusions in Steel
ASTM E 1245. Standard Practice for Determining the Inclusion or Second Phase Constituent Content of
Metals by Automatic Image Analysis.
ASTM E45. Standard Test Methods for Determining the Inclusion Content of Steel.
DIN 50602. Metallographic examination; microscopic examination of special steels using standard
diagrams to assess the content of non-metallic inclusions.
DIN EN 10247-2007. Micrographic examination of the non-metallic inclusion content of steels using
standard pictures.
GOST 1778-70. Steel. Metallographic Methods for Determining of the non-metallic inclusions.
Few comments about only two of them:

1. ASTM E 1245 is based on the fundamental stereology principles and provides an assessment of volume fraction, size and
distribution pattern of NMIs in steel. These features of inclusions are enough to develop “structure-properties” relationships.
2. Russian GOST 1778 describes all possible morphological types of NMIs in steel (9!), but visual assessment of them is too old.

Non-metallic Inclusions in Steel – Estimation 8

 Monitoring of Ladle Treatment and Continuous Casting of Steel

Capabilities of ASTM E 1245 for NMI assessment in final metal are well known. But this standard can be used also for
monitoring of ladle treatment and continuous casting of steel.

Here is just one example from our R&D works on the monitoring of re-oxidation. At all stages of ladle treatment the volume
fraction of inclusions does not exceed 0.005%, but during continuous casting, the inclusion volume fraction increases 3-4 times
due to re-oxidation during the technological process from “ladle to tundish” and from “tundish to mould”.
Non-metallic Inclusions in Steel – Estimation 9
 An Example of SEM EDS Analysis of NMIs

Main elements of NI composition, Wt.%

Mg Al Si S Ca
2.1 18.6 0.9 2.7 14.9
Let’s start with interpretation. As a result of energy-dispersive spectroscopic analysis we obtain the approximate
elemental composition of NMIs (in this case, without oxygen analysis), but this is not enough to understand when the
inclusions were formed and how to control their quantity and composition.

Non-metallic Inclusions in Steel – Interpretation 10

 Four-Steps Method for Interpretation of Non-Metallic Inclusions in Steel

• Recalculation of the wt.% of elements (SEM EDS) into the composition of oxides
Step # 1

• Improvement of the oxide’s composition according to the phase diagram

Step # 2

• Assessment of residual concentrations of elements in the liquid steel from which the
Step # 3 oxides with the composition found in step #2 were formed

• Revealing the NMI’s thermal nature in liquid and solidifying steel with composition
Step # 4 found in step #3

This method helps to explain the origin of inclusions and provides a sufficient information to improve the technology.

Non-metallic Inclusions in Steel – Interpretation 11

 Step 1: Recalculation of the wt. % of elements (SEM EDS) into
the composition of oxides (based on the example of calcium aluminates)
If Ca and S were found in the complex oxy-sulfide NMIs, to calculate Ca in the oxides (mCa’) we have to extract Ca fixed in
CaS from the total Ca (mCa) in the NMIs:

𝐴𝐶𝐶 ⋅ 𝑚𝑆 𝑦 ⋅ 𝐴𝑂 𝑚𝑀𝑀𝑥𝑂𝑦 ⋅ 100%

𝑚𝐶𝐶′ = 𝑚𝐶𝐶 − 𝑚𝑀𝑀𝑥 𝑂𝑦 = 𝑚𝑀𝑀 ⋅ 1 + 𝑀𝑀𝑥 𝑂𝑦 , % =
𝐴𝑆 𝑥 ⋅ 𝐴𝑀𝑀 ∑𝑖 𝑚𝑀𝑀𝑥 𝑂𝑦
𝑖

Elements mMe (SEM EDS), wt.% Oxides in non-metallic inclusions, wt.%

stoichiometric
composition
Ca S Al Mg (CaO),% (MgO),% (Al2O3),%

28,32 0,12 27,86 1,91 42 3 55 CaO·Al2O3

Non-metallic Inclusions in Steel – Interpretation 12

 Step 2: Improvement of the composition according to the phase diagram

(L)
L+CA
(C6A)
L+CA+C2A
L+MA
L+C2A+MA
(C2A)

MA+C2A+C6A(CA)

(MA)

For line pipe steel X70: ([Ca]≈0.0015-0.0045% [Al]≈0.030-0.045% [S]≈0.002-0.003%)

Let’s place these compositions of inclusions on the corresponding phase diagram at the temperature of their formation (1550oC).

The part of these points has got into the field with the same composition as was found in the step 1 and in this case an improvement is
not needed. Another points have got into the liquid slag or into different phase fields and these compositions have to be improved
according to the phase diagram.
Non-metallic Inclusions in Steel – Interpretation 13
 Step 3: Assessment of residual concentrations of elements in liquid
steel at which oxides with composition found in step 2 are formed

Here is a solution for the inverse task: by means of a solubility surface diagram, we define the residual concentrations of
elements in liquid steel from which inclusions with the composition found in the previous step were formed.

Non-metallic Inclusions in Steel – Interpretation 14

 Step 4-1: Revealing of the thermal nature of non-metallic
inclusions in liquid steel with the compositions found in step 3

[C]=0.07%
[Si]=0.25%
[Mn]=1.3%
[Al]=0.02%
[Ca]=0.012%
[S]=0.005%

Here is simulation of inclusions formation with composition of liquid steel found in previous step. So, interpretation of NMIs
composition is following: On the secondary calcium aluminate as on substrate, tertiary calcium sulfides are formed.
Non-metallic Inclusions in Steel – Interpretation 15
Step 4-2: Revealing of the thermal nature of non-metallic inclusions
in liquid steel with the compositions found in step 3

[C]=0.09%
[Si]=0.25%
[Mn]=1.7%
[Al]=0.04%
[Ca]=0.0005%
[Mg]=0.0001%
[S]=0.003%

The next example of NMIs interpretation: on the substrate of a magnesia spinel inclusion, the liquid slag inclusions based
on calcium aluminates were precipitated. At the end of solidification, manganese-iron sulfides were formed on the surface
of these inclusions.
Non-metallic Inclusions in Steel – Interpretation 16
 Step 4-3: Revealing the thermal nature of non-metallic inclusions
in liquid steel with the composition found in step 3

a b
a) Primary and secondary liquid inclusions and solid magnesia spinel (from the steel: [Mg]=0.005%; [Ca]=0.0026%; [Al]=0.02%).
b) Crystallization of liquid inclusions (CaO≈42%; MgO≈ 28%; Al2O3≈23%; SiO2≈6%; CaS≈0.12%)

All compounds revealed by the thermodynamic simulation were found as constituents of the investigated inclusion.
Non-metallic Inclusions in Steel – Interpretation 17
Step 4-4: Revealing of the thermal nature of non-metallic inclusions in
liquid steel with the compositions found in step 3

a b
a) Primary and secondary liquid inclusions and secondary solid calcium aluminates ([Mg]=10-6 %; [Ca]=0.007%; [Al]=0.02%).
b) Crystallization of liquid inclusions (Al2O3≈25%; CaO≈35%; MgO≈32%; SiO2≈7%; CaS≈0.05%).

All compounds revealed by the thermodynamic simulation were found as constituents of the investigated inclusion.

Non-metallic Inclusions in Steel – Interpretation 18

 Cluster Analysis for Interpretation of NMI Database
Material:
obtained by SEM-EDS Method
rail steel: [C] = 0.8%; [Mn] = 0.9%; [Si] = 0.35%; [Al] = 0.004%;
Up to now we talked about the interpretation of
[Ca] = 0.00035 %, [Ti] = 0.006%, [S] = 0.01%, [O] = 35 ppm, [N] = 40 ppm complicated but only one inclusion.
Methods: To make decision about industrial technology
1) automated feature analysis based on SEM-EDS method. we have to analyze a lot of them.

2) thermodynamic modeling by FactSage with FACT, FToxid and SGTE databases.

3) k-means clustering method to identify the clusters of NMIs from the raw data of
their compositions. Elements, wt. %
In this method, inclusions are separated according to the similarity of their Cluster without oxygen
and nitrogen
chemical composition. Separation of the inclusions into the clusters is completed mainly oxides
1 43-20-14-13-6
when it does not lead to the appearance of cluster with essentially different Al-Ca-Si-Mn-S-O
mainly sulfides
chemical composition. 2 44-28-13-11
Mn-S-Al-Ti-O
Results: Oxy-sulfides
3 59-39
Mn-S-O
>650 inclusions combined into four clusters.
4 Ti-(O,N) 61
Elements (without oxygen and nitrogen) were arranged in order of reduction of their
concentration in the cluster .
Non-metallic Inclusions in Steel – Control 19
 Interpretation of Inclusions in Clusters
Thermodynamic simulation of the non-metallic inclusion formation
a) in liquid and solidifying steel; and, b) during crystallization of liquid inclusion

First cluster is the primary and

secondary inclusions of liquid oxy-sulfides
and alumina (mainly oxides).

Second Cluster is tertiary titanium oxides

and manganese sulfides along with the
remaining alumina (mainly sulfides).

Last two clusters Mn-S-O and Ti-(O,N)

form at the second half of solidification.

Elements, wt. %
Cluster Origin
(without oxygen and nitrogen)
1 Al-Ca-Si-Mn-S-O 43-20-14-13-6 Primary and Secondary
2 Mn-S-Al-Ti-O 44-28-13-11 Tertiary at the first half of solidification
3 Mn-S-O 59-39
Tertiary at the second
4 Ti-(O,N) 61 half of solidification

Non-metallic Inclusions in Steel – Interpretation 20

 Evolution of non-metallic inclusions composition in rail steel

All detected inclusion compositions were plotted on

the ternary diagram Al-Mn-S .

They lineup from the aluminum corner to the MnS

point.

Evolution of non-metallic inclusion composition is

as follows:
1) from mainly oxides of primary and secondary
inclusions of the first cluster in the liquid steel
2) to the mainly sulfides of tertiary inclusions
of the second cluster at the beginning of steel
Elements, wt. % solidification;
Cluster without oxygen Origin 3) and, finally, two last clusters at the second half
and nitrogen of solidification.
1 Al-Ca-Si-Mn-S-O 43-20-14-13-6 Primary and Secondary
2 Mn-S-Al-Ti-O 44-28-13-11 Tertiary at the first half of solidification
3 Mn-S-O 59-39 Tertiary at the second half of solidification
4 Ti-(O,N) 61

Non-metallic Inclusions in Steel – Interpretation 21

 Control of non-metallic inclusions in steels for deep drawing:
Surface defect “film” in cold-rolled sheet

1 3

1) photo of surface defect,

2) defect panoramic image under it’s surface.
3) composition of inclusions which were the reason for the defect formation. Elements, wt.%
Point Fe Al O
Let’s note, we have found hercynite-like inclusion (FeOx·Al2O3) instead of 80g 20.25 19.35
balance
expected alumina (Al2O3) as a product of deoxidation of steel killed by aluminum.
80j 1.82 31.73

Non-metallic Inclusions in Steel – Control 1-1 22

 Hercynite-like non-metallic inclusion (FeOx·Al2O3)
in previous steps of technology: hot rolling and casting
In semi-finished hot-rolled stock In slab point inhomogeneity
near to surface of small radius
Elements, Wt.%
Point
number Fe Al О
3 3.40 34.38
4 27.95 40.76
balance
5 15.21 32.34

Elements, Wt.%
Point
number Fe Al О
39 18.36 39.05
Rest
40 18.60 36.40

Non-metallic Inclusions in Steel – Control 1-2 23

 Mechanism of hercynite formation
Aluminum wire

Al2O3

Steel melt
FeO∙AlxAl
(FeO) 2O2O
3 3

There are volumes with a very small concentration of aluminum and high oxygen content at the beginning of deoxidation, if the Al was
added first before Mn or Si. In these volumes hercynite forms as an equilibrium product of deoxidation (**).

When aluminum is completely dissolved in the steel (*), hercynite becomes non-equilibrium and the aluminum from liquid steel begins to
reduce iron from these inclusions. This is in the solid state and the very slow reaction provides high adhesion of hercynite with liquid steel
and prevents the removal of them during ladle treatment. Therefore, to avoid hercynite formation, the liquid steel should be treated first
with the addition of manganese or silicon. In this way, we have eliminated the defect “film” in the industrial product condition.
Non-metallic Inclusions in Steel – Control 1-3 24
 Control of calcium aluminates in line pipe steels
SiCa wire

Elements, Wt.%
Point #
Al Fe Ca О

1 0 96 0

2 0 96 0
CaO∙6Al2O3
3 37 0.5 18
Steel melt
Rest
4 37 0.4 15

5 27 0,6 5

6 28 1 7

Formation of hexa- and bi-aluminates of calcium is a common problem with Ca-treated steels. When the Ca-concentration in
the melt is too small the calcium hexa- and bi- aluminates will form. These compounds (especially hexa-) have a high melting
point and this is the main reason why these inclusions don’t sinter during the coagulation. The liquid steel has become
entrapped inside of such a conglomerate and capillarity forces prevent the removal of these inclusions during ladle treatment.
Non-metallic Inclusions in Steel – Control 2-1 25
 Optimum calcium/aluminum ratio in pipeline steel X70
[C]=0.06%; [Si]=0.20%; [Mn]=1.2%; [S]=0.005%, T= 1580оС

CaO∙Al2O3

The goal of technology improvement is to provide such residual concentrations of [Ca] and [Al] in liquid steel to prevent
formation of calcium hexa- and bi-alumitates. Liquid calcium aluminate (CaO∙Al2O3) is the best composition for coagulation and
removing from the liquid metal during ladle treatment.

Non-metallic Inclusions in Steel – Control 2-2 26

 Technology improvement results
0.2-1 μm
1-3 μm
3-5 μm
>5 μm

NMI reduction by new technology

Non-metallic inclusions Old New
In line pipe steel X70 GOST 1778 Vol.% GOST 1778 Vol.%
nondeformable oxides SN 2,5 0.15 SN 1,5 0.1
deformable oxides SB 4 0.5 SB 0,5 0.05
Due to optimum calcium/aluminum ratio in the new technology, the steel inclusion content is ten times better.
The coarse inclusions (more than 5 μm) are absent in steel produced by new technology.
Non-metallic Inclusions in Steel – Control 2-3 27
 Example of the positive impact of NMIs on the properties of steel

The distribution of inclusions by size Inclusion, found in the weld

Panoramic image of the weld joint, ×50, ×1000

In the beginning of the 1990’s “Nippon Steel” developed a technology called “oxide metallurgy” to obtain intragranular acicular ferrite
(IAF) in steel. Here is an example of a similar technology, but in welding of pipes. Welding materials and technology were designed
to obtain inclusions based on titanium oxides with size <1 µm. All parts of the weld consist of IAF, formed on these inclusions as on
substrates, and the mechanical properties of this weld are excellent. But, the heat-affected zone has remained as a weak point.

Non-metallic Inclusions in Steel – Control 3-1 28

 Solutions for the heat-affected zone problem
Acicular Ferrite on 0.06C-0.3Si-1.93Mn-0.002S-0.003Al- Titanium Oxy-nitrides
the active inclusions XTi-0.008O-0.009N-0.05Nb-0.05V to austenite grain size control

1st technology is similar to “oxide metallurgy” from Nippon Steel.

2nd technology is based on formation of TiNyOz to prevent austenite grain growth during welding.

Both technologies were realized by additives of Ti, but with different concentrations. We have made these steels and
here are the examples of inclusions which have been found. The results of thermodynamic simulation explain their composition.

Non-metallic Inclusions in Steel – Control 3-2 29

 Heat-affected zone microstructures
after different technologies

1st technology: 2nd technology conventional technology

titanium oxides for IAF formation titanium oxy-nitrides to suppress
the grain growth

The first two new technologies produce much better microstructures than the conventional approach.

Non-metallic Inclusions in Steel – Control 3-3 30

 Conclusions
1. It has been shown how the critical problems of non-metallic
inclusions in steel could be solved by interdisciplinary knowledge:
• Based upon steel making theory and practice,
• quantitative metallography; and,
• automated feature analysis based on SEM-EDS method.

2. The developed methods can be used for non-metallic inclusion

interpretation to improve steelmaking technology.

Nonmetallic Inclusions in Steel – Origin, Estimation, Interpretation and Control 31

 Thank you for your attention!

Nonmetallic Inclusions in Steel – Origin, Estimation, Interpretation and Control 32

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