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Steel Cleanliness and Clean Steel Technologies
Steel Cleanliness and Clean Steel Technologies
Steel cleanliness is an important factor which decides the quality of the steel.
It can have a remarkable influence on steel properties, such as tensile strength,
formability, toughness, weldability, cracking-resistance, corrosion resistance,
and fatigue-resistance etc. The demand for better mechanical properties of
steels from the steel consumers has urged the steel producers to improve the
cleanliness of steel.
Clean steels refer to the steels which are free from inclusions. Inclusions are
non metallic particles embedded in the steel matrix. In addition to lowering of
the non-metallic oxide inclusions and controlling their morphology,
composition and size distribution, clean steels require lowering of other
residual impurity elements such as phosphorus (P), sulphur (S), total oxygen
(O2), nitrogen (N2), hydrogen (H2), also sometimes carbon (C), and trace
elements such as arsenic (As), tin (Sn), antimony (Sb), selenium (Se), copper
(Cu), lead (Pb), and bismuth (Bi). These impurity elements vary with different
grades of steel. Some elements are harmful to certain steel grade, but can be
less harmful or even useful to another steel grade. In other words, the control
elements are different for different performance requirements needed from the
steel.
For achieving a satisfactory cleanliness in steel, it is necessary to control and
improve a wide range of operating practices throughout the steelmaking
processes. These include (i) additions of deoxidizing agents and ferro-alloys,
(ii) secondary metallurgical treatments, and (iii) shrouding systems and casting
practice.
The term ‘clean steel’ was coined in the middle of the 20th century. This was
the time when the steel production has started to increase globally. At that time,
it was understood that quality of steel is also to be considered as a special and
important issue. Advances in steelmaking since then have resulted in the
development of many steel grades with very low level of impurities. In recent
years, new ‘clean and ultra-clean’ steels have been developed and
commercialized for addressing the current and future quality requirements
needed by the steel consuming industry. Steel cleanliness has also significantly
improved mechanical properties (such as fatigue strength and impact
toughness) and corrosion resistance of the steels.
The concept of cleanliness was born initially from the observation under the
optical microscope of non-metallic inclusions (NMIs) by the newborn
discipline of metallography during the middle of the 20th century. Cleanliness
was rated against standard images of microscopic fields, where geometry
(shape and size) and distribution of the NMIs was distinguished against various
image types. The trained observer had established that some shapes were
acceptable in some steel grades and that smaller inclusions generally were
more acceptable than the larger ones. Although the composition of inclusions
was not available by then, the observer had established a correspondence
between grades and inclusion composition by families (sulphides, silicates,
aluminates, alumina, and composite inclusions) based on the S content and
deoxidation history of the steel.
These methods developed in the 20th century were soon standardized. They
pre-empted the general use of the secondary steelmaking processes and the
continuous casting of the steels. The further development of the concept of
cleanliness went on by exploring various issues in parallel, connected with the
physical chemistry of steelmaking, development of new process reactors, and
new, innovative solutions to control inclusions composition, shape, size and
distribution which overtime became the routines of the steelmaking practice.
A modern vision of cleanliness has emerged from this concept-building effort
made during the initial 30 years to 40 years. Further, the subject of the steel
cleanliness has reached some degree of maturity now, especially for the new
secondary steelmaking processes and for those steels produced by the
continuous casting process.
Exogenous inclusions – These inclusions are from other sources, such as loose
dirt, broken refractory brickwork and refractory lining particles. They are
generally large and irregular-shaped. They can act as sites for heterogeneous
nucleation of Al2O3.
The inclusion size distribution is very important since large inclusions are the
most harmful to the mechanical properties of the steel. One kg of LCAK steel
typically contains 10,000,000 to 1000,000,000 inclusions, including only 400
inclusions of size 80 microns to 130 microns, ten inclusions of size 130
microns to 200 microns, and less than one inclusion of size 200 microns to 270
microns. Obviously, detecting the rare large inclusions is very difficult.
Though the large inclusions are far outnumbered by the small ones, their total
volume fraction can be large. Sometimes a catastrophic defect is caused by just
a single large inclusion in a whole steel heat. Thus, clean steel involves not
only controlling the mean inclusion content in the steel but also on avoiding
inclusions larger than the critical size harmful to the product.
NMIs constitute a cloud of phases dispersed in the matrix of steel and defined
by a multi-dimensional set of parameters, including composition, shape, size
and distribution. This full description is normally not readily available and one
of the main issues related to assessing cleanliness is to observe representative
samples to estimate these parameters with a reasonable accuracy and
representativity. One difficulty is related to large inclusions (of size 100
microns or more), which are very rare and hence difficult to see, unless very
large size samples are analyzed.
Another issue is due to the fact that the population of the NMIs depends on
time (in the process timeline of the steel melting shop) and on temperature.
Thus a ladle sample, collected and analyzed with care and finesse, can give a
reasonably good estimate of the cleanliness there and then, but it can have
almost no connection, whatsoever, with the cleanliness of the solid steel.
Hence, there is necessity to assess when a representative sample of liquid steel
is to be taken in order to assess both steel composition and NMI cleanliness.
Based on their size, the inclusions are either micro-inclusions (size 1 micron
to 100 microns) or macro-inclusions (size more than 100 microns). Macro-
inclusions are harmful. Micro-inclusions are beneficial as they restrict grain
growth, increase yield strength and hardness. Micro-inclusions act as nuclei
for precipitation of carbides and nitrides. Macro-inclusions are required to be
removed. Micro-inclusions can be used to enhance strengthening by dispersing
them uniformly in the matrix.
NMIs have a strong influence on the quality and performance of steels. These
inclusions are mainly chemical compounds of metals like iron (Fe), manganese
(Mn), Al, silicon (Si), and Ca etc. with the non metals such as O2, S, N2, C,
and H2.
Various types of the NMIs are (i) oxides such as FeO, Al2O3, SiO2, MnO,
Al2O3.SiO2, FeO.Al2O3, MgO.Al2O3, and MnO.SiO2 etc. (ii) sulphides such
as FeS, CaS, MnS, MgS, Ce2S3, (iii) nitirides such as TiN (titanium nitrides),
AlN, VN (vanadium nitride),and BN (boron nitride) etc., (iv) oxysulphides
such as MnS.MnO, and Al2O3.CaS etc., (v) carbonitrides such as carbonitrides
of titanium (Ti), vanadium (V), and niobium (Nb) etc., and (vi) phosphides
such as Fe3P, Fe2P, Mn5P2. The fundamental tool for the description of the
chemical composition of the oxide NMIs is the ternary phase diagram (CaO-
SiO2-Al2O3), because this is the main system ruling the formation of these
non-metallic compounds. This class of NMIs is formed by the deoxidizing
elements added to the steel melt for removing the O2 content. The nitride
inclusions perform a detrimental effect worsened by the peculiar edged shape
which increases the amplification of the stresses which are developed at the
interface between the NMI and the metal matrix.
As per the morphology of inclusions, the inclusions can have (i) globular
shape, (ii) platelet shape, or (iii) polyhedral shape. Globular shape of the
inclusions is desirable. Certain inclusions like MnS, oxy-sulphides, iron
aluminates and silicates are globular. Platelet shape of the inclusions is
undesirable. Al deoxidized steels contain MnS in the form of thin films located
along the grain boundaries. Inclusions with polyhedral shape are not very
harmful.
The chemical elements initially involved in cleanliness are mostly the non-
metals of the Mendeleev periodic table, because they show higher solubility in
liquid steel than in the solid. These are mainly C, N2, O2, P, S, Se, and H2. To
this list, the metalloid neighbours in the table such as B (boron), As, Sb, and
Te (tellurium) can be added. Some of these elements originate from primary
raw materials (P, S, As, Sb) or from hot metal from the blast furnace, while
most of the others are either due to contamination by the atmosphere (O2, N2,
and H2) and the operating practice used in steelmaking, or are voluntarily
added (C, Se, Te, and B).
The sulphides are often the consequence of the Ca treatment applied in order
to modify the oxide inclusions, but the little and finely dispersed highly
refractory CaS inclusions can be detrimental for the casting (nozzle clogging)
and for the damaging effect. On the contrary the MnS NMIs (often modified
by the combination with CaS) are useful for cutting tool workability during the
machining of the steel.
Three main mechanisms have been recognized at the origin of the NMI. These
mechanisms are related to the damaging effects played by the non-metallic
phases against the metal matrix. These mechanisms consider the NMIs as (i)
notching elements which amplify the stress field around the NMIs, (ii)
pressurized tanks of gas which progressively migrates into the NMIs
generating a stress field around the NMIs, and (iii) non-metallic phases which
generate a residual stress due to the different thermal expansion coefficient
associated to the metal phase and the glassy-ceramic ones.
Knowing accurately the realistic inclusion content in the steel is vital for both
improving steel quality and also in predicting how a component made of the
steel is going to perform. In order to study and control steel cleanliness, it is
critical to have accurate methods for its evaluation. The amount, size
distribution, shape and composition of inclusions are to be measured at all
stages in steel production. Measurement techniques range from direct methods,
which are accurate but costly, to indirect methods, which are fast and
inexpensive, but only reliable as relative indicators.
Direct methods
There are several direct methods to evaluate steel cleanliness and they are
summarized below.
Metallographical microscope observation (MMO) – This is the traditional
method in which two-dimensional slices through steel samples, are examined
with an optical microscope and quantified by the eye. In it, the results are
evaluated using charts such as the JK reference scale. This technique is only
suitable for qualifying inclusions between 2 microns to 15 microns and is
limited to very small sample sizes. This method does not provide any data on
the chemical composition of inclusions. Problems arise when interpreting
slices through complex-shaped inclusions. Although there are some methods
to relate two-dimensional results to three-dimensional reality, this is generally
very problematic.
Cold crucible (CC) melting – Inclusions are first concentrated at the surface
of the melted sample as in the EB melting. After cooling, the sample surface is
then dissolved, and the inclusions are filtered out of the solute. This method
improves on slime extraction.
Laser diffraction particle size analyzer (LDPSA) – This laser technique can
evaluate the size distribution of inclusions which have been extracted from a
steel sample using another method such as slime.
Indirect methods
Because of the cost, time requirements, and sampling difficulties, steel
cleanliness is normally measured in the steel industry using total O2, N2 pick-
up, and other indirect methods.
Total O2 measurement -The total O2 in the steel is the sum of the free O2
(dissolved O2) and the O2 combined as NMIs. Free O2 or ‘active’ O2 can be
measured relatively easily using the O2 sensors. It is controlled by equilibrium
thermodynamics with deoxidation elements, such as Al. Since the free O2 does
not vary much, the total O2 is a reasonable indirect measure of the total amount
of the oxide inclusions in the steel. Due to the small population of large
inclusions in the steel and the small sample size for total O2 measurement
(normally 20 g), there are likely no large inclusions in the sample. Even if a
sample has a large inclusion, it is likely to be discounted because of the
anomalously high reading. Thus, total O2 content really represents the level of
small oxide inclusions but not the larger ones. A low total O2 content, however,
decreases the probability of large oxide inclusions. Thus total O2 is still a very
important and common index of steel cleanliness. Total O2 in LCAK steel has
steadily decreased with passing years, as new technology is getting
implemented. For example, steel plants with the vacuum degassing achieve
lower total O2 (10 ppm to 30 ppm) than the steel plants with only ladle gas-
stirring (35 ppm to 45 ppm)). Total O2 generally drops after every processing
step such as at the ladle 40 ppm, at the tundish 25 ppm, at the mould 20 ppm,
and in the cast steel 15 ppm.
Dissolved Al loss measurement – For LCAK steels, Al loss also indicates that
reoxidation has occurred. However, this is a less accurate measure than N2
pick-up since Al can also be reoxidized by the slag.
Submerged entry nozzle (SEN) clogging – Short SEN life due to clogging is
generally an indicator of low level of steel cleanliness. Small Al2O3 inclusions
in LCAK steel are known to cause nozzle clogging. Hence, SEN clogging
frequency is another crude method to evaluate steel cleanliness.
The formation and the control of the chemical composition of the NMIs
involve the different steps of the production processes and the industrial
systems through which they are performed. The production process has to be
carefully implemented in each step in order to avoid problems related to
(i) difficulties during the casting operation associated with the nozzle clogging
between the tundish and the mould (continuous casting process) and between
the ladle and the casting column (ingot casting process), and (ii) detrimental
effect on the mechanical properties of the steel.
At the end of steelmaking in the BOF (basic oxygen furnace) or the EAF
(electric arc furnace), O2 is at equilibrium with C, which means very high
levels for low C steel grades (1250 ppm O2 for 0.02 % C). If steel is to simply
solidify as such, eutectics of Fe, S, and O2 precipitate in the inter-dendritics,
while a strong C deoxidation take place in the initial stages of solidification,
thus producing rimming steels, full of blowholes near the surface. The resulting
steel in addition to being porous is brittle during hot rolling or hot forging
operation and subsequent use at room temperature.
The population NMIs changes all the time, since the existing inclusions
coalesce, float out and get finally adsorbed in a slag or a simple covering
powder or flux, by aggregation against refractory in the ladle, the tundish or
inside nozzles that some of them (solid non-metallic inclusions, like Al2O3 or
spinels) tend to clog. Steel and slag change as well, and inclusions entertain
complex connection with them, at equilibrium, if time allows, or out of it. Gas
evolution at the solidification front can still take place if N2 and H2 are not
properly controlled. More inclusions appear, since temperature drops, which
generally means more precipitation, or solidification starts, or O2 penetrates
the system (reoxidation),from the slag, the refractories, from the atmosphere at
refractory junctions (sliding gates, submerged nozzle mounting, and across the
refractories etc.), or because the slag or the refractories generate new inclusions
or release inclusions previously captured. The latter is known as the exogenous
NMIs. Of course, the trend is generally towards improved cleanliness with all
these mechanisms are being deeply looked into for finding counter-measures.
An important point regarding reoxidation is that the phenomenon does not take
place at thermo-dynamic equilibrium, but rather generates oxides of whichever
element happens to meet the incoming O2, most often generating Fe oxides.
Out of the equilibrium in deoxidized liquid steel, these oxides later reverse
back to equilibrium NMIs, if time permits.
NMIs are large enough to interact with the metal matrix as mechanical
discontinuities, basically like holes. There are other third phases in steel of
much smaller dimensions called precipitates, which interact with the matrix as
the scale of dislocations or even at atomic scale. Precipitates, normally carbides
or nitrides, constitute the key features of the micro-alloying of steels or of more
substantial alloying like in tool steels or in stainless steels.
Ladle operations
The tap O2 content is measured during tapping the liquid steel in the ladle or
before the addition of the deoxidizing agents. The value is typically high. It
varies in a wide range (250 ppm to 1200 ppm) depending on the primary
steelmaking practice. Al additions when used to deoxidize the steel, create
larger amounts of Al2O3. This suggests that a limitation on tap O2 content is
to be imposed for clean steel grades. However, there is no correlation between
furnace practice and steel cleanliness, since around 85 % of the Al2O3 clusters
formed after large additions of Al, float out to the ladle slag, and that the
remaining clusters are smaller than 30 microns. Naturally, the decision to
ignore tap O2 depends on the time available to float inclusions and on the
availability of ladle refining, which can remove most of the generated
inclusions. However the tap O2 content strongly affects the decarburization
rate for producing ultra low C steel.
Ladle slag reduction treatment – It has been found that minimizing slag
carryover, together with adding a basic ladle slag and basic lining to lower the
ladle slag to less than 1 % to 2 % of FeO + MnO, can reduce total O2 content
to 10 ppm for LCAK steel. Another way to lower the FeO + MnO content of
the ladle slag is to add a slag conditioner (i.e. slag reduction or deoxidation
treatment), which is a mixture of Al and burnt lime or limestone. There is a
drop in FeO + MnO content after ladle slag reduction treatment. On an average,
this treatment lowers the FeO + MnO level to below 5 %. This results in sharp
improvement of coil cleanliness.
Ladle stirring and the ladle degassing processes greatly promote inclusion
growth and removal. The effect of vacuum treatments on the cast steel
inclusion levels shows the improvement of steel cleanliness over argon (Ar)
stirring in the ladle. The pronounced benefit of Ca-based powder injection is
due to its greater stirring power in addition to its primary effect of
deoxidization and liquefying inclusions. The vacuum degassing and Ca
treatment together can drop the total O2 to 15 ppm level.
Tundish operation
Important phenomena which are taking place in the tundish are shown the Fig
2. The factors which are affecting the steel cleanliness are (i) casting
transitions, (ii) tundish refractory lining, (iii) tundish flux, (iv) gas stirring,
and (v) tundish flow control.
Fig 2 Important phenomena taking place in the continuous casting
tundish
During the first casting heat, the entrainment of air and slag in the tundish pour
box due to the turbulence during ladle open is accompanied by an initial
maximum in total O2 content in the tundish (including both slag and Al2O3
inclusions). Open pouring at the start of the casting causes total O2 in tundish
to increase to twice normal levels for more than an entire heat. Several minutes
of filling are needed before tundish flux can be added. Eventually, during
steady casting, the total O2 decreases to lower levels, consisting mainly of
Al2O3.
One improvement during ladle transitions is to stop the flow of liquid into the
mould until the tundish is filled and to bubbling gas through the stopper to
promote inclusion flotation. Another improvement effect is to open new ladles
with submerged shrouding. With this measure, the total O2 is decreased with
more consistent quality throughout the sequence. Near the end of a ladle, ladle
slag can enter the tundish, due in part to the vortex formed in the liquid steel
near the ladle exit. This phenomenon needs some steel to be kept in the ladle
upon closing (example 5 ton ‘heel’). In addition, the tundish depth drops after
ladle close, which disrupts normal tundish flow and can produce slag
vortexing, slag entrainment, and increased total O2 in the mould.
Tundish flux – The tundish flux is to carry out many functions. Firstly, it is to
insulate the liquid steel both thermally (to prevent excessive heat loss) and
chemically (to prevent air entrainment and reoxidation). Further, the tundish
flux with lower SiO2 content can decrease N2 pick-up from the ladle to the
mould substantially. Secondly, in ideal circumstances, the flux is also to absorb
inclusions to provide additional steel refining. A normal tundish flux is burnt
rice husk, which is inexpensive, a good insulator, and provides good coverage
without crusting. However, rice husk is high in SiO2 (around 80 %), which can
be reduced to form a source of inclusions. Also, rice husk is very dusty and
with their high C content, (C around 10 %), can contaminate ultra low C steel.
Basic flux (CaO-Al2O3-SiO2 based) is theoretically better than burnt rice husk
at refining LCAK steels, and has been correlated with lower O2 in the tundish.
Use of basic tundish flux (CaO-40 %, Al2O3-24 %, MgO-18 %, SiO2-5 %,
Fe2O3-0.5 %, and C-8 %), together with baffles, significantly lowers the total
O2 fluctuation, as compared to the flux (CaO-3 %, Al2O3-10 % to 15 %, MgO-
3 %, SiO2- 65 % to 75 %, and Fe2O3-2 % to 3 %). The basic flux, however,
show similar results for other parameters as compared to rice husk, may be
because the basic flux also contains a high content of SiO2. The basic flux is
thus ineffective since it easily forms a crust at the surface, owing to its faster
melting rate and high crystallization temperature. Also, basic flux normally has
lower viscosity, and hence it is more easily entrained. To avoid these issues,
some steel plants use a two-layer flux, with a low-melting point basic flux at
the bottom to absorb the inclusions, and a top layer of rice husk to provide
insulation, which lowers the total O2.
Tundish stirring – Injecting inert gas into the tundish from its bottom
improves mixing of the liquid steel, and promotes the collision and removal of
inclusions. This technology lowers the total O2 in the tundish. The danger with
this technology is that any inclusions-laden bubbles which escape the tundish
and become entrapped in product result into severe defects in the product.
Transfer operations
Ladle opening – Ladle self open is a heat in which the ladle nozzle does not
have to be lanced open, but opens on its own. When the nozzle is to be lanced
open, then the shroud is to be removed. The cast is unshrouded from ladle to
tundish during the first 600 mm to 1200 mm of the cast, and hence the
reoxidation by air occurs. Hence, the total O2 level for the self-open ladle is
lower than the lanced-opened ladle. Careful packing ladle opening sand is
helpful to realize ladle self open.
Argon protection – Argon protection is used to prevent the liquid steel from
air reoxidation. When adding the tundish flux too early, the flux can be
entrapped into liquid steel and cast into the steel, thus normally there is no
protective cover for the first few minutes of a cast. Also at the period of ladle
opening, air is very easy to reach liquid steel. The effects of these two factors
can last upto 15 minutes into the cast for a tundish of 60 ton capacity. For
countering this problem, purging the tundish with inert gases (to displace the
air) prior to opening the ladle into the tundish is adopted in some steel plants.
Another measure to improve shrouding system for lowering of total O2 is to
incorporate an appropriate gas injection.
Sealing issues –For decreasing the N2 pick-up during continuous casting, the
factors normally considered are sealing of shroud from ladle to tundish, and
SEN from tundish to the mould.
The mould is the last refining equipment where inclusions are either safely
removed into the top slag layer or get entrapped into the solidifying shell to
form permanent defects in the cast product. Important insight into inclusion
entrapment has been obtained in the past through collecting statistical data and
conducting trials on the operating CCMs. It has been noticed that increasing
steel flow rate increases the level of pencil blisters (from Ar bubble
entrapment) considerably, while it reduces the level of slivers (from slag
entrapment). While measuring the inclusion and bubble distribution in the cast
steel, it has been observed that individual 1 mm bubbles are often coated with
inclusion clusters, and can be carried from far upstream, even if no gas is
injected into the tundish nozzle. It has been also observed that the inclusion
entrapment varies from side to side, which suggests a link with variations in
the transient flow structure of the lower recirculation zone.
Defects are frequently found associated with transients in the process, such as
changes in casting speed, tundish changes, or clogged nozzles. Pencil pipe
defects occur intermittently and are rare, relative to the quantity of injected gas.
The conclusions made in one of the study are that 80 % the particle are
eventually removed to meniscus (20 % entrapped in cast product), and a given
particle circulate for upto 300 seconds before being removed or entrapped.
It has been reported that the cast speed has its effect on the slivers. High speeds
and high variation in casting speed result in a higher rate of slivers. Adequate
stable casting speeds can be obtained with the use of a stopper. With a stopper,
the speed is no longer determined by the level of steel in the tundish, but by
the level of steel in the mould. It is better to control mould level control in the
range +/- 3 mm. A beneficial tool for the optimizing of the fluid flow and hence
improving the quality of the cast product is the electromagnetic brake (EMBR),
which bends the jet and shortens its impingement depth, inclusions thus move
more upwards, tend to top powder or be captured by the solidified shell at the
surface of the cast product. After the use of EMBR, the inclusions distribution
shows that there is a shift to the surface of the cast product.