EP0838534B1 - Process for obtaining an improved resulfurized fine-austenitic-grain steel - Google Patents

Process for obtaining an improved resulfurized fine-austenitic-grain steel Download PDF

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Publication number
EP0838534B1
EP0838534B1 EP97203234A EP97203234A EP0838534B1 EP 0838534 B1 EP0838534 B1 EP 0838534B1 EP 97203234 A EP97203234 A EP 97203234A EP 97203234 A EP97203234 A EP 97203234A EP 0838534 B1 EP0838534 B1 EP 0838534B1
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EP
European Patent Office
Prior art keywords
steel
sulfides
austenitic
fine
obtaining
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP97203234A
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German (de)
French (fr)
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EP0838534A1 (en
Inventor
Gianfranco Chioatto
Giovanni Maccio'
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LUCCHINI SpA
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LUCCHINI SIDERURGICA SpA
LUCCHINI SpA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur

Definitions

  • the present invention relates to the relevant process used to obtain an improved resulfurized, fine-austenitic-grain steel.
  • iron sulfide in steel generates an eutectic phase with metal iron, which displays a melting point at 988°C; therefore, the presence of iron sulfide in steel is harmful because it causes steel to display hot-shortness (i.e., high temperature brittleness) -- and steel forging and rolling temperatures are normally higher than 988°C.
  • Adding manganese to steel causes manganese sulfides to be formed which do not produce eutectic phases with iron and have higher melting temperatures than steel forging and rolling temperatures.
  • Manganese sulfides can be present in steel in three characteristic forms and are known as Type 1 sulfides, Type 2 sulfides and, respectively Type 3 sulfides.
  • Type 1 sulfides display a globular shape and are obtained in the presence of high oxygen levels (see, for example, unkilled steels, semi-killed steels and free-machining steels).
  • Type 2 sulfides display a dendritic structure and precipitate at the boundaries of the primary solidification grains; they appear in killed steels, with aluminum amounts which are just sufficient to deoxidize steel.
  • Type 3 sulfides are formed as the levels are increased of aluminum or other elements displaying high affinity for oxygen (titanium or vanadium), until such values are reached as to regulate the austenitic grain.
  • steels used in the industry of motor vehicles in general and, in particular, in car industry are resulfurized, fine-austenitic-grain, carbon and alloy steels suitable for casehardening and hardening-tempering treatments, containing additions of aluminum and/or titanium and/or niobium in such amounts as to secure the presence of fine austenitic grains (Type 3 sulfides).
  • a proposed solution is adding to steel containing Type 3 sulfides, such metal elements as lead or tellurium, which are known to improve the machinability of steel, but are very dangerous for the health of those attending steel production and, then, users during steel processing.
  • the purpose of the present invention therefore is of providing a process for obtaining a resulfurized, fine-austenitic-grain steel which obviates the above reminded drawbacks and, in particular, can be used by the motor vehicles industry in general and car industry in particular, because it is such as to allow a complete steel deoxidizing, a fine-austenitic-grain structure and a better machinability of steel to be obtained, as compared to the prior art.
  • Another purpose of the present invention is of providing a process for obtaining a resulfurized, fine-austenitic-grain steel which is not dangerous to the health of those who produce it at the steel factory and use it during the following processing.
  • Still a further purpose of the present invention is of providing a process for obtaining low cost, improved resulfurized, fine-austenitic-grain steel, without using complex and expensive technologies.
  • rare earths as plain metal wire or as a wire sheltered by metals, metal alloys and other deposited coatings (for example, ceramic coatings), to resulfurized, fine-austenitic-grain carbon steels and alloy steels in ingot mould or in tundish, makes it possible a good diffusion and homogenizing of the product, and a homogeneous distribution of the globular sulfides throughout the cast section, to be obtained.
  • the sulfides contained in steel improve the steel machinability, as compared to the traditional techniques, while simultaneously securing the absence of hot-shortness, the regulation of the austenitic grain and the complete deoxidizing of steel.
  • the Type 1 manganese sulfides display a globular structure and are obtained in the presence of high oxygen levels
  • the Type 2 sulfides (which are formed in steels containing minimal amounts of aluminum) display a dendritic structure and precipitate at the boundaries of the primary solidification grains, with the drawback that the resulting steel will display a considerably high hot-shortness.
  • Type 3 sulfides appear which distribute randomly throughout steel with angular and irregular shapes.
  • Type 1 sulfides After hot rolling, the Type 1 sulfides display a lenticular shape, whilst Type 2 and Type 3 sulfides turn into very thin bands or plaques; this feature of Type 1 sulfides contributes to improve the machinability of steel. In fact, during the machining, the cutting edge of the tool applies a force on its contact region of steel, causing microcracks to be formed in it.
  • microcracks succeed in breaking the chip into fragments, the necessary force for creating said microcracks decreases and steel displays a better machinability.
  • Type 2 and Type 3 sulfides do not cause the chip to break into fragments.
  • the cristallographic form of manganese sulfides can be controlled by means of the addition of transition metals of Group III (lanthanides or rare earths); such an addition results in the formation of globular sulfides, but implies the formation of oxides, which obstruct the continuous casting nozzle bores.
  • transition metals of Group III lanthanides or rare earths
  • rare earths display high affinity for oxygen (higher than of aluminum and magnesium), and, if they are present at high levels (0.03%-0.04% by weight), said rare earths undergo oxidation with simultaneously both alumina contained in steel in the form of inclusions and alumina which composes the refractory material of slabs, nozzle bores, and plugs being all reduced to aluminum metal.
  • the sulfides of Type 3 can be turned into globular sulfides and continuous casting steels can be obtained which display a better machinability, than corresponding steels known from the prior art.
  • the lanthanides are added in a sufficient amount to cause sulfides to turn into globular, as plain metal wires, or metal wires sheltered by metal elements, metal alloys or other deposited materials (for example, ceramic coatings).
  • the steel produced according to the present invention contains levels of lanthanides which are enough in order to obtain from 20% to 100% of globular sulfides in the solidified steel.
  • the desired amount of metal wire is metered to the ingot mould or to the tundish, with, in the latter case, particular refractory materials displaying the property of not chemically reacting with lanthanides being used for manufacturing slabs or nozzle bores.
  • globular sulfides are obtained in casehardening and hardening-tempering carbon steels and/or alloy steels with fine austenitic grain structure which contain amounts of sulfur equal to or higher than 0.02% by weight, produced by continuous casting, for use by mechanical industry in general and automobile industry in particular.
  • the above said steels display a fine austenitic grain structure and are obtained by means of the addition of such levels of metal elements, such as aluminum, titanium, niobium, vanadium, or alloys of these elements, that the end level of these elements in steel is higher than 0.015% by weight.
  • the amount of rare earths to be added to the sulfides in the form of metal wire of any shapes (with circular, square, hexagonal cross-section, and so forth), to be added to the tundish or to the ingot mould, is comprised within the range of from 0.05 kg/t to 0.35 kg/t per each 0.01% by weight of sulfur.
  • rare earths as individual elements, or as alloys, in the form of metal wire to the ingot mould makes it possible lanthanides to be perfectly diffused an homogenized on the product and an equally homogeneous distribution of globular sulfides to be obtained throughout the cast section.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Heat Treatment Of Steel (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

Disclosed is a particular type of fine-austenitic-grain globular-sulfides resulfurized carbon and/or alloy steel suitable for casehardening and hardening-tempering treatments, with the addition of transition metals of Group III (rare earth metals or lanthanides), in form of non-coated wire or wire coated with metals, metal alloys or still other coatings, such as ceramic coating or other types of coatings. The addition of rare earths as metal wire to ingot mould or tundish allows rare earth elements to be perfectly diffused and homogenized throughout the product and globular sulfides to be homogeneously distributed as well throughout the cast section; the resulting steel displays better machinability properties than steel produced by means of traditional techniques.

Description

The present invention relates to the relevant process used to obtain an improved resulfurized, fine-austenitic-grain steel.
It is well-known that iron sulfide in steel generates an eutectic phase with metal iron, which displays a melting point at 988°C; therefore, the presence of iron sulfide in steel is harmful because it causes steel to display hot-shortness (i.e., high temperature brittleness) -- and steel forging and rolling temperatures are normally higher than 988°C.
Adding manganese to steel causes manganese sulfides to be formed which do not produce eutectic phases with iron and have higher melting temperatures than steel forging and rolling temperatures.
From technical literature, it is well-known as well that the minimal amount of manganese to be added to steel must, when expressed as percent level, be eight times as high as the percent level of present sulfur, so as to secure that steel will not display hot-shortness.
Manganese sulfides can be present in steel in three characteristic forms and are known as Type 1 sulfides, Type 2 sulfides and, respectively Type 3 sulfides.
Type 1 sulfides display a globular shape and are obtained in the presence of high oxygen levels (see, for example, unkilled steels, semi-killed steels and free-machining steels).
Type 2 sulfides display a dendritic structure and precipitate at the boundaries of the primary solidification grains; they appear in killed steels, with aluminum amounts which are just sufficient to deoxidize steel.
Type 3 sulfides are formed as the levels are increased of aluminum or other elements displaying high affinity for oxygen (titanium or vanadium), until such values are reached as to regulate the austenitic grain.
At present, steels used in the industry of motor vehicles in general and, in particular, in car industry, are resulfurized, fine-austenitic-grain, carbon and alloy steels suitable for casehardening and hardening-tempering treatments, containing additions of aluminum and/or titanium and/or niobium in such amounts as to secure the presence of fine austenitic grains (Type 3 sulfides).
However, it was demonstrated as well that the levels of grain regulating elements necessary for complete steel deoxidizing and for controlling the austenitic grain structure originate sulfides (Type 3 sulfides), which endanger the machinability properties of the resulting steel.
From this viewpoint, the most suitable sulfides for improving the machinability of steel are Type 1 sulfides which, on the other hand, cannot be obtained under such conditions as described in the preceding paragraph.
Consequently, the need arises for the development to be studied of a product which meets both above reminded requirements.
A proposed solution is adding to steel containing Type 3 sulfides, such metal elements as lead or tellurium, which are known to improve the machinability of steel, but are very dangerous for the health of those attending steel production and, then, users during steel processing.
The purpose of the present invention therefore is of providing a process for obtaining a resulfurized, fine-austenitic-grain steel which obviates the above reminded drawbacks and, in particular, can be used by the motor vehicles industry in general and car industry in particular, because it is such as to allow a complete steel deoxidizing, a fine-austenitic-grain structure and a better machinability of steel to be obtained, as compared to the prior art.
Another purpose of the present invention is of providing a process for obtaining a resulfurized, fine-austenitic-grain steel which is not dangerous to the health of those who produce it at the steel factory and use it during the following processing.
Still a further purpose of the present invention is of providing a process for obtaining low cost, improved resulfurized, fine-austenitic-grain steel, without using complex and expensive technologies.
Such purposes are achieved by a process for producing a resulfurized, fine-austenitic-grain steel according to claim 1, to which claim reference is made herein for the sake of brevity.
Advantageously, the addition of rare earths as plain metal wire or as a wire sheltered by metals, metal alloys and other deposited coatings (for example, ceramic coatings), to resulfurized, fine-austenitic-grain carbon steels and alloy steels in ingot mould or in tundish, makes it possible a good diffusion and homogenizing of the product, and a homogeneous distribution of the globular sulfides throughout the cast section, to be obtained.
In such a way, the sulfides contained in steel improve the steel machinability, as compared to the traditional techniques, while simultaneously securing the absence of hot-shortness, the regulation of the austenitic grain and the complete deoxidizing of steel.
According to as discussed hereinabove, adding manganese to steel secures the absence of hot-shortness; the Type 1 manganese sulfides display a globular structure and are obtained in the presence of high oxygen levels, whereas the Type 2 sulfides (which are formed in steels containing minimal amounts of aluminum) display a dendritic structure and precipitate at the boundaries of the primary solidification grains, with the drawback that the resulting steel will display a considerably high hot-shortness.
By increasing the amount of aluminum or other elements which display high affinity for oxygen (such as titanium or vanadium), up to such levels which allow the austenitic grain to be easily regulated (i.e., at values higher than 0.015% by weight), Type 3 sulfides appear which distribute randomly throughout steel with angular and irregular shapes.
After hot rolling, the Type 1 sulfides display a lenticular shape, whilst Type 2 and Type 3 sulfides turn into very thin bands or plaques; this feature of Type 1 sulfides contributes to improve the machinability of steel. In fact, during the machining, the cutting edge of the tool applies a force on its contact region of steel, causing microcracks to be formed in it.
It is evident that the presence of non-metal inclusions considerably reduces the necessary force for generating the microcracks, and the chip shape.
In those cases when the microcracks are such as not to cause the chip to break into fragments, problems will be met during the mechanical machining (turning, drilling).
When, on the contrary, said microcracks succeed in breaking the chip into fragments, the necessary force for creating said microcracks decreases and steel displays a better machinability.
In the subject case, Type 2 and Type 3 sulfides do not cause the chip to break into fragments.
On the contrary, it was observed that, for globular sulfides of Type 1, which display a coarser morphology, a considerably improved machinability of steel is obtained.
At present, the cristallographic form of manganese sulfides can be controlled by means of the addition of transition metals of Group III (lanthanides or rare earths); such an addition results in the formation of globular sulfides, but implies the formation of oxides, which obstruct the continuous casting nozzle bores.
In fact, rare earths display high affinity for oxygen (higher than of aluminum and magnesium), and, if they are present at high levels (0.03%-0.04% by weight), said rare earths undergo oxidation with simultaneously both alumina contained in steel in the form of inclusions and alumina which composes the refractory material of slabs, nozzle bores, and plugs being all reduced to aluminum metal.
Therefore, the continuous casting of steel cannot be performed if one wants to add to the ladle such an amount of rare earths as to completely bind sulfur, i.e., theoretically, an amount of 0.29 kg/t (kilograms per product ton) per each 0.01% by weight of sulfur contained in steel.
According to the present invention, on the contrary, the sulfides of Type 3 can be turned into globular sulfides and continuous casting steels can be obtained which display a better machinability, than corresponding steels known from the prior art.
The lanthanides are added in a sufficient amount to cause sulfides to turn into globular, as plain metal wires, or metal wires sheltered by metal elements, metal alloys or other deposited materials (for example, ceramic coatings).
In particular, the steel produced according to the present invention contains levels of lanthanides which are enough in order to obtain from 20% to 100% of globular sulfides in the solidified steel.
The desired amount of metal wire is metered to the ingot mould or to the tundish, with, in the latter case, particular refractory materials displaying the property of not chemically reacting with lanthanides being used for manufacturing slabs or nozzle bores.
So, globular sulfides are obtained in casehardening and hardening-tempering carbon steels and/or alloy steels with fine austenitic grain structure which contain amounts of sulfur equal to or higher than 0.02% by weight, produced by continuous casting, for use by mechanical industry in general and automobile industry in particular.
The above said steels display a fine austenitic grain structure and are obtained by means of the addition of such levels of metal elements, such as aluminum, titanium, niobium, vanadium, or alloys of these elements, that the end level of these elements in steel is higher than 0.015% by weight.
The presence of the above said metal elements in larger amounts than 0.015% by weight in steel causes, as already mentioned, sulfides (of Type 3) to be formed, the shape of which has a negligible influence on the machinability characteristics of steel.
The amount of rare earths to be added to the sulfides in the form of metal wire of any shapes (with circular, square, hexagonal cross-section, and so forth), to be added to the tundish or to the ingot mould, is comprised within the range of from 0.05 kg/t to 0.35 kg/t per each 0.01% by weight of sulfur.
The addition of rare earths as individual elements, or as alloys, in the form of metal wire to the ingot mould makes it possible lanthanides to be perfectly diffused an homogenized on the product and an equally homogeneous distribution of globular sulfides to be obtained throughout the cast section.
All the more reason, this homogeneousness of distribution is obtained if the addition is performed to tundish.
From the above disclosure, the characteristics will be clear of the improved, resulfurized, fine-austenitic-grain steel and of the process for obtaining it, which process is the subject-matter of the present invention, as well as the advantages thereof will be clear.
In particular, said advantages are represented by:
  • possibility of obtaining simultaneously resulfurized, fine-austenitic-grain, casehardening and hardening-tempering carbon steels and alloy steels which display a highly enough machinability, to be used by the mechanical industry and, in particular, by the automobile industry;
  • reduced costs as compared to the prior art, on considering the obtained advantages.

Claims (3)

  1. A process for obtaining a resulfurized fine-austenitic-grain steel, of the type of carbon steel and alloy steel, produced by continuous casting and suitable for casehardening and hardening-tempering treatments, said steel containing S in amounts equal to or higher than 0.02% by weight, in which said process comprises a first addition of Mn to said steel in amounts equal to or higher than 8 times as high as the value of the sulfur percentage by weight, a second addition of metal elements in a total amount equal to or higher than 0.015% by weight to secure a fine austenitic grain structure and a further addition of rare earths or lanthanides in amounts comprised from 0.05 Kg/t to 0.35 Kg/t per each 0.01% by weight of S, so as to obtain from 20% to 100% of globular sulfides in the solidified steel, wherein said rare earths or lanthanides are added in the form of wires into a continuous casting tundish or into a continuous casting ingot mould.
  2. A process for obtaining a steel as claimed in claim 1, characterised in that said metal elements comprise Al, Ti, Nb, V or their mixtures.
  3. A process for obtaining a steel as claimed in claim 1, characterised in that said wires are non-coated wires or wires coated with metals, metal alloys or ceramic coatings.
EP97203234A 1996-10-25 1997-10-16 Process for obtaining an improved resulfurized fine-austenitic-grain steel Expired - Lifetime EP0838534B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI9730207T SI0838534T1 (en) 1996-10-25 1997-10-16 Process for obtaining an improved resulfurized fine-austenitic-grain steel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI962219 1996-10-25
IT96MI002219A IT1286045B1 (en) 1996-10-25 1996-10-25 IMPROVED RESOLFORATED FINE AUSTENITIC GRAIN STEEL AND RELATED PROCEDURE TO OBTAIN IT

Publications (2)

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EP0838534A1 EP0838534A1 (en) 1998-04-29
EP0838534B1 true EP0838534B1 (en) 2001-07-18

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EP (1) EP0838534B1 (en)
AT (1) ATE203282T1 (en)
DE (1) DE69705691T2 (en)
DK (1) DK0838534T3 (en)
ES (1) ES2160891T3 (en)
GR (1) GR3036834T3 (en)
IT (1) IT1286045B1 (en)
PT (1) PT838534E (en)
SI (1) SI0838534T1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10047642A1 (en) 2000-09-26 2002-04-11 Basf Ag Process for the dehydrogenation of hydrocarbons
DE10060099A1 (en) 2000-12-04 2002-06-06 Basf Ag Regeneration of a dehydrogenation catalyst
DE10150811A1 (en) 2001-10-15 2003-04-24 Basf Ag Dehydrogenation of alkanes, e.g. propane to propene, comprises dehydrogenation of ethylbenzene to styrene to form hydrogen containing waste gas stream and heterogeneous catalyzed dehydrogenation of the alkane mixed with the hydrogen
JP4041511B2 (en) * 2005-10-17 2008-01-30 株式会社神戸製鋼所 Low-carbon sulfur free-cutting steel with excellent machinability
RU2553265C2 (en) 2009-05-20 2015-06-10 Басф Се Monolith catalyst and application thereof

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FR2421948A1 (en) * 1978-04-06 1979-11-02 Pro Chi Met Produits Chim Meta PROCESS FOR THE PREPARATION OF FERROUS ALLOYS SENSITIVELY FREE OF CERIUM, ALLOWING IN PARTICULAR IMPROVEMENT OF THEIR MECHANICAL PROPERTIES THANKS TO THE USE OF LANTHANE, AND FERROUS ALLOYS OBTAINED BY THIS PROCESS
EP0011365A1 (en) * 1978-10-02 1980-05-28 W.A. TYZACK & COMPANY LIMITED Agricultural mould-boards and method for manufacturing same
US4806304A (en) * 1983-05-09 1989-02-21 Daido Tokushuko Kabushiki Kaisha Free cutting steel
JPS6223970A (en) * 1985-07-24 1987-01-31 Nippon Steel Corp Continuously cast low-carbon sulfur-lead free-cutting steel
US4786466A (en) * 1987-02-19 1988-11-22 Frema, Inc. Low-sulfur, lead-free free machining steel alloy
JP2671086B2 (en) * 1992-09-22 1997-10-29 新日本製鐵株式会社 Low carbon sulfur free cutting steel by continuous casting method

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Also Published As

Publication number Publication date
DE69705691T2 (en) 2002-07-04
PT838534E (en) 2001-12-28
DE69705691D1 (en) 2001-08-23
ITMI962219A1 (en) 1998-04-25
DK0838534T3 (en) 2001-11-05
SI0838534T1 (en) 2001-12-31
EP0838534A1 (en) 1998-04-29
IT1286045B1 (en) 1998-07-07
GR3036834T3 (en) 2002-01-31
ATE203282T1 (en) 2001-08-15
ES2160891T3 (en) 2001-11-16

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