EP2380996B1 - Wire for treating metal melts in a steel pan - Google Patents

Wire for treating metal melts in a steel pan Download PDF

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Publication number
EP2380996B1
EP2380996B1 EP20110003415 EP11003415A EP2380996B1 EP 2380996 B1 EP2380996 B1 EP 2380996B1 EP 20110003415 EP20110003415 EP 20110003415 EP 11003415 A EP11003415 A EP 11003415A EP 2380996 B1 EP2380996 B1 EP 2380996B1
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EP
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Prior art keywords
wire
calcium
steel
flux
metal
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EP20110003415
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German (de)
French (fr)
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EP2380996A1 (en
Inventor
V. Rogatkin
V. Kysilenko
D. Dyudkin
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PLUS TRADE AG
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PLUS TRADE AG
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires

Definitions

  • the invention relates to a wire for the treatment of molten metal in a steel pan according to the preamble of claim 1.
  • the invention can be used in metallurgy in the treatment of molten metal in a steel pan (not in an oven) using powdery reactants.
  • a wire for steel ladle treatment of molten metals which consists of a steel shell and an additional component, namely iron powder with an iron-to-calcium ratio of (1.2-3.0) : 1 exists (s. RU 2289631 C1, 15.03.2006 ).
  • This wire is used to convert non-metallic inclusions and to ensure cast steel, especially in the low-silicon assortment.
  • additional reagents are used for metal desulfation.
  • the non-metallic inclusions created during calcium conversion remain largely in the steel.
  • the iron powder in the wire composition is used as a passivating agent.
  • the granulated calcium (eg, Fe Ca 60:40) in the wire is three times as large as the circumference occupied by iron powder.
  • the iron powder acts more as a ballast and much less as a passivating agent and does not ensure a stable calcium intake level.
  • the use of this wire also does not ensure a required level of metal desulfurization.
  • the non-metallic inclusions produced by treatment in the steel pan by means of calcium are also insufficiently removed. All these facts cause an increased calcium fire, a low efficiency and an increased wire consumption.
  • GB 1 494 668 A is a wire known for steel pan treatment of molten metals. This consists of a steel shell and a powder filling. The powder filling consists of calcium and an additional ingredient. As an additional component, a flux with CaO and SiO 2 is provided.
  • the flux used is the molten slag mixture, which additionally comprises C, CaF 2 , Al 2 O 3 , MgO, P 2 O 5 , Na 2 O, K 2 O individually or together in any amount and in any ratio, as well as sintered dolomite or dolomitized lime , Calcium is in the filling composition in the form of metal grains with a pure calcium Ca content of min. 95.0% (weight) present.
  • the composition of the filling is changed.
  • a melt flow is used therein, and an optimum ratio is established both between the filling components and between the constituents of the entire wire.
  • the distinguishing feature of the flux of the disclosed composition is its high flowability and low water absorption capacity.
  • the high flowability of the flux provides for the production of a homogeneous mechanical batch of calcium and flux powder immediately during the manufacture of the powder wire.
  • the trough-shaped profile of a metal strip is filled with calcium and flux.
  • the calcium and the flux are supplied from different containers.
  • Another feature of the flux of the disclosed composition is that it does not contain components that decompose at high temperature, thereby releasing gaseous species. This remarkably reduces dust and gas evolution during the treatment of the melt with the wire according to the invention.
  • the additional presence of C, CaF 2 , Al 2 O 3 , MgO, P 2 O 5 , Na 2 O, K 2 O in the indicated amount in the flux promotes the most efficient course of desulfation, assimilation and removal of non-metallic inclusions.
  • the metal calcium melts in the wire.
  • the melting temperature of calcium is 851 ° C, the evaporation temperature is 1492 ° C).
  • the flux also melts (the melting temperature of the flux having the disclosed composition is 1200 to 1260 ° C, depending on the particular chemical composition). Then, a homogeneous molten mixture with a relatively high melting temperature (over 1200 ° C) is formed which contains liquid calcium.
  • the calcium dissolves in the local area of interaction with calcium and rounds off all non-metallic inclusions.
  • the high sulfide absorptivity flux is a required level for the steel desulfurization process.
  • Such flux properties such as low toughness, high flow, surface and interfacial tension, are intrinsic to non-metallic inclusions and assimilate the calcium-modified inclusions and during the desulfation process resulting sulfides and for their rapid emergence in the slag.
  • the ratio between the flux and calcium (0.2-3.2): 1 makes it possible to synchronize the processes of forming a homogeneous molten and liquid calcium-containing mixture and their release in the steel bath, without causing a calcium vapor formation in the wire or a release of the filling in the solid state in the melt is allowed.
  • the use of such a wire has achieved a considerable increase in calcium utilization efficiency, a reduction in the proportion of non-metallic inclusions in the steel, a reduction in wire consumption, a reduction in the overall cost of steel pan treatment and an increase in the quality of the finished metal.
  • the powder wire is manufactured in the following way.
  • a metal band is formed into a channel-like shell.
  • the shell is metered filled in powdered flux and powdery (granular) metal calcium in the required amount of two containers. These two powders are evenly distributed over the gutter of the shell. Thereafter, the sheath is compressed by means of a roller stand, and a closure is formed.
  • the finished wire is placed on a spool and fed to the respective production areas of the steel treatment.
  • the trial production and application of the wire according to the invention has been carried out in an iron and steel works.
  • the flux to calcium ratio in the powder filling was 1.51: 1.
  • the ratio between the powder filling and the steel shell was,% (wt), 57.4: 42.6.
  • the wire was wound by means of a wire-winding system into the ladle steel pan after equalizing bubbles during a 1008 select steel production.
  • the wire consumption was 180 meters per 130 t pan (0.119 kg Ca / t steel). There were 10 steel treatments done.
  • the calcium content in the finished metal (sample in the continuous casting plant) averaged 0.0030% (min - 0.0025%, max - 0.0035%), the pick-up level - 25.2% (min - 21.0%, max - 29.4%), degree of desulfurization - 34.0% (min - 31.1%, max - 36.9%). All non-metallic inclusions are rounded. The proportion of non-metallic inclusions in the steel was 0.008%.
  • the metal is completely poured off in the continuous casting plant and has exhibited increased casting capabilities and mechanical properties.
  • Comparative treatments have also been carried out in the same iron and steel works.
  • This wire has been used with a calcium and iron powder filling.
  • the filling of the wire ⁇ 13 mm was 236 g / m [calcium - 86 g / m, iron powder - steel sand - 150 g / m] and the iron powder-calcium ratio in the powder filling 1.74: 1.
  • the ratio between the powder filling and the steel shell was 59.5: 40.5.
  • the wire has been inserted into the steel ladle pan after balancing blowing during a 1008 select steel production by means of a wire spooling system.
  • the wire consumption to ensure the same calcium content in the metal was 230 m per 130 t pan (0.152 kg Ca / t steel) and was thus 27.8% higher.
  • the calcium content in the finished metal was on average 0.0030% (min - 0.0012%, max - 0.0035%), the degree of absorption was 19.7% (min - 7,9%, max - 23 , 0%) and the degree of desulfurization 12.0% (min - 6.1%, max - 17.9%).
  • the proportion of non-metallic inclusions in steel was 0.032%. He was 4 times as high as in the testing of the wire according to the invention. Calcium uptake was unstable, sometimes contributing to incomplete rounding of non-metallic inclusions. In addition to the high content of inclusions in the steel, this caused an increase in rejects during metal casting in the continuous casting plant and a loss of quality in the finished metal.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Steel In Its Molten State (AREA)

Description

Die Erfindung betrifft einen Draht zur Behandlung von Metallschmelzen in einer Stahlpfanne nach dem Oberbegriff des Anspruchs 1.The invention relates to a wire for the treatment of molten metal in a steel pan according to the preamble of claim 1.

Die Erfindung ist in der Eisenhüttenkunde und zwar bei der Behandlung von Metallschmelzen in einer Stahlpfanne (nicht in einem Ofen) unter Einsatz von pulverartigen Reaktionsmitteln einsetzbar.The invention can be used in metallurgy in the treatment of molten metal in a steel pan (not in an oven) using powdery reactants.

Zur Zeit wird bei der Behandlung des flüssigen Stahls in einer Stahlpfanne ein Draht zur Stahlpfanne-Behandlung von Metallschmelzen verwendet, welcher aus einer Stahlhülle und einer zusätzlichen Komponente, nämlich Eisenpulver mit einem Eisen-Kalzium- Verhältnis von (1,2 - 3,0) : 1 besteht (s. RU 2289631 C1, 15.03.2006 ). Dieser Draht ist zur Umwandlung von nichtmetallischen Einschlüssen und zur Sicherstellung einer Stahlgießbarkeit insbesondere beim siliziumarmen Sortiment benutzt. In diesem Fall sind zusätzliche Reagenzien zwecks Metalldesulfierung eingesetzt. Die bei der Kalziumumwandlung entstehenden nichtmetallischen Einschlüsse bleiben weitgehend im Stahl. Das Eisenpulver in der Drahtzusammensetzung ist als Passivierungsmittel verwendet. Da die Schüttmassen von gekörntem Kalzium und Eisenpulver (Eisensand) sich um das 4- bis 5-fache unterscheiden, ist der durch gekörntes Kalzium (z. B. Fe Ca 60 : 40) im Draht eingenommene Umfang dreimal so groß wie der Umfang, welcher durch Eisenpulver besetzt ist. In diesem Fall wirkt das Eisenpulver eher als Ballast und viel weniger als Passivierungsmittel und stellt keinen stabilen Kalziumaufnahmegrad sicher. Die Verwendung dieses Drahts stellt auch kein erforderliches Niveau der Metalldesulfierung sicher. Die bei der Behandlung in der Stahlpfanne mittels Kalziums entstehenden nichtmetallischen Einschlüsse sind auch ungenügend entfernt. Alle diese Tatsachen bedingen einen erhöhten Kalziumbrand, einen niedrigen Nutzungsgrad und einen erhöhten Drahtverbrauch.At present, in the treatment of liquid steel in a steel ladle, a wire for steel ladle treatment of molten metals is used, which consists of a steel shell and an additional component, namely iron powder with an iron-to-calcium ratio of (1.2-3.0) : 1 exists (s. RU 2289631 C1, 15.03.2006 ). This wire is used to convert non-metallic inclusions and to ensure cast steel, especially in the low-silicon assortment. In this case, additional reagents are used for metal desulfation. The non-metallic inclusions created during calcium conversion remain largely in the steel. The iron powder in the wire composition is used as a passivating agent. Since the bulk solids of granular calcium and iron powder (iron sand) differ 4 to 5 times, the granulated calcium (eg, Fe Ca 60:40) in the wire is three times as large as the circumference occupied by iron powder. In this case, the iron powder acts more as a ballast and much less as a passivating agent and does not ensure a stable calcium intake level. The use of this wire also does not ensure a required level of metal desulfurization. The non-metallic inclusions produced by treatment in the steel pan by means of calcium are also insufficiently removed. All these facts cause an increased calcium fire, a low efficiency and an increased wire consumption.

Durch GB 1 494 668 A ist ein Draht zur Stahlpfanne-Behandlung von Metallschmelzen bekannt. Dieser besteht aus einer Stahlhülle und einer Pulverfüllung. Die Pulverfüllung besteht aus Kalzium und einem zusätzlichen Bestandteil. Als zusätzlicher Bestandteil ist ein Flussmittel mit CaO und Si02 vorgesehen.By GB 1 494 668 A is a wire known for steel pan treatment of molten metals. This consists of a steel shell and a powder filling. The powder filling consists of calcium and an additional ingredient. As an additional component, a flux with CaO and SiO 2 is provided.

Es ist Aufgabe der Erfindung, den Draht zur Stahlpfanne-Behandlung von Metallschmelzen zu verbessern.It is an object of the invention to improve the wire for steel ladle treatment of molten metals.

Die gestellte Aufgabe wird durch die Merkmale des Anspruchs 1 gelöst.The stated object is solved by the features of claim 1.

Der Draht zur Stahlpfanne-Behandlung von Metallschmelzen besteht aus einer Stahlhülle und einer Pulverfüllung. Die Pulverfüllung weist Kalzium und einen zusätzlichen Bestandteil auf. Als zusätzlicher Bestandteil ist ein Flussmittel mit einem CaO-Gehalt von ≥ 45,0% (Gew.), SiO2 ≤ 15.0% (Gew.) und Basizität (CaO/SiO2) ≥ 3,2 eingesetzt. Das Mengenverhältnis zwischen dem Flussmittel und Kalzium in der Pulverfüllung liegt im Bereich von (0,2-3,2) : 1. Das Verhältnis zwischen den Drahtbestandteilen ist folgenderweise festgelegt, % (Gew.):

  • Pulverfüllung    25 - 60
  • Stahlhülle    40 - 75.
The wire for steel pan treatment of molten metals consists of a steel shell and a powder filling. The powder filling contains calcium and an additional ingredient. As an additional ingredient is a flux with a CaO content of ≥ 45.0% (wt), SiO 2 ≤ 15.0% (wt) and basicity (CaO / SiO 2 ) ≥ 3.2. The ratio between the flux and calcium in the powder filling is in the range of (0.2-3.2): 1. The ratio between the wire components is set as follows,% (wt):
  • Powder filling 25 - 60
  • Steel cover 40 - 75.

Als Flussmittel ist die geschmolzene Schlackenmischung eingesetzt, die zusätzlich C, CaF2, Al2O3, MgO, P2O5, Na2O, K2O einzeln oder zusammen in beliebiger Menge und im beliebigen Verhältnis sowie Sinterdolomit oder dolomitisierten Kalk aufweist. Kalzium ist in der Füllungszusammensetzung in Form von Metallkörnern mit einem Reinkalziumgehalt Ca von min. 95,0% (Gew.) präsent.The flux used is the molten slag mixture, which additionally comprises C, CaF 2 , Al 2 O 3 , MgO, P 2 O 5 , Na 2 O, K 2 O individually or together in any amount and in any ratio, as well as sintered dolomite or dolomitized lime , Calcium is in the filling composition in the form of metal grains with a pure calcium Ca content of min. 95.0% (weight) present.

Dabei ist die Zusammensetzung der Füllung verändert. Als zusätzlicher Bestandteil ist darin ein Schmelzfluss benutzt, und es ist ein optimales Verhältnis sowohl zwischen den Füllungskomponenten als auch zwischen den Bestandteilen des gesamten Drahts festgelegt.The composition of the filling is changed. As an additional constituent, a melt flow is used therein, and an optimum ratio is established both between the filling components and between the constituents of the entire wire.

Die Lösung dieser Aufgabe ermöglicht es, je nach Eintauchen des Drahts in das Metallbad

  • die homogene Mischschmelze mit einer relativ hohen Schmelztemperatur (über 1200° C) im Draht schnell zu bilden,
  • die Temperatur des zu behandelnden Metalls im lokalen Zusammenwirkungsbereich zu verringern,
  • die Vorgänge zur Bildung der Mischung im Draht sowie zur Freisetzung der Mischung in der Schmelze zu synchronisieren,
  • den Stahldesulfierungsgrad zu steigern,
  • gleichzeitig eine Umwandlung von nichtmetallischen Einschlüssen, ihre Assimilation durch das geschmolzene Flussmittel und ein schnelles Auftauchen in der Schlacke sicherzustellen.
The solution to this problem allows, depending on the immersion of the wire in the metal bath
  • rapidly forming the homogeneous mixed melt with a relatively high melting temperature (above 1200 ° C) in the wire,
  • to reduce the temperature of the metal to be treated in the local area of interaction,
  • to synchronize the processes to form the mixture in the wire and to release the mixture in the melt,
  • to increase the degree of steel desulfation,
  • to ensure at the same time a conversion of non-metallic inclusions, their assimilation by the molten flux and a rapid appearance in the slag.

Das ermöglicht es, die Einsatzwirksamkeit von Kalzium wesentlich zu steigern, den Gehalt an nichtmetallischen Einschlüssen im Stahl zu verringern, den Drahtverbrauch und die Gesamtkosten für die Pfannenbehandlung zu vermindern sowie die Metallqualität zu verbessern.This makes it possible to substantially increase the potency of calcium, to reduce the content of non-metallic inclusions in the steel, to reduce the wire consumption and the total cost of the ladle treatment and to improve the metal quality.

Die kennzeichnende Besonderheit des Flussmittels mit der offenbarten Zusammensetzung ist seine hohe Fließfähigkeit und sein niedriges Wasseraufnahmevermögen. Die hohe Fließfähigkeit des Flussmittels sorgt für die Herstellung von einem homogenen mechanischen Gemenge von Kalzium- und Flussmittelpulver unmittelbar während der Fertigung des Pulverdrahts. Bei der Pulverdrahtfertigung ist das rinnenförmige Profil aus einem Metallband mit Kalzium und Flussmittel gefüllt. Das Kalzium und das Flussmittel sind aus verschiedenen Behältern zugeführt. Ein weiteres Merkmal des Flussmittels mit der offenbarten Zusammensetzung besteht darin, dass es keine Komponenten enthält, welche bei hoher Temperatur zerfallen und dabei gasförmige Stoffe freisetzen. Das vermindert beachtlich eine Staub- und eine Gasentwicklung während der Behandlung der Schmelze mit dem erfindungsgemäßen Draht. Diese Eigenschaften des Flussmittels mit der offenbarten Zusammensetzung ermöglichen es, das Flussmittel als Kalzium-Passivierungsmittel zu benutzen, so dass die gestellte technische Aufgabe gelöst ist. Darüber hinaus ist ein Flussmittel mit CaO-Gehalt von ≥ 45,0% (Gew.), SiO2 ≤ 15,0% (Gew.) und Basizität (CaO/SiO2) ≥ 3,2 selbst ein gutes Desulfierungsmittel für flüssigen Stahl, und der Schwefel aus der Schmelze ist entfernt. Folglich nimmt die Einsatzwirksamkeit von Kalzium zu. Der Einsatz dieses Flussmittels als Bestandteil des Drahts ermöglicht es auch, während der Behandlung mit Kalzium neben einer Umwandlung von nichtmetallischen Einschlüssen gleichzeitig ihre Assimilation als auch die Assimilation von den entstehenden Sulfiden durchzuführen. Das stellt seinerseits ihr stabiles Auftauchen in der Schlacke sicher. Das zusätzliche Vorhandensein von C, CaF2, Al2O3, MgO, P2O5, Na2O, K2O in der angegebenen Menge im Flussmittel fördert den wirksamsten Verlauf des Desulfierungsvorgangs, die Assimilation und die Entfernung der nichtmetallischen Einschlüsse. Je nach Eintauchen des Drahts in die flüssige Schmelze (Stahlbad) schmilzt das metallene Kalzium im Draht ab. (Die Schmelztemperatur von Kalzium beträgt 851° C, die Verdampfungstemperatur ist 1492° C). Danach schmilzt auch das Flussmittel (die Schmelztemperatur des Flussmittels mit der offenbarten Zusammensetzung ist 1200 bis 1260° C je nach der jeweiligen chemischen Zusammensetzung). Dann ist eine homogene geschmolzene Mischung mit einer relativ hohen Schmelztemperatur (über 1200° C) gebildet, die flüssiges Kalzium enthält. Das Kalzium löst sich im lokalen Bereich der Zusammenwirkung mit Kalzium auf und rundet alle nichtmetallischen Einschlüsse ab. Zugleich stellt das eine hohe Sulfidaufnahmefähigkeit aufweisende Flussmittel ein erforderliches Niveau für den Desulfierungsvorgang für Stahl dar. Solche Eigenschaften des Flussmittels, wie niedrige Zähigkeit, hohe Fließfähigkeit, Oberflächen- und Grenzflächenspannung, sind nichtmetallischen Einschlüssen eigen und sorgen für eine Assimilation der kalziummodifizierten Einschlüsse und der während des Desulfierungsvorgangs entstehenden Sulfide sowie für ihr schnelles Auftauchen in der Schlacke. Das festgelegte Verhältnis zwischen der Menge der Pulverfüllung und der Masse der Stahlhülle (25 - 60) : (40 - 75), % (Gew.) stellt eine erforderliche Drahtsteifigkeit für die Drahteinspulung auf ausreichende Tiefe in die tieferen Schichten von Flüssigmetall in der Pfanne sicher. Damit schmilzt die gesamte Ca-Menge und scheidet sich in das Stahlbad im geschmolzenen Zustand aus. Die Reaktion der Zusammenwirkung zwischen dem Kalzium und der Schmelze muss den größtmöglichen Metallumfang abdecken. Die Abweichung von diesem Verhältnis wird führt einerseits dazu, dass das Kalzium noch vor der Hüllenabschmelzung im Draht in den Dampfzustand übergeht. Dies benachteiligt seine Ausnutzungseffektvitätswerte wesentlich. Andererseits führt das zu einem erhöhten Drahtverbrauch. Das Verhältnis zwischen dem Flussmittel und Kalzium (0,2 - 3,2) :1 ermöglicht es, die Prozesse der Bildung einer homogenen geschmolzenen und flüssiges Kalzium enthaltenden Mischung und ihre Freisetzung im Stahlbad zeitlich zu synchronisieren, ohne dass dabei eine Kalziumdampfbildung im Draht oder eine Freisetzung der Füllung im Festzustand in die Schmelze zugelassen wird. Beim Einsatz eines solchen Drahts ist eine beachtliche Steigerung der Kalziumnutzungseffektivität, eine Reduzierung des Anteils von nichtmetallischen Einschlüssen im Stahl, eine Minderung des Drahtverbrauchs, eine Senkung der Gesamtkosten bei der Stahlpfanne-Behandlung sowie eine Qualitätssteigerung des Fertigmetalls erreicht. Um den Drahtverbrauch zu optimieren, ist als Flussmittel mit einem CaO-Gehalt ≥ 45,0% (Gew.), SiO2 ≤ 15,0% (Gew.) und einer Basizität (CaO/SiO2) ≥ 3,2 eine geschmolzene Schlackenmischung verwendet, die zusätzlich C, CaF2, Al2O3, MgO, P2O5, Na2O, K2O einzeln oder zusammen in beliebiger Menge und im beliebigen Verhältnis sowie Sinterdolomit oder dolomitisierten Kalk aufweist. In der Füllungszusammensetzung ist Kalzium in Form von Metallkörnern mit einem Reinkalziumgehalt Ca von min. 95,0% (Gew.) verwendet.The distinguishing feature of the flux of the disclosed composition is its high flowability and low water absorption capacity. The high flowability of the flux provides for the production of a homogeneous mechanical batch of calcium and flux powder immediately during the manufacture of the powder wire. In powder wire manufacturing, the trough-shaped profile of a metal strip is filled with calcium and flux. The calcium and the flux are supplied from different containers. Another feature of the flux of the disclosed composition is that it does not contain components that decompose at high temperature, thereby releasing gaseous species. This remarkably reduces dust and gas evolution during the treatment of the melt with the wire according to the invention. These properties of the flux having the disclosed composition make it possible to use the flux as a calcium passivating agent, so that the stated technical problem is solved. In addition, a flux with CaO content of ≥ 45.0% (wt), SiO 2 ≤ 15.0% (wt) and basicity (CaO / SiO 2 ) ≥ 3.2 is itself a good desulfating agent for liquid steel , and the sulfur from the melt is removed. As a result, the potency of calcium increases. The use of this flux as a constituent of the wire also makes it possible, during the treatment with calcium, to perform not only a conversion of non-metallic inclusions but also their assimilation as well as the assimilation of the resulting sulphides. This in turn ensures their stable emergence in the slag. The additional presence of C, CaF 2 , Al 2 O 3 , MgO, P 2 O 5 , Na 2 O, K 2 O in the indicated amount in the flux promotes the most efficient course of desulfation, assimilation and removal of non-metallic inclusions. Depending on the immersion of the wire into the liquid melt (steel bath), the metal calcium melts in the wire. (The melting temperature of calcium is 851 ° C, the evaporation temperature is 1492 ° C). Thereafter, the flux also melts (the melting temperature of the flux having the disclosed composition is 1200 to 1260 ° C, depending on the particular chemical composition). Then, a homogeneous molten mixture with a relatively high melting temperature (over 1200 ° C) is formed which contains liquid calcium. The calcium dissolves in the local area of interaction with calcium and rounds off all non-metallic inclusions. At the same time, the high sulfide absorptivity flux is a required level for the steel desulfurization process. Such flux properties, such as low toughness, high flow, surface and interfacial tension, are intrinsic to non-metallic inclusions and assimilate the calcium-modified inclusions and during the desulfation process resulting sulfides and for their rapid emergence in the slag. The fixed relationship between the amount of powder filling and the mass of the steel shell (25-60): (40-75),% (wt) ensures a required wire stiffness for wire winding to sufficient depth into the deeper layers of liquid metal in the pan , This melts the entire amount of Ca and separates out into the steel bath in the molten state. The reaction of the interaction between the calcium and the melt must cover the largest possible metal circumference. The deviation from this ratio leads on the one hand to the fact that the calcium goes into the vapor state before the enamel is melted in the wire. This significantly penalizes its utilization efficiency values. On the other hand, this leads to increased wire consumption. The ratio between the flux and calcium (0.2-3.2): 1 makes it possible to synchronize the processes of forming a homogeneous molten and liquid calcium-containing mixture and their release in the steel bath, without causing a calcium vapor formation in the wire or a release of the filling in the solid state in the melt is allowed. The use of such a wire has achieved a considerable increase in calcium utilization efficiency, a reduction in the proportion of non-metallic inclusions in the steel, a reduction in wire consumption, a reduction in the overall cost of steel pan treatment and an increase in the quality of the finished metal. To optimize the wire consumption is as a flux with a CaO content ≥ 45.0% (wt), SiO 2 ≤ 15.0% (wt) and basicity (CaO / SiO 2 ) ≥ 3.2 used a molten slag mixture containing additionally C, CaF 2 , Al 2 O 3 , MgO, P 2 O 5 , Na 2 O, K 2 O individually or together in any amount and in any ratio as well as sintered dolomite or dolomitized lime. In the filling composition calcium is in the form of metal grains with a pure calcium Ca content of min. 95.0% (wt) used.

Der Pulverdraht wird auf folgende Weise gefertigt. Ein Metallband ist zu einer rinnenähnlichen Hülle geformt. Die Hülle ist mit pulverartigem Flussmittel und pulverartigem (gekörntem) Metallkalzium in erforderlicher Menge aus zwei Behältern dosiert einsatzweise gefüllt. Diese zwei Pulver werden gleichmäßig über die Rinne der Hülle verteilt. Danach ist die Hülle mittels eines Rollengerüsts gestaucht, und ein Verschluss ist ausgebildet. Der fertige Draht ist auf eine Spule gebracht und den jeweiligen Produktionsbereichen der Stahlbehandlung zugeführt.The powder wire is manufactured in the following way. A metal band is formed into a channel-like shell. The shell is metered filled in powdered flux and powdery (granular) metal calcium in the required amount of two containers. These two powders are evenly distributed over the gutter of the shell. Thereafter, the sheath is compressed by means of a roller stand, and a closure is formed. The finished wire is placed on a spool and fed to the respective production areas of the steel treatment.

Die Probeproduktion und -anwendung des erfindungsgemäßen Drahts ist in einem Eisenhüttenwerk durchgeführt worden. Die Füllung des Draht mit ∅ 13 mm umfasste 216 g/m (gekörntes) Kalzium, 86 g/m Flussmittel [CaO-Gehalt = 52,0% (Gew.), SiO2 = 12,0% (Gew.), Basizität (CaO/SiO2) = 4,33) - 130 g/m]. Das Flussmittel-Kalzium-Verhältnis in der Pulverfüllung war 1,51 : 1. Das Verhältnis zwischen der Pulverfüllung und der Stahlhülle betrug, % (Gew.), 57,4 : 42,6. Der Draht wurde mittels eines Drahteinspulsystems in die Stahlpfanne im Pfannenofen nach dem Ausgleichsblasen während einer 1008-Select-Stahlproduktion eingespult. Der Drahtverbrauch betrug 180 Meter pro eine 130 t Pfanne (0,119 kg Ca/t von Stahl). Es wurden 10 Stahlbehandlungen vorgenommen. Der Kalziumgehalt im Fertigmetall (Probe in der Stranggussanlage) betrug durchschnittlich 0,0030% (min. - 0,0025 %, max. - 0,0035 %), der Aufnahmegrad - 25,2% (min. - 21,0%, max. - 29,4%), der Desulfierungsgrad - 34,0% (min. - 31,1%, max. - 36,9%). Alle nichtmetallischen Einschlüsse sind abgerundet. Der Anteil der nichtmetallischen Einschlüsse im Stahl betrug 0,008%. Das Metall ist in der Stranggussanlage völlig abgegossen und hat erhöhte Gießfähigkeiten und mechanische Eigenschaften aufgewiesen.The trial production and application of the wire according to the invention has been carried out in an iron and steel works. The filling of the mit 13 mm wire included 216 g / m (grained) calcium, 86 g / m flux [CaO content = 52.0% (wt), SiO 2 = 12.0% (wt), basicity (CaO / SiO 2 ) = 4.33) - 130 g / m]. The flux to calcium ratio in the powder filling was 1.51: 1. The ratio between the powder filling and the steel shell was,% (wt), 57.4: 42.6. The wire was wound by means of a wire-winding system into the ladle steel pan after equalizing bubbles during a 1008 select steel production. The wire consumption was 180 meters per 130 t pan (0.119 kg Ca / t steel). There were 10 steel treatments done. The calcium content in the finished metal (sample in the continuous casting plant) averaged 0.0030% (min - 0.0025%, max - 0.0035%), the pick-up level - 25.2% (min - 21.0%, max - 29.4%), degree of desulfurization - 34.0% (min - 31.1%, max - 36.9%). All non-metallic inclusions are rounded. The proportion of non-metallic inclusions in the steel was 0.008%. The metal is completely poured off in the continuous casting plant and has exhibited increased casting capabilities and mechanical properties.

In demselben Eisenhüttenwerk sind auch Vergleichsbehandlungen durchgeführt worden. Dabei ist Draht mit einer Kalzium- und Eisenpulverfüllung eingesetzt worden. Die Füllung des Drahts ∅ 13 mm betrug 236 g/m [Kalzium - 86 g/m, Eisenpulver - Stahlsand - 150 g/m] und das Eisenpulver-Kalzium-Verhältnis in der Pulverfüllung 1,74 : 1. Das Verhältnis zwischen der Pulverfüllung und der Stahlhülle betrug 59,5 : 40,5. Der Draht ist mittels eines Drahteinspulsystems in die Stahlpfanne im Pfannenofen nach dem Ausgleichsblasen während einer 1008-Select-Stahlproduktion eingeführt worden. Der Drahtverbrauch zur Sicherstellung des gleichen Kalziumgehalts im Metall betrug 230 m pro 130 t Pfanne (0,152 kg Ca/t Stahl) und war somit um 27,8% höher. Der Kalziumgehalt im Fertigmetall betrug dabei auch durchschnittlich 0,0030% (min. - 0,0012%, max. - 0,0035%), der Aufnahmegrad war 19,7% (min. - 7,9%, max. - 23,0%) und der Desulfierungsgrad 12,0% (min. - 6,1%, max. - 17,9%). Der Anteil von nichtmetallischen Einschlüssen im Stahl betrug 0,032%. Er war 4-mal so hoch wie bei der Erprobung des erfindungsgemäßen Drahts. Die Kalziumaufnahme war unstabil, was manchmal zur unvollständigen Abrundung der nichtmetallischen Einschlüsse beitrug. Neben dem zu hohen Gehalt an Einschlüssen im Stahl verursachte das eine Erhöhung des Ausschusses beim Metallgießen in der Stranggussanlage und einen Qualitätsverlust beim Fertigmetall.Comparative treatments have also been carried out in the same iron and steel works. This wire has been used with a calcium and iron powder filling. The filling of the wire ∅ 13 mm was 236 g / m [calcium - 86 g / m, iron powder - steel sand - 150 g / m] and the iron powder-calcium ratio in the powder filling 1.74: 1. The ratio between the powder filling and the steel shell was 59.5: 40.5. The wire has been inserted into the steel ladle pan after balancing blowing during a 1008 select steel production by means of a wire spooling system. The wire consumption to ensure the same calcium content in the metal was 230 m per 130 t pan (0.152 kg Ca / t steel) and was thus 27.8% higher. The calcium content in the finished metal was on average 0.0030% (min - 0.0012%, max - 0.0035%), the degree of absorption was 19.7% (min - 7,9%, max - 23 , 0%) and the degree of desulfurization 12.0% (min - 6.1%, max - 17.9%). The proportion of non-metallic inclusions in steel was 0.032%. He was 4 times as high as in the testing of the wire according to the invention. Calcium uptake was unstable, sometimes contributing to incomplete rounding of non-metallic inclusions. In addition to the high content of inclusions in the steel, this caused an increase in rejects during metal casting in the continuous casting plant and a loss of quality in the finished metal.

Claims (4)

  1. A wire for steel-ladle treatment of metal melts, comprising a steel casing and a powder filling, in which
    - the powder filling comprises calcium and an additional ingredient, and
    - as the additional ingredient, a fluxing agent CaO and SiO2 is used,
    characterized in that
    - a fluxing agent with a CaO content ≥ 45.0% (by weight), an SiO2 content ≤ 15.0% (by weight), and a basicity (CaO/SiO2) ≥ 3.2 are used;
    - the quantitative ratio between the fluxing agent and the calcium in the powder mixture is in the range from (0.2 - 3.2):1; and
    - the ratio between the wire ingredients in % (by weight) is defined as follows: powder filling 25 - 60 steel casing 40 - 75.
  2. The wire according to claim I,
    characterized in that
    as the fluxing agent, a molten slag mixtures is used; and
    that this mixture additionally has C, CaF2, Al2O3, MgO, P2O5, Na2O, K2O*, individually or together in an arbitrary quantity and in an arbitrary ratio.
  3. The wire according to claim 1,
    characterized in that
    as the fluxing agent, sintered dolomite or dolomitized lime is used.
  4. The wire according to claim 1,
    characterized in that
    calcium in the filling composition is used in the form of metal granules with a pure-calcium content Ca of at least 95.0% (by weight).
EP20110003415 2010-04-26 2011-04-26 Wire for treating metal melts in a steel pan Not-in-force EP2380996B1 (en)

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CN110484808B (en) * 2019-09-04 2020-10-27 鞍钢股份有限公司 Method for improving castability of phosphorus-containing ultra-low carbon steel

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Publication number Priority date Publication date Assignee Title
GB1494668A (en) * 1975-06-05 1977-12-07 Sumitomo Metal Ind Process for the addition of calcium to molten steel
US5397379A (en) * 1993-09-22 1995-03-14 Oglebay Norton Company Process and additive for the ladle refining of steel
JP3827010B2 (en) * 2002-12-26 2006-09-27 トピー工業株式会社 LF treatment method without fluorite
RU2289631C1 (en) 2006-03-15 2006-12-20 Открытое Акционерное Общество "Завод "Универсальное Оборудование" Wire for out-of-furnace treatment of metallurgical melts

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