GB2067985A - Refractory Materials - Google Patents

Refractory Materials Download PDF

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Publication number
GB2067985A
GB2067985A GB8100458A GB8100458A GB2067985A GB 2067985 A GB2067985 A GB 2067985A GB 8100458 A GB8100458 A GB 8100458A GB 8100458 A GB8100458 A GB 8100458A GB 2067985 A GB2067985 A GB 2067985A
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GB
United Kingdom
Prior art keywords
pref
refractory
silicon
steel
binding agent
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.)
Granted
Application number
GB8100458A
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GB2067985B (en
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Vodafone GmbH
Original Assignee
Mannesmann AG
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Filing date
Publication date
Application filed by Mannesmann AG filed Critical Mannesmann AG
Publication of GB2067985A publication Critical patent/GB2067985A/en
Application granted granted Critical
Publication of GB2067985B publication Critical patent/GB2067985B/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/50—Pouring-nozzles
    • B22D41/52—Manufacturing or repairing thereof
    • B22D41/54—Manufacturing or repairing thereof characterised by the materials used therefor
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/482—Refractories from grain sized mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0087—Uses not provided for elsewhere in C04B2111/00 for metallurgical applications
    • C04B2111/00887—Ferrous metallurgy
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/386—Boron nitrides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • C04B2235/9676—Resistance against chemicals, e.g. against molten glass or molten salts against molten metals such as steel or aluminium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Ceramic Products (AREA)

Abstract

A refractory ceramic material comprising a base (e.g. Al2O3, ZrO2, SiO2) with carbon and a binding agent, also comprises 5-15 wt % of calcium silicon, ferrosilicon and/or boron nitride.

Description

SPECIFICATION Refractory Ceramic Materials This invention relates to refractory ceramic materials for use in the casting of steels, and to the problem of agglomeration of oxidic compounds precipitated from molten steel on the refractory material in the casting process.
In the production of aluminium-killed steels, alumina occurs as a solid oxidic phase in the liquid steel after the deoxidisation and alloying of tbe crude steel. In the continuous casting of steel, a submerged outlet of refractory material is situated between the distributing vessel and the mould. On flowing through the outlet, some of the alumina present in the liquid steel is precipitated on the outlet; large alumina agglomerates are formed, which from time to time are carried away by the flowing steel and, when the steel solidifies, form inclusions therein.
Hitherto known submerged outlets are composed of refractory mixtures comprising one or more refractory oxides (Al203, SiO2,ZrO2and the like), carbon (graphite, coke, carbon black) and a binding agent. These compositions are not effective in preventing the depositing of alumina particles from the steel.
The invention has as its aim the provision of a refractory ceramic mixture for the production of submerged outlets, or other shaped or moulded components in contact with liquid steel, which inhibit the deposition of oxidic suspensions, more particularly alumina, which are present in the liquid steel and which have a tendency to agglomeration, on surfaces of the components which come into contact with the liquid steel. We have found that this can be accomplished by including certain materials in the refractory material.
Accordingly, the invention provides a refractory ceramic material having a base comprising carbon and a binding agent, and including 5% to 15% by weight of at least one of calcium silicon (met.), ferro-silicon (met.), and boron nitride. Using materials of the invention solid oxidic suspensions (e.g. alumina) present in the steel at the phase transition between steel and refractory part undergo a lowering of their melting points on contact with the refractory material with the result that at first solid alumina particles (typically of around 1 to 30 ,um in diameter) liquefy after contact with the refractory material and thus do not remain adherant thereto.
The substance which acts on the suspension in the refractory part forms with the suspension an oxidic melt i.e., the melting point of this slag is below the operating temperature of the steel. The appended examples list possible embodiments of refractory mixtures according to the invention.
Example 1 consists of corundum, graphite, calcium silicon and binding agent. The metallic calcium and silicon present in the mixture, or calcium silicon present as alloy, is matallically stable. This stable state is achieved through the relatively low temperature of the refractory mixture as compared with the steel temperature and reducing conditions provided through the presence of carbon.
These reducing conditions are transformed into oxidising conditions at the interphase boundaries refractory mixture -- air; refractory mixture liquid steel). At the air -- refractory phase boundary the metallic constituent is oxidised after gradual carbon burn-off, and forms and oxidic mixed phase with the basic mixture. This mixed phase is in fact subjected to a lowering of melting point, but not to any eroding force, so that removal of material and therefore wear does not occur.
After the carbon burn an oxidation begins of the metallic constituent (calcium, silicon, calcium silicon) with Al -killed steel at the phase boundary between refractory and liquid steel. This oxidation can occur since in the case of Al -killed steel calcium further has a deoxidising effect. The calcium silicon mixed oxide forming has a melting point lowering effect on alumina at the phase transition, and results in a mixed oxide which is liquid at the phase boundary (slag film). This slag film is then carried by the eroding action of the flowing steel into the bath in the mould. Here the slag is in spheroidal form and can be separated out.
The phenomen brought about with the present invention results in a deliberate internal wear at the refractory wall, and obviates the depositing of alumina on this wall. The wall thickness and the composition of the refractory mixture must be related to the intended pouring time.
A further example of use (see Example 2) can be Bled, which is not stable under oxidising conditions and forms B203 and is a liquefier for alumina (present as suspension in steel), and has a similar effect to that indicated in the case of Example 1.
Moreover the erosion in the slag region can be counter-acted by an already known mixture composition including zirconium oxide (Example 3).
It is also possible to replace the alumina by quartz glass (Examples 4 and 5).
Example 1 4070% pref. 60% corundum 5-1 5% pref. 10% calcium silicon 1 5-30% phef. 25% graphite 5-15% pref, 5% binding agent Example 2 4070% pref. 60% corundum 5-1 5% pref. 10% boron nitride 1 5-30% pref. 25% graphite 5-1 5% pref. 5% binding agent Example 3 4070% pref. 60% zirconium oxide 15-30% pref. 25% graphite 515% pref. 10% ferro-silicon 5-1 5% pref. 5% binding agent Example 4 40--70% pref. 60% quartz glass 5-15% pref. 10% calcium silicon 1 5-30% pref. 25% graphite 5--15% pref. 5% binding agent Example 5 40-70% pref. 60% quartz glass 5--15% pref. 10% boron nitride 1 5-30% pref. 25% graphite 5-15% pref. 5% binding agent Example 6 40--70% pref. 60% corundum 515% pref. 5% calcium silicon 5--15% pref. 5% boron nitride 5-1 5b/0 pref. 5% ferro-silicon 15--30% pref. 20% graphite 5-15% pref. 5% binding agent.

Claims (4)

Claims
1. A refractory ceramic material having a base comprising carbon and a binding agent, and including 5% to 15% by weight of at least one of calcium silicon (met.), ferro-silicon (met.), and boron nitride.
2. A material according to Claim 1 wherein the total amount of said at least one of calcium silicon (met.), ferro-silicon (met.), and boron nitride is in the range 5% to 15% by weight.
3. A material according to Claim 1 or Claim 2 wherein the base comprises one of aluminium oxide, zirconium oxide, and silicon dioxide.
4. A refractory material substantially as described in any of the Examples herein.
GB8100458A 1980-01-25 1981-01-08 Refractory materials Expired GB2067985B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE3003046A DE3003046C2 (en) 1980-01-25 1980-01-25 Refractory ceramic mass

Publications (2)

Publication Number Publication Date
GB2067985A true GB2067985A (en) 1981-08-05
GB2067985B GB2067985B (en) 1983-08-24

Family

ID=6093148

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8100458A Expired GB2067985B (en) 1980-01-25 1981-01-08 Refractory materials

Country Status (4)

Country Link
JP (1) JPS56109868A (en)
DE (1) DE3003046C2 (en)
FR (1) FR2474481A1 (en)
GB (1) GB2067985B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2572724A1 (en) * 1984-11-02 1986-05-09 Didier Werke Ag REFRACTORY WEAR PIECE FOR DRAINING LIQUID MASS MASSES
EP0256217A2 (en) * 1986-08-12 1988-02-24 Didier-Werke Ag Submerged casting pipe and its manufacturing process
FR2609419A1 (en) * 1987-01-14 1988-07-15 Intracon Handel Indbedarf Bottom tap-hole closure material
US5171495A (en) * 1988-08-12 1992-12-15 Didier-Werke Ag Immersion nozzles for metal melts

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5895642A (en) * 1981-11-28 1983-06-07 黒崎窯業株式会社 Calcium alloy-containing casting nozzle
JPS58107252U (en) * 1981-12-10 1983-07-21 品川白煉瓦株式会社 Immersion nozzle for continuous casting
JPS6246951A (en) * 1985-08-22 1987-02-28 黒崎窯業株式会社 Manufacture of plate refractories for sliding nozzle
US4909484A (en) * 1988-08-02 1990-03-20 Dresser Industries, Inc. Prevention of slag buildup in steel ladles
DE3827424A1 (en) * 1988-08-12 1990-02-15 Didier Werke Ag SUBMERSIBLE SPOUTS FOR METAL MELTING

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE817271C (en) * 1950-08-20 1951-10-15 Friedrich Dr-Ing Badenheuer Process for the manufacture of ovens and oven components
GB1058461A (en) * 1962-10-02 1967-02-08 Int Minerals & Chem Corp Refractory and cupola operation
DE2441494C3 (en) * 1974-08-29 1978-04-20 Mannesmann Ag, 4000 Duesseldorf Refractory ceramic mass
JPS5227405A (en) * 1975-08-12 1977-03-01 Shinagawa Refractories Co Lining refractories for ingot iron transfer furnace or desulfurization treatment furnace

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2572724A1 (en) * 1984-11-02 1986-05-09 Didier Werke Ag REFRACTORY WEAR PIECE FOR DRAINING LIQUID MASS MASSES
EP0256217A2 (en) * 1986-08-12 1988-02-24 Didier-Werke Ag Submerged casting pipe and its manufacturing process
EP0256217A3 (en) * 1986-08-12 1988-11-30 Didier-Werke Ag Submerged casting pipe and its manufacturing process
FR2609419A1 (en) * 1987-01-14 1988-07-15 Intracon Handel Indbedarf Bottom tap-hole closure material
US5171495A (en) * 1988-08-12 1992-12-15 Didier-Werke Ag Immersion nozzles for metal melts

Also Published As

Publication number Publication date
JPS56109868A (en) 1981-08-31
DE3003046A1 (en) 1981-07-30
DE3003046C2 (en) 1982-01-28
FR2474481A1 (en) 1981-07-31
GB2067985B (en) 1983-08-24

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PCNP Patent ceased through non-payment of renewal fee