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WO2007079806A1 - Mix for a refractory ceramic product and refractory ceramic product produced therefrom - Google Patents

Mix for a refractory ceramic product and refractory ceramic product produced therefrom Download PDF

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Publication number
WO2007079806A1
WO2007079806A1 PCT/EP2006/010582 EP2006010582W WO2007079806A1 WO 2007079806 A1 WO2007079806 A1 WO 2007079806A1 EP 2006010582 W EP2006010582 W EP 2006010582W WO 2007079806 A1 WO2007079806 A1 WO 2007079806A1
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WO
WIPO (PCT)
Prior art keywords
ceramic product
offset according
offset
refractory
mass
Prior art date
Application number
PCT/EP2006/010582
Other languages
German (de)
French (fr)
Inventor
Christian Majcenovic
Dieter Pirkner
Original Assignee
Refractory Intellectual Property Gmbh & Co. Kg
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Refractory Intellectual Property Gmbh & Co. Kg filed Critical Refractory Intellectual Property Gmbh & Co. Kg
Priority to EP06806683A priority Critical patent/EP1966106A1/en
Publication of WO2007079806A1 publication Critical patent/WO2007079806A1/en

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    • 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
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    • 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
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    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
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    • 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
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Definitions

  • the invention relates to an offset for a refractory under normal use ceramic product, such as a molding or a casting.
  • Refractory ceramic products both masses (such as castables, shotguns, ramming masses, mortar) and molded parts (such as bricks, cuboids, cones, plates) are used for lining metallurgical melting vessels as well as for use as functional parts (such as slide plates, sleeves, Plugs, lances, pipes), in particular in the context of secondary metallurgical processes.
  • masses such as castables, shotguns, ramming masses, mortar
  • molded parts such as bricks, cuboids, cones, plates
  • functional parts such as slide plates, sleeves, Plugs, lances, pipes
  • the refractory material comes into contact not only with the metallurgical melts but also with corresponding slags.
  • the refractory material is subject to considerable wear, in particular wear due to a chemical / metallurgical corrosion attack, wherein an infiltration of melt and / or slag into the refractory material may be a cause of wear.
  • additives which can lead to a reduction in the wear of the refractory material.
  • These additives which are said to make the finished refractory material more corrosion resistant and / or which better protect the refractory material from infiltration of contaminants, are hereinafter referred to as "corrosion / infiltration inhibitors.”
  • Barium sulfate (BaSO 4 ) and calcium fluoride (CaF 2 ) are such substances.
  • Barium sulfate decomposes at higher temperatures.
  • BaSO 4 reacts to Celsian (BaAl 2 Si 2 Oe) and the protective effect of the additive is lost. This is especially true in the temperature range> 900 ° C.
  • a refractory lining in a melting vessel may become hot during heating between 1100 and 1250 ° C. It is then often hotter than the subsequently treated in the vessel melt. BaSO 4 then fails completely as wear protection.
  • the invention is so far the object of demonstrating a way to improve the infiltration / corrosion behavior of refractory ceramic products, especially in the high-temperature application (> 1,200 ° C).
  • the calcium sulfate can be used anhydrous, ie as anhydrite (CaSO 4 ), or hydrous, for example as hemihydrate (CaSO 4 • Vi H 2 O) or dihydrate (CaSO 4 • 2H 2 O), as a fine powder or in various coarser particle fractions.
  • anhydrite CaSO 4
  • hydrous for example as hemihydrate (CaSO 4 • Vi H 2 O) or dihydrate (CaSO 4 • 2H 2 O), as a fine powder or in various coarser particle fractions.
  • Blaine's specific surface area may be> 2000 cm 2 / g. It can be over 4000 cm 2 / g and reach values> 7000 cm 2 / g.
  • the residue on a sieve according to DIN 4188 is then for example: R 0.02 mm:> 40%, R 0.02 mm> 25% or R 0.02 mm: ⁇ 20%.
  • Usually Blaine's specific surface area is> 1000 cm 2 / g.
  • the said corrosion-inhibiting substances are used as an offset component, optionally also added to the finished product, for example by infiltration by means of vacuum treatment.
  • the CaSO 4 decomposes, but forms new compounds with the surrounding refractory material, which are likewise infiltrations / corrosion inhibitors.
  • the reasons / phenomena are not fully understood yet. However, it was found, inter alia, that CaSO 4 reacts at higher temperatures with alumina from the refractory product to yeelimite (Ca 4 AloOi 2 SO 4 ). Yeelimit is stable up to> 1200 ° C and obviously takes over the protective function of the calcium sulfate additive at higher temperatures.
  • the invention comprises an offset for a refractory under normal use ceramic product, the
  • Basic refractory components are substances (compounds such as oxides) that are refractory or fire-resistant at higher temperatures (> 900 ° C). They are used according to the invention in grain sizes ⁇ 6 mm and may contain a fine grain fraction ( ⁇ 250 microns).
  • the raw material offset shall be adjusted accordingly, provided that the corrosion-inhibiting component (s) are not first introduced by impregnation of the finished fired product.
  • the offset thus contains corresponding additives (additives).
  • the amount of the infiltration-inhibiting component in the offset can be adjusted to ⁇ 15, ⁇ 10, ⁇ 7, ⁇ 5, to ⁇ 3% by mass, based on the total offset from the refractory base component and the admixture. Usually their share amounts to>1,> 3 or> 5 M .-%. Accordingly, the proportion of the refractory base component (sum of refractory base components and additives calculated in each case to 100% by mass) increases or decreases.
  • a binder e.g. based on phosphate or cement, or antioxidants (total of all offset components then added to 100 M .-%).
  • the invention includes the processing of the offset to ceramic bonded refractory products as well as the processing into chemically bonded products.
  • the refractory ceramic products may be monolithic compositions, mortars, moldings, for example in the form of stones, plates, sleeves or the like.
  • a suitable base component may at least partially be a non-basic basic component, for example from the group: alumina, corundum, ZrO 2 , zirconium silicate (ZrO 2 .SiO 2 ), mullite, TiO 2 , SiC, andalusite, chromium oxide, microsilica.
  • Cr 2 O 3 -free products are preferred.
  • BaSO 4 and / or CaF 2 can be dispensed with.
  • a suitable offset can be prepared in a conventional manner, for example by mixing the refractory base component (s) with the additive (s) and a binder, then shaping (for example by pressing) and firing for sintering, especially at temperatures> 1200 ° C ,
  • Example 3 Offset for a stone to be pressed
  • Example 1 From the offset according to Example 1 four test specimens of size 25x25x51 mm were prepared. The so-called “fill immersion test” was carried out on these test specimens, as it results from "Aluminum Transactions, Vol. 3, No. 1, 2000, 105-120", to which reference is made. The specimens were placed at a distance from each other on the bottom of a lined with silicon carbide casting compound test vessel, which was filled with 3.5 kg of an aluminum melt of the following specification so that the specimens were completely covered by the melt.
  • the surface of the molten bath was covered with a salt to prevent oxidation.
  • composition of aluminum melt is Composition of aluminum melt:

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Abstract

The invention relates to a mix for a ceramic product which is refractory when used as intended, for example a shaped body or a casting composition.

Description

Versatz für ein feuerfestes keramisches Produkt und daraus gebildetes feuerfestes keramisches Produkt Offset for a refractory ceramic product and refractory ceramic product formed therefrom
B e s c h r e i b u n gDescription
Die Erfindung betrifft einen Versatz für ein bei bestimmungsgemäßer Anwendung feuerfestes keramisches Produkt, beispielsweise einen Formkörper oder eine Gießmasse.The invention relates to an offset for a refractory under normal use ceramic product, such as a molding or a casting.
Feuerfeste keramische Produkte, und zwar sowohl Massen (wie Gießmassen, Spritzmassen, Stampfmassen, Mörtel) als auch Formteile (wie Ziegel, Quader, Kegel, Platten), finden zur Auskleidung metallurgischer Schmelzgefäße ebenso Anwendung wie zur Verwendung als Funktionalteile (wie Schieberplatten, Hülsen, Stopfen, Lanzen, Rohre), insbesondere im Rahmen sekundärmetallurgischer Verfahren. -I-Refractory ceramic products, both masses (such as castables, shotguns, ramming masses, mortar) and molded parts (such as bricks, cuboids, cones, plates) are used for lining metallurgical melting vessels as well as for use as functional parts (such as slide plates, sleeves, Plugs, lances, pipes), in particular in the context of secondary metallurgical processes. -I-
Dies gilt sowohl für bestimmungsgemäße Anwendungen in der Eisenmetall- Industrie wie für Anwendungen in der Nichteisenmetall-Industrie.This applies both to intended applications in the ferrous metal industry and to applications in the non-ferrous metal industry.
Das feuerfeste Material kommt nicht nur mit den metallurgischen Schmelzen, sondern auch mit korrespondierenden Schlacken in Berührung. Insoweit unterliegt das Feuerfestmaterial einem erheblichen Verschleiß, insbesondere einem Verschleiß durch einen chemischen/metallurgischen Korrosionsangriff, wobei eine Infiltration von Schmelze und/oder Schlacke in das Feuerfestmaterial eine Verschleißursache sein kann.The refractory material comes into contact not only with the metallurgical melts but also with corresponding slags. In that regard, the refractory material is subject to considerable wear, in particular wear due to a chemical / metallurgical corrosion attack, wherein an infiltration of melt and / or slag into the refractory material may be a cause of wear.
In diesem Zusammenhang ist die Verwendung von Additiven bekannt, die zu einer Verringerung des Verschleißes des Feuerfestmaterials führen können. Diese Additive (Versatz-Bestandteile), die das fertige Feuerfestmaterial korrosionsstabiler machen sollen und/oder die das Feuerfestmaterial besser vor Infiltrationen von Fremdstoffen schützen, werden nachstehend als „Korrosions-/Infiltrationsinhibitoren" bezeichnet. Bariumsulfat (BaSO4) und Calciumfluorid (CaF2) sind solche Stoffe.In this context, the use of additives is known, which can lead to a reduction in the wear of the refractory material. These additives, which are said to make the finished refractory material more corrosion resistant and / or which better protect the refractory material from infiltration of contaminants, are hereinafter referred to as "corrosion / infiltration inhibitors." Barium sulfate (BaSO 4 ) and calcium fluoride (CaF 2 ) are such substances.
Bariumsulfat zerfällt jedoch bei höheren Temperaturen. Zum Beispiel im Kontakt mit Bauxit aus dem Versatz des Feuerfest-Produkts reagiert BaSO4 zu Celsian (BaAl2Si2Oe) und die Schutzwirkung des Additivs geht verloren. Dies gilt insbesondere im Temperaturbereich > 900° C.Barium sulfate, however, decomposes at higher temperatures. For example, in contact with bauxite from the offset of the refractory product, BaSO 4 reacts to Celsian (BaAl 2 Si 2 Oe) and the protective effect of the additive is lost. This is especially true in the temperature range> 900 ° C.
Beispielsweise durch Verwendung moderner Brenner kann eine feuerfeste Auskleidung in einem Schmelzgefäß beim Aufheizen zwischen 1 100 und 1250° C heiß werden. Sie ist dann oft heißer als die nachfolgend im Gefäß behandelte Schmelze. BaSO4 versagt dann als Verschleißschutz vollständig.For example, by using modern burners, a refractory lining in a melting vessel may become hot during heating between 1100 and 1250 ° C. It is then often hotter than the subsequently treated in the vessel melt. BaSO 4 then fails completely as wear protection.
CaF2 ist zwar thermisch stabiler als BaSO4, die infiltrations-/korrosions- hemmende Wirkung ist jedoch schlechter als bei Verwendung von BaSO4. Der Erfindung liegt insofern die Aufgabe zugrunde, eine Möglichkeit aufzuzeigen, das Infiltrations-/Korrosionsverhalten feuerfester keramischer Produkte insbesondere auch im Hochtemperatur-Anwendungsbereich (> 1.200° Celsius) zu verbessern.Although CaF 2 is thermally more stable than BaSO 4 , the infiltration / corrosion inhibiting effect is worse than when using BaSO 4 . The invention is so far the object of demonstrating a way to improve the infiltration / corrosion behavior of refractory ceramic products, especially in the high-temperature application (> 1,200 ° C).
In Versuchen wurde festgestellt, dass durch Calciumsulfat im Versatz der Verschleiß eines zugehörigen gebrannten fertigen Produktes drastisch herabsetzt wird, und zwar ohne negative Auswirkungen auf das mechanische Verhalten der Produkte und ohne negative Auswirkungen auf die Temperaturbeständigkeit und Temperaturwechselbeständigkeit.In experiments it has been found that calcium sulfate in offset drastically reduces the wear of an associated fired finished product without adversely affecting the mechanical performance of the products and without adversely affecting temperature and thermal shock resistance.
Das Calciumsulfat kann wasserfrei, also als Anhydrit (CaSO4), oder wasserhaltig, beispielsweise als Halbhydrat (CaSO4 • Vi H2O) oder Dihydrat (CaSO4 • 2 H2O) eingesetzt werden, als feines Pulver oder auch in verschiedenen gröberen Kornfraktionen.The calcium sulfate can be used anhydrous, ie as anhydrite (CaSO 4 ), or hydrous, for example as hemihydrate (CaSO 4 • Vi H 2 O) or dihydrate (CaSO 4 • 2H 2 O), as a fine powder or in various coarser particle fractions.
Die spezifische Oberfläche nach Blaine kann beispielsweise > 2000 cm2/g betragen. Sie kann über 4000 cm2/g liegen und Werte > 7000 cm2/g erreichen. Der Rückstand auf einem Sieb gemäß DIN 4188 beträgt dann beispielsweise: R 0,02 mm: > 40 %, R 0,02 mm > 25 % oder R 0,02 mm: < 20 %. Üblicherweise ist die spezifische Oberfläche nach Blaine > 1000 cm2/g.For example, Blaine's specific surface area may be> 2000 cm 2 / g. It can be over 4000 cm 2 / g and reach values> 7000 cm 2 / g. The residue on a sieve according to DIN 4188 is then for example: R 0.02 mm:> 40%, R 0.02 mm> 25% or R 0.02 mm: <20%. Usually Blaine's specific surface area is> 1000 cm 2 / g.
Die genannten korrosionshemmenden Substanzen (Additive) werden als Versatzkomponente eingesetzt, gegebenenfalls auch dem fertigen Produkt zugesetzt, zum Beispiel mittels Vakuumbehandlung infiltriert. Bei anschließender Temperaturbehandlung (beim Brand/Sintern der Produkte oder bei ihrer bestimmungsgemäßen Anwendung) zersetzt sich das CaSO4 zwar, bildet aber mit dem umgebenden Feuerfestmaterial neue Verbindungen, die ebenfalls infiltrations/-korrosionshemmend sind. Die Gründe/Phänomene dafür sind noch nicht abschließend vollständig geklärt. Es wurde aber unter anderem festgestellt, dass CaSO4 bei höheren Temperaturen mit Aluminiumoxid aus dem refraktären Produkt zu Yeelimit (Ca4AIoOi2SO4) reagiert. Yeelimit ist bis > 1200° C beständig und übernimmt offensichtlich bei höheren Temperaturen die Schutzfunktion des Calciumsulfat-Additivs.The said corrosion-inhibiting substances (additives) are used as an offset component, optionally also added to the finished product, for example by infiltration by means of vacuum treatment. During subsequent heat treatment (during the firing / sintering of the products or during their intended use), the CaSO 4 decomposes, but forms new compounds with the surrounding refractory material, which are likewise infiltrations / corrosion inhibitors. The reasons / phenomena are not fully understood yet. However, it was found, inter alia, that CaSO 4 reacts at higher temperatures with alumina from the refractory product to yeelimite (Ca 4 AloOi 2 SO 4 ). Yeelimit is stable up to> 1200 ° C and obviously takes over the protective function of the calcium sulfate additive at higher temperatures.
In ihrer allgemeinsten Ausführungsform umfasst die Erfindung einen Versatz für ein bei bestimmungsgemäßer Anwendung feuerfestes keramisches Produkt, derIn its most general embodiment, the invention comprises an offset for a refractory under normal use ceramic product, the
a) 75 - 99,5 Masse-% mindestens einer refraktären Grundkomponente und b) 0,5 - 25 Masse-% mindestens eines Additivs aus der Gruppe: Calciumsulfat, Calciumsulfathydrata) 75-99.5% by mass of at least one refractory base component and b) 0.5-25% by mass of at least one additive from the group: calcium sulfate, calcium sulfate hydrate
enthält.contains.
Refraktäre Grundkomponenten sind Stoffe (Verbindungen, wie Oxide), die feuerfest sind oder bei höheren Temperaturen (> 900° C) feuerfest werden. Sie werden erfindungsgemäß in Korngrößen < 6 mm eingesetzt und können einen Feinkornanteil (< 250 μm) enthalten.Basic refractory components are substances (compounds such as oxides) that are refractory or fire-resistant at higher temperatures (> 900 ° C). They are used according to the invention in grain sizes <6 mm and may contain a fine grain fraction (<250 microns).
Verschiedene Weiterbildungen ergeben sich aus den Merkmalen der Unteransprüche und den sonstigen Beschreibungsunterlagen. Der Rohstoffversatz ist entsprechend einzustellen, sofern die korrosions- hemmende(n) Komponente(n) nicht erst durch Tränkung des fertigen gebrannten Produktes eingebracht wird (werden). Der Versatz enthält also entsprechende Additive (Zusatzmittel). Die Menge der infiltrations- hemmenden Komponente im Versatz kann auf < 15, < 10, < 7, < 5, bis < 3 M.-%, bezogen auf den Gesamtversatz aus refraktärer Grundkomponente und Zusatzmittel, eingestellt werden. Meist beträgt ihr Anteil > 1 , > 3 oder > 5 M.-%. Entsprechend erhöht beziehungsweise verringert sich der Anteil der refraktären Grundkomponente (Summe aus refraktären Grundkomponenten und Additiven jeweils auf 100 M.-% gerechnet).Various developments emerge from the features of the subclaims and the other description documents. The raw material offset shall be adjusted accordingly, provided that the corrosion-inhibiting component (s) are not first introduced by impregnation of the finished fired product. The offset thus contains corresponding additives (additives). The amount of the infiltration-inhibiting component in the offset can be adjusted to <15, <10, <7, <5, to <3% by mass, based on the total offset from the refractory base component and the admixture. Usually their share amounts to>1,> 3 or> 5 M .-%. Accordingly, the proportion of the refractory base component (sum of refractory base components and additives calculated in each case to 100% by mass) increases or decreases.
Ebenso ist es möglich, weitere Komponenten dem Versatz zuzumischen, beispielsweise ein Bindemittel, z.B. auf Phosphat- oder Zementbasis, oder Antioxidantien (Gesamtsumme aller Versatzkomponenten dann wiederum auf 100 M.-% addiert).It is also possible to mix further components with the offset, for example a binder, e.g. based on phosphate or cement, or antioxidants (total of all offset components then added to 100 M .-%).
Die Erfindung schließt die Verarbeitung des Versatzes zu keramisch gebundenen feuerfesten Produkten ebenso ein wie die Verarbeitung zu chemisch gebundenen Produkten. Die feuerfesten keramischen Produkte können monolithische Massen, Mörtel, Formteile, beispielsweise in Form von Steinen, Platten, Hülsen oder dergleichen sein.The invention includes the processing of the offset to ceramic bonded refractory products as well as the processing into chemically bonded products. The refractory ceramic products may be monolithic compositions, mortars, moldings, for example in the form of stones, plates, sleeves or the like.
Soweit Massen angesprochen sind schließt dies auch hydraulisch gebundene Massen ein.As far as masses are concerned this also includes hydraulically bound masses.
Eine geeignete Grundkomponente kann zumindest anteilig eine nichtbasische Grundkomponente sein, beispielsweise aus der Gruppe: Tonerde, Korund, ZrO2, Zirkonsilikat (ZrO2 . SiO2), Mullit, TiO2, SiC, Andalusit, Chromoxid, Mikrosilika. Allerdings sind Cr2Ü3-freie Produkte bevorzugt. Auf BaSO4 und/oder CaF2 kann verzichtet werden. Ein entsprechender Versatz kann in üblicher Weise aufbereitet werden, beispielsweise durch Vermischen der refraktären Grundkomponente(n) mit dem Additiv (den Additiven) und einem Bindemittel, anschließender Formgebung (zum Beispiel durch Pressen) und Brand zur Sinterung, insbesondere bei Temperaturen > 1.200° Celsius.A suitable base component may at least partially be a non-basic basic component, for example from the group: alumina, corundum, ZrO 2 , zirconium silicate (ZrO 2 .SiO 2 ), mullite, TiO 2 , SiC, andalusite, chromium oxide, microsilica. However, Cr 2 O 3 -free products are preferred. BaSO 4 and / or CaF 2 can be dispensed with. A suitable offset can be prepared in a conventional manner, for example by mixing the refractory base component (s) with the additive (s) and a binder, then shaping (for example by pressing) and firing for sintering, especially at temperatures> 1200 ° C ,
Die Erfindung wird nachstehend anhand von vier Versätzen beispielhaft dargestellt:The invention is exemplified below with reference to four offsets:
Beispiel 1 : Versatz für eine GießmasseExample 1: Offset for a casting compound
Figure imgf000007_0001
Figure imgf000007_0001
Beispiel 2: Versatz für eine StampfmasseExample 2: Offset for a ramming mass
Figure imgf000007_0002
Beispiel 3 : Versatz für einen zu pressenden Stein
Figure imgf000007_0002
Example 3: Offset for a stone to be pressed
Figure imgf000008_0001
Figure imgf000008_0001
Beispiel 4: Versatz für eine SpritzmasseExample 4: Offset for a spray mass
Figure imgf000008_0002
Figure imgf000008_0002
Aus dem Versatz gemäß Beispiel 1 wurden vier Prüfkörper der Größe 25x25x51 mm hergestellt. An diesen Probekörpern wurde der so genannte „füll immersion test" durchgeführt, wie er sich aus „Aluminium Transactions, Vol. 3, No. 1 , 2000, 105-120" ergibt, auf den Bezug genommen wird. Dabei wurden die Probekörper mit Abstand zueinander auf den Boden eines mit Siliziumcarbid-Gießmasse ausgekleideten Prüfgefäßes gestellt, welches mit 3,5 kg einer Aluminiumschmelze nachstehender Spezifierung so gefüllt war, dass die Prüfkörper komplett von der Schmelze überdeckt waren.From the offset according to Example 1 four test specimens of size 25x25x51 mm were prepared. The so-called "fill immersion test" was carried out on these test specimens, as it results from "Aluminum Transactions, Vol. 3, No. 1, 2000, 105-120", to which reference is made. The specimens were placed at a distance from each other on the bottom of a lined with silicon carbide casting compound test vessel, which was filled with 3.5 kg of an aluminum melt of the following specification so that the specimens were completely covered by the melt.
Die Oberfläche des Schmelzbades wurde mit einem Salz abgedeckt, um eine Oxidation zu vermeiden. Die Prüfkörper, die jeweils mindestens eine Oberfläche in Kontakt mit der Schmelze aufwiesen, die durch ein Schneidwerkzeug freigelegt wurde, blieben 4 Tage (96 Stunden) in der auf 850° C gehaltenen Schmelze, wobei die Schmelzzusammensetzung jeweils nach 24 Stunden nachreguliert wurde.The surface of the molten bath was covered with a salt to prevent oxidation. The specimens, each having at least one surface in contact with the melt exposed by a cutting tool, remained in the melt maintained at 850 ° C for 4 days (96 hours) with the melt composition each readjusted after 24 hours.
Zusammensetzung der Aluminiumschmelze:Composition of aluminum melt:
Figure imgf000009_0001
Figure imgf000009_0001
An dem bei 1200° C vorgebrannten Prüfkörpern wurde keine durchgehende Anhaftung von Metall festgestellt. Es konnte keine makroskopisch sichtbare Infiltration festgestellt werden. Mikroskopisch ergab sich eine dünne, circa 500 μm starke Reaktionszone im Oberflächenbereich der Prüfkörper. Weitere Untersuchungen ergaben, dass Calziumsulfat als solches nicht mehr vorhanden war. Dagegen konnte in der Probe ein Anteil an Yeelimit (Ca4AIoOi2SO4) festgestellt werden. Yeelimit hatte sich dabei insbesondere im Grenzflächenbereich des zuvor von Calziumsulfat eingenommenen Raumes zum umgebenden Matrixmaterial gebildet.At the test pieces prebaked at 1200 ° C, no continuous adhesion of metal was observed. No macroscopically visible infiltration could be detected. Microscopy revealed a thin, about 500 micron thick reaction zone in the surface region of the specimens. Further investigations revealed that calcium sulfate was no longer present as such. In contrast, a proportion of yeelimite (Ca 4 AloOi 2 SO 4 ) was found in the sample. In particular, Yeelimit had formed in the interface area of the previously occupied by calcium sulfate space to the surrounding matrix material.
Die aus einem Versatz der genannten Art gebildeten ungebrannten oder gebrannten Produkte, letztere mit einem Gehalt an Yeelimit, sind ebenfalls Gegenstand der Erfindung. The unfired or fired products formed from an offset of the type mentioned, the latter containing yeelimite, are also the subject of the invention.

Claims

Versatz für ein feuerfestes keramisches Produkt und daraus gebildetes feuerfestes keramisches ProduktA n s p r ü c h e Offset for a refractory ceramic product and refractory ceramic product formed therefrom
1. Versatz für ein bei bestimmungsgemäßer Anwendung feuerfestes keramisches Produkt, der a) 75 - 99,5 Masse-% mindestens einer refraktären Grundkomponente und b) 0,5 - 25 Masse-% mindestens eines Additivs aus der Gruppe:1. offset for a refractory ceramic product when used as intended, containing: a) 75-99.5% by mass of at least one refractory base component and b) 0.5-25% by mass of at least one additive selected from the group consisting of:
Calciumsulfat, Calciumsulfathydrat enthält.Calcium sulfate, calcium sulfate hydrate.
2. Versatz nach Anspruch 1 , bei dem der Anteil des Additivs < 10 Masse-% beträgt.2. Offset according to claim 1, wherein the proportion of the additive is <10% by mass.
3. Versatz nach Anspruch 1 , bei dem der Anteil des Additivs < 5 Masse-% beträgt. 3. Offset according to claim 1, wherein the proportion of the additive is <5% by mass.
4. Versatz nach Anspruch 1 , bei dem der Anteil des Additivs > 1 Masse-% beträgt.4. offset according to claim 1, wherein the proportion of the additive> 1 mass%.
5. Versatz nach Anspruch 1 , bei dem der Anteil des Additivs > 5 Masse-% beträgt.5. Offset according to claim 1, wherein the proportion of the additive is> 5 mass%.
6. Versatz nach Anspruch 1 , bei dem mindestens eine refraktäre Grundkomponente eine nicht-basische Grundkomponente ist.6. An offset according to claim 1, wherein at least one refractory base component is a non-basic base component.
7. Versatz nach Anspruch 6, bei dem die nicht-basische Grundkomponente zumindest anteilig aus der Gruppe: Tonerde, Bauxit, Korund, ZrO2, Siliziumcarbid, Andalusit, Chromoxid, Mikrosilika, Zirkonsilikat, Mullit, TiO2 stammt.7. An offset according to claim 6, wherein the non-basic base component at least partially from the group: alumina, bauxite, corundum, ZrO 2 , silicon carbide, andalusite, chromium oxide, microsilica, zirconium silicate, mullite, TiO 2 originated.
8. Versatz nach Anspruch 1 , bei dem das Additiv als feinteiliges Pulver mit einer spezifischen Oberfläche nach Blaine > 1000 cm2/g vorliegt.8. An offset according to claim 1, wherein the additive is present as a finely divided powder having a specific surface area of Blaine> 1000 cm 2 / g.
9. Versatz nach Anspruch 1 , der bis auf etwaige Verunreinigungen frei von mindestens einer der folgenden Bestandteile ist: BaSO4, CaF2 Cr2O3.9. An offset according to claim 1, which is free from at least one of the following constituents except for possible impurities: BaSO 4 , CaF 2 Cr 2 O 3 .
10. Ungebranntes keramisches Produkt, hergestellt aus einem Versatz nach Anspruch 1.10. Unburned ceramic product made from an offset according to claim 1.
1 1 . Gebranntes feuerfestes keramisches Produkt, hergestellt aus einem Versatz gemäß Anspruch 1 mit einem Anteil an Yeelimit (Ca4Al6Oi2SO4). 1 1. A burned refractory ceramic product made from an offset according to claim 1 having a content of yeelimite (Ca 4 Al 6 Oi 2 SO 4 ).
PCT/EP2006/010582 2005-12-23 2006-11-04 Mix for a refractory ceramic product and refractory ceramic product produced therefrom WO2007079806A1 (en)

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Publication number Priority date Publication date Assignee Title
CN113387706A (en) * 2021-04-22 2021-09-14 北京金隅通达耐火技术有限公司 Wear-resistant corrosion-resistant silicon carbide cap for waste heat boiler water-cooling wall lining

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