WO1992016472A1 - Process for producing a refractory composite material - Google Patents
Process for producing a refractory composite material Download PDFInfo
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- WO1992016472A1 WO1992016472A1 PCT/EP1992/000617 EP9200617W WO9216472A1 WO 1992016472 A1 WO1992016472 A1 WO 1992016472A1 EP 9200617 W EP9200617 W EP 9200617W WO 9216472 A1 WO9216472 A1 WO 9216472A1
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- Prior art keywords
- mixture
- carbon
- mullite
- aluminum
- corundum
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Classifications
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- 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
- C04B35/64—Burning or sintering processes
- C04B35/65—Reaction sintering of free metal- or free silicon-containing compositions
-
- 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
- B22D41/14—Closures
- B22D41/22—Closures sliding-gate type, i.e. having a fixed plate and a movable plate in sliding contact with each other for selective registry of their openings
- B22D41/28—Plates therefor
- B22D41/30—Manufacturing or repairing thereof
- B22D41/32—Manufacturing or repairing thereof characterised by the materials used therefor
-
- 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
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/597—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon oxynitride, e.g. SIALONS
Definitions
- the invention relates to a method for producing a refractory composite material by mixing ceramic materials with a graphite-containing binder, pressing the mixture into moldings, drying and firing.
- Refractory composite materials generally consist of roughly 2/3 coarse-grained raw materials with a grain size> 0.1 mm and a binding matrix formed from fine particles. Mainly MgO, mullite, corundum etc. are used as granular refractories.
- the refractory composite materials are usually subject to wear and tear due to erosion, corrosion and oxidation upon contact with hot metals and slags. Corrosion primarily starts with the binding matrix, which is why almost all development efforts are aimed at optimizing the binding matrix. It is therefore less the overall composition of a refractory stone that determines the corrosion resistance and more the type of binding phase. This also plays a decisive role in the thermal shock resistance of a refractory product, which among other things by adding certain phases such as graphite.
- Immersion spouts for (steel) continuous casting, slide plates of slide closures on pans are particularly exposed to temperature changes, steel and slag corrosion as well as deposits of AI 0 (clogging) made of corundum and graphite (coarse grain) with a binding matrix made of (fine) carbon.
- This binding matrix is produced from pitch, synthetic resin or the like by cracking.
- Slider plates are impregnated with pitch or the like because of their particularly high temperature shock load and for better sliding action.
- the fine carbon bond, which is created from pitch or synthetic resin, is very good for resistance to slag, but is very badly attacked by liquid steel and atmospheric oxygen.
- the object of the present invention is now to develop a material which has a bond which, while maintaining good resistance to temperature changes guaranteed by graphite, has a better resistance to the erosive and corrosive attack of hot metals, such as steel, and of slag and against oxidation than the previously common carbon-bonded ceramics and which can dispense with environmentally harmful substances such as pitch.
- corundum which is wholly or partly replaced by at least one substance from the group consisting of chamotte, ZrO, spinel, SiO, SiC, mullite, chrome ore, MgO, zirconium mullite, and with 2 - ⁇ % aqueous solution of an organic binder and with 1 -4% water, after drying to press moisture, pressed to shaped bodies, dried and in a nitrogen atmosphere.
- Sphere is heated and heated under nitrogen in the temperature range of 1200 to 1600 C until a binding phase consisting of SiAlON has formed
- a preferred mixture consists of (in% by weight)
- corundum which is wholly or partly replaced by at least one material made from chamotte, ZrO,
- Heating for nitriding is preferably carried out in the temperature range from 1350 to 1500 C.
- the durability of the ceramic material is considerably improved by the creation of a SiAlON bond that is resistant to steel and oxygen while maintaining good temperature change resistance guaranteed by graphite.
- the corrosion resistance of the SiAlON bond can be increased by installing BN.
- the amount provided is 3 to 30% BN, preferably 5 to 15% BN as a replacement for a corresponding amount of all other mixture fractions.
- Natural graphite, carbon black or electrographite can be used as carbon.
- SiAlON silicon aluminum oxynitride
- Alumina and aluminum at a temperature in the range of 1300 to 1400 C is already in the
- EP-PS 0242 849 describes a carbon-bonded refractory body, produced from a mixture of grains of carbon, SiAlON, antioxidants such as SiC, SiO, Si, as well as corundum or other refractory
- the carbon mainly consists of graphite and the smaller part of a carbon-containing binder, such as pitch or synthetic resin, which changes into fine carbon when fired under a reducing atmosphere. Slag zones of immersion spouts, crucibles, slide plates are proposed for use there. JP-PS 60 / 145963A2 (85/145963) describes tear-off rings for horizontal continuous casting, consisting of 60 to
- EP-PS 0 153 000 describes a composite material made of ⁇ -SiC which is bonded with SiAlON. They are produced by mixing Si, Al, SiC (without Al 0), pressing and nitriding at 1350 to 1600 C. The nitrating gas should contain enough oxygen to form SiAlON. Blast furnace lining is specified as use.
- Binder cellulose derivatives (methyl cellulose)
- the mixtures listed in Table 3 were pressed isostatically into tubes or pressed into sheets, dried at 120 ° C at 120 ° C / h at 1200 ° C, from 1200 to 1400 ° C at 10 ° C / h from 1400 to 1500 ° C at 30 ° C / h heated and o held at 1500 C for 12 h in a stream of nitrogen.
- Slider plates showed an improvement in the shelf life of 1-2 batches, and the plates could be used without tar soaking.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Products (AREA)
Abstract
Description
Beschreibung description
Verfahren zur Herstellung eines feuerfesten VerbundwerkstoffsProcess for the production of a refractory composite
Die Erfindung betrifft ein Verfahren zur Herstellung eines feuerfesten Verbundwerkstoffs durch Mischen von keramischen Stoffen mit einem Graphit enthaltenden feinteiligen Bindemittel, Pressen der Mischung zu Formkörpern, Trocknen und Brennen.The invention relates to a method for producing a refractory composite material by mixing ceramic materials with a graphite-containing binder, pressing the mixture into moldings, drying and firing.
Feuerfeste Verbundwerkstoffe bestehen im allgemeinen zu etwa 2/3 aus grobkörnigen Rohstoffen mit einer Körnung > 0,1 mm und einer aus Feinanteilen gebildeten Bindematrix. Als körnige Feuerfeststoffe verwendet man hauptsächlich MgO, Mullit, Korund u.a.. Die feuerfesten Verbundwerkstoffe unterliegen meist einem Verschleiß durch Erosion, Korrosion und Oxidation bei Kontakt mit heißen Metallen und Schlacken. Die Korrosion setzt in erster Linie an der Bindematrix an, weshalb fast alle Entwicklungsbemühungen auf die Optimierung der Bindematrix gerichtet sind. Es ist somit weniger die Gesamtzusammensetzung eines feuerfesten Steines, der die Korrosionsbeständigkeit bestimmt, sondern mehr die Art der Bindephase. Diese hat auch einen entscheidenden Anteil für die Temperaturwechselbeständigkeit eines Feuerfestprodukts, die u.a. durch den Zusatz bestimmter Phasen, wie Graphit, verbessert wird.Refractory composite materials generally consist of roughly 2/3 coarse-grained raw materials with a grain size> 0.1 mm and a binding matrix formed from fine particles. Mainly MgO, mullite, corundum etc. are used as granular refractories. The refractory composite materials are usually subject to wear and tear due to erosion, corrosion and oxidation upon contact with hot metals and slags. Corrosion primarily starts with the binding matrix, which is why almost all development efforts are aimed at optimizing the binding matrix. It is therefore less the overall composition of a refractory stone that determines the corrosion resistance and more the type of binding phase. This also plays a decisive role in the thermal shock resistance of a refractory product, which among other things by adding certain phases such as graphite.
Tauchausgüsse für den (Stahl-) Strangguß, Schieberplatten von Schieberverschlüssen an Pfannen werden insbesondere auf Temperaturwechsel, Stahl- und Schlackenkorrosion sowie durch Ablagerungen aus AI 0 (Clogging) beansprucht Marktgängige Tauchausgüsse und Schieberplatten bestehen aus Korund und Graphit (Grobkorn) mit einer Bindematrix aus (feinem) Kohlenstoff. Diese Bindematrix wird aus Pech, Kunstharz oder ähnlichem durch Cracken erzeugt. Schieberplatten werden wegen ihrer besonders hohen Temperaturschockbelastung und zur besseren Gleitwirkung mit Pech oder ähnlichem getränkt. Die feine Kohlenstoffbindung, die aus Pech oder Kunstharz entsteht, ist zwar sehr gut für die Beständigkeit gegen Schlacken, wird aber von flüssigem Stahl und Luftsauerstoff sehr stark angegriffen.Immersion spouts for (steel) continuous casting, slide plates of slide closures on pans are particularly exposed to temperature changes, steel and slag corrosion as well as deposits of AI 0 (clogging) made of corundum and graphite (coarse grain) with a binding matrix made of (fine) carbon. This binding matrix is produced from pitch, synthetic resin or the like by cracking. Slider plates are impregnated with pitch or the like because of their particularly high temperature shock load and for better sliding action. The fine carbon bond, which is created from pitch or synthetic resin, is very good for resistance to slag, but is very badly attacked by liquid steel and atmospheric oxygen.
Aufgabe der vorliegenden Erfindung ist es nun, einen Werkstoff zu entwickeln, der eine Bindung besitzt, die unter Beibehaltung einer guten durch Graphit gewährleisteten Temperaturwechselbeständigkeit eine bessere Beständigkeit gegen den erosiven und korrosiven Angriff von heißen Metallen, wie Stahl, und von Schlacke sowie gegen Oxidation besitzt als die bisher üblichen kohlenstoffgebundenen Keramiken und der auf ökologisch bedenkliche Stoffe, wie Pech, verzichten kann.The object of the present invention is now to develop a material which has a bond which, while maintaining good resistance to temperature changes guaranteed by graphite, has a better resistance to the erosive and corrosive attack of hot metals, such as steel, and of slag and against oxidation than the previously common carbon-bonded ceramics and which can dispense with environmentally harmful substances such as pitch.
Zur Lösung dieser Aufgabe wird erfindungsgemäß ein Verfahren zur Herstellung von feuerfesten Verbundwerkstoffen vorgeschlagen, nach dem eine Mischung aus (in Gew.-#)To achieve this object, a method for producing refractory composite materials is proposed according to the invention, according to which a mixture of (in% by weight)
4 - 16 % Silizium 1 - 8 % Aluminium 5 - 20 % reaktive Tonerde 3 - 50 % Kohlenstoff4 - 16% silicon 1 - 8% aluminum 5 - 20% reactive alumina 3 - 50% carbon
Rest Korund, das ganz oder teilweise ersetzt wird durch mindestens einen Stoff aus der aus Schamotte, ZrO , Spinell, SiO , SiC, Mullit, Chromerz, MgO, Zirkonmullit bestehenden Gruppe, und mit 2 - ~ % wäßriger Lösung eines organischen Binders und mit 1-4 % Wasser nach Trocknen auf Preßfeuchte zu Form¬ körpern gepreßt, getrocknet und in einer Stickstoffatmo- Sphäre aufgeheizt und solange unter Stickstoff im o Temperaturbereich von 1200 bis 1600 C erhitzt wird, bis sich eine aus SiAlON bestehende Bindephase gebildet hat,Rest of corundum, which is wholly or partly replaced by at least one substance from the group consisting of chamotte, ZrO, spinel, SiO, SiC, mullite, chrome ore, MgO, zirconium mullite, and with 2 - ~ % aqueous solution of an organic binder and with 1 -4% water, after drying to press moisture, pressed to shaped bodies, dried and in a nitrogen atmosphere. Sphere is heated and heated under nitrogen in the temperature range of 1200 to 1600 C until a binding phase consisting of SiAlON has formed,
Eine bevorzugte Mischung besteht aus (in Gew.-#)A preferred mixture consists of (in% by weight)
7 - 13 % Silizium7 - 13% silicon
2 - 6 % Aluminium2 - 6% aluminum
10 - 15 % reaktive Tonerde10 - 15% reactive alumina
10 - 25 % Kohlenstoff10 - 25% carbon
Rest Korund, das ganz oder teilweise ersetzt wird durch mindestens einen Stoff aus der aus Schamotte, ZrO ,Rest of corundum, which is wholly or partly replaced by at least one material made from chamotte, ZrO,
2 Spinell, SiO , SiC, Mullit, Chromerz, MgO,2 spinel, SiO, SiC, mullite, chrome ore, MgO,
Zirkonmullit, und mit 3 - ^ % wäßriger Lösung eines organischen Binders und 2 - 3 % Wasser.Zircon mullite, and with 3 - ^% aqueous solution of an organic binder and 2 - 3% water.
Vorzugsweise erfolgt die Erhitzung zur Nitridierung im o Temperaturbereich von 1350 bis 1500 C.Heating for nitriding is preferably carried out in the temperature range from 1350 to 1500 C.
Durch die Schaffung einer gegen Stahl und Sauerstoff beständigen SiAlON-Bindung unter Beibehaltung einer guten durch Graphit gewährleisteten Temperaturwechselbeständig¬ keit wird die Haltbarkeit des keramischen Materials erheblich verbessert. Die Korrosionsbeständigkeit der SiAlON-Bindung kann durch den Einbau von BN noch gesteigert werden.The durability of the ceramic material is considerably improved by the creation of a SiAlON bond that is resistant to steel and oxygen while maintaining good temperature change resistance guaranteed by graphite. The corrosion resistance of the SiAlON bond can be increased by installing BN.
Die dafür vorgesehene Menge beträgt 3 bis 30 % BN, vorzugsweise 5 bis 15 % BN als Ersatz für eine entsprechende Menge aller anderen Mischungsanteile.The amount provided is 3 to 30% BN, preferably 5 to 15% BN as a replacement for a corresponding amount of all other mixture fractions.
Als Kohlenstoff kann Naturgraphit, Ruß oder Elektrographit eingesetzt werden.Natural graphite, carbon black or electrographite can be used as carbon.
Überraschenderweise zeigt sich, daß bei der Nitridierung der Mischung aus Si, AI, AI 0 , Korund, Graphit und ggf. Bornitrid eine Mischung aus SiAlON und SiC entsteht.Surprisingly, it is found that a mixture of SiAlON and SiC is formed when the mixture of Si, Al, Al 0, corundum, graphite and optionally boron nitride is nitrided.
ERSATZBLATT Das Verhältnis dieser beiden Verbindungen richtet sich dabei nach der Art des Kohlenstoffs. Grober Graphit ergibt viel SiAlON und wenig SiC, dagegen ergibt sich bei der Verwendung von feinem Ruß mehr SiC und weniger SiAlON gemäßREPLACEMENT LEAF The ratio of these two compounds depends on the type of carbon. Coarse graphite results in a lot of SiAlON and little SiC, but when using fine carbon black more SiC and less SiAlON results
Tafel 1Plate 1
(Mischung mit 10 % Ruß bzw. 10 % Graphit als Kohlenstoff)(Mixture with 10% carbon black or 10% graphite as carbon)
Graphit RußGraphite carbon black
Vol.-# Anteil in der Bindung SiAlON SiC SiAlON ß'-SiC 80 20 50 50Vol .- # fraction in the bond SiAlON SiC SiAlON ß'-SiC 80 20 50 50
SiAlON (Silizium-Aluminium-Oxinitrid) ist einSiAlON (silicon aluminum oxynitride) is a
Mischkristall der allgemeinen FormelMixed crystal of the general formula
Si AI 0 Nft 6-z z z 8-z mit z im Bereich von 0,5 bis 4,2.Si AI 0 N ft 6-zzz 8-z with z in the range from 0.5 to 4.2.
Die Herstellung eines pulverförmigen SiAlON-Vormaterials durch Nitridieren einer Pulvermischung aus Silizium,The production of a powdery SiAlON raw material by nitriding a powder mixture of silicon,
Aluminiumoxid und Aluminium bei einer Temperatur im o Bereich von 1300 bis 1400 C ist bereits in derAlumina and aluminum at a temperature in the range of 1300 to 1400 C is already in the
US-PS 4 184 884 beschrieben.U.S. Patent No. 4,184,884.
Die EP-PS 0242 849 beschreibt einen kohlenstoffgebunde¬ nen feuerfesten Körper, hergestellt aus einer Mischung aus Körnungen von Kohlenstoff, SiAlON, Antioxidantien, wie SiC, SiO , Si, sowie Korund oder anderen Feuerfest-EP-PS 0242 849 describes a carbon-bonded refractory body, produced from a mixture of grains of carbon, SiAlON, antioxidants such as SiC, SiO, Si, as well as corundum or other refractory
2 Stoffen sowie borhaltigen Stoffen, wie Boroxid, als2 substances as well as substances containing boron, such as boron oxide
Sinterhilfsmittel. Der Kohlenstoff besteht zum überwie¬ genden Teil aus Graphit zum kleineren Teil aus einem kohlenstoffhaltigen Binder, wie Pech oder Kunstharz, der beim Brennen unter reduzierender Atmosphäre in feinen Kohlenstoff übergeht. Als Verwendung werden dort Schlackenzonen von Tauchausgüssen, Tiegel, Schieberplatten, vorgeschlagen. Die JP-PS 60/145963A2 (85/145963) beschreibt Abreißringe für den Horizontalstrangguß, bestehend aus 60 bisSintering aids. The carbon mainly consists of graphite and the smaller part of a carbon-containing binder, such as pitch or synthetic resin, which changes into fine carbon when fired under a reducing atmosphere. Slag zones of immersion spouts, crucibles, slide plates are proposed for use there. JP-PS 60 / 145963A2 (85/145963) describes tear-off rings for horizontal continuous casting, consisting of 60 to
97% ß'- SiAlON und 3 bis 40 % Bornitrid (BN). Sie werden hergestellt durch Granulieren eines Schlickers von Si,97% β'-SiAlON and 3 to 40% boron nitride (BN). They are made by granulating a slip of Si,
AI, AI 0 , BN und Verpressen der Granalien zu Ringen undAI, AI 0, BN and pressing the granules into rings and
2 3 o2 3 o
Nitridieren bei 1500 C in N -Atmosphäre.Nitriding at 1500 C in an N atmosphere.
Die EP-PS 0 153 000 beschreibt einen Verbundwerkstoff aus ß -SiC, der mit SiAlON gebunden ist. Die Herstellung erfolgt durch Mischen von Si, AI, SiC (ohne AI 0 ) , Verpressen und Nitridieren bei 1350 bis 1600 C. Das Nitriergas soll genügend Sauerstoff zur SiAlON-Bildung enthalten. Als Verwendung ist Hochofenauskleidung angegeben.EP-PS 0 153 000 describes a composite material made of β-SiC which is bonded with SiAlON. They are produced by mixing Si, Al, SiC (without Al 0), pressing and nitriding at 1350 to 1600 C. The nitrating gas should contain enough oxygen to form SiAlON. Blast furnace lining is specified as use.
Bei allen vorerwähnten Verfahren werden temporäre organische Binder zur Erzeugung der Grünfestigkeit verwendet.In all of the aforementioned processes, temporary organic binders are used to produce the green strength.
Typische Zusammensetzungen und Korngrößen von für die Erfindung verwendbaren Rohstoffe sind in Tafel 2 aufge¬ listet. Die Bereichsangaben sind nicht beschränkend.Typical compositions and grain sizes of raw materials which can be used for the invention are listed in Table 2. The range specifications are not restrictive.
Tafel 2Plate 2
Rohstoffe:Raw materials:
Korund (Schmelzkorund)Corundum
AI 0AI 0
2 3 SiO :2 3 SiO:
2 TiO : 2 Fe 0 :
AI 0 : > 99 % 2 3AI 0:> 99% 2 3
SiO : < 0,1 % 2SiO: <0.1% 2
Fe 0 : < 0,1 % 2 3Fe 0: <0.1% 2 3
- 10 μm Korngröße- 10 μm grain size
2 - 20 μm Korngöße2 - 20 μm grain size
10 - 80 μm Korngröße10 - 80 μm grain size
Bornitrid:Boron nitride:
S2 SxS2 Sx
BN: > 98,5 % > 95 %BN:> 98.5%> 95%
B 0 : < 0,1 % < 4 % 2 3 C: < 0,2 % < 0,1 %B 0: <0.1% <4% 2 3 C: <0.2% <0.1%
Metalle: < 0,2 Ü < 0,2 %Metals: <0.2 Ü <0.2%
< 3 jαm < 5 μm Korngröße<3 jαm <5 μm grain size
ERSATZBLATT Kohlenstoff: Graphit RußREPLACEMENT LEAF Carbon: graphite carbon black
40 - 200 μm 0,1 - 10 μm C: 94 - 98 % C > 99 %40 - 200 μm 0.1 - 10 μm C: 94 - 98% C> 99%
org. Binder: Zellulosederivate (Methylzellulose)org. Binder: cellulose derivatives (methyl cellulose)
5 %-ige wässrige Lösung5% aqueous solution
C: 2 - 4 %C: 2 - 4%
H O: 93 - 97 %H O: 93-97%
22
Anhand des folgenden Beispiels wird das erfindungsgemäße Verfahren erläutert:The method according to the invention is explained using the following example:
Beispielexample
Die in Tafel 3 aufgelisteten Mischungen wurden zu Rohren o isostatisch verpreßt oder zu Platten gepreßt, bei 120 C o o o getrocknet mit 120 C/h auf 1200 C, von 1200 bis 1400 C o o o mit 10 C/h von 1400 bis 1500 C mit 30 C/h aufgeheizt und o bei 1500 C 12 h im Stickstoffstrom gehalten.The mixtures listed in Table 3 were pressed isostatically into tubes or pressed into sheets, dried at 120 ° C at 120 ° C / h at 1200 ° C, from 1200 to 1400 ° C at 10 ° C / h from 1400 to 1500 ° C at 30 ° C / h heated and o held at 1500 C for 12 h in a stream of nitrogen.
Die Ergebnisse sind in Tafel 3 mitgeteilt. Tauchausgußrohre (Versätze 1, la, lb) wurden im Vergleich zu herkömmlichen, kohlenstoffgebundenen Rohren in einer Stranggußkokille eingesetzt und zeigten 20 bis 35 % bessere Verschlackungsbeständigkeit im Vergleich zu den marktüblichen Tauchausgüssen. Die Thermoschockbestänig- keit entsprach den marktgängigen Tauchausgüssen.The results are shown in Table 3. Immersion pouring pipes (offsets 1, la, lb) were used in a continuous casting mold compared to conventional, carbon-bonded pipes and showed 20 to 35% better slag resistance compared to the commercially available immersion nozzles. The thermal shock resistance corresponded to the standard diving spouts.
Schieberplatten (Versätze 2, 2a) zeigten eine Verbesserung der Haltbarkeit von 1 - 2 Chargen, dabei konnten die Platten ohne eine Teertränkung eingesetzt werden.Slider plates (offsets 2, 2a) showed an improvement in the shelf life of 1-2 batches, and the plates could be used without tar soaking.
ERSATZBLATT Tafel 3REPLACEMENT LEAF Table 3
1 la lb 2 2a1 la lb 2 2a
Korund 1 - 3 mmCorundum 1 - 3 mm
Korund 0,5 - 1 mmCorundum 0.5 - 1 mm
Korund 0,25 - 0,5 mm 24,5
64 5464 54
100 100 100 100 100100 100 100 100 100
Zusätzlich: wässrige Lösung von +4 +4 +4 +4 Zellulosederivat Wasser +3 +3 +3 +2 +2Additionally: aqueous solution of +4 +4 +4 +4 cellulose derivative water +3 +3 +3 +2 +2
Rohdichte (trocken) g/cιτf 2,65 2,80 2,75 2,85 2,70 scheinbare Porosität % 17 17 19 16 29 (gebrannt)Bulk density (dry) g / cιτf 2.65 2.80 2.75 2.85 2.70 Apparent porosity% 17 17 19 16 29 (fired)
Kaltdruckfestigkeit N/mm 55 65 70 53 48 Schlackenbeständigkeit besser als marktgängiger +35 +20 +30 Tauchausguß % Haltbarkeit von Schieber¬ platten besser als marktgängige +2 +1 Schieberplatten (Chargen) Cold compressive strength N / mm 55 65 70 53 48 Slag resistance better than standard +35 +20 +30 immersion spout% Durability of slide plates better than standard +2 +1 slide plates (batches)
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4109375.5 | 1991-03-22 | ||
| DE19914109375 DE4109375A1 (en) | 1991-03-22 | 1991-03-22 | METHOD FOR PRODUCING A FIRE-RESISTANT COMPOSITE MATERIAL |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992016472A1 true WO1992016472A1 (en) | 1992-10-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1992/000617 Ceased WO1992016472A1 (en) | 1991-03-22 | 1992-03-20 | Process for producing a refractory composite material |
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| Country | Link |
|---|---|
| DE (1) | DE4109375A1 (en) |
| WO (1) | WO1992016472A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994018140A1 (en) * | 1993-02-01 | 1994-08-18 | Nils Claussen | Method of producing ceramic moldings containing fine-grained alumina, using powdered aluminum metal |
| WO1996015999A1 (en) * | 1994-11-24 | 1996-05-30 | Savoie Refractaires | Novel materials consisting of refractory grains bonded by a titanium nitride-containing aluminium nitride or sialon matrix |
| CN115636679A (en) * | 2022-11-03 | 2023-01-24 | 中钢洛耐科技股份有限公司 | Sialon corundum mullite for firing electronic ceramic kiln |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4330584C1 (en) * | 1993-09-09 | 1994-09-01 | Fraunhofer Ges Forschung | Process for producing refractory materials |
| DE19936973A1 (en) * | 1999-08-05 | 2001-02-08 | Induga Industrieoefen Und Gies | Device for low pressure casting of metals |
| DE602004022073D1 (en) * | 2003-08-22 | 2009-08-27 | Krosakiharima Corp | TUBE NOZZLE FOR STEEL STEELING AND STEEL STEELING METHOD USING THE DIVING NOZZLE |
| US20050280192A1 (en) * | 2004-06-16 | 2005-12-22 | Graham Carson | Zirconia refractories for making steel |
| DE112009004278B4 (en) * | 2008-12-18 | 2016-11-17 | Krosakiharima Corp. | Method for producing a tile and tile |
| CN105254319B (en) * | 2015-11-19 | 2018-02-16 | 长兴兴鹰新型耐火建材有限公司 | A kind of castable of feeding chamber preformed bricks and preparation method thereof |
| CN108083784B (en) * | 2018-01-29 | 2020-11-03 | 武汉科技大学 | Alumina-carbon composite material based on microcrystalline graphite and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0153000A1 (en) * | 1984-01-23 | 1985-08-28 | The Carborundum Company | Refractories of silicon carbide and related materials having a modified silicon nitride bonding phase |
| ATE29710T1 (en) * | 1983-02-11 | 1987-10-15 | Shinagawa Refractories Co | CARBON REFRACTORY. |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59152269A (en) * | 1983-02-08 | 1984-08-30 | 九州耐火煉瓦株式会社 | Silicon nitride composite refractories |
| JPS60145963A (en) * | 1983-12-30 | 1985-08-01 | 工業技術院長 | Break ring for horizontal continuous casting machine and manufacture |
| KR870009789A (en) * | 1986-04-21 | 1987-11-30 | 원본미기재 | Carbon Bond Refractory |
-
1991
- 1991-03-22 DE DE19914109375 patent/DE4109375A1/en not_active Withdrawn
-
1992
- 1992-03-20 WO PCT/EP1992/000617 patent/WO1992016472A1/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE29710T1 (en) * | 1983-02-11 | 1987-10-15 | Shinagawa Refractories Co | CARBON REFRACTORY. |
| EP0153000A1 (en) * | 1984-01-23 | 1985-08-28 | The Carborundum Company | Refractories of silicon carbide and related materials having a modified silicon nitride bonding phase |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994018140A1 (en) * | 1993-02-01 | 1994-08-18 | Nils Claussen | Method of producing ceramic moldings containing fine-grained alumina, using powdered aluminum metal |
| US5607630A (en) * | 1993-02-01 | 1997-03-04 | Claussen; Nils | Process for the production of fine-grained ceramic bodies molded containing Al2 O3 |
| WO1996015999A1 (en) * | 1994-11-24 | 1996-05-30 | Savoie Refractaires | Novel materials consisting of refractory grains bonded by a titanium nitride-containing aluminium nitride or sialon matrix |
| FR2727400A1 (en) * | 1994-11-24 | 1996-05-31 | Savoie Refractaires | NEW MATERIALS IN THE FORMS OF REFRACTORY GRAINS BOUND BY A MATRIX OF ALUMINUM OR SIALON NITRIDE CONTAINING TITANIUM NITRIDE AND DISPERSED GRAPHITE AND / OR BORON NITRIDE PARTICLES |
| US5925585A (en) * | 1994-11-24 | 1999-07-20 | Savoie Refractaires | Materials formed by refractory grains bound in a matrix of aluminum nitride or sialon containing titanium nitride |
| CN115636679A (en) * | 2022-11-03 | 2023-01-24 | 中钢洛耐科技股份有限公司 | Sialon corundum mullite for firing electronic ceramic kiln |
| CN115636679B (en) * | 2022-11-03 | 2023-08-11 | 中钢洛耐科技股份有限公司 | Sialon corundum mullite for firing electronic ceramic kiln |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4109375A1 (en) | 1992-09-24 |
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