DE10019600A1 - Refractory material with improved resistance to slag attack - Google Patents
Refractory material with improved resistance to slag attackInfo
- Publication number
- DE10019600A1 DE10019600A1 DE2000119600 DE10019600A DE10019600A1 DE 10019600 A1 DE10019600 A1 DE 10019600A1 DE 2000119600 DE2000119600 DE 2000119600 DE 10019600 A DE10019600 A DE 10019600A DE 10019600 A1 DE10019600 A1 DE 10019600A1
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- refractory material
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- 239000011819 refractory material Substances 0.000 title claims description 20
- 239000002893 slag Substances 0.000 title description 12
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims abstract description 13
- 150000004679 hydroxides Chemical class 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000005272 metallurgy Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 230000009189 diving Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 5
- 229910007948 ZrB2 Inorganic materials 0.000 abstract description 3
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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
- C04B35/515—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
- C04B35/5805—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 borides
- C04B35/58064—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 borides based on refractory borides
- C04B35/58078—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 borides based on refractory borides based on zirconium or hafnium borides
-
- 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
- C04B35/48—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
- C04B35/01—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
- C04B35/486—Fine ceramics
- C04B35/488—Composites
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
Die Erfindung betrifft einen feuerfesten Werkstoff mit verbes sertem Widerstand gegen Schlackenangriff.The invention relates to a refractory material with verbes resistance to slag attack.
In der Schmelzmetallurgie werden in hoch beanspruchten Berei chen Kohlenstoff gebundene, feuerfeste Werkstoffe eingesetzt. Typische Kohlenstoff-Verbundwerkstoffe sind Al2O3-C, Al2O3-SiC- C, MgO-C und ZrO2-C. Speziell im Bereich oxidischer Schlacken (Gießpulver), z. B. bei Tauchausgüssen in Stranggußanlagen, werden zunehmend ZrO2-C Werkstoffe eingesetzt. Dieser Feuer festwerkstoff zeichnet sich durch ein gutes Thermoschockver halten und hohen Oxidationswiderstand aus. Trotzdem ist das feuerfeste Material im Schlackenbereich verstärkter Korrosion ausgesetzt und somit ein Schwachpunkt beim Einsatz.In melt metallurgy, carbon-bonded, refractory materials are used in highly stressed areas. Typical carbon composite materials are Al 2 O 3 -C, Al 2 O 3 -SiC- C, MgO-C and ZrO 2 -C. Especially in the field of oxidic slags (casting powder), e.g. B. in immersion pouring in continuous casting plants, ZrO 2 -C materials are increasingly used. This refractory material is characterized by good thermal shock behavior and high oxidation resistance. Nevertheless, the refractory material in the slag area is exposed to increased corrosion and is therefore a weak point in use.
Die Arbeiten auf diesem Gebiet wurden vornehmlich an Tauchaus güssen durchgeführt. Noboru Tsukamoto in Taikabutsu Overseas, Vol. 13, No. 4, S. 55 bis 61 gibt eine Übersicht über den An griff auf Tauchausgüsse beim Stranggießen von Stahl.The work in this area was mainly on diving castings performed. Noboru Tsukamoto in Taikabutsu Overseas, Vol. 13, No. 4, pp. 55 to 61 provides an overview of the type resorted to immersion spouts when continuously casting steel.
Aus JP-A-57156370 ist bekannt, dem ZrO2-C Werkstoff B4C zuzu setzen, um den Korrosionswiderstand von ZrO2-C zu verbessern. In dieser Veröffentlichung wurden auch metallische Zusätze (Si, Al) in Kombination mit B4C getestet, ohne daß eine signi fikante Verbesserung des Korrosionswiderstandes gemessen wur de, die auf diesen Zusatz zurückgeführt werden kann.From JP-A-57156370 it is known to add B 4 C to the ZrO 2 -C material in order to improve the corrosion resistance of ZrO 2 -C. In this publication, metallic additives (Si, Al) were also tested in combination with B 4 C, without a significant improvement in corrosion resistance being measured, which can be attributed to this additive.
Aus US 5,185,300 ist bekannt ZrB2/TiB2 zuzusetzen, um den Kor rosionswiderstand von ZrO2-C zu verbessern.From US 5,185,300 it is known to add ZrB 2 / TiB 2 in order to improve the corrosion resistance of ZrO 2 -C.
Ogota, K et al. beschreiben in XXXIX. Internationales Feuer fest-Kolloquium (XXXIX. International Colloquium on Refracto ries), 24. und 25. Sept. 1996, auf S. 128 bis 130, daß der Korrosionswiderstand von ZrO2-C durch den Austausch eines Teils des ZrO2 durch ZrB2 verbessert werden kann. Durch die Oxidation von ZrB2 entstehen ZrO2 und B2O3. Letzteres schützt den C-Anteil vor Oxidation. Gleichzeitig wird die Infiltration von flüssiger Schlacke bzw. Metall blockiert. Nachteilig wirkt sich aus, daß B2O3 zur Destabilisierung des ZrO2 beiträgt.Ogota, K et al. describe in XXXIX. International Feuer fest-Kolloquium (XXXIX. International Colloquium on Refracto ries), 24th and 25th September 1996, on pages 128 to 130, that the corrosion resistance of ZrO 2 -C by replacing part of the ZrO 2 by ZrB 2 can be improved. The oxidation of ZrB 2 produces ZrO 2 and B 2 O 3 . The latter protects the C component from oxidation. At the same time, the infiltration of liquid slag or metal is blocked. The disadvantage is that B 2 O 3 contributes to the destabilization of ZrO 2 .
Aufgabe der Erfindung ist es, Feuerfestwerkstoffe auf der Ba sis von ZrO2-ZrB2-C mit weiter verbesserter Korrosionsbestän digkeit zur Verfügung zu stellen.The object of the invention is to provide refractory materials based on ZrO 2 -ZrB 2 -C with further improved corrosion resistance.
Die Aufgabe wird gelöst durch einen Werkstoff enthaltend
3-25 Gew.-% C
20-90 Gew.-% ZrB2
5-60 Gew.-% stabilisiertes ZrO2
und 0,2-10 Gew.-% eines Materials ausgewählt aus der
Gruppe Al, Mg, deren Oxide, deren Hydroxide oder Gemische die
ser Materialien.The object is achieved by containing a material
3-25 wt% C
20-90% by weight ZrB 2
5-60% by weight of stabilized ZrO 2
and 0.2-10% by weight of a material selected from the group Al, Mg, their oxides, their hydroxides or mixtures of these materials.
Stabilisiertes ZrO2 ist ZrO2, welches als Stabilisatoren typi scherweise CaO oder Y2O3 in Mengen von 2 bis 10 Gew.-% enthält. Es ist käuflich erhältlich (beispielsweise bei der Firma Zir conia Sales, Inc. in 814-C Livingston Court, Franklin Business Park, Marietta, Georgia 30067, USA unter der Bezeichnung HSY- 3.OSD).Stabilized ZrO 2 is ZrO 2 , which typically contains CaO or Y 2 O 3 in amounts of 2 to 10% by weight as stabilizers. It is commercially available (for example from Zir conia Sales, Inc. at 814-C Livingston Court, Franklin Business Park, Marietta, Georgia 30067, USA under the designation HSY-3.OSD).
Vorzugsweise enthält das feuerfeste Material
8-20 Gew.-% C
30-70 Gew.-% ZrB2
20-50 Gew.-% stabilisiertes ZrO2
2-8 Gew.-% eines Materials aus der Gruppe Al, Mg deren
Oxide, deren Hydroxide oder Gemische dieser Materialien.Preferably contains the refractory material
8-20% by weight of C
30-70% by weight ZrB 2
20-50% by weight of stabilized ZrO 2
2-8% by weight of a material from the group Al, Mg, their oxides, their hydroxides or mixtures of these materials.
Besonders bevorzugt enthält das feuerfeste Material Al oder Mg in metallischer Form.The refractory material particularly preferably contains Al or Mg in metallic form.
Zusätzliche können oxidische Komponenten wie z. B. SiO2 in Mengen von 0-20 Gew.-% in der erfindungsgemäßen Zusammenset zung vorhanden sein. Eine solche Zusammensetzung zeigt ein verändertes Korrosionsverhalten, welches bei einigen Schlackenzusammensetzungen von Vorteil ist. Die erfindungsgemäße. Korrosionsverbesserung tritt auch bei solchen Zusammensetzun gen auf.In addition, oxidic components such as. B. SiO 2 in amounts of 0-20 wt .-% in the composition according to the invention. Such a composition shows a changed corrosion behavior, which is advantageous with some slag compositions. The invention. Corrosion improvement also occurs with such compositions.
Insbesondere bevorzugt besteht das erfindungsgemäße Material aus den genannten Komponenten.The material according to the invention particularly preferably consists from the components mentioned.
Im erfindungsgemäßen Feuerfestwerkstoff wird weitgehend ausge schlossen, daß das kubische ZrO2 durch den Angriff von B2O3 auf den Stabilisator, z. B. CaO oder Y2O3, in monoklines und weni ger resistentes ZrO2 überführt wird, da es Additive enthält, die mit dem B2O3 reagieren und Borverbindungen, z. B. Borate bilden. Diese Borverbindungen greifen das stabilisierte oder teilstabilisierte ZrO2 nicht an.In the refractory material according to the invention it is largely ruled out that the cubic ZrO 2 by the attack of B 2 O 3 on the stabilizer, for. B. CaO or Y 2 O 3 , is converted into monoclinic and less resistant ZrO 2 since it contains additives which react with the B 2 O 3 and boron compounds, e.g. B. form borates. These boron compounds do not attack the stabilized or partially stabilized ZrO 2 .
Zu diesem Zweck haben sich metallische Zusätze wie Mg und Al als sehr wirkungsvoll erwiesen. Ein vergleichbares Ergebnis läßt sich auch mit dem Zusatz feiner Metalloxide oder -hydro xide obiger Metalle erreichen.For this purpose, metallic additives such as Mg and Al proven to be very effective. A comparable result can also with the addition of fine metal oxides or hydro xide of the above metals.
Das erfindungsgemäße Material besitzt eine erhöhte Korrosions beständigkeit. Sein Einsatz erhöht daher die Haltbarkeit von Werkstoffen in der Schmelzmetallurgie. So kann der Korrosions widerstand eines Tauchrohres gegen Schlackenangriff nahezu um den Faktor 2 verbessert werden und die Lebensdauer des Bautei les entsprechend verlängert werden.The material according to the invention has increased corrosion resistance. Its use therefore increases the durability of Materials in smelting metallurgy. So can the corrosion resistance of an immersion tube against slag attack almost be improved by a factor of 2 and the lifespan of the component les can be extended accordingly.
Das erfindungsgemäße Material läßt sich herstellen, wie für übliche ZrO2-ZrB2-C Materialien bekannt. In die ZrO2-ZrB2-C Mi schung werden die genannten metallischen Zusätze in feinver teilter Form eingebracht. Dies kann vorzugsweise bereits wäh rend des Mischens der ZrO2-ZrB2-C Materialien geschehen.The material according to the invention can be produced as is known for conventional ZrO 2 -ZrB 2 -C materials. The metallic additives mentioned are introduced in finely divided form into the ZrO 2 -ZrB 2 -C mixture. This can preferably already take place during the mixing of the ZrO 2 -ZrB 2 -C materials.
Die Komponenten Kohlenstoff, Zirkoniumdiborid und Zirkoniumdi oxid werden beispielsweise wie im Stand der Technik bekannt eingesetzt. The components carbon, zirconium diboride and zirconium di oxides are known, for example, as in the prior art used.
Vorzugsweise wird stabilisiertes ZrO2 mit einem ZrO2-Gehalt von < 93% Gew.-% und einer Teilchengröße vorzugsweise von < 500 µm eingesetzt.Stabilized ZrO 2 with a ZrO 2 content of <93% by weight and a particle size of preferably <500 μm is preferably used.
C wird vorzugsweise als Flockengrafit mit einem C-Gehalt von < 96 Gew.-% und einer Teilchengröße von < 500 µm eingesetzt.C is preferably used as flake graphite with a C content of <96 wt .-% and a particle size of <500 microns used.
ZrB2 wird vorzugsweise mit einem ZrB2-Gehalt von < 94 Gew.-% und mit einer Teilchengröße von vorzugsweise < 150 µm eingesetzt. Al, Mg bzw. deren Oxide, deren Hydroxide oder Gemische dieser Materialien werden vorzugsweise mit einer Teilchengröße von < 50 µm eingesetzt.ZrB 2 is preferably used with a ZrB 2 content of <94% by weight and with a particle size of preferably <150 µm. Al, Mg or their oxides, their hydroxides or mixtures of these materials are preferably used with a particle size of <50 μm.
Als Binder wird ein flüssiges Phenolharz in Mengen von vor zugsweise 3-6 Gew.-%, zugesetzt.A liquid phenolic resin is used as a binder in amounts of before preferably 3-6 wt .-% added.
Die Rohstoffe werden in einem Zwangsmischer homogenisiert und zu Tauchrohren kaltisostatisch verpresst. Um die Maßgenauig keit zu garantieren, schließt sich in der Regel eine an sich bekannte Grünbearbeitung an. Anschließend werden die Formkör per bei ca. 1000°C thermisch behandelt, wobei sich Phenolharz zu C zersetzt. Falls notwendig kann sich eine Endbearbeitung anschließen.The raw materials are homogenized in a compulsory mixer and cold isostatically pressed to immersion tubes. To the exact dimensions guaranteeing, there is usually one in itself known green processing. Then the shaped body per thermally treated at approx. 1000 ° C, whereby phenolic resin decomposed to C. If necessary, finishing can be done connect.
Vorzugsweise werden die genannten Materialien in folgenden
Mengenverhältnissen (in Gew.-%) eingesetzt:
The materials mentioned are preferably used in the following proportions (in% by weight):
- - Kohlenstoff: 3-25%- carbon: 3-25%
- - Zirkoniumdiborid: 20-90%- Zirconium diboride: 20-90%
- - Zirkoniumdioxid: 5-60%- Zirconium dioxide: 5-60%
- - Die metallischen Zusätze bzw. deren Oxide oder Hydroxide: 0,2 bis 10%.- The metallic additives or their oxides or hydroxides: 0.2 to 10%.
Der erfindungsgemäße Feuerfestwerkstoff wird vorzugsweise in der Metallurgie, besonders bevorzugt in der Schmelzmetallurgie im Bereich oxidischer Schlacken verwendet. So lassen sich z. B. Tauchausgüsse in Stranggußanlagen aus dem Material fertigen. The refractory material according to the invention is preferably in metallurgy, particularly preferably in melt metallurgy used in the field of oxidic slags. So z. B. Manufacture immersion spouts from the material in continuous casting plants.
Die Erfindung betrifft somit auch Tauchausgüsse, die dadurch gekennzeichnet sind, daß sie aus dem erfindungsgemäßen Materi al bestehen.The invention thus also relates to diving spouts which are thereby are characterized that they from the materi al exist.
Das folgende Beispiel dient der weiteren Erläuterung der Er findung:The following example serves to further explain the Er finding:
Hergestellt wurden Probekörper (20 × 20 × 120 mm) folgender Endzu sammensetzung nach der thermischen Behandlung (in Gew.-%):Test specimens (20 × 20 × 120 mm) of the following end were produced composition after thermal treatment (in% by weight):
Zur Probenherstellung wurden ein mit 5,4% Y2O3-stabilisiertes ZrO2 (Teilchengröße < 500 µm), ZrB2 (Teilchengröße < 100 µm), Flockengrafit (Teilchengröße < 200 µm) und Al-Pulver (Teilchen größe < 50 µm) in einem Flugscharmischer ca. 15 min. vermischt. Danach wurden, bezogen auf die eingesetzte Pulvermenge, 5 Gew.-% Phenolharz in den Mischer gegeben und weitere 10 min gemischt. Das erhaltene Pulver wurde in einer Kaltisostatpres se bei 100 MPa zu Probekörpern der Abmessung 20 × 20 × 120 mm verdichtet und unter atmosphärischen Bedingungen bei 1050°C thermisch behandelt. Der durch die Zersetzung des Phenolharzes gebildete Kohlenstoff ist in obiger Tabelle berücksichtigt. A 5.4% Y 2 O 3 stabilized ZrO 2 (particle size <500 µm), ZrB 2 (particle size <100 µm), flake graphite (particle size <200 µm) and Al powder (particle size <50 µm) were used to prepare the samples ) in a flight share mixer approx. 15 min. mixed. Then, based on the amount of powder used, 5% by weight of phenolic resin were added to the mixer and mixed for a further 10 minutes. The powder obtained was compressed in a cold isostatic press at 100 MPa to test specimens measuring 20 × 20 × 120 mm and thermally treated at 1050 ° C. under atmospheric conditions. The carbon formed by the decomposition of the phenolic resin is taken into account in the table above.
Die geformten und geglühten Proben wiesen eine Dichte von 90% der theoretischen Dichte auf.The molded and annealed samples had a density of 90% the theoretical density.
Die folgenden Versuche wurden in einem Induktionsofen in einem Tiegel aus feuerfestem Korundmaterial durchgeführt. Verwendet wurde ULC-Stahl und eine Schlacke folgender Zusammensetzung (in Gew.-%): 35,8% CaO, 32,1% SiO2, 5,7% Al2O3, 7,4% Na2O, 2,6% MgO, 13,1% CaF2, 0,1% B2O3, 3,2% Fe2O3 The following experiments were carried out in an induction furnace in a crucible made of refractory corundum material. ULC steel and a slag of the following composition (in% by weight) were used: 35.8% CaO, 32.1% SiO 2 , 5.7% Al 2 O 3 , 7.4% Na 2 O, 2, 6% MgO, 13.1% CaF 2 , 0.1% B 2 O 3 , 3.2% Fe 2 O 3
Die Probekörper wurden 5 h bei 1550°C dem Stahl und Schlacken angriff ausgesetzt. Hierbei tauchte die Probe in einen Tiegel mit flüssigen ULC-Stahl mit der flüssigen Schlacke.The test specimens were exposed to steel and slag at 1550 ° C. for 5 h exposed to attack. The sample was immersed in a crucible with liquid ULC steel with the liquid slag.
Anschließend wurde die Tiefe der Rinne, die durch den Korrosi
onsangriff hervorgerufen wurde, im Schlackenbereich an mehre
ren Stellen vermessen und gemittelt.
The depth of the gutter, which was caused by the corrosion attack, was then measured and averaged at several points in the slag area.
Claims (9)
3-25 Gew.-% C
20-90 Gew.-% ZrB2
5-60 Gew.-% stabilisiertes ZrO2
und 0,2-10 Gew.-% eines Materials, ausgewählt aus der Gruppe Al, Mg, deren Oxide, deren Hydroxide oder Gemische dieser Materialien.1. Containing refractory material based on ZrO 2 -ZrB 2 -C with improved corrosion resistance
3-25 wt% C
20-90% by weight ZrB 2
5-60% by weight of stabilized ZrO 2
and 0.2-10% by weight of a material selected from the group Al, Mg, their oxides, their hydroxides or mixtures of these materials.
8-20 Gew.-% C
30-70 Gew.-% ZrB2
20-50 Gew.-% stabilisiertes ZrO2
2-8 Gew.-% eines Materials aus der Gruppe Al, Mg deren Oxide, deren Hydroxide oder Gemische dieser Materialien enthält.2. Refractory material according to claim 1, characterized in that it
8-20% by weight of C
30-70% by weight ZrB 2
20-50% by weight of stabilized ZrO 2
2-8 wt .-% of a material from the group Al, Mg contains their oxides, their hydroxides or mixtures of these materials.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2000119600 DE10019600A1 (en) | 2000-04-20 | 2000-04-20 | Refractory material with improved resistance to slag attack |
| PCT/EP2001/002932 WO2001081271A1 (en) | 2000-04-20 | 2001-03-15 | Fireproof material having an improved resistance against erosion by slags |
| AU2001252207A AU2001252207A1 (en) | 2000-04-20 | 2001-03-15 | Fireproof material having an improved resistance against erosion by slags |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2000119600 DE10019600A1 (en) | 2000-04-20 | 2000-04-20 | Refractory material with improved resistance to slag attack |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE10019600A1 true DE10019600A1 (en) | 2001-10-31 |
Family
ID=7639455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2000119600 Ceased DE10019600A1 (en) | 2000-04-20 | 2000-04-20 | Refractory material with improved resistance to slag attack |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2001252207A1 (en) |
| DE (1) | DE10019600A1 (en) |
| WO (1) | WO2001081271A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453502C (en) * | 2002-02-07 | 2009-01-21 | 郑州振中电熔锆业有限公司 | Production method of electric melting magnesium-aluminium-zirconium synthetic material |
| CN109534825A (en) * | 2019-01-16 | 2019-03-29 | 电子科技大学 | In-situ synthesis of ZrB2 coated with inert glass phase and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336723C (en) * | 2005-05-23 | 2007-09-12 | 哈尔滨工业大学 | Combustion synthesis method of zirconium diboride micro-powder |
| RU2336245C1 (en) * | 2007-04-24 | 2008-10-20 | Открытое акционерное общество "Композит" | Composite ceramic material for high-temperature application (versions) |
| CN101914810B (en) * | 2010-08-16 | 2012-05-02 | 山东大学 | Zirconium diboride whisker material and preparation method thereof |
| CN111018521B (en) * | 2019-12-06 | 2022-03-25 | 广东工业大学 | A kind of zirconia-zirconium boride composite ceramic and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57156370A (en) * | 1981-03-19 | 1982-09-27 | Kurosaki Refractories Co | Continuous casting refractories |
| JPH0360859A (en) * | 1989-07-28 | 1991-03-15 | Kawasaki Refract Co Ltd | Sliding nozzle plate |
| EP0503316A2 (en) * | 1991-03-11 | 1992-09-16 | Vesuvius Crucible Company | Erosion, thermal shock and oxidation resistant refractory compositions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63134571A (en) * | 1986-11-25 | 1988-06-07 | 旭硝子株式会社 | Zirconium diboride-graphite-containing unfired refractories |
| JPS63288968A (en) * | 1987-05-22 | 1988-11-25 | Asahi Glass Co Ltd | Composite refractories |
-
2000
- 2000-04-20 DE DE2000119600 patent/DE10019600A1/en not_active Ceased
-
2001
- 2001-03-15 AU AU2001252207A patent/AU2001252207A1/en not_active Abandoned
- 2001-03-15 WO PCT/EP2001/002932 patent/WO2001081271A1/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57156370A (en) * | 1981-03-19 | 1982-09-27 | Kurosaki Refractories Co | Continuous casting refractories |
| JPH0360859A (en) * | 1989-07-28 | 1991-03-15 | Kawasaki Refract Co Ltd | Sliding nozzle plate |
| EP0503316A2 (en) * | 1991-03-11 | 1992-09-16 | Vesuvius Crucible Company | Erosion, thermal shock and oxidation resistant refractory compositions |
| US5185300A (en) * | 1991-03-11 | 1993-02-09 | Vesuvius Crucible Company | Erosion, thermal shock and oxidation resistant refractory compositions |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453502C (en) * | 2002-02-07 | 2009-01-21 | 郑州振中电熔锆业有限公司 | Production method of electric melting magnesium-aluminium-zirconium synthetic material |
| CN109534825A (en) * | 2019-01-16 | 2019-03-29 | 电子科技大学 | In-situ synthesis of ZrB2 coated with inert glass phase and preparation method thereof |
| CN109534825B (en) * | 2019-01-16 | 2021-06-01 | 电子科技大学 | In-situ synthesis of ZrB2 coated with inert glass phase and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001081271A1 (en) | 2001-11-01 |
| AU2001252207A1 (en) | 2001-11-07 |
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Owner name: WACKER-CHEMIE GMBH, 81737 MUENCHEN, DE |
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| 8131 | Rejection |