(19)
(11)EP 1 493 515 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
24.01.2018 Bulletin 2018/04

(21)Application number: 03715657.7

(22)Date of filing:  31.03.2003
(51)Int. Cl.: 
C04B 35/581  (2006.01)
C04B 35/584  (2006.01)
B22D 11/06  (2006.01)
C04B 35/583  (2006.01)
C04B 35/597  (2006.01)
C04B 35/44  (2006.01)
(86)International application number:
PCT/JP2003/004090
(87)International publication number:
WO 2003/082498 (09.10.2003 Gazette  2003/41)

(54)

CERAMIC PLATE AS SIDE DAM FOR TWIN DRUM TYPE THIN-SHEET CONTINUOUS CASTING

KERAMIKPLATTE ALS SEITENDAMM FÜR DAS DÜNNBANDSTRANGGIESSEN MIT DOPPELWALZE

PLAQUE EN CÉRAMIQUE UTILISÉE COMME PETITE FACE LATÉRALE POUR COULÉE CONTINUE DE FEUILLE MINCE DU TYPE COULÉE ENTRE CYLINDRES


(84)Designated Contracting States:
DE FR IT

(30)Priority: 02.04.2002 JP 2002100372

(43)Date of publication of application:
05.01.2005 Bulletin 2005/01

(73)Proprietor: Nippon Steel & Sumitomo Metal Corporation
Tokyo 100-8071 (JP)

(72)Inventors:
  • NOSE, Tetsuro, NIPPON STEEL CORPORATION
    Futtsu-shi, Chiba 293-8511 (JP)
  • TAKEUCHI, Tomohide, NIPPON STEEL CORPORATION
    Futtsu-shi Chiba 293-8511 (JP)

(74)Representative: Vossius & Partner Patentanwälte Rechtsanwälte mbB 
Siebertstrasse 3
81675 München
81675 München (DE)


(56)References cited: : 
EP-A- 0 338 718
JP-A- 8 164 452
JP-A- 8 243 690
JP-A- 2001 150 106
EP-A- 0 654 456
JP-A- 8 243 689
JP-A- 8 243 691
  
  • MITOMO M ET AL: "Stability of [alpha]-sialons in low temperature annealing" JOURNAL OF THE EUROPEAN CERAMIC SOCIETY ELSEVIER UK, vol. 19, no. 1, 1999, pages 7-15, XP002319812 ISSN: 0955-2219
  • PATENT ABSTRACTS OF JAPAN vol. 1995, no. 09, 31 October 1995 (1995-10-31) & JP 07 165462 A (KUROSAKI REFRACT CO LTD), 27 June 1995 (1995-06-27)
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description


[0001] This invention relates to ceramic plates for side dams that form a liquid steel pool, with a pair of cooling drums interposed therebetween, in twin-drum continuous strip casters for continuously casting strips of stainless and other steels while forming a solidifying shell at the peripheral surface of the pair of cooling drums having parallel axes and rotating in opposite directions.

[0002] Side dams forming a liquid steel pool, with a pair of cooling drums interposed therebetween, in twin-drum continuous strip casters are required to have high corrosion resistance against stainless and other steels, high wear resistance to friction with the drums, high resistance to the thermal shock occurring when hot metal is poured and a low enough thermal conductivity to inhibit the adhesion of skulls.

[0003] Conventionally Al2O3+C, Si3N4, BN, Sialon, AlN, TiB2, TiN, Si3N4+BN, Si3N4+AlN+BN, Sialon+BN, Sialon+AlN+BN, Sialon+TiB2+BN, Sialon+TiN+BN and some other types of ceramics have been used for side dams. However, none of them have proved to have the long life required of side dams.

[0004] Generally Al2O3+C ceramics, which have high corrosion resistance to molten steel and good thermal shock resistance, tend to become roughened where contact is made with moving drums and, thus, show poor sealability to molten steel. While having high resistance to penetration of molten steel, Si3N4, Sialon, AlN, TiB2, and TiN ceramics do not have good corrosion resistance. Because of poor thermal shock resistance, they tend to crack when subjected alone to rapid heating and cooling.

[0005] While having good thermal shock resistance, BN ceramics are soft and do not have good wear resistance. Because of high thermal conductivity, they tend to cause the adhesion of skulls to plates, thereby inhibiting the implementation of stable continuous casting.

[0006] Combinations of BN ceramics with Si3N4, Sialon, AlN, TiB2, and TiN ceramics sometimes exhibit better thermal shock and wear resistance than those seen when they are used alone. However, the problem of poor corrosion resistance remains unsolved.

[0007] As described above, conventional ceramics do not have the good reliability required of structural materials because they do not have the desired high corrosion, wear and thermal shock resistances and do not have low thermal conductivity.

A REAG phase



[0008] The object of the present invention is to provide ceramic plates for side dams of twin-drum continuous strip casters having high corrosion, wear and thermal shock resistances and low thermal conductivity.

[0009] The ceramic plates for side dams of twin-drum continuous strip casters according to this invention comprise a Sialon phase of 20 to 45 vol. % and a BN phase of 15 to 35 vol. %, optionally an amorphous phase of 3 to 10 vol. %, and the balance being a REAG phase up to 100 vol.%.

[0010] Preferably the REAG phase comprises at least one rare-earth aluminum garnet phase selected from YAG, ErAG, YbAG and DyAG phases and the Sialon phase has a chemical formula Si6-zAlzOzN8-z wherein Z is between 0.05 and 1.9. A relative density of 80 % or more is particularly preferable.

Fig. 1 is a perspective view of a twin-drum continuous strip caster.

Fig. 2 is a front view of a side dam.



[0011] Through various studies the inventor discovered that ceramic plates having high corrosion, wear and thermal shock resistances and low thermal conductivity by controlling the percentages of the REAG, Sialon and BN (plus amorphous) phases to within specified ranges.

[0012] Here, the REAG phase is a high melting point compound comprising rare-earth metal oxide RE2O3 and aluminum oxide in the proportions of 3RE2O3 : 5Al2O3. The REAG phase according to this invention comprises at least one rare-earth aluminum garnet phase selected from YAG, ErAG, YbAG and DyAG phases. The REAG phase may comprise two or more rare-earth aluminum garnet phases in given proportions.

[0013] Each of the YAG, ErAG, YbAG and DyAG phases comprises 3Y2O3 : 5Al2O3, 3Er2O3 : 5Al2O3, 3Yb2O3 : 5Al2O3, and 3Dy2O3 : 5Al2O3.

[0014] In the course of the studies it was discovered that the REAG phase is very stable when in contact with the molten metal of stainless and other steels and scarcely forms product of reaction at the contact interface.

[0015] The cause of this high corrosion resistance is inferred to be as follows: When rare-earth oxides are present alone in ceramics, they react with Fe2O3 in molten steel and form rare-earth iron garnet, thereby allowing the progress of erosion. If, in contrast, they are formed in advance as a stable REAG phase, rare-earth oxides inhibit the reaction with Fe2O3.

[0016] The ceramic plates according to this invention comprise a REAG phase of 10 to 90 vol.%, a Sialon phase of 20 to 45 vol.%, a BN phase of 15 to 35 vol.% and optionally an amorphous phase of 3 to 10 vol.%. Adequate corrosion resistance is unobtainable if the REAG phase is less than 10 vol.%.

[0017] The Sialon phase does not provide high strength and thermal shock if the quantity thereof is less than 20 vol.% and does not have high corrosion resistance if the quantity thereof is over 45 vol.%. z in the chemical formula for the Sialon phase Si6-zAlzOzN8-z is 0.05 to 1.9. If Z is smaller than 0.05, high corrosion resistance is unobtainable and if Z exceeds 1.9 adequate thermal shock resistance is unobtainable. It is particularly preferable that Z is between 0.1 and 1.5.

[0018] For the attainment of high thermal shock resistance, it is preferable to add the BN phase. It is desirable to add a BN phase of 15 or more vol.% as adequate thermal shock resistance is unattainable thereunder. If the quantity of the BN phase exceeds 35 vol.%, however, hardness drops significantly. Wear resistance drops, thermal conductivity rises, and a propensity for skull adhesion appears.

[0019] It is therefore necessary to add the BN phase in the range of 15 to 35 vol.%. To obtain high wear resistance, it is preferable that the h-BN phase having a hexagonal crystal structure is used. The t-BN phase having a random crystal structure may also be used.

[0020] Essentially, an amorphous phase need not be contained. If the quantity of the amorphous phase exceeds 10 vol.%, corrosion resistance and high-temperature strength sometimes deteriorate. Therefore, the preferable quantity of the amorphous phase is between 3 and 10 vol.%. While the preferable constituent elements of the amorphous phase are rare-earth elements, aluminum, silicon, oxygen, nitrogen and some unavoidable impurities may also be contained.

[0021] It is furthermore preferable that the ceramic plates according to this invention have a relative density of 80 % or higher. At under 80 %, adequate wear and corrosion resistances are unobtainable. The particularly preferable relative density is 90 % or higher.

[0022] The REAG phase in the ceramic plates according to this invention can be synthesized by forming and sintering a powder prepared by mixing compounds in a predetermined given volume percentage. It may also be possible, before forming and sintering, to synthesize a powder of the REAG phase by mixing, pre-sintering, pulverizing and/or electromelting.

[0023] Powders of Y2O3, Er2O3, Yb2O3, Dy2O3, Al2O3, Si3N4 and BN can be used as materials. From the viewpoint of a good sintering.property, material powders approximately between 0.2 µm and 5 µm in size are preferable.

[0024] Forming can be carried out by any of uniaxial mold pressing, cold isostatic pressing (CIP), casting and injection molding.

[0025] Sintering can be carried out by any of atmospheric sintering, gas-pressure sintering, hot pressing and hot isostatic pressing (HIP). To inhibit oxidation of material powders during sintering, it is preferable to carry out sintering in inert gases such as nitrogen and argon gases. The desired properties are likely to be obtained if sintering is carried out between 1650 °C and 1800 °C.

[0026] The ceramic plates according to this invention comprise a Sialon phase of 20 to 45 vol.%, a BN phase of 15 to 35 vol.% and optionally an amorphous phase of 3 to 10 vol.%, with the balance being the REAG phase consisting of at least one rare-earth aluminum garnet phase chosen from the YAG, ErAG, YbAG and DyAG phases and the Sialon phase having a chemical formula Si6-zAlzOzN8-z wherein Z is between 0.05 and 1.9. A relative density of 80 % or more is particularly preferable.

[0027] Combinations of these features provide thermally, mechanically and chemically stable ceramic plates for side dams of twin-drum continuous strip casters having high corrosion, wear and thermal shock resistances and low thermal conductivity.

[Examples]



[0028] Tables 1 and 2 show the phases and properties of ceramic plates according to this invention and examples prepared for comparison are shown, with the results of casting.

[0029] Powders of Y2O3, Er2O3, Yb2O3, Dy2O3, Al2O3, Si3N4 and BN were mixed, formed by cold isostatic pressing (CIP) under a pressure of 140 MPa, sintered in nitrogen gas at 1750 °C for 4 hours to produce plates of 20 mm thick. The plates thus obtained were made into side dam members.

[0030] Crystal phases of the obtained plates were examined by X-ray diffraction to identify crystal structure. Volume proportions of the individual phases were determined by the area proportions thereof determined by micro-texture observation through a transmission electron microscope.

[0031] Relative densities were determined by Archimedes' method and by measuring the porosity of the mirrorpolished surfaces by an optical microscope.

[0032] Corrosion resistance was determined by measuring the erosion rate of test specimens immersed in a molten metal of SUS304 stainless steel at 1550 °C in argon gas. Wear resistance was determined by measuring the specific abrasion caused by rotating test drums in a hot atmosphere at 950 °C with a pressure of 4.5 kg/cm2. Thermal shock resistance was determined by suddenly dropping test specimens kept at a given temperature into water and measuring the temperature difference ΔT, which is expressed by the upper limit temperature at which strength drop does not occur, created by water quenching. Thermal conductivity was determined by the laser flash method at 800 °C.

[0033] Fig. 1 is a perspective view of a twin-drum continuous strip caster which consists essentially of a pair of cooling drums la, 1b (for example, made of copper alloy) and side dams 2a, 2b. The twin-drum continuous strip caster continuously casts thin, wide section 4 by cooling and solidifying molten metal 3 in a liquid metal pool on the rotating drums la, 1b.

[0034] The side dams 2a, 2b are pressed from both sides against the end faces of the cooling drums by a pressing system comprising a hydraulic actuator so that the molten metal does not leak from the ends of the cooling drums.

[0035] Fig. 2 shows the whole of the side dam. A side dam case 6 (for example, made of SS400 steel) forming the frame of each side dam holds a heat-insulating material 7 of a monolithic refractory (for example, made of fused SiO2) into which base members 8 (for example, made of high alumina brick) are planted. Multiple ceramic plates 9 (17 plates in the figure) are bonded to the part of the base members 8 that faces the peripheral edge (flange portion) of the cooling drums.

[0036] Casting tests were conducted by using the twin-drum continuous strip caster and side dam shown in Figs. 1 and 2. Thin, wide section SUS304 stainless steel strip having a width of 1330 mm and a thickness of 4 mm was continuously cast for two hours. While the molten steel was kept at 1550 °C, the side dams were pressed against the moving surfaces of the water-cooled drums with a pressure of 0.2 MPa and the water-cooled drums were rotated with respect to the ceramic plates at a speed of 1 m/sec. Casting was preceded by preheating with a silicon carbide heater (not shown) integrated into the frame of the side dams.

[0037] For the purpose of comparison, ceramic plates comprising a BN phase of 50 vol.% and an AlN phase of 50 vol.% and ceramic plates comprising a BN phase of 20 vol.%, a Si3N4 phase of 75 vol.% and an amorphous phases of 5 vol.% were also used. Tables 1 and 2 show the properties and results of casting tests with the ceramic plates according to this invention and those prepared for the purpose of comparison.

[0038] The ceramic plates according to this invention have REAG, Sialon (Z = 0.05 and 1.9) and BN phases as crystalline phases. The erosion rate by molten steel and the specific abrasion in the rotating tests, for examples of this invention, at 0.2 mm/hr. and 2.5 µm/m, were less than those for the comparison examples. The temperature difference created by water quenching was as large as 450 °C or more, and the thermal conductivity was as small as 9 w/(m·K).

[0039] In the casting tests with the ceramic plates according to this invention, properly shaped sections were stably cast for two hours without causing any leakage of molten steel. In the casting tests with the ceramic plates prepared for the purpose of comparison, molten steel often leaked from the interface between both ends of the rotating drums and the side dams. The side dams lost their function in a short time and it became impossible to continue casting.
Table 1
 Examples of the invention
12345
YAG phase vol.% 29 - - 25*1 27*2
ErAG phase vol.% - 46 - - -
YbAG phase vol. % - - 33 - 20*2
DyAG phase vol. % - - - 10*1 -
Sialon phase vol.% (Z value) 31 (1.3) 29 (0.1) 45 (0.5) 30 (0.8) 20 (0.3)
Si3N4 phase vol. % - - - - -
AlN phase vol. % - - - - -
BN phase vol. % 30 22 15 35 28
Amorphous phase vol. % 10 3 7 - 5
Relative density % 95 94 97 91 95
Erosion by molten steel mm/hr 0.0 0.1 0.2 0.1 0.0
Specific abrasion µm/m 2.1 1.5 2.5 1.8 1.9
Thermal shock resistance ΔT °C 500 450 500 450 500
Thermal conductivity W/(m·K) 9.0 7.0 8.0 6.5 6.0
Casting test 2 hours Complete Casting 2 hours Complete Casting 2 hours Complete Casting 2 hours Complete Casting 2 hours Complete Casting
Note) *1 and *2 formed REAG solid solutions. Vol.% was calculated from the proportions of materials.
Table 2
 Examples for comparison
678910
YAG phase vol.% 10 18 80 - -
ErAG phase vol.% - - - - -
YbAG phase vol.% - - - - -
DyAG phase vol.% - - - - -
Sialon phase vol.% (Z value) 55 (2.0) 21 (0.02) - - -
Si3N4 phase vol.% - - - - 75
AlN phase vol.% - - - 50 -
BN phase vol. % 10 54 20 50 20
Amorphous phase vol.% 25 7 - - 5
Relative density % 90 86 94 78 76
Erosion by molten steel mm/hr 1.5 2.5 0.4 2.8 3.6
Specific abrasion µm/m 0.5 12 0.8 6.1 3.1
Thermal shock resistance ΔT °C 300 400 200 350 400
Thermal conductivity w/(m·K) 12 11 4.5 14 6.0
Casting test 0.5 hour Molten metal leakage 1 hour Molten metal leakage 0.5 hour Molten metal leakage 0.3 hour Molten metal leakage 1.5 hours Molten metal leakage


[0040] The present invention, that provides ceramic plates for side dams of twin-drum continuous strip casters having high corrosion, wear and thermal shock resistances and low thermal conductivity, has great industrial applicability.


Claims

1. A refractory composition for ceramic plates for side dams of twin-drum continuous strip casters; comprising a Sialon phase having a chemical formula Si6-zAlzOzN8-z, wherein z is between 0.05 and 1.9, of 20 to 45 vol.% and a BN phase of 15 to 35 vol.%, optionally an amorphous phase of 3 to 10 vol. %, and the balance up to 100 vol.% being a REAG (Rare Earth Aluminium Garnet) phase having a chemical formula 3RE2O3·5Al2O3 and unavoidable impurities.
 
2. A refractory composition for ceramic plates for side dams of twin-drum continuous strip casters according to claim 1, in which said REAG phase comprises at least one rare-earth aluminium garnet phase selected from YAG, ErAG, YbAG and DyAG phases.
 
3. A refractory composition for ceramic plates for side dams of twin-drum continuous strip casters according to claim 1 or 2, in which said refractory composition has a relative density of not less than 80 %.
 


Ansprüche

1. Eine feuerfeste Zusammensetzung für Keramikplatten für Seitendämme von Stranggießanlagen mit Doppelwalzen; umfassend eine Sialon-Phase mit einer chemischen Formel Si6-zAlzOzN8-z, wobei z zwischen 0,05 und 1,9 liegt, von 20 bis 45 Vol.-% und eine BN-Phase von 15 bis 35 Vol.-%, gegebenenfalls eine amorphe Phase von 3 bis 10 Vol.-%, und wobei der Rest bis zu 100 Vol.% eine REAG (Seltene Erde Aluminium Granat)-Phase mit einer chemischen Formel 3RE2O3 · 5Al2O3 und unvermeidbaren Verunreinigungen ist.
 
2. Eine feuerfeste Zusammensetzung für Keramikplatten für Seitendämme von Stranggießanlagen mit Doppelwalzen gemäß Anspruch 1, in der die REAG-Phase mindestens eine Seltene-Erde-Aluminium-Granat-Phase, ausgewählt aus YAG-, ErAG-, YbAG- und DyAG-Phasen, umfasst.
 
3. Eine feuerfeste Zusammensetzung für Keramikplatten für Seitendämme von Stranggießanlagen mit Doppelwalzen gemäß Anspruch 1 oder 2, in der die feuerfeste Zusammensetzung eine relative Dichte von nicht mehr als 80% aufweist.
 


Revendications

1. Composition réfractaire pour plaques en céramique destinées à des déversoirs latéraux de machine de coulée en continu de feuille mince du type à double tambour ; comprenant une phase de Sialon répondant à la formule chimique Si6-zAlzOzN8-z dans laquelle z est compris entre 0,05 et 1,9, à raison de 20 à 45 % en volume, et une phase de BN à raison de 15 à 35 % en volume, éventuellement une phase amorphe à raison de 3 à 10 % en volume, le reste, jusqu'à 100 % en volume, étant une phase de REAG (grenat d'aluminium et de terres rares) répondant à la formule chimique 3RE2O3•5Al2O3, et des impuretés inévitables.
 
2. Composition réfractaire pour plaques en céramique destinées à des déversoirs latéraux de machine de coulée en continu de feuille mince du type à double tambour selon la revendication 1, dans laquelle ladite phase de REAG comprend au moins une phase de grenat d'aluminium et de terres rares choisie parmi les phases de YAG, ErAG, YbAG et DyAG.
 
3. Composition réfractaire pour plaques en céramique destinées à des déversoirs latéraux de machine de coulée en continu de feuille mince du type à double tambour selon la revendication 1 ou 2, laquelle composition réfractaire a une densité relative non inférieure à 80 %.
 




Drawing