Description
Name of the invention: refractories for casting and casting nozzle after using it and for sliding nozzle plate
Technology areas
[0001] 　This invention is a sliding nozzle device for casting nozzle used for casting refractories used in the casting of steel and refractory materials, and molten steel flow control (hereinafter referred to as 'Device SN'. ) To the sliding nozzle plate used (hereinafter referred to as "SN plate". ) On.
His innovations.
[0002] 　Flow road of molten steel in the casting of steel from molten steel container and ladle and tundish discharged SN equipment nozzle for casting of molten steel flow control is used. SN equipment used SN plate with a refractory nozzle 3 hole or two. SN plates was detained under the overlay adapted, added further pressure in dynamic regulated flow of molten steel in and adjust the opening of the nozzle hole.
[0003] 　Characteristics such as "rough skin surface durability" to face rough composition on thermal stresses during casting, mechanical strength, can withstand under captive conditions using SN plates, thermal shock resistance, molten steel and slag, etc for corrosion resistance, oxidation resistance, surfaces and production will further subjected to wear and tear are required.
[0004] 　Are divided into high-temperature firing and fired at a temperature of about 1000 ° C under low-temperature baking products, SN plate, alumina carbon refractories used in General, and fired at high temperatures of approx. 1000 ° C or more from the process. Generally more firing of high-temperature baking products, higher porosity than the low-temperature baking products from further tar, pitch, etc. including I soak manufactured by. Thus, products with high temperature firing by firing at high temperatures and impregnated and formed dense, strong body, and is fired at high temperatures to heat up to high temperatures with stability, and excellent thermal shock resistance. Tar and pitch, and fired at high temperatures, however, including that soak on SN plate to occur, and when you use the smoke or toxic substances to remove previously impregnated after caulking process, including manufacturing, energy processes in the must be friendly to the environment became very expensive, and you use tar, pitch, etc.
[0005] 　It compared, low-temperature sintering and high-temperature baking products, and lower energy costs and eco-friendly. To give strength and oxidation resistance of this low-temperature baking products as containing the low melting point of aluminum and aluminum alloys are added, fired at different temperatures of less than 1000 ° C, so-called puff products or so-called 不焼成 products and what are referred to as much disclosure.
[0006] 　For example compounds of metal aluminium powder consisting of refractory raw material, phenolic resin, and spherical atomized powder in the patent literature 1, kneading, formed after the 550-heat treatment at a temperature of 650 ° C manufacturing methods have been disclosed. Aluminium carbide generates causing gas with less oxidation resistance of phenolic resin under 550 ° C, heating temperature, when you use an odor and then exceed 650 ° C and has been. Also, is often accompanied by swelling and weight gain, and produce aluminum hydroxide to produce aluminium carbide, and react with water readily at room temperature and under atmospheric storage plate collapses.
[0007] 　In the patent literature 2, fire resistance of inorganic materials aggregate 90-99. 0 of 5 mass % and aluminum or aluminum alloys. 5-10 mass % from compound, phenol resin, 700 ° C, the thermal treatment at 850 ° C and 1000 ° C that may have been disclosed. With heat treatment at the melting point of aluminum or aluminum alloys (metallic aluminium is 660 ° C) or more grain from surrounding tissue into metallic aluminium, dramatically improves the strength of refractory materials, and thermal shock resistance also significantly increase; And may cause voids and cannot hold higher than 1000 ° C annealing temperature and excellent characteristics as fibers of aluminum or aluminum alloys, eliminates the difference between the nature of the powder and fiber, and the penetration of aluminum progresses, fiber existed, but rather deteriorate corrosion resistance;
[0008] 　In the patent literature 3, fire-resistant inorganic raw materials, carbon materials, and metallic materials and those raw materials, particle size is 0. 4000 µm and 1 µm in continuous grain distribution system, plus the phenolic resins, non-oxidizing atmosphere 800-and then fired at 1500 ° C and no impregnation method is disclosed. In addition, its embodiment, and firing at 850 ° C, apparent porosity 5. 0% of refractory materials is disclosed.
[0009] 　In the patent literature 4, aluminum and aluminum alloys up 0. 5-20 mass % containing refractory raw material composition and added organic binder, after mixing, molding and heated at 400 ° C to 1000 ° c, then such as tar, pitch-carbon liquid inclusions, including compressive strength is the rate of weight gain in the digestibility of 180 MPa and autoclave disclosed less than 1% refractory and refractory not steeped in.
[0010] 　These patent literature 1-SN 4. as disclosed to a conventional is required casting refractories, a particularly high degree of corrosion resistance and wear resistance such as refractory plate (hereinafter referred to as plate refractory products and. ), Oxide, alumina, magnesia, spinel, Zirconia quality on the main construction materials. However, that runs out because of these oxides is greater coefficient of thermal expansion thermal shock resistance.
[0011] 　Means of using raw materials containing silica, mullite etc as a method to improve on the thermal shock resistance of refractories for casting, especially plate of refractories in the, or raw materials containing zirconia zirconium light and arminazirconia are adopted.
[0012] 　Silica-containing raw materials (silica-containing materials), to improve thermal shock resistance, lower thermal expansion coefficient of refractory products by adjusting its content mullite thermal expansion coefficient smaller than mineral oxide, alumina, magnesia, spinel, Zirconia quality the mineral itself, so you can for example.
[0013] 　Zirconia-containing raw materials (zirconia containing material) compared with alumina raw material low coefficient of thermal expansion, and also characteristic of zirconia phase is considered to be granted at the effect to reduce the thermal expansion coefficient and elastic modulus, has the effect of reducing the modulus of refractory products by generating microcracks or micro space organization has a singular expansion behavior associated with the transition from shock resistance.
[0014] 　These silica and zirconia-containing raw materials combined with improved thermal shock resistance, for example 5. 0 mass %~15. You have 0 mass % of be contained in relatively large amounts. However, these have a raw volume use rather durability compromising.
[0015] 　I.e., easily reduced in about silica, coexisting with carbon atmospheres SiO gas, and be easy to lose organizational refractories rough, and organized by iron oxide or slag components becomes easier to deep in the infiltration, oxidation resistance also decreased. In addition to silica, reacts with molten steel comes from iron oxide inclusions in steel and slag components low to melt, melt to generate. Therefore, to large amounts of silica, mullite and zirconia m light reduce durability degradation such as corrosion resistance, oxidation resistance is obtained in the case.
[0016] 　Zirconia constituents, stress relaxation effect of micro-cracks and micro spaces, etc., etc., so less is used repeatedly, casting time is relatively short and relatively terms of use loose in there. However, refractories using zirconia-containing material, long use and repeated many times the terms of use, damage due to abrasion edge defect due to expansion of the crack and tissue degradation and surface increases, become a rather compromising durability.
[0017] 　Here and repeated use, for example in SN plate for pot use and tundish at hot means Foundry after the nozzle hole around the criteria used in the rotation, high temperatures of over 1000 ° C and cooling plate itself is, repeated high temperature heating and cooling in temperature of about 500 ° C or less until the next casting terms of use. Ladle for many multiple times, that the criteria used (e.g. 8-channel or more) ch, hot "means a condition which is used for rotating tundish 2 cast more than.
[0018] 　And if prolonged use and used in ladle casting total for example condition for a long time about 500 times more than steel to good, tundish by hot rotation, refers to a condition of more than 800 minutes for example.
[0019] 　Terms of use repeated heating and cooling, bring plates of organizational change from more exposed to high temperatures for a long time. That by a large plate refractory wear tough use conditions.
[0020] 　Employed the carbon bond connective tissue of refractories for casting a lot more. So we often used to this carbon to protect from oxidative loss such as oxygen affinity of strong aluminum metal. 1 the above patent literature-metal aluminum is applied to low temperature or was fired at high temperature refractory materials were exposed to 4.
[0021] 　On the other hand cause 1 reduce the durability of refractory products refractories containing the low melting point metal oxygen affinity, such as aluminum, Zirconia-containing raw materials in conjunction.
[0022] 　Has this factors and mechanisms as possible.
[0023] 　Partly due to that condition is exposed to high temperature, such as the surface of the nozzle holes around the casting nozzles and SN plates, atmosphere in the porosity of refractory materials, carbon, reducing atmosphere. Decreased oxygen concentration further aluminum reside in a strongly reducing atmosphere. Silica in this strongly reducing atmosphere zirconia also reduced easily, then reacts with carbon to produce nitric oxide zirconium, zirconium, zirconium Carbide. Nitric oxide zirconium, zirconium, zirconium carbide produced high oxygen affinity to zirconia, readily oxidized in oxidizing atmospheres. In this case, volume expansion, cause defects in the organization. Induces various damage, such as the aforementioned thus deteriorated in the cast of the long-running and when you use the repeat organizational refractories.
[0024] 　To reduce tissue degradation of refractory or durability, transformed by reduction in refractory oxide material of refractory materials in cost-effective as an antioxidant substances like this high oxygen affinity, such as aluminum, on the other hand, is exposed to high temperatures for a long time, and the results.
[0025] 　Although there are differences such as temperatures, other metals such as magnesium to the active metal each caused a reaction of aluminium metal and aluminium as well as by its oxygen affinity. From things like this, including aluminum, magnesium and their alloys for refractory products, applied with copious amounts of raw material containing silica and zirconia zirconium light and arminazirconia technology of the past, trying to improve thermal shock resistance by the raw material and the long-running cast and many in severe heat conditions such as once again the improvement in durability is limited.
[0026] 　Extent of reaction, such as zirconia and silica-containing material with metal aluminum refractory damage varies by these relative content, forms. In addition, in compositions such as fire resistance of aluminum with a lot of use of densification of refractories by reaction of aluminium metal with high elastic modulus and reduce thermal shock resistance, so especially in the large shape SN plate repeated use becomes difficult.
[0027] 　On the other hand, in the patent literature 5, mineral phase and the Al4O4c 5-SN plate mass 95% content and thermal expansion coefficient is 8 × 10-6 / k, is at 10 MPa to 60 MPA flexural strength at room temperature have been disclosed.
[0028] 　Al4O4c low thermal expansivity, thermal shock resistance improvement is expected this. However, Al4O4C for a long time are numerous and are used once and is exposed to oxidizing conditions and progress of Al2O3 , low will reduce the effect of thermal expansion of material. Therefore only containing Al4O4C to get to 10-improvement of thermal shock resistance and durability.
Prior art documents
Patent documents
[0029] Patent literature: open public 2000-94121 issue report
Patent literature 2: special square no. 1-313358 bulletin
Patent literature 3: special square 11-199328 Gazette
Patent literature 4: international publication No. 2009 / 119683,
Patent literature 5: open 2011-104596 issue public report

Summary of the invention
Inventors are trying to solve a problem
[0030] 　To improve the durability of refractory materials is repeatedly subjected to the use or tries to resolve the invention challenge is casting nozzle for casting refractories, and SN plate used for a long time.
Means for resolving problems
[0031] 　The invention: 1 ~ recorded 6 casting refractories, nozzle for casting & SN plate.
[0032] 1.
　Al4O4C, the aluminum content of 15% or more, 60 percent less than the metal one... 2% or more in 10... 0 mass 85% or more by, and containing less than %, the remainder consisting of Al2O3, free in C and other fire-resistant components for casting refractory products in total of Al of Al4O4C, Al2O3 and metal content of Al4O4C (4 C) and Al components as the metal content (Al) and C-free content (C) the following formula 1 casting refractory characteristics to satisfy the formula and 2,.
　1. 0 ≤ C / (Al4O4C×0. 038 + Al×0. 33). Formula 1
　1. 0 ≥ C / (Al4O4×0. 13 + Al×0. 67). Expression 2
[0033] 2.
　Casting refractory particles containing Al said Al4O4C manufactured by electrical fusion4O4C to 1, derived from the above mentioned.
[0034] 3.
　Wherein Al4O4C-containing raw material particles in Al4O4C Crystal size is Al4O4C Crystal Cross Yen to 20 µ m more than in the equivalent of the average diameter, above 2 casting refractories stated.
[0035] 4.
　In refractory substances above the rest selected from the Group of MgO, SiO2, Orthorhombic or monoclinic ZrO2, SiC,B 4C , BN, Si3N4 and metal on one or more than one, said 1 in one of the 3 above mentioned casting refractories.
[0036] 5.
　Containing more than 10% and less than 200% of metal silicon mass percentage of Al components as previous metal content, wherein one-to one of the above 4 in casting refractories.
[0037] 6.
　From claim 1 claim 5, refractories for casting one of the mentioned in part or in full provided, nozzle for casting or SN plate.
[0038] 　The invention describing in detail.
[0039] 　To resolve the problems described above, such as zirconia and silica-containing materials within the invention Al4O4C to main materials for refractory products. In about half of 4 × 10-6 / K, the alumina is the thermal expansion coefficient of the Al4O4C low in thermal expansion coefficient. This low thermal expansion of the refractory with high thermal shock resistance that can be. Cost-effective and conventional zirconia-containing raw materials technology arminazirconia coefficient of thermal expansion lower than that. Also, Al4O4c of zirconia in high temperature phase transition, is a singular expansion behavior has the effect of reducing the elasticity from that do not show benefit do not repeatedly use tissue deterioration that could cause hard to.
[0040] 　Al4O4c Al2O3 precipitation reactions in a carbon monoxide atmosphere below 850 ° C or higher, shown in Equation 3. And form a dense alumina layer working face first, Al4O4C protects the alumina layer inhibits further oxidation of Al4O4C variations. C Al4O4alumina protective layer on the surface including the refractory in low corrosion resistance silica with a lot of the show because it does not contain the high corrosion resistance, abrasion resistance, etc.
　　　Al4O4C+2CO = 2 Al2O3+3 C. Formula 3
[0041] 　The Al4O4C to form a layer containing nitrides and carbides by atmosphere.
[0042] 　Al4O4C as Al2O3 deposited in this way from the alumina - zirconia raw materials and has excellent corrosion resistance, against the wear and tear of the surface can be expected to improve compared with zirconia-containing materials such as zirconium light stuff.
[0043] 　As content as the mineral phase Al4O4c weight 15% less than the reduction of the coefficient of thermal expansion is small, inadequate thermal shock resistance. Al only by the regulator and on the other hand, Al4O4c 60 weight percent more than Al4O4C relative to overload, according to Al constituents for free C and metal content of4O4C Al2O3 . in sintering with suppression to that is difficult to get.
[0044] 　Furthermore, the refractory plates generally stator with iron bands was bound by the circumference of, or placed in metal containers, used often. Content of refractory Al4O4C coinciding with increases is the thermal expansion coefficient of refractory from reducing during casting than the expansion of the refractory wherein steel bands or steel containers of more increases may cause gaps between and out of refractory steel bands or steel containers. This phenomenon becomes particularly expands the crack of refractory materials in use for a long time and causes to repeatedly use the dropping of refractory materials (of the plate); Reason, as mineral phases Al4O4C content of 15% or more, 60 percent less than that should be
[0045] 　In Al4O4C for a long time are numerous and are used once is exposed to oxidizing conditions and progress of Al2O3 , low will reduce the effect of thermal expansion of material. In addition, the density of Al2O3 3... Density of 9, C 2... 0, Al4O4C density is 2. Due to the reaction of the foregoing formula 3 to 7 and 3. From 1% of volume expansion with Al4O4C Al2O3 for you and appears a tendency also decreases resistance to thermal shock due to the progress of sintering, densification is in progress as it progresses.
[0046] 　Therefore Al as a major refractory aggregates for thermal shock resistance of4O4C, survive as Al4O4C, holding to the Al2O3 is preferable.
[0047] 　We made with aluminum to the present invention includes the Al4O4C as the aggregate of the aluminum to capture oxygen preferentially to C Al4O4, Al4O4C to protect and raise the remaining amount.
[0048] 　Aluminum or aluminum alloys by 660 ° C below the melting point and then cast from the vicinity of approximately 660 ° C until the temperature can develop resistant oxidation effect in a wide temperature range. Therefore, you can for example to further enhance the oxidation resistance of SN plates on repeating use the temperature distribution in the plate of refractory in low temperature part. That can prevent and control with the Suppression and prevention of oxidation of refractory materials (carbon compounds) at temperatures below about 850 ° C oxidation resistance of Al4O4C may develop that can be oxidized Al4O4C in the temperature range of approximately 850 ° C or higher.
[0049] 　Al components of metal casting Refractories in the invention contained here, and, except in compounds with other elements, consisting of aluminum raw material to Al components, including aluminum alloy material to Al components including, 1. Content of 2% or more, 10% less than the amount equivalent of Al components of metal;
[0050] 　Content of Al components of this metal is one... You can't get the antioxidative effect of refractory products in C and Al4O4C in less than 2 weight percent. You can't get enough due to overly progressive densification, sintering, etc, and on the other hand, over 10 mass % reacting aluminum used when receiving heat from the thermal shock resistance.
[0051] 　Content of Al components as this metal can be adjusted depending on the shape of the nozzle for casting distinct, SN plate or terms of use (operation). And can be used as a component of Al alloys, metal aluminum - magnesia alloy, metal aluminium - silicon alloy, etc.;
[0052] 　These aluminum and aluminum alloys is the particle Al4O4C (spherical regardless of whether the plate is) the preferable to spread around. From this point, aluminum or aluminum alloys is 0. 3 mm or less atomized or fiber that is preferred.
[0053] 　Progress and reaction from the surface of the particles with the atmosphere in a carbon monoxide atmosphere above 850 ° C, indicated in the foregoing formula 3 Al4O4C, to generate a phase to Al2O3 and C. By Al4O4C surface is bordered by Al4O4C, Al2O3and SiO2 aggregate materials and easier if the sintering, to form a network. To suppress the oxidation of Al4O4C, preventing you from having this reaction layer is formed by Al4O4C direct contact with atmosphere and excessive reaction comes to reduce thermal shock resistance, and lead, coupled with excessive or high modulus of on the sintering and the surrounding components, etc..
[0054] 　Also, aluminum or aluminum alloys exposed to temperatures above the melting point and melt, infiltrated in the matrix and form the network components between the Al as the metal also depending on ambient conditions, 4 of the following reactions indicated by the formula and 5 C with Al2O3 or Al2O3 formation, along with the Organization of dense high-strength and. But on the other hand noticeably, becomes a high elastic modulus. As well as also of ease sintering of ultrafine alumina particle and oxide sintered form network, could become high modulus and high strength, increased significantly.
　4 Al (l) +3 C(s) = Al4C3(s)... Type 4
　2Al+3CO = 2 Al2O3+3 C. Type 5
[0055] 　Density of Al 2... Density of 7, C 2... 0, the density of Al4C3 to 2. The density of 36, Al2O3 up 3. From 9 and Al is deposited as shown in the above equation 5 Al2O3 and C if you 120% of volume expansion with remarkably organization densification to. Reacts with the aluminum melting if C-free is dispersed in a matrix, is easy to produce the charcoal aluminum. Volumetric expansion due to oxidation of aluminium carbide is 5. Not increase the densification of densification effect of the Organization, to form the Al2O3 and by around 2 percent as much as that.
[0056] 　To curb excessive increases elasticity and excessive progression of the densification of these reactions require the existence of a certain amount of free C. That do not form compounds with other elements, such as carbon due to the binder, such as phenolic resins, graphite and Coke powder, pitch powder, carbon black, powdered resin, whether in the amorphous or crystalline free C and carbonaceous materials C ingredients. I.e., do not contain carbon as a compound such as Al4O4C, SiC, B4C is.
[0057] 　By reaction of Al of Al4O4C, or metal that exists in a matrix of refractory materials, especially Al4O4c particle free C is spread across around the Al2O3(& C) of can suppress the deposition itself. And as well to cut off the network of sintering and other aggregate materials due to this reaction or alteration, etc., etc..
[0058] 　To suppress the reaction itself and fire-resistant components and other ingredients as above Al4O4C, or metal Al and Al2O3 , because for a long time, or a number with resistance to use the proper and fair in Al4O4C content (Al4O4C), Al ingredient as the metal content (Al) And C free content (C) the formula 1 should meet the formula and 2.
　1. 0 ≤ C / (Al4O4h×0. 038 + Al×0. 33). Formula 1
　1. 0 ≥ C / (Al4O4C×0. 13 + Al×0. 67). Expression 2
[0059] 　As mentioned above in a carbon monoxide atmosphere Al4O4C and deposited by the reaction of carbon monoxide and Al2O3 and C the effect dense tissue is obtained, one in 1 mol Al... Effect back to 5 moles of carbon monoxide for Al4O4C is effective to return to 3 moles 1 mole of carbon monoxide. This is for Al:1 mass % Al4O4c 5... 1 mass % suggests that antioxidant effect as well.
[0060] 　Free to suppress Al4O4C reaction sintering or densification is excessive (such as high-modulus) at least caused Al4O4C particles at the interface between the surface layer of a matrix in C and Caco, wherein the surface layer of oxide Al2O3 , etc. and not as direct contact is desirable.
[0061] 　Samples ingredients and raw materials that contain C-free raw materials that contain Al4O4C in Figure 1, changing the content of Al4O4C and C free content, free C and Al4O4C volumetric ratio fabrication and 1300 ° C non-oxide atmosphere in baking the refractories of elastic modulus show. As a result, Al4O4c 5 C-free... Tend to reduce the elasticity to 0% more than it was found.
[0062] 　In Figure 2, the average particle size is 0. After firing at 1500 ° C in non-oxidizing atmosphere after temporarily fired alumina 6 µm, and added a 5 nm carbon black (free C) primary particle size, change the amount of mixing formed in the shape of a given sample rate shown. Decreased shrinkage, sinter from the contact surface of alumina particles contract conditions with the addition of C, and c the amount of more, C concentration is about 10 bodies in area % almost contraction rate is zero. Possible to prevent bonding of alumina particles, temporarily fired alumina particles surface coated by carbon black (C), or by CACO and inhibits the sintering.
[0063] 　To be easy to check it was thought, particles for sintering speed and extent of the thickness of the layer of particles around C, depending on the type of particle is no difference and sintering behavior of, temporarily fired alumina using Al4O4C here.
[0064] 　Table 1 (and table 1 chart of Figure 3), which approximate the thickness of the coated surface of the particles of the Al4O4C from this result or a CACO carbon black. Approximate results, C amount of 10 volume percent from (7. 66%) of the cases Al40 0 is the thickness of the coated particles around the4C C layer thickness, i.e. Al4O4C particles or to CACO carbon black (C). You can inhibit the sintering of Al4O4C 02 μ m or more if the shows.
[0065] [Table 1]

[0066] 　The elastic modulus of sintered Al4O4C rise, by foregoing formula 3 by sintering and densification of the organization by volume expansion during the deposition of C and deposited Al2O3 and around Al2O3 and Al2O3 oxide component is considered.
[0067] 　The following table 2 (and table 2 graph of Figure 4) the Al4O4C average particle size to change the 0 on the surface of the particle. Calculation of volume and mass ratios of covered free 02 µm thick C or the CACO Al4O4C and C free shows.
[0068] [Table 2]

[0069] 　On the surface of Al4O4C 0. Reduction of elastic modulus based on the results shown in Figure 1 C layer-free 02 µm thickness, and above Al4O4c to get free to have Al4O4C C amount: minimum size meets criteria 5 volume % 2-Al4O4C 1 from the calculation results (table 2). 2 μm; That is, Al4O4C particle size is 1. To help reduce the elasticity around the Al4O4C particles or particles, even at 2 µm, for this Al4O4particles carbon free C minimum 5 volume % added, can get the C horizon thickness necessary and sufficient free and Al4O4C particle size bigger and free of C of thickness thicker. In other words, Al4O4C average particle diameter is 1. If more than 2 µ m C-free content volume is 5 Al4O4C content of the volume of... 0% below can be even Al4O4C whole grain surface coated carbon-free or to CACO. I.e. sintered suppression is obtained.
[0070] 　The casting Refractories in the invention Al4O4C, which especially impact resistant capabilities as part of the main composition material or the material here. Is large (coarse grain also referred to) or moderate (where even larger than the matrix powder, also called intermediate-grains) relative to common general knowledge is size of the substrate to demonstrate these features. Namely, essentially casting Refractories in the invention Al4O4C average particle size is 1. Preferred that because also in the later Al4O4C Crystal size is 20 μm preferred m more than 2 µ m is greater than the Al4O4C particle size is 20 μ m or more.
[0071] 　From this inventive casting Refractories in the, at least free c is 5 Al4O4C content amount. 0 body containing volume percent or more that is within the scope of the above knowledge Al4O4C particle size or will enable to reduce sintering and other fire-resistant ingredients Al4O4C particles around that day.
[0072] 　Al4O4c 5. 0 of 2 is C-free volume percent or more density of Al4O4C. Density of 7, free C 2... 0, this converted to mass fraction and mass of Al4O4C 3. 8% or more;
[0073] 　C-free coated particles containing Al4O4C, surface or by CACO, there is as a matrix of refractories coupled organization itself or not to exist as a part.
[0074] 　You can calculate the C is required to exist around C layer sintering for the Al as a metal,. The ability to generate, at Al components as shown the above 5 Al2O3 to promote the reaction shown above 4 suppresses that expansion of larger and smaller amount of expansion more preferable. In other words, C the amount needed to produce charcoal aluminum Al component as the metal is indicated by equation 4 free free 3 / 4 MOL C, Al ingredient 33% or more of need for Al ingredients 1 mole.
[0075] 　Content of C-free coated Al constituents as particles containing Al4O4C for more than thermal shock resistance, and a metal surface or a need exists to CACO 3 Al4O4C content... 8% or more, and be combined with Al concentration of metal mass 33% more than that.
[0076] 　Relationship between content of this free C and Al concentration of metal and Al4O4C content is represented in equation 6.
　C greater than (Al4O4C×0. 038 + Al×0. 33). For 6 expression
　Said formula one would transform it.
[0077] 　Inhibits progress by Al4O4C and Al reaction and sintering densification excessive, excessive elasticity increases if you do not meet the expression 6 i.e. 1, small, cast on for a long time, causing damage such as cracks or chipped edges.
[0078] 　If If you have excessive amounts of free C on the other hand, particularly exposed to oxidizing atmospheres, etc. near the running surface is oxidized by the following reaction.
　2c+O2= 2 CO.　-7
　C+co2= 2 CO. -8
[0079] 　Be invited tissue degradation and oxidation-free C, and promotes erosion, reduce the durability factor. Especially that tend to become prolonged or repeated use.
[0080] 　Oxidized Al and Al4O4C, as mentioned earlier, C, Equation 3 can get the antioxidant effect and reduced the response shown in expression and 5, made a deposit as a C as densification to your organization.
[0081] 　Al is type 5, 1 1 mole. Effective 5 moles of oxidized C again as C to deposit in tissues, but 1. You can't deposit as C for the oxidation of the C more than 5 mmol. This is Al:1 mass % 0... To show inhibited the oxidation of 67 WT % C.
[0082] 　You can't deposit as C for more than 2 mol Al4O4C is effective as the original C deposit the 2 Mole oxidation of the C-4 than one Mole in the oxidation of the C. This equivalent to mass, Al4O4C 1 mass % with 0's. With the antioxidant effect of the 13 WT % C;
[0083] 　You can represent maximum amount by Al components in refractories Al4O4C as a metal able to prevent oxidation of the C-free is this WT % c-free translated and rewritten in equation 9.
　C = (Al4O4C×0. 13 + Al×0. 67). -9
　To transform this, above 2;
[0084] 　Be able to suppress the oxidation of all C Al if C-free content does not meet the above-9 or 2 containing4O4C and Al containing free.
[0085] 　You can also derive the following equation from 6-9.
　(Al4O4C×0. 038 + Al×0. 33) ≤ C ≤ (Al4O4C×0. 13 + Al×0. 67). 10 mm
[0086] 　You can get the antioxidant effect shown above, degrading components as the metal Al and Al4O4C thermal shock resistance can make densification organization in C and deposited as a C C oxidized, reduced, along with the oxide, not free.
Advantageous effects of invention
[0087] 　While maintaining required casting refractory to the invention by oxidation, corrosion and abrasion resistance can increase the thermal shock resistance and prolonged or repeated use would be. Therefore, refractories for casting of the invention using the casting nozzles and SN plate is suitable for prolonged or repeated use, you can get excellent durability.
A brief description of the drawings
[0088] An example of test results indicating the relationship of refractories in the [Fig. 1]-free C and Al4O4C volumetric ratio and elastic modulus.
Experiment illustrates the relationship between firing rate and amount of [Fig. 2] carbon black (free C)
Experimental results show the relationship between average particle size [Fig. 3] Al2O3 and C layer thickness (C/Al4O4C volumetric ratio, mass ratio) example (table 1, chart of things).
Experimental results show the relationship between average particle size [Fig. 4] Al4O4c and C layer thickness (C/Al4O4C volumetric ratio, mass ratio) example (table 2, chart of things).
[Figure 5] the invention Al4O4C content of carbon-free range (Formula 1 referred to in expressions and range) conceptual illustration showing.

For carrying out the invention
[0089] 　Depending on the shape of the refractory materials used in the invention Al4O4C-containing raw material particle for the individual conditions and needs, the particle size classification and selecting proportion, etc.. For example 5 mm-3 mm, 3 mm-1 mm, 1 mm and 0 mm or 0. 074 mm over the classification, these apply at any rate where possible. To apply as a relatively large particles, the so-called coarse aggregate materials including to increase the effect of reducing the thermal expansion coefficient of refractory materials with low thermal expansion material itself Al4O4C is desirable. Al4O4C and preferred the shape of spherical or nearly so, even though the plate I don't care.
[0090] 　Al4O4C-containing raw material particles in Al4O4C Crystal size, Al4O4C Crystal Cross Yen to 20 µ m more than in the equivalent of the average diameter is preferable. Larger size of Al of Al4O4C-containing raw material particle in4O4C in terms of use of the long-running Al4O4C Al2O3 for more advanced to suppression, Al4O4C remaining that can be.
[0091] 　Particles containing Al4O4C is electro-fused arc-melting material, corundum (Al2O3) Al4O4C with the main components of the electro-fused material is preferable. Al4O4C-containing raw material is on the sintering of the existing productivity, industrialization of realistic and feasible and also produce raw materials can be dense and large crystals of Al4O4C aggregate and harder in. Electro-fused materials by ARC melting on the other hand, can get any grain productivity is high, dense, large Crystal Al4O4C aggregate materials. From this dense, high temperature and oxidation conditions smaller surface area for oxygen and carbon monoxide inhibits oxidation of Al4O4C, alumina for a long time, low heat expansion ratio that becomes possible. You can also maintain a high corrosion resistance by corundum (Al2O3) is the other main components of Al4O4C. Electro-fused materials containing the Al4O4C is 0. You can also for example organize about 20 µm or larger so-called intermediate grain and coarse grain area around, including coarse particles of 5 mm or more in the reduction of the coefficient of thermal expansion of the refractory materials to increase the long, low to keep that thermal expansion characteristics becomes possible. Along with this, alumina for prolonged use under Al4O4C also inhibit (low speed);
[0092] 　As the aluminum source of Al components as the metal form, none of the spherical form of the form of flakes or fibre-like morphology where applicable. Can be applied such as Si and Mg alloys as is feasible.
[0093] 　Preferably spherical forms, including as a form of aluminum casting refractories-of the present invention is fired at temperatures above 660 ° C, applying a surface area smaller relatively high temperatures remaining atomized and fiber-like form, average particle size is 0. should be added to aluminum metal 074 mm grain, apply to 100 mass of more than 30 mass, of less than 90.
[0094] 　Be preferable to generate the charcoal aluminum from alumina densification due to reaction of aluminium metal and high elastic modulus of curb because swelling is less than producing alumina from aluminum to produce charcoal aluminum. As shown in the above equation 4 assumed to generate total hydrocarbon aluminum containing aluminum (Al components of metal), Al:4 MOL C:3 MOL, i.e. Al:1 (WT %) on C:0 to... Will be good if containing free 33 mass %, i.e. 1/3 C.
[0095] 　But for example key parts of the surface of the molten steel surface and plate for refractory products despite high temperatures or low temperatures of several hundred degrees Celsius below regardless of the atmosphere contains the process exposed to water vapor derived from other terms used repeatedly, also in the fire to large amounts of aluminum there is digestion of the charcoal aluminum if in particular, shown in equation 11, that brought about the destruction of organizational refractories.
　　　Al4C3+6 H2O = 4 Al (OH)3+3CO+9 / 2 H2 . Type 11
[0096] 　In General just how many times and for a long time, even if no charcoal aluminum digestive conditions, namely, refractory organization, structure, composition, etc., also there are differences arising at the environment of refractory materials, but generally below about 200 ° C or evils of aluminium carbide generates in terms of Gastrointestinal reactions due to water vapor does not like because there is no, aluminium carbide generates itself is desirable.
[0097] 　Preferable to contain small metal Si and SiO2 ingredient to curb wherein digestion reaction conditions occur repeatedly prohibited, namely hydrocarbon aluminum digestive reactions like this other than that. By replacing Silicon in aluminium carbide Al part, resistant to digestion.
[0098] 　If this repetitive use 0 metal Si in the refractory of the invention... 5 mass % over desirable weight percentage of Al components as a mass of 10% or less, or metal containing at least 10%, 200% or less.
[0099] 　Desirable as aggregate Al4O4C other than Al2O3 to the principal. It should be that in the refractory of the present invention, total Al components as Al4O4C, metal and Al2O3 content of 85% or more, the rest should be a refractory composition containing metal such as magnesia free C and carbide, nitride, boride, or silicon,.
[0100] 　As the rest of the ingredients as Al4O4C, metal Al and Al2O3 content of minimum total amount 85 mass % said formula one and free based on the 2 C amount and other refractory components should oxides of metals, carbides, borides, nitrides, or Si, Mg, or magnesia, trace amounts of zirconia and silica.
[0101] 　Thus the remainder improved resistance invasive, oxidation resistance and corrosion resistance of slag, etc., etc. as carbides, borides, nitrides, etc to can contained. But to rest on carbides, borides, nitrides, etc is not oxidation degradation of these and wear and tear due to leaching into the molten steel are larger and larger erosion of refractories. Also, large amounts of metal such as Si and Mg (for example the remainder all) to contain significant progresses sintering of the refractory organization, declined due to the rise of elastic modulus in thermal shock resistance, increases wear and tear such as crack or fracture. Become a factor conducive to tissue deterioration or wear and tear, and reducing these ingredients such as zirconia and silica that often. In addition, reaction and if magnesite MgO content of magnesia, often this coefficient of thermal expansion of large, fire-resistant materials in the alumina spinel of reaction indicating the big expansion behavior, so larger crack due to thermal shock resistance of the decline or erosion. However, when as an already-made raw materials, magnesia alumina raw material as well as handling and care.
[0102] 　These as the oxide minerals, β-may contain Zirconia Alumina spinel, mullite, clays, kaolinite, monoclinic, Tetragonal zirconia, glass, etc. Zirconia is preferable from a singular expansion behavior during metamorphosis, in the monoclinic or Orthorhombic.
[0103] 　How to manufacture refractories for the invention of SN plate shown. SN plate applied to the invention of fire can get common SN plate manufacturing method.
[0104] 　That is, otherwise the production including stage training to the addition of organic binder to form carbon combined process other refractory materials make up the aggregate particles to Al2O3 , aluminum, carbon-based quality aggregates, the remainder consisting of grain mix, phenolic resin, etc., SN plate into place forming process, drying and heat treatment process, processing of the surface, etc.. These detailed criteria can optimize any design according to individual conditions. Heat treatment is a non-oxidizing atmosphere, more preferable in an inert gas atmosphere.
Implementation example [0105] 　Al4O4C-containing raw material, alumina raw materials, aluminum and carbon materials and other refractory aggregates organic binder in addition after kneading and then, in the oil press-formed refractory shapes, dried and annealed at a given temperature, refractory got. Conductive molten particles made with corundum Al4O4C except below for raw materials that contain Al4O4C implementation example D (table 6), with a maximum particle size (top six) 1 mm, Crystal size of Al4O4C Al4O4 C Crystal cross circle to 50 µm, used in the equivalent of the average diameter.
[0106] 　Refractory materials were studied composition in the following manner.
[0107] 　Refractory composition, Al4O4C, Al2O3(corundum) and Al (Al components of metal) and Si according to x-ray internal standard method and standard samples without lead Veld law profile made the determination. Of C (F. C... ) And for the total (TOTAL C) quantification according to JIS-R-2012. According to the JIS-R-2216 be quantified by x-ray fluorescence and other ingredients that the ZrO2, SiO2 and MgO.
[0108] 　Also, cut out shapes of refractory obtained from the following evaluation.
(1) is equivalent to specific gravity:JIS-R-2205.
(2) based on thermal expansion coefficient:JIS-R-2207.
[0109] 　As well as by how many evaluate the suitability for use on oxidation resistance abrasion resistance and thermal shock resistance test, heating in oxidizing atmosphere, cooling repeat three times then the gastrointestinal (hydrates) test.
[0110] 　Specific findings described below.
[0111] (3) oxidation resistance abrasion resistance: repeated the operation to cool after using a rotary kiln annealed samples air atmosphere, 1000 ° C in two hours, three times. Pursuant to BS (British Standard) wear the blasting grit in this sample after oxidation, we quantify the amount of wear. Further abrasion comparison example 6 (refer to table 5) as 100 relative index of. Indicates that smaller exponent is better oxidation resistance abrasion.
[0112] (4) shock resistance: thermal shock resistance evaluations of organizational changes due to radiation purpose, in an electric furnace in non-oxidizing atmosphere, 1400 ° C 3 hours heat went to the samples for evaluation after evaluation, using a high-frequency induction furnace, 1600 ° C in hot metal pretreatment 3 minutes after immersion cooling to repeat three times.
[0113] (5) resistance: using autoclaved samples according to the method of digestion test of magnesia clinker in by vibration method 4, cool to room temperature after heating of samples of 50 mm x 50 mm x 50 mm 3 hours in non-oxidizing atmosphere, 1400 ° C, 0... 49 MPa humidity conditions and 150 ° C for 3 hours and then hold the appearance of the sample after testing.
[0114] Implementation example A:
　Embodiment A will here investigated the content of refractory Al4O4C. Table 3 these configuration examples and shows the results.
[0115] [Table 3]

[0116] 　Comparative example 1 does not contain Al4O4C entity the Al2O3 with conventional and typical of technology. Shows that thermal expansion is significantly smaller than that with the increased content of Al4O4C. Al4O4C content of 14 mass comparative example 2%, conventional comparison examples of technology than the coefficient of thermal expansion after heat treatment of reducing thermal shock resistance isn't enough also the oxidation resistance abrasion resistance comparison example 1 on par with, but for the impact resistant long repeatedly used to consider is not enough.
[0117] 　Al4O4C content is 15-60 WT % example 1 ~ May 3 and improved shock resistance than resisting abrasion of the repeated enough for conditions of use, etc. Al4O4C content 62 mass comparison example 3%, conventional comparison examples of technology oxidation resistance abrasion resistance is significantly better than that, but show decline in thermal shock resistance.
[0118] [Example B]
　Example B is studied, about the total amount of Al components in refractories Al4O4C, Al2O3 and metal case. Table 4 lists these configuration examples and shows the results.
[0119] [Table 4]

[0120] 　In comparison example 4% in total amount of 83 mass 7 mass % containing ZrO2 in the fire collapsed in the thermal shock resistance test. Considered by it and the digestion of the ZrC. However, in example 4 4 mass % containing the ZrO2 , where the total amount of mass 85% collapse is not, can be repeatedly reused as conditions. Total amount of implementation example 4 except the above-mentioned example 5 of 85% or more and example 1 and example 3 also in oxidation resistance abrasion resistance excellent repeated use in the condition for a long time that where possible.
[0121] Implementation example C
　Implementation example c C content amount of free time, said formula one case investigated and formula 2. Table 5 these configuration examples and shows the results.
[0122] [Table 5]

[0123] 　Above formula 1 example 6 to satisfy the formula and 2-12 in example 1 with better thermal shock resistance, oxidation resistance abrasion resistance. Comparison example 5 not satisfied to shock resistance impact formula 1 on the other hand, comparative examples 8 and comparison example 10 oxidation resistance abrasion resistance, thermal shock resistance of one declined. Comparison example 6 not satisfied, on the other hand, the larger effect of the wear resistant oxide formula 2, comparative example 7 and comparison example 9 thermal shock resistance oxidation resistance abrasion resistance of dramatically declining.
[0124] Implementation example D
　Implementation example d here examine the effect of Crystal size of the raw material manufacturing method, as well as Al4O4C and its particle size distribution (top six) as a raw material containing Al4O4C. Table 6 lists these configuration examples and shows the results. The Al4O4C Crystal Crystal size (size of the crystals) and the Al4O4C Crystal cross circle to mean the equivalent of the average diameter. In other words, each Al4O4C Crystal cross circle to "means the diameter of the pie when the equivalent of the average value.
[0125] [Table 6]

[0126] 　Implementation example 13, 16, 5, 17, is made by melting (ARC melting method), 0 is the top six. more than 21 mm and Al4O4C Crystal Crystal size 20 µ m example implementation example 14 is manufactured by sintering, and 0 is the top six. 074 mm and Al4O4C Crystal Crystal size 5 μ m example.
[0127] 　Increases thermal expansion coefficient and elastic modulus for implementation example 14 is manufactured by sintering, Al4O4C Crystal Crystal size 5 μ m small and fine, low thermal expansion coefficient of reduction and Al2O3(of corundum) progressed by heat treatment, even though Al4O4C content is 20% in the less thermal shock resistance.
[0128] 　Example 15 is an example of the raw materials produced by the smelting reduction (arc fusion method) Al4O4C, Al4O4C Crystal Crystal size is 15 m and smaller rises and coefficient of thermal expansion and elastic modulus from from fine, slightly smaller reduction of the coefficient of thermal expansion due to heat treatment Al2O3(of corundum) proceed further and easier to be Al 4shock resistant declined slightly, even though content of4O C is 20% in.
[0129] Implementation example E
　Implementation example e in the cases investigated the effect of metallic Si. Table 7 these configuration examples and shows the results.
[0130] [Table 7]

[0131] 　Not containing metal silicon implementation example 18 a rift in autoclave testing. Also example 15 metal Si for Al as the metal concentration of mass compared with 8% containing the autoclave testing caused small cracks. Metal Si in mass for the Al as the metal concentration of 10-containing 200% example 20-22 without change in the autoclave test, with good results. Implementation example 23 metal Si for Al as the metal concentration of mass compared with 220% containing the autoclave testing without changes, but was in good condition, thermal shock resistance of Al4O4C content is 20% even though somewhat reduced. Considered for this metal on the strong bond formed further.
[0132] Implementation example F
　Implementation example F shows example refractories for the invention of the trial equipment the device SN SN plate. Table 8 these configuration examples and shows the results.
[0133] [Table 8]

[0134] 　Table 8 in the "results of actual use A" in terms of use indicated that 250 tons of SN plate for pot use and average length of 1 ch casting time is 40 minutes at around 8-channel and many times used condition. Also, "results of actual use play with A" a real oven results SN plate was used in A process again, ring in results using playback SN plate after inserting the polished surface, the play.
[0135] 　On the other hand, the "results of actual use B" in terms of use indicated that 300 tons of conditions used as a plate of pot for SN, 1ch casting times on average were used in 120 min. 5 ch or more coined more than 500 minutes in total time.
[0136] 　Comparison example 11 does not contain metal Al and in conventional refractories technology was used in one case surfaces caused greater erosion (surface roughness). Could not get through with good durability. Comparison example 12 containing metals Al, etc., as well as conventional materials in the furnace using the results, edge tear any large cracks in A and B. Could not get through a good life. Results of actual use, could not diverge after machining SN plate after use of A playing conditions, and to play. This is possible due to digestion of the charcoal aluminum.
[0137] 　On the other hand, the implementation example 24 shows minor and good durability wear and tear of the surface (surface roughness) can crack any conditions.
Of the claims
[Paragraph 1] 　Al4O4C, the aluminum content of 15% or more, 60 percent less than the metal one... 2% or more in 10... 0 mass 85% or more by, and containing less than %, the remainder consisting of Al2O3, free in C and other fire-resistant components for casting refractory products in total of Al of Al4O4C, Al2O3 and metal content of Al4O4C (4 C) and Al components as the metal content (Al) and C-free content (C) the following formula 1 casting refractory characteristics to satisfy the formula and 2,.
　1. 0 ≤ C / (Al4O4C×0. 038 + Al×0. 33). Formula 1
　1. 0 ≥ C / (Al4O4C×0. 13 + Al×0. 67). Expression 2
[Paragraph 2] 　Al said Al4O4C manufactured by electrical fusion4O4C-containing particles in claim 1 derives from the listed casting refractories.
[Invoice section 3] 　Al said Al4O4C-containing raw material particle in4O4C Crystal size is Al4O4C Crystal Cross Yen to 20 µ m more than in the equivalent of the average diameter, claim 2, casting refractories stated.
[Paragraph 4] 　From claim 1 or claim 3 in for casting, is selected from the Group of MgO, SiO2, Orthorhombic or monoclinic ZrO2, SiC,B 4C , BN, Si3N4 and metal on the fire-resistant substances above the rest one or more fire-resistant materials.
[Bill 5] 　Containing more than 10% and less than 200% of metal silicon mass percentage of Al components as previous metal content, from claim 1 or claim 4 in casting refractories.
[Bill 6] 　From claim 1 claim 5, refractories for casting one of the mentioned in part or in full provided, nozzle for casting or for sliding nozzle plate.