WO2024038720A1 - Matériau réfractaire - Google Patents

Matériau réfractaire Download PDF

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Publication number
WO2024038720A1
WO2024038720A1 PCT/JP2023/026121 JP2023026121W WO2024038720A1 WO 2024038720 A1 WO2024038720 A1 WO 2024038720A1 JP 2023026121 W JP2023026121 W JP 2023026121W WO 2024038720 A1 WO2024038720 A1 WO 2024038720A1
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WIPO (PCT)
Prior art keywords
mass
less
sic
refractory
proportion
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PCT/JP2023/026121
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English (en)
Japanese (ja)
Inventor
常夫 古宮山
雅章 長谷川
智也 星野
Original Assignee
日本碍子株式会社
エヌジーケイ・アドレック株式会社
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Publication of WO2024038720A1 publication Critical patent/WO2024038720A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—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
    • C04B35/56—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 carbides or oxycarbides
    • C04B35/565—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 carbides or oxycarbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/597—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon oxynitride, e.g. SIALONS
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/12—Travelling or movable supports or containers for the charge

Definitions

  • Patent Document 1 JP-A-10-29866 discloses a refractory (sialon bonded SiC brick) in which SiC particles are bonded with sialon (SiAlON). Patent Document 1 discloses that by adjusting the bonding part to Si 6-z Al z O z N 8-z (z value is 1.5 to 3.3), the CO gas oxidation resistance and alkali resistance of the refractory can be improved. , improving hot strength.
  • a refractory whose joint portion is adjusted to be SiAlON (Si 6-z Al z O z N 8-z : z value is 1.5 to 3.3) has good properties. It exhibits excellent CO gas oxidation resistance, alkali resistance, and hot strength.
  • SiAlON is heated in a low oxygen atmosphere
  • SiO 2 produced by oxidation is reduced and SiO is produced. Therefore, when the refractory of Patent Document 1 is heated in a low oxygen atmosphere, SiO is generated at the bonding portion. Then, the generated SiO evaporates, reducing the strength of the refractory.
  • the first technology disclosed in this specification is a refractory in which aggregates containing SiC are bonded by bonding portions made of Si, Al, O, and N.
  • the proportion of SiC in the refractory is 60% by mass or more and 90% by mass or less, and the proportion of each element constituting the joint is Si: 0.1% by mass or more and 1.1% by mass or less.
  • Al 4% by mass or more and 21% by mass or less
  • O 4.8% by mass or more and 19% by mass or less
  • N 7.2% by mass or more and 13.1% by mass or less.
  • a second technique disclosed in this specification is the refractory of the first technique, in which the proportion of Si element constituting the bonding portion may be 0.3% by mass or more and 0.8% by mass or less.
  • a third technology disclosed in this specification is the refractory of the second technology, in which the proportion of each element constituting the bonding portion is Al: 7.0% by mass or more and 7.6% by mass or less, O: N may be 4.8% by mass or more and 7.2% by mass or less, and N: 7.2% by mass or more and 7.8% by mass or less.
  • a fourth technique disclosed in this specification is a refractory according to any one of the first to third techniques, in which the peak intensity in X-ray diffraction of the bonded portion is equal to the peak intensity in X-ray diffraction of the SiC aggregate. On the other hand, it may be 4% or more and 30% or less.
  • a fifth technique disclosed in this specification is the refractory of the fourth technique, in which the peak intensity in X-ray diffraction of the bonded portion is 10% or more with respect to the peak intensity in X-ray diffraction of the SiC aggregate. It may be 30% or less.
  • the refractories disclosed in this specification are parts used in a firing furnace, such as a setter for placing an object to be fired, a spacer for ensuring a gap between the setters, a sagger, or a firing furnace. It can be used as the inner wall of In the refractory, aggregates containing SiC are bonded by bonding portions made of Al, Si, O, and N. The bond may be referred to as SiAlON. Sialon-bonded SiC is less likely to produce SiO 2 through oxidation than, for example, silicon nitride (Si 3 N 4 )-bonded SiC, and as a result, SiO does not form even when heated in a low-oxygen atmosphere.
  • a firing furnace such as a setter for placing an object to be fired, a spacer for ensuring a gap between the setters, a sagger, or a firing furnace. It can be used as the inner wall of In the refractory, aggregates containing SiC are bonded by
  • SiC bonded with sialon generates mullite through oxidation, and the mullite acts as an oxidation protective film to suppress the generation of SiO 2 .
  • the refractory disclosed in this specification can suppress a decrease in strength even when used in a low oxygen atmosphere by suppressing a decrease in mass of a joint. Note that by suppressing the mass reduction (evaporation of SiO) of the joint, it is possible to prevent the evaporated gas from solidifying (sublimating) in the low-temperature part of the furnace and forming SiO deposits in the low-temperature part. By suppressing SiO deposits, maintenance work (deposit removal) for the firing furnace can be suppressed.
  • the proportion of SiC (aggregate) in the refractory may be 60% by mass or more and 90% by mass or less. By setting the proportion of aggregate to 60% by mass or more, the strength of the refractory can be improved. Furthermore, by setting the proportion of aggregate to 90% by mass, the volume of the bonding portion can be secured, and the aggregates can be firmly bonded. As a result, the strength of the refractory is improved.
  • the proportion of SiC in the refractory may be 65% by mass or more, 70% by mass or more, 75% by mass or more, or 80% by mass or more. It may be 85% by mass or more. Further, the proportion of SiC in the refractory may be 85% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less. It may be 65% by mass or less.
  • the refractory disclosed herein is formed by firing aggregate (SiC), alumina (Al 2 O 3 ), and silica (SiO 2 ) in a nitrogen atmosphere.
  • the bonding portion is made of Al, Si, O, and N.
  • the bond is formed by the reaction between alumina and silica under a nitrogen atmosphere.
  • the proportions of each element constituting the bonding part are: Si: 0.1 mass% or more and 1.1 mass% or less, Al: 4 mass% or more and 21 mass% or less, O: 4.8 mass% or more and 19 mass% or less, N: may be 7.2% by mass or more and 13.1% by mass or less.
  • the proportion of the Si element constituting the bonding portion may be 0.3% by mass or more, 0.4% by mass or more, or 0.5% by mass or more. However, it may be 0.8% by mass or more. Further, the proportion of the Si element constituting the bonding portion may be 0.8% by mass or less, 0.5% by mass or less, or 0.4% by mass or less. However, it may be 0.3% by mass or less. Although the details will be described later, by adjusting the proportion of Si element constituting the bond to 0.3% by mass or more and 0.8% by mass or less, a refractory with even higher strength and even higher hypoxic resistance can be obtained. It has been experimentally confirmed that
  • the proportion of Al element constituting the bonding portion may be 7.0% by mass or more, 7.5% by mass or more, or 7.6% by mass or more. However, it may be 7.8% by mass or more. Further, the proportion of Al element constituting the bonding portion may be 7.8% by mass or less, 7.6% by mass or less, or 7.5% by mass or less. However, it may be 7.0% by mass or less. Although the details will be described later, by adjusting the proportion of Al element constituting the bond to 7.0% by mass or more and 7.6% by mass or less, a refractory with even higher strength and even higher hypoxic resistance can be obtained. It has been experimentally confirmed that
  • the proportion of the O element constituting the bonding portion may be 7.1% by mass or more, or may be 7.2% by mass or more. Further, the proportion of O element constituting the bonding portion may be 7.8% by mass or less, 7.6% by mass or less, or 7.2% by mass or less. However, it may be 7.1% by mass or less. Although the details will be described later, by adjusting the proportion of O element constituting the joint to 4.8% by mass or more and 7.2% by mass or less, a refractory with even higher strength and even higher hypoxic resistance can be obtained. It has been experimentally confirmed that
  • the proportion of the N element constituting the bonding portion may be 7.4% by mass or more, 7.5% by mass or more, or 7.6% by mass or more. However, it may be 7.8% by mass or more. Further, the proportion of N element constituting the bonding portion may be 7.8% by mass or less, 7.6% by mass or less, or 7.5% by mass or less. However, it may be 7.4% by mass or less. Although the details will be described later, by adjusting the proportion of N element constituting the joint to 7.2% by mass or more and 7.8% by mass or less, a refractory with even higher strength and even higher hypoxic resistance can be obtained. It has been experimentally confirmed that
  • the proportion of SiC (aggregate) in the refractory may be 60% by mass or more and 90% by mass or less.
  • the ratio of aggregate and bonding parts constituting the refractory can also be determined from the peak intensity ratio in X-ray diffraction. Specifically, when the refractory is subjected to X-ray diffraction, the peak intensity of the joint (the peak intensity that appears at 26.82°) is the same as the peak intensity (the peak intensity that appears at 34.11°) in the X-ray diffraction of the SiC aggregate. It may be 4% or more and 30% or less with respect to the sum of the peak intensity and the peak intensity appearing at 34.77°.
  • the peak intensity ratio may be 5% or more, 10% or more, 12% or more, or 20% or more. Further, the peak intensity ratio may be 20% or less, 12% or less, 10% or less, or 5% or less. Although details will be described later, it has been confirmed through experiments that even higher strength and even higher hypoxic resistance can be obtained if the peak strength ratio of the joint to the aggregate is 10% or more and 30% or less.
  • a mixed raw material of SiC (aggregate), Al 2 O 3 and SiO 2 was fired in a nitrogen atmosphere to create a refractory, and the bending strength and X-ray diffraction of the refractory were measured.
  • mixed raw materials with varying proportions of SiC, Al 2 O 3 and SiO 2 were prepared and fired at 1450° C. for 3 hours in a nitrogen atmosphere to create refractories (samples 1 to 12). Note that sample 1 used a mixed raw material of SiC (aggregate) and Si, and sample 11 used a mixed raw material of SiC (aggregate) and Al 2 O 3 to create a refractory.
  • sample 1 used a mixed raw material of SiC (aggregate) and Si
  • sample 11 used a mixed raw material of SiC (aggregate) and Al 2 O 3 to create a refractory.
  • SiCI contains 5% or less of SiC with a particle size of 2830 to 2000 ⁇ m, 15 to 30% of SiC with a particle size of 1000 to 500 ⁇ m, and the remainder is SiC with a particle size of 500 ⁇ m or less.
  • SiCII contains 5% or less of SiC with a particle size of 500 to 250 ⁇ m, 30 to 50% of SiC with a particle size of 75 ⁇ m or less, and the remainder is SiC with a particle size of 250 to 75 ⁇ m.
  • SiCIII contains 5% or less of SiC with a particle size of 45 to 15 ⁇ m, 40 to 70% of SiC with a particle size of 15 to 2 ⁇ m, and the remainder is SiC with a particle size of 2 ⁇ m or less.
  • Samples 1-4, 9 and 12 used only SiCI.
  • Samples 5 to 7, 10, and 11 used SiCI and SiCII.
  • Sample 8 used SiCI and SiCIII.
  • Peak intensity ratio (SiAlON peak intensity)/(SiC peak intensity) x 100
  • the bending strength of each sample was measured before and after Ar exposure treatment (heat treatment in a low oxygen atmosphere). In the Ar exposure treatment, each sample was heated at 1450° C. for 30 hours in an Ar atmosphere. The bending strength was measured by preparing a sample of 30 mm x 140 mm and 15 mm in thickness and performing a three-point bending strength test.
  • FIG. 1 shows the bending strength before and after Ar exposure treatment, the bending strength change rate before and after Ar exposure treatment, and the mass change rate before and after Ar exposure treatment.
  • N 7.2% by mass or more and 13.1% by mass or less (Samples 4 to 10) have a strength change rate of -5% or less (strength decrease rate of 5% or less) before and after Ar exposure treatment. ) was confirmed.
  • This result shows that if SiC (aggregate) is simply bonded with SiAlON, the strength of the refractory may decrease when the refractory is heated in a low oxygen atmosphere (Ar atmosphere). It shows.
  • the proportion of each element constituting the bonding part is Si: 0.1% by mass or more and 1.1% by mass or less, Al: 4% by mass or more and 21% by mass or less, O: 4.8% by mass or more and 19% by mass or less, N.
  • samples (samples 5 to 9) in which the proportion of Si element constituting the bonding part is 0.3% by mass or more and 0.8% by mass or less have a strength change rate of "-3%" or less before and after Ar exposure treatment. It was confirmed that very good results could be obtained. Note that Samples 5 to 9 had peak intensity ratios of 10% or more and 30% or less. Note that Samples 6 and 7 had extremely high bending strength (25 MPa or more), and the rate of change in strength was "0%" before and after the Ar exposure treatment.
  • Samples 1 to 11 were comprehensively evaluated as refractories.
  • Figure 1 shows the overall evaluation as a refractory. Specifically, samples with a bending strength of 25 MPa or more after the Ar exposure treatment and a strength change rate of "0%" before and after the Ar exposure treatment were rated as "A". In addition, samples with a bending strength of 25 MPa or more after Ar exposure treatment and a strength change rate of -3% or less before and after Ar exposure treatment (excluding strength change rate of 0%), or samples with a bending strength of 20 MPa after Ar exposure treatment A sample that was less than 25 MPa and had a strength change rate of "0%" before and after the Ar exposure treatment was given a "B rating".
  • Samples with a bending strength of 10 MPa or more and less than 20 MPa after Ar exposure treatment and a strength change rate of "-5%" or less before and after Ar exposure treatment were rated as “C”.
  • samples that did not satisfy either or both of the bending strength after Ar exposure treatment of 10 MPa or more and less than 20 MPa and the strength change rate before and after Ar exposure treatment of "-5%” or less were rated as "D”.
  • Refractories rated A to C are at an acceptable level as refractories that are unlikely to lose strength even when heated in a low-oxygen atmosphere.

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  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
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Abstract

Ce matériau réfractaire est lié à un agrégat contenant du SiC par une partie de liaison composée de Si, d'Al, d'O et de N. Selon le matériau réfractaire, la proportion de SiC dans le matériau réfractaire est de 60 à 90 % en masse, et les proportions d'éléments respectifs constituant la partie de liaison sont de 0,1 à 1,1 % en masse pour le Si, de 4 à 21 % en masse pour l'Al, de 4,8 à 19 % en masse pour l'O, et de 7,2 à 11,1 % en masse pour le N.
PCT/JP2023/026121 2022-08-19 2023-07-14 Matériau réfractaire WO2024038720A1 (fr)

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JP2022131208 2022-08-19

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6197165A (ja) * 1984-10-17 1986-05-15 東京高級炉材株式会社 β′サイアロン結合炭化珪素質材料およびその製造方法
JPS63129072A (ja) * 1986-11-14 1988-06-01 黒崎窯業株式会社 炭化珪素質耐火物の製造方法
US5521129A (en) * 1994-09-14 1996-05-28 The Carborundum Company Sialon-bonded silicon carbide refractory
JPH10500095A (ja) * 1994-09-14 1998-01-06 ザ カーボランダム カンパニー 反応結合型炭化ケイ素耐火物製品
CN102050625A (zh) * 2010-10-28 2011-05-11 中钢集团洛阳耐火材料研究院有限公司 一种赛隆-石墨复合碳化硅材料及其制备方法
JP2016538212A (ja) * 2013-09-30 2016-12-08 サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン サイアロン・マトリックスを有する耐火物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6197165A (ja) * 1984-10-17 1986-05-15 東京高級炉材株式会社 β′サイアロン結合炭化珪素質材料およびその製造方法
JPS63129072A (ja) * 1986-11-14 1988-06-01 黒崎窯業株式会社 炭化珪素質耐火物の製造方法
US5521129A (en) * 1994-09-14 1996-05-28 The Carborundum Company Sialon-bonded silicon carbide refractory
JPH10500095A (ja) * 1994-09-14 1998-01-06 ザ カーボランダム カンパニー 反応結合型炭化ケイ素耐火物製品
CN102050625A (zh) * 2010-10-28 2011-05-11 中钢集团洛阳耐火材料研究院有限公司 一种赛隆-石墨复合碳化硅材料及其制备方法
JP2016538212A (ja) * 2013-09-30 2016-12-08 サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン サイアロン・マトリックスを有する耐火物

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