WO2019054222A1 - Refractory for siliconizing furnaces - Google Patents

Refractory for siliconizing furnaces Download PDF

Info

Publication number
WO2019054222A1
WO2019054222A1 PCT/JP2018/032582 JP2018032582W WO2019054222A1 WO 2019054222 A1 WO2019054222 A1 WO 2019054222A1 JP 2018032582 W JP2018032582 W JP 2018032582W WO 2019054222 A1 WO2019054222 A1 WO 2019054222A1
Authority
WO
WIPO (PCT)
Prior art keywords
refractory
silicon
furnace
mass
siliconizing
Prior art date
Application number
PCT/JP2018/032582
Other languages
French (fr)
Japanese (ja)
Inventor
崇 土居
勝司 笠井
輝彦 戸部
琢実 小山
Original Assignee
Ｊｆｅスチール株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ｊｆｅスチール株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to KR1020207006888A priority Critical patent/KR102401344B1/en
Priority to JP2018560694A priority patent/JP6747520B2/en
Priority to CN201880058716.3A priority patent/CN111094212A/en
Publication of WO2019054222A1 publication Critical patent/WO2019054222A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
    • 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
    • C04B35/584—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 nitride
    • 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
    • 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
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/06—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases
    • C23C10/08—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases only one element being diffused
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
    • C23C10/44—Siliconising
    • C23C10/46—Siliconising of ferrous surfaces
    • 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
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/0003—Linings or walls
    • F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • the present invention relates to a refractory used in a furnace using silicon chloride gas, such as a continuous siliconization furnace for steel strip.
  • Silicon steel sheets are widely used as core materials for transformers and motors because they have excellent soft magnetic properties. It is known that a silicon steel sheet exhibits excellent magnetic properties such as the core loss decreases as the Si content increases, the magnetostriction becomes zero at about 6.5 wt% of Si, and the maximum permeability becomes a peak.
  • a manufacturing method by a gas siliconizing method as shown, for example, in Patent Document 1 is known. According to this manufacturing method, a steel strip having a relatively low Si content is heated and siliconized by siliconizing treatment in a non-oxidizing gas atmosphere containing silicon chloride gas (SiCl 4 ), and then the thickness of Si is determined.
  • SiCl 4 silicon chloride gas
  • the continuous siliconizing furnace in which the above siliconizing treatment is performed is operated for a long time at a furnace temperature of 1200 ° C. or higher, and silicon chloride gas (SiCl 4 ) contained in the atmosphere gas is very reactive. It is a rich and corrosive gas. For this reason, there is a problem that silicon chloride gas activated in a high temperature furnace reacts with a refractory which is a furnace material of the continuous siliconizing treatment furnace to deteriorate the refractory.
  • Patent Literatures 2 and 3 As a refractory for a continuous siliconization furnace, for example, applying a refractory described in Patent Literatures 2 and 3 is known.
  • JP-A-62-227078 JP-A-10-147856 Japanese Patent Application Publication No. 08-169750
  • the iron chloride deposited in the refractory absorbs the moisture in the atmosphere and expands.
  • the refractory of the furnace wall and the hearth may come out inside the furnace or the refractory may be cracked and collapsed. Therefore, there is a problem that the life of the refractory is shortened and the update cycle is shortened.
  • Patent Documents 2 and 3 When the refractories described in Patent Documents 2 and 3 can be used to suppress the alteration and embrittlement of refractories caused by silicon chloride gas, the alteration and embrittlement of refractories caused by iron chloride can be prevented. It turned out that it is difficult to suppress until promotion.
  • the present invention has been made in view of the above-mentioned circumstances, and an object thereof is to provide a refractory for a siliconization treatment furnace having a short life and a small amount of deterioration or embrittlement.
  • the present inventors have found that the use of a refractory having a predetermined component composition and a low porosity can improve the life of the refractory and extend the renewal period.
  • the present invention has been made based on such findings, and the gist of the present invention is as follows.
  • [1] 35% by mass or more in total of one or more selected from oxides of silicon, nitrides of silicon and oxynitrides of silicon, and 0.05% by mass or less in total of alkali metals Refractory for siliconizing treatment furnace having a porosity of 25% by volume or less and a compressive strength of 5 MPa or more.
  • the refractory for siliconization treatment furnace according to [1] further containing not more than 1.0% by mass in total of oxides of Mg, Ca, Ti, Fe, Cr and Zr.
  • the present invention it is possible to provide a refractory for a siliconization treatment furnace which is less in deterioration or embrittlement and has a long life. Therefore, when the refractory of the present invention is applied as a refractory of a continuous siliconizing furnace using silicon chloride gas, it does not cause deterioration or embrittlement over a long time, and exhibits excellent durability. For this reason, in the continuous production line of high silicon steel plate by gas siliconizing method, stable operation can be performed for a long time without causing deterioration of the refractory.
  • FIG. 1 is a schematic view of a continuous siliconization treatment facility for producing a high silicon steel plate.
  • Refractories made of various materials were prepared. These refractories are placed in a furnace for an atmosphere containing silicon chloride gas (SiCl 4 : about 15 vol%, furnace temperature: about 1200 ° C.) for 3 months, and changes in appearance, weight, volume, etc. of each refractory are examined.
  • silicon chloride gas SiCl 4 : about 15 vol%, furnace temperature: about 1200 ° C.
  • a refractory having a total content of one or more selected from oxides of silicon, nitrides of silicon, and oxynitrides of silicon is less than 35% by mass, the surface is altered or embrittled.
  • refractories having a total content of at least 35% by mass of one or more selected from oxides of silicon, nitrides of silicon, and oxynitrides of silicon are partially cracked Although some were generated, there was no deterioration or embrittlement leading to the falling-off of the surface layer of the furnace material, and it was judged that it could be used almost continuously.
  • the content of the oxide of silicon, the nitride of silicon, and the oxynitride of silicon contained in the refractory are the oxide of silicon, the nitride of silicon, and the oxynitride of silicon. 1 or 2 types selected from is specified as 35 mass% or more in total. Preferably, it contains 90% by mass or more in total of one or more selected from oxides of silicon, nitrides of silicon, and oxynitrides of silicon.
  • silicon nitride and fused silica are preferable, and fused silica is particularly preferable.
  • the total content of alkali metals contained in the refractory is specified as 0.05 mass% or less.
  • the alkali metal contained in the refractory contributes to the reactivity with silicon chloride gas. If the content of the alkali metal exceeds 0.05% by mass, the reaction between the refractory and the silicon chloride gas proceeds, and the surface of the refractory may be cracked or broken.
  • the total content of the respective oxides of Mg, Ca, Ti, Fe, Cr and Zr contained in the refractory is preferably 1.0 mass% or less.
  • the oxides such as Mg and Ca contained in the refractory also contribute to the reactivity with silicon chloride gas.
  • the content of oxides such as Mg and Ca exceeds 1.0% by mass, the reaction between the refractory and the silicon chloride gas proceeds, and the surface of the refractory may be cracked or may be broken.
  • the remainder other than the above in the refractory may be Al 2 O 3 or an impurity, and may contain metal oxides other than the above as an impurity.
  • iron chloride (gas) generated as a by-product in the process of manufacturing the high silicon steel plate penetrates into the refractory in the furnace and condenses or solidifies in the temperature reduction portion near the furnace wall or the hearth.
  • the accumulation or aggregation of the coagulated or solidified iron chloride in the refractory promotes the reduction reaction with the oxide in the refractory, thereby promoting the deterioration or embrittlement of the refractory.
  • the iron chloride deposited in the refractory absorbs the moisture in the atmosphere and expands.
  • the present inventors diligently studied the deterioration and embrittlement of the refractory caused by such iron chloride. As a result, it has been found that by making the porosity of the refractory not more than 25% by volume, it is possible to suppress the deterioration and embrittlement of the refractory.
  • Iron chloride (solid) deposited in the refractory is likely to be deposited in the refractory as the number of pores in the refractory increases.
  • the iron chloride deposited in the refractory is expanded by exposure to the atmosphere, which applies pressure to the refractory from the inside, which causes deterioration of the refractory. From such a thing, it is desirable that the number of pores in the refractory is small, and by setting the porosity to 25% by volume or less, the deposition of iron chloride in the refractory is suppressed, and the deterioration of the refractory is prevented. Is possible.
  • the present invention by setting the porosity to 25% by volume or less, deterioration or embrittlement of the refractory can be suppressed. As a result, long-term stable operation in a continuous production line of high silicon steel plates can be realized.
  • the compressive strength is less than 5 MPa, the by-product iron chloride gas penetrates into the refractory, the refractory expands, and the refractory collapses, which affects the surface appearance.
  • the compressive strength is 20 to 200 MPa.
  • the compressive strength is preferably 200 MPa or less.
  • the method of measuring the porosity and the compressive strength is not particularly limited, and may be determined by an ordinary method.
  • a refractory having a porosity of 25% by volume or less and a compressive strength of 5 MPa or more can also be used.
  • Refractories 50 mm ⁇ 50 mm ⁇ 50 mm having various component compositions were prepared and placed in the silicon treatment furnace of the high-silicon steel sheet continuous production line shown in FIG. After continuously operating the atmosphere of the siliconizing furnace with SiCl 4 concentration: 15 vol% and the temperature in the furnace: 1200 ° C. for 3 months, the damage state of each refractory was examined. Table 1 shows the composition of each refractory, the porosity, the compressive strength and the damage state.
  • the state of damage was judged by surface observation and reactivity.
  • Surface observation observed the appearance of the refractory, and evaluation was performed in four steps from the deterioration condition: defected> cracked> discoloration> no change.
  • reactivity 4 stages of ⁇ , ⁇ , ⁇ , ⁇ from the deterioration situation ( ⁇ : not reacting, ⁇ : hardly reacting, (: small reaction (refractory deterioration is observed Evaluation was made at the level where continuous use is possible, and x: reaction is remarkable. The surface observation gave discoloring and no change as pass, and the reactivity gave ⁇ , ⁇ and ⁇ as pass.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The purpose of the present invention is to provide a refractory for siliconizing furnaces, which is suppressed in change of properties and embrittlement, and which has a long service life. A refractory for siliconizing furnaces, which contains 35% by mass or more in total of one or more substances that are selected from among silicon oxides, silicon nitrides and silicon oxynitrides and 0.05% by mass or less in total of alkali metals, while having a porosity of 25% by volume or less and a compressive strength of 5 MPa or more.

Description

浸珪処理炉用耐火物Refractory for siliconizing furnace
　本発明は、鋼帯の連続浸珪処理炉のように塩化珪素ガスを使用する炉に用いられる耐火物に関する。 The present invention relates to a refractory used in a furnace using silicon chloride gas, such as a continuous siliconization furnace for steel strip.
　珪素鋼板は優れた軟磁気特性を有するため、トランスやモータの鉄心材料として広く用いられている。珪素鋼板はＳｉ含有量が増すほど鉄損が低減し、Ｓｉが約６．５ｗｔ％では磁歪が０となり、最大透磁率がピークとなるなど優れた磁気特性を示すことが知られている。このような高珪素鋼板を工業的に製造する方法として、例えば特許文献１に示されるような気体浸珪法による製造方法が知られている。この製造方法は、Ｓｉ含有量が比較的低い鋼帯を加熱して塩化珪素ガス（ＳｉＣｌ4）を含む無酸化性ガス雰囲気中で浸珪処理することによりＳｉを浸透させ、次いでＳｉを板厚方向に拡散させる拡散熱処理を施し、冷却後コイル状に巻き取る一連のプロセスを連続ライン化し、高珪素鋼帯を効率よく製造することができる。 Silicon steel sheets are widely used as core materials for transformers and motors because they have excellent soft magnetic properties. It is known that a silicon steel sheet exhibits excellent magnetic properties such as the core loss decreases as the Si content increases, the magnetostriction becomes zero at about 6.5 wt% of Si, and the maximum permeability becomes a peak. As a method of industrially manufacturing such a high silicon steel plate, a manufacturing method by a gas siliconizing method as shown, for example, in Patent Document 1 is known. According to this manufacturing method, a steel strip having a relatively low Si content is heated and siliconized by siliconizing treatment in a non-oxidizing gas atmosphere containing silicon chloride gas (SiCl 4 ), and then the thickness of Si is determined. A series of processes which are subjected to diffusion heat treatment to diffuse in a direction and wound up in a coil shape after cooling can be made into a continuous line to efficiently produce a high silicon steel strip.
　上記のような浸珪処理が行われる連続浸珪処理炉は、１２００℃以上の炉内温度で長時間運転され、しかも、雰囲気ガスに含まれる塩化珪素ガス（ＳｉＣｌ４）は非常に反応性に富み、腐食性の強いガスである。このため、高温の炉内で活性化した塩化珪素ガスが連続浸珪処理炉の炉材である耐火物と反応し、耐火物を劣化させるという問題がある。 The continuous siliconizing furnace in which the above siliconizing treatment is performed is operated for a long time at a furnace temperature of 1200 ° C. or higher, and silicon chloride gas (SiCl 4 ) contained in the atmosphere gas is very reactive. It is a rich and corrosive gas. For this reason, there is a problem that silicon chloride gas activated in a high temperature furnace reacts with a refractory which is a furnace material of the continuous siliconizing treatment furnace to deteriorate the refractory.
　連続浸珪処理炉用の耐火物としては、例えば特許文献２、３に記載の耐火物を適用することが知られている。 As a refractory for a continuous siliconization furnace, for example, applying a refractory described in Patent Literatures 2 and 3 is known.
特開昭６２－２２７０７８号公報JP-A-62-227078 特開平１０－１４７８５６号公報JP-A-10-147856 特開平０８－１６９７５０号公報Japanese Patent Application Publication No. 08-169750
　一方、高珪素鋼板の製造途中に副産物として発生する塩化鉄（ガス）が、炉内の耐火物中に浸透し、炉壁または炉床付近の温度低下部分で凝集または凝固するという問題がある。この凝集・凝固した塩化鉄が耐火物内に堆積することで、耐火物中の酸化物との還元反応が進み、耐火物の変質や脆化が促進される。 On the other hand, there is a problem that iron chloride (gas) generated as a by-product in the process of manufacturing the high silicon steel plate penetrates into the refractory in the furnace and condenses or solidifies in the temperature reduction portion near the furnace wall or the hearth. By depositing the coagulated and solidified iron chloride in the refractory, the reduction reaction with the oxide in the refractory proceeds to promote the transformation and embrittlement of the refractory.
　また、補修等で炉内の耐火物が大気中に暴露された場合に、耐火物中に堆積した塩化鉄が大気中の水分を吸収し、膨張する。その結果、耐火物自体の体積が増加して膨張するため、炉壁や炉床の耐火物が炉内側に競り出てきたり、耐火物に亀裂が生じて崩壊してしまう。したがって、耐火物の寿命が短くなり、更新周期が短くなるという問題がある。 Also, when the refractory in the furnace is exposed to the atmosphere due to repair etc., the iron chloride deposited in the refractory absorbs the moisture in the atmosphere and expands. As a result, since the volume of the refractory itself increases and expands, the refractory of the furnace wall and the hearth may come out inside the furnace or the refractory may be cracked and collapsed. Therefore, there is a problem that the life of the refractory is shortened and the update cycle is shortened.
　特許文献２、３に記載の耐火物を用いると、塩化珪素ガスに起因する耐火物の変質・脆化を抑制することはできても、塩化鉄を起因とする耐火物の変質・脆化の促進までは抑制することが難しいことがわかった。 When the refractories described in Patent Documents 2 and 3 can be used to suppress the alteration and embrittlement of refractories caused by silicon chloride gas, the alteration and embrittlement of refractories caused by iron chloride can be prevented. It turned out that it is difficult to suppress until promotion.
　本発明は上記実情に鑑みてなされたものであり、変質や脆化が少なく、寿命が長い浸珪処理炉用耐火物を提供することを目的とする。 The present invention has been made in view of the above-mentioned circumstances, and an object thereof is to provide a refractory for a siliconization treatment furnace having a short life and a small amount of deterioration or embrittlement.
　本発明者らは鋭意検討した結果、所定の成分組成を有するとともに気孔率の低い耐火物を用いることで、耐火物の寿命が向上し、更新周期を延長することができるという知見を得た。 As a result of intensive investigations, the present inventors have found that the use of a refractory having a predetermined component composition and a low porosity can improve the life of the refractory and extend the renewal period.
　本発明は、このような知見に基づきなされたもので、以下を要旨とするものである。
［１］珪素の酸化物、珪素の窒化物および珪素の酸窒化物の中から選ばれる１種または２種以上を合計で３５質量％以上と、アルカリ金属を合計で０．０５質量％以下とを含有し、気孔率が２５体積％以下であり、圧縮強度が５ＭＰａ以上である浸珪処理炉用耐火物。
［２］さらに、Ｍｇ、Ｃａ、Ｔｉ、Ｆｅ、ＣｒおよびＺｒの各酸化物を合計で１．０質量％以下を含有する［１］に記載の浸珪処理炉用耐火物。
［３］珪素の酸化物、珪素の窒化物および珪素の酸窒化物の中から選ばれる１種または２種以上を合計で９０質量％以上含有する［１］または［２］に記載の浸珪処理炉用耐火物。 The present invention has been made based on such findings, and the gist of the present invention is as follows.
[1] 35% by mass or more in total of one or more selected from oxides of silicon, nitrides of silicon and oxynitrides of silicon, and 0.05% by mass or less in total of alkali metals Refractory for siliconizing treatment furnace having a porosity of 25% by volume or less and a compressive strength of 5 MPa or more.
[2] The refractory for siliconization treatment furnace according to [1], further containing not more than 1.0% by mass in total of oxides of Mg, Ca, Ti, Fe, Cr and Zr.
[3] Silicon nitride according to [1] or [2], containing 90% by mass or more in total of one or more selected from oxides of silicon, nitrides of silicon and oxynitrides of silicon Refractories for processing furnaces.
　本発明によれば、変質や脆化が少なく、寿命が長い浸珪処理炉用耐火物を提供することができる。したがって、塩化珪素ガスを使用する連続浸珪処理炉の耐火物として本発明の耐火物を適用すると、長時間にわたって変質や脆化を生じることがなく、優れた耐久性を示す。このため、気体浸珪法による高珪素鋼板の連続製造ラインにおいては、耐火物の劣化等を生じることなく、長期間安定した操業が可能となる。 According to the present invention, it is possible to provide a refractory for a siliconization treatment furnace which is less in deterioration or embrittlement and has a long life. Therefore, when the refractory of the present invention is applied as a refractory of a continuous siliconizing furnace using silicon chloride gas, it does not cause deterioration or embrittlement over a long time, and exhibits excellent durability. For this reason, in the continuous production line of high silicon steel plate by gas siliconizing method, stable operation can be performed for a long time without causing deterioration of the refractory.
図１は、高珪素鋼板を製造する連続浸珪処理設備の概略図である。FIG. 1 is a schematic view of a continuous siliconization treatment facility for producing a high silicon steel plate.
　種々の材質からなる耐火物を作製した。これら耐火物を、塩化珪素ガスを含む雰囲気（ＳｉＣｌ４：約１５ｖｏｌ％、炉内温度：約１２００℃）の炉内に３ヵ月間置き、各耐火物の外観、重量、体積等の変化を調べた。その結果、珪素の酸化物（シリカ）、珪素の窒化物（窒化珪素）および珪素の酸窒化物（酸窒化珪素）のいずれか１種または２種以上を多く含む耐火物が塩化珪素ガスに対して最も損傷が少ないことがわかった。これに対して、珪素の炭化物からなる耐火物は損傷の度合いが大きいことが判明した。 Refractories made of various materials were prepared. These refractories are placed in a furnace for an atmosphere containing silicon chloride gas (SiCl 4 : about 15 vol%, furnace temperature: about 1200 ° C.) for 3 months, and changes in appearance, weight, volume, etc. of each refractory are examined The As a result, a refractory containing a large amount of one or more of an oxide of silicon (silica), a nitride of silicon (silicon nitride) and an oxynitride of silicon (silicon oxynitride) is used relative to silicon chloride gas. It turned out that the damage was the least. On the other hand, it was found that the refractory made of carbide of silicon has a high degree of damage.
　次に、耐火物の塩化珪素ガスに対する耐損傷性の評価として、耐火物表面の変質状況や脆化状況を調べ、変質状況や脆化状況と珪素の酸化物、珪素の窒化物、珪素の酸窒化物の合計含有量との関係を検討した。 Next, in order to evaluate the damage resistance of the refractory to silicon chloride gas, the state of deterioration or embrittlement of the surface of the refractory is examined, and the state of deterioration or embrittlement, oxide of silicon, nitride of silicon, acid of silicon The relationship with the total content of nitrides was examined.
　その結果、珪素の酸化物、珪素の窒化物、珪素の酸窒化物の中から選ばれる１種または２種以上の合計の含有量が３５質量％未満の耐火物は、表面が変質や脆化して欠損ありの状態或いはヘアークラックを生じた状態となり、また亀裂やスポーリングの発生も著しかった。これに対し、珪素の酸化物、珪素の窒化物、珪素の酸窒化物の中から選ばれる１種または２種以上の合計の含有量が３５質量％以上の耐火物は、一部に亀裂の発生するものも見られたが炉材表層部の脱落に至るような変質や脆化はなく、ほぼ継続使用可能であると判断できた。 As a result, a refractory having a total content of one or more selected from oxides of silicon, nitrides of silicon, and oxynitrides of silicon is less than 35% by mass, the surface is altered or embrittled. In addition, it was in the state of having a defect or in the state of causing a hair crack, and the occurrence of the crack and the spalling was also remarkable. On the other hand, refractories having a total content of at least 35% by mass of one or more selected from oxides of silicon, nitrides of silicon, and oxynitrides of silicon are partially cracked Although some were generated, there was no deterioration or embrittlement leading to the falling-off of the surface layer of the furnace material, and it was judged that it could be used almost continuously.
　以上より、本発明において、耐火物中に含まれる珪素の酸化物、珪素の窒化物、珪素の酸窒化物の含有量は、珪素の酸化物、珪素の窒化物、珪素の酸窒化物の中から選ばれる１種または２種以上を合計で３５質量％以上と規定する。好ましくは、珪素の酸化物、珪素の窒化物、珪素の酸窒化物の中から選ばれる１種または２種以上を合計で９０質量％以上含有する。９０質量％以上にすることで、変質・脆化が著しく低減され、亀裂の発生もなく、良好な結果が得られる。 From the above, in the present invention, the content of the oxide of silicon, the nitride of silicon, and the oxynitride of silicon contained in the refractory are the oxide of silicon, the nitride of silicon, and the oxynitride of silicon. 1 or 2 types selected from is specified as 35 mass% or more in total. Preferably, it contains 90% by mass or more in total of one or more selected from oxides of silicon, nitrides of silicon, and oxynitrides of silicon. By setting the content to 90% by mass or more, deterioration and embrittlement are significantly reduced, and no crack is generated, and good results can be obtained.
　本発明において、耐火物中に含まれる珪素の酸化物、珪素の窒化物、珪素の酸窒化物としては、窒化珪素や溶融シリカが好ましく、溶融シリカが特に好ましい。 In the present invention, as the oxide of silicon, the nitride of silicon, and the oxynitride of silicon contained in the refractory, silicon nitride and fused silica are preferable, and fused silica is particularly preferable.
　本発明では、耐火物中に含まれるアルカリ金属の含有量を合計で０．０５質量％以下と規定する。耐火物中に含まれるアルカリ金属は塩化珪素ガスとの反応性に寄与する。アルカリ金属の含有量が０．０５質量％を超えると耐火物と塩化珪素ガスとの反応が進行し、耐火物表面に亀裂が生じたり、欠損ありとなる恐れがある。 In the present invention, the total content of alkali metals contained in the refractory is specified as 0.05 mass% or less. The alkali metal contained in the refractory contributes to the reactivity with silicon chloride gas. If the content of the alkali metal exceeds 0.05% by mass, the reaction between the refractory and the silicon chloride gas proceeds, and the surface of the refractory may be cracked or broken.
　本発明では、耐火物中に含まれるＭｇ、Ｃａ、Ｔｉ、Ｆｅ、ＣｒおよびＺｒの各酸化物の含有量の合計を１．０質量％以下とすることが好ましい。耐火物中に含まれるＭｇ、Ｃａ等の酸化物についても、塩化珪素ガスとの反応性に寄与する。Ｍｇ、Ｃａ等の酸化物の含有量が１．０質量％を超えると耐火物と塩化珪素ガスとの反応が進行し、耐火物表面に亀裂が生じたり、欠損ありになる恐れがある。 In the present invention, the total content of the respective oxides of Mg, Ca, Ti, Fe, Cr and Zr contained in the refractory is preferably 1.0 mass% or less. The oxides such as Mg and Ca contained in the refractory also contribute to the reactivity with silicon chloride gas. When the content of oxides such as Mg and Ca exceeds 1.0% by mass, the reaction between the refractory and the silicon chloride gas proceeds, and the surface of the refractory may be cracked or may be broken.
　耐火物における上記以外の残部としては、Ａｌ２Ｏ３や不純物であり、不純物として上記以外の金属酸化物等を含んでいてもよい。 The remainder other than the above in the refractory may be Al 2 O 3 or an impurity, and may contain metal oxides other than the above as an impurity.
　高珪素鋼板の製造途中に副産物として発生する塩化鉄（ガス）が、炉内の耐火物中に浸透し、炉壁や炉床付近の温度低下部分で凝集もしくは凝固するという問題がある。この凝集もしくは凝固した塩化鉄が耐火物内に堆積することで、耐火物中の酸化物との還元反応が進み、耐火物の変質や脆化が促進される。また、補修等で炉内の耐火物が大気中に暴露された場合に、耐火物中に堆積した塩化鉄が大気中の水分を吸収し、膨張する。その結果、耐火物自体の体積が増加して膨張するため、炉壁や炉床の耐火物が炉内側に競り出てきたり、耐火物に亀裂が生じて崩壊してしまう。したがって、耐火物の寿命が短くなり、更新周期が短くなるという問題がある。 There is a problem that iron chloride (gas) generated as a by-product in the process of manufacturing the high silicon steel plate penetrates into the refractory in the furnace and condenses or solidifies in the temperature reduction portion near the furnace wall or the hearth. The accumulation or aggregation of the coagulated or solidified iron chloride in the refractory promotes the reduction reaction with the oxide in the refractory, thereby promoting the deterioration or embrittlement of the refractory. Also, when the refractory in the furnace is exposed to the atmosphere due to repair etc., the iron chloride deposited in the refractory absorbs the moisture in the atmosphere and expands. As a result, since the volume of the refractory itself increases and expands, the refractory of the furnace wall and the hearth may come out inside the furnace or the refractory may be cracked and collapsed. Therefore, there is a problem that the life of the refractory is shortened and the update cycle is shortened.
　このような塩化鉄を原因とする耐火物の変質や脆化について本発明者らが鋭意検討した。その結果、耐火物の気孔率を２５体積％以下にすることにより、耐火物の変質や脆化を抑制できることを見出した。 The present inventors diligently studied the deterioration and embrittlement of the refractory caused by such iron chloride. As a result, it has been found that by making the porosity of the refractory not more than 25% by volume, it is possible to suppress the deterioration and embrittlement of the refractory.
　耐火物中に堆積する塩化鉄（固体）は耐火物中の気孔が多ければ多いほど、耐火物中に堆積し易い。耐火物中に堆積した塩化鉄は大気と触れることにより膨張し、耐火物に内側から圧力を付与することになるので、耐火物を劣化させる原因となる。このようなことから、耐火物中の気孔は少ない方が望ましく、気孔率を２５体積％以下にすることで、耐火物中への塩化鉄の堆積を抑制し、耐火物の劣化を防止することが可能となる。したがって、本発明では、気孔率を２５体積％以下にすることにより、耐火物の変質や脆化を抑制することができる。その結果、高珪素鋼板の連続製造ラインにおける長期間の安定操業を実現することができる。 Iron chloride (solid) deposited in the refractory is likely to be deposited in the refractory as the number of pores in the refractory increases. The iron chloride deposited in the refractory is expanded by exposure to the atmosphere, which applies pressure to the refractory from the inside, which causes deterioration of the refractory. From such a thing, it is desirable that the number of pores in the refractory is small, and by setting the porosity to 25% by volume or less, the deposition of iron chloride in the refractory is suppressed, and the deterioration of the refractory is prevented. Is possible. Therefore, in the present invention, by setting the porosity to 25% by volume or less, deterioration or embrittlement of the refractory can be suppressed. As a result, long-term stable operation in a continuous production line of high silicon steel plates can be realized.
　また、各種成分組成は一定で、圧縮強度の異なる耐火物を準備した。これら耐火物を、塩化鉄ガスを含む雰囲気（ＦｅＣｌ２濃度）：約１５ｖｏｌ％、炉内温度：約１２００℃）の炉内に１週間置いた後、２ヶ月間大気中に暴露した後の膨張状態の変化を調べた。その結果、圧縮強度と塩化鉄による膨張状態には密接な関係があり、圧縮強度が５ＭＰａを下回ると膨張状態が大きくなり、崩壊してしまうことがわかった。この為、本発明では、耐火物の圧縮強度を５ＭＰａ以上とする。圧縮強度が５ＭＰａ未満では、副産物である塩化鉄ガスが耐火物中に浸透して耐火物が膨張し、耐火物が崩壊してしまい、表面外観に影響を及ぼす。好ましくは、圧縮強度は２０～２００ＭＰａである。なお、圧縮強度は２００ＭＰａ以下であることが好ましい。 In addition, various component compositions were constant, and refractories having different compressive strengths were prepared. These refractories are expanded after being exposed to the atmosphere for 2 months after being placed in a furnace for an atmosphere containing iron chloride gas (FeCl 2 concentration: about 15 vol%, furnace temperature: about 1200 ° C.) The change of state was examined. As a result, it was found that the compressive strength and the expansion state by iron chloride have a close relationship, and when the compressive strength is less than 5 MPa, the expansion state becomes large and collapses. For this reason, in the present invention, the compressive strength of the refractory is 5 MPa or more. If the compressive strength is less than 5 MPa, the by-product iron chloride gas penetrates into the refractory, the refractory expands, and the refractory collapses, which affects the surface appearance. Preferably, the compressive strength is 20 to 200 MPa. The compressive strength is preferably 200 MPa or less.
　また、本発明において、気孔率および圧縮強度の測定方法については特に制限がなく、常法により求めればよい。また、気孔率が２５体積％以下であり、圧縮強度が５ＭＰａ以上の耐化物を用いることもできる。 Further, in the present invention, the method of measuring the porosity and the compressive strength is not particularly limited, and may be determined by an ordinary method. In addition, a refractory having a porosity of 25% by volume or less and a compressive strength of 5 MPa or more can also be used.
　種々の成分組成を有する耐火物（５０ｍｍ×５０ｍｍ×５０ｍｍ）を作製し、これらを図１に示す高珪素鋼板の連続製造ラインの浸珪処理炉内に設置した。浸珪処理炉の雰囲気をＳｉＣｌ４濃度：１５ｖｏｌ％、炉内温度：１２００℃として３ヵ月間連続運転した後、各耐火物の損傷状況を調べた。各耐火物の成分組成、気孔率、圧縮強度および損傷状況の結果を表１に示す。 Refractories (50 mm × 50 mm × 50 mm) having various component compositions were prepared and placed in the silicon treatment furnace of the high-silicon steel sheet continuous production line shown in FIG. After continuously operating the atmosphere of the siliconizing furnace with SiCl 4 concentration: 15 vol% and the temperature in the furnace: 1200 ° C. for 3 months, the damage state of each refractory was examined. Table 1 shows the composition of each refractory, the porosity, the compressive strength and the damage state.
　損傷状況としては、表面観察および反応性により判断した。表面観察は耐火物の外観を観察し、劣化状況から欠損あり＞亀裂あり＞変色＞変化無しの４段階で評価を行った。また、反応性に関しては、劣化状況から◎◎、◎、○、×の４段階（◎◎：反応せず、◎：ほとんど反応せず、○：反応が小さい（耐火物の劣化が認められるが、継続使用可能なレベル）、×：反応が顕著）で評価を行った。表面観察は変色、変化無しを合格とし、反応性は◎◎、◎および○を合格とした。 The state of damage was judged by surface observation and reactivity. Surface observation observed the appearance of the refractory, and evaluation was performed in four steps from the deterioration condition: defected> cracked> discoloration> no change. In addition, regarding reactivity, 4 stages of ◎, ◎, 、, × from the deterioration situation (◎: not reacting, ◎: hardly reacting, (: small reaction (refractory deterioration is observed Evaluation was made at the level where continuous use is possible, and x: reaction is remarkable. The surface observation gave discoloring and no change as pass, and the reactivity gave ◎, ◎ and を as pass.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の結果から、本発明例はいずれも良好な結果であった。 From the results of Table 1, all of the inventive examples were good results.
　実施例１において良好な結果を示したＮｏ．１０、１９、３１について、浸珪処理炉の耐火物として使用した際の更新周期について調べた。その結果、Ｎｏ．１０、１９を使用した場合、従来の耐火物（特許文献３の耐火物）の更新周期を１とした場合に、更新周期が１．５倍に延長することが可能となった。さらに、Ｎｏ．３１を使用した場合、更新周期を従来の３倍に延長することが可能となった。 No. 1 showing good results in Example 1. 10, 19 and 31 were examined about the renewal cycle at the time of using as a refractory of a siliconization treatment furnace. As a result, no. When 10 and 19 were used, when the update period of the conventional refractory (refractory of patent document 3) was set to 1, it became possible to extend an update period 1.5 times. Furthermore, no. When 31 was used, it became possible to extend the update cycle to three times the conventional one.

Claims (3)

  1. 　珪素の酸化物、珪素の窒化物および珪素の酸窒化物の中から選ばれる１種または２種以上を合計で３５質量％以上と、アルカリ金属を合計で０．０５質量％以下とを含有し、
    気孔率が２５体積％以下であり、圧縮強度が５ＭＰａ以上
    である浸珪処理炉用耐火物。     35% by mass or more in total of one or more selected from oxides of silicon, nitrides of silicon and oxynitrides of silicon, and 0.05% by mass or less in total of alkali metals ,
    Refractory for siliconizing treatment furnace having a porosity of 25 volume% or less and a compressive strength of 5 MPa or more.
  2. 　さらに、Ｍｇ、Ｃａ、Ｔｉ、Ｆｅ、ＣｒおよびＺｒの各酸化物を合計で１．０質量％以下を含有する請求項１に記載の浸珪処理炉用耐火物。 The refractory for siliconization furnace according to claim 1, further comprising not more than 1.0% by mass in total of respective oxides of Mg, Ca, Ti, Fe, Cr and Zr.
  3. 　珪素の酸化物、珪素の窒化物および珪素の酸窒化物の中から選ばれる１種または２種以上を合計で９０質量％以上含有する請求項１または２に記載の浸珪処理炉用耐火物。 The refractory for a siliconization treatment furnace according to claim 1 or 2, which contains one or more selected from oxide of silicon, nitride of silicon and oxynitride of silicon in total at 90% by mass or more in total. .
PCT/JP2018/032582 2017-09-12 2018-09-03 Refractory for siliconizing furnaces WO2019054222A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020207006888A KR102401344B1 (en) 2017-09-12 2018-09-03 Refractory materials for acupuncture furnaces
JP2018560694A JP6747520B2 (en) 2017-09-12 2018-09-03 Refractories for furnaces using silicon chloride gas
CN201880058716.3A CN111094212A (en) 2017-09-12 2018-09-03 Refractory for siliconizing treatment furnace

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017174424 2017-09-12
JP2017-174424 2017-09-12

Publications (1)

Publication Number Publication Date
WO2019054222A1 true WO2019054222A1 (en) 2019-03-21

Family

ID=65723673

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/032582 WO2019054222A1 (en) 2017-09-12 2018-09-03 Refractory for siliconizing furnaces

Country Status (4)

Country Link
JP (1) JP6747520B2 (en)
KR (1) KR102401344B1 (en)
CN (1) CN111094212A (en)
WO (1) WO2019054222A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01282148A (en) * 1988-05-06 1989-11-14 Shinagawa Refract Co Ltd Melted siliceous refractory brick resistant to gaseous chlorine
JPH08169750A (en) * 1994-12-15 1996-07-02 Nkk Corp Refractory for furnace using gaseous silicon chloride
JP2000283655A (en) * 1999-03-31 2000-10-13 Nkk Corp Silicifying furnace

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE837268A (en) * 1975-12-31 1976-06-30 IMPROVED REFRACTORY MATERIALS INTENDED TO CONSTITUTE THE INTERIOR COATING OF OVENS FOR METALLURGIC USE AND MORE SPECIFICALLY OF ELECTRIC INDUCTION OVENS
JPS62227078A (en) 1986-03-28 1987-10-06 Nippon Kokan Kk <Nkk> Manufacture of high silicon steel strip continuous line
JP2947107B2 (en) * 1994-12-29 1999-09-13 日本鋼管株式会社 Continuous production method of high silicon steel strip
JP3259646B2 (en) 1996-11-15 2002-02-25 日本鋼管株式会社 Continuous siliconizing equipment for steel strip
DE102007004242B4 (en) * 2007-01-23 2018-01-04 Schott Ag A method for producing a shaped body of quartz glass by sintering, molding and use of the molding
CN101323530A (en) * 2008-07-01 2008-12-17 山东中齐耐火材料集团有限公司 Fused quartz block for coke oven hot repair
CN101407421B (en) * 2008-11-04 2011-08-31 西安交通大学 Method for preparing non-grain boundary phase porous silicon nitride ceramic based on siliconizing nitridation
CN102976720B (en) * 2012-11-07 2016-07-06 洛阳北苑特种陶瓷有限公司 A kind of preparation method of quartz ceramic
CN104628399B (en) * 2015-02-11 2017-04-19 江苏中正耐火材料有限公司 Crack-resistant and zero-expansion fused-silica brick and preparation method thereof
CN105924183A (en) * 2016-04-21 2016-09-07 武汉科技大学 Quartziferous side dam and preparation method thereof
CN106783132B (en) * 2016-12-26 2019-03-19 安徽工业大学 A kind of high silicon steel core and preparation method thereof to insulate between particle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01282148A (en) * 1988-05-06 1989-11-14 Shinagawa Refract Co Ltd Melted siliceous refractory brick resistant to gaseous chlorine
JPH08169750A (en) * 1994-12-15 1996-07-02 Nkk Corp Refractory for furnace using gaseous silicon chloride
JP2000283655A (en) * 1999-03-31 2000-10-13 Nkk Corp Silicifying furnace

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TECHNICAL ASSOCIATION OF REFRACTORIES, 1981, pages 160 - 163 *

Also Published As

Publication number Publication date
KR20200039740A (en) 2020-04-16
JP6747520B2 (en) 2020-08-26
KR102401344B1 (en) 2022-05-23
CN111094212A (en) 2020-05-01
JPWO2019054222A1 (en) 2019-11-07

Similar Documents

Publication Publication Date Title
JP7067998B2 (en) Stainless steel
CA2940179C (en) Cast product having alumina barrier layer
WO2019054222A1 (en) Refractory for siliconizing furnaces
Wang et al. A superficial coating to improve oxidation and decarburization resistance of bearing steel at high temperature
JP6624028B2 (en) Manufacturing method of grain-oriented electrical steel sheet
JP4892190B2 (en) Manufacturing method of heat-curable steel plate, and steel plate and parts obtained by the manufacturing method
JP2005281793A (en) Method for producing wire rod for steel wire, and wire rod for steel wire
JP4332449B2 (en) Thermal spray coating coated on hearth roll for continuous annealing furnace of steel sheet
JP5664286B2 (en) Method for producing high silicon steel sheet
JP5664287B2 (en) Method for producing high silicon steel sheet
UA74872C2 (en) A structural isotropic steel, a method for the preparation of plate of this steel and resulting plates
KR20100020740A (en) Radiant tube with excellent high temperature properties and manufacturing method thereof
JP3158921B2 (en) Refractories for furnaces using silicon chloride gas
JP4675771B2 (en) Ferritic stainless steel wire for glass encapsulation
CN108546091A (en) A kind of preparation method of surface coated magnesia crucible
JP4031267B2 (en) Steel wire for spring and manufacturing method thereof
JP6687864B2 (en) Sliding plate refractory
JPH0812432A (en) Refractory resistant to atmosphere containing silicon chloride gas
JP2010001504A (en) Stock for cold rolled stainless steel sheet capable of suppressing occurrence of roping and ear crack can be suppressed, and method for producing the same
JP2013067548A (en) Monolithic refractory
JPH10147856A (en) Continuous siliconizing treating equipment for steel strip
JP5157142B2 (en) High corrosion resistance, thermal shock resistance, difficult adhesion ceramics
TWI355422B (en)
CN116426839A (en) Enamelled steel sheet and preparation method thereof
JPWO2020149348A1 (en) Manufacturing method of grain-oriented electrical steel sheet

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018560694

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18856060

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20207006888

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18856060

Country of ref document: EP

Kind code of ref document: A1