JP2543308B2 - Silicon carbide refractory and manufacturing method thereof - Google Patents
Silicon carbide refractory and manufacturing method thereofInfo
- Publication number
- JP2543308B2 JP2543308B2 JP5093937A JP9393793A JP2543308B2 JP 2543308 B2 JP2543308 B2 JP 2543308B2 JP 5093937 A JP5093937 A JP 5093937A JP 9393793 A JP9393793 A JP 9393793A JP 2543308 B2 JP2543308 B2 JP 2543308B2
- Authority
- JP
- Japan
- Prior art keywords
- refractory
- present
- weight
- silicon carbide
- firing
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims description 43
- 229910010271 silicon carbide Inorganic materials 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000010304 firing Methods 0.000 claims description 21
- 239000004927 clay Substances 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 14
- 239000011819 refractory material Substances 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 1
- 238000003763 carbonization Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003513 alkali Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- 239000011449 brick Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000004901 spalling Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、炭化珪素質耐火物及び
その製造方法に関し、特に高炉用内張り耐火物として極
めて好適な炭化珪素質耐火物及びその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon carbide refractory and a method for producing the same, and more particularly to a silicon carbide refractory which is extremely suitable as a lining furnace refractory for a blast furnace and a method for producing the same.
【０００２】[0002]
【従来の技術】従来の炭化珪素質耐火物としては、(1)
使用原料として、SiC(骨材成分)、金属Si及びAl2O3を用
いた耐火物であり、窒素雰囲気中で焼成して得られる炭
化珪素質耐火物(窯業協会誌、82,(7),P351-357,(1974)
他 参照)、(2) 使用原料として、SiC(骨材成分)、Si3N4
及びAl2O3を用いた耐火物であり、酸化雰囲気中で焼成
して得られる炭化珪素質耐火物(特開平3−45560号公報
参照)、(3) 骨材成分としてAl2O3及びSiCを、また、結
合材成分としてSi3N4及びAl2O3を用いた耐火物であり、
中性又は還元雰囲気中コ−クスブリ−ズ詰めにて焼成し
て得られるAl2O3及びSiC骨材とSi-Al-O-N系固溶体から
なる耐火物（特公昭57−267号公報参照）、が知られて
いる。2. Description of the Related Art Conventional silicon carbide refractories include (1)
As a raw material used, SiC (aggregate component), a refractory using Si and Al 2 O 3 , a silicon carbide refractory obtained by firing in a nitrogen atmosphere (ceramics association magazine, 82, (7) , P351-357, (1974)
(See other), (2) As raw materials used, SiC (aggregate component), Si 3 N 4
And a refractory using Al 2 O 3 , a silicon carbide refractory obtained by firing in an oxidizing atmosphere (see Japanese Patent Laid-Open No. 3-45560), (3) Al 2 O 3 as an aggregate component and SiC is a refractory material using Si 3 N 4 and Al 2 O 3 as the binder component,
Refractory consisting of Al 2 O 3 and SiC aggregates and Si-Al-ON solid solution obtained by firing with coke breeze filling in a neutral or reducing atmosphere (see JP-B-57-267), It has been known.
【０００３】[0003]
【発明が解決しようとする課題】ところで、従来の上記
炭化珪素質耐火物では、いずれも1700℃以上という高温
焼成により得られるものであり、そのため、かなりコス
ト高になる欠点を有している。By the way, all of the above-mentioned conventional silicon carbide refractories can be obtained by firing at a high temperature of 1700 ° C. or higher, and therefore have a drawback that the cost becomes considerably high.
【０００４】その他、従来の上記(1)の耐火物では、窒
素雰囲気中で焼成する方法であり、窒化反応によりサイ
アロンボンドを形成するものであるが、窒化反応炉の建
設、窒素の使用等で高コストになり、またバッチ炉であ
るがゆえに、大量生産には不向きである等の問題点を有
している。また上記(2)の耐火物では、酸化焼成である
がゆえに、酸化物（SiO2）の生成が促進され、最も使用
上重要視される対アルカリ性が劣る。さらに上記(3)の
耐火物では、微粉部がSi3N4-Al2O3系であり、高炉内張
り耐火物のような大型形状では、成形性が悪く、製造が
困難である等の問題点を有している。In addition, the conventional refractory (1) above is a method of firing in a nitrogen atmosphere and forms a sialon bond by a nitriding reaction. However, in the construction of a nitriding reactor, the use of nitrogen, etc. It has problems such as high cost and unsuitability for mass production because it is a batch furnace. Further, in the refractory material of the above (2), since it is an oxidative calcination, the production of an oxide (SiO 2 ) is promoted, and the alkali resistance, which is most important for use, is poor. Further, in the refractory of the above (3), the fine powder part is a Si 3 N 4 -Al 2 O 3 system, and in a large shape such as a blast furnace lining refractory, moldability is poor, and problems such as manufacturing are difficult. Have a point.
【０００５】本発明者等は、炭化珪素質耐火物について
鋭意研究を重ねた結果、本発明を完成したものであっ
て、本発明の目的は、上記欠点、問題点を解消する炭化
珪素質耐火物を提供することにあり、また、大量生産を
することができ、低コストで製造することができる炭化
珪素質耐火物の製造方法を提供することにある。The inventors of the present invention have completed the present invention as a result of intensive studies on silicon carbide-based refractory materials, and the object of the present invention is to solve the above-mentioned drawbacks and problems. Another object of the present invention is to provide a method for manufacturing a silicon carbide refractory material that can be mass-produced and can be manufactured at low cost.
【０００６】[0006]
【課題を解決するための手段】そして、本発明の炭化珪
素質耐火物は、 (1)“SiC(骨材)間の結合、即ちマトリックス部に微粉の
β-Si3N4を配し、該Si3N4に固溶させるAl2O3源として耐
火粘土を用い、この耐火粘土を化学反応により分解さ
せ、それをSi3N4に固溶させる点”、さらに、 (2)“成形性を高めるべく耐火粘土を使用する点” を特徴とし、これにより耐アルカリ性に優れた耐火物を
提供するものである。The silicon carbide refractory material of the present invention comprises (1) "bonding between SiC (aggregates)", that is, fine particles in the matrix portion.
Placing β- Si 3 N 4 and using solid refractory clay as an Al 2 O 3 source to be solid-dissolved in the Si 3 N 4 , the refractory clay is decomposed by a chemical reaction, and it is solid-dissolved in Si 3 N 4 . In addition, "(2)" Use of refractory clay to improve moldability "is a feature, which provides refractories with excellent alkali resistance.
【０００７】また、本発明の製造方法は、焼成条件とし
て、(3)“低温(1500〜1650℃)のトンネルキルンでブリ
−ズ詰めにて焼成する点”を特徴とし、これにより大量
生産が可能になり、特に1500〜1650℃という低温の焼成
では、サヤの耐用性についても問題なく、低コストで製
造することができるものである。Further, the manufacturing method of the present invention is characterized by (3) as a firing condition, "a point of firing in a tunnel kiln at a low temperature (1500 to 1650 ° C) in a breeze-filled state", which enables mass production. It becomes possible, and especially by firing at a low temperature of 1500 to 1650 ° C., the durability of the sheath is not a problem, and the product can be manufactured at low cost.
【０００８】即ち、本発明の炭化珪素質耐火物は、「60
〜80重量％のSiC骨材、10〜30重量％のβ-Si3N4、2〜10
重量％の耐火粘土、1〜10重量％の金属アルミニウム及
び3〜6重量％の金属珪素を焼成してなることを特徴とす
る炭化珪素質耐火物。」を要旨とする。That is, the silicon carbide-based refractory material of the present invention is "60
80 wt% of SiC aggregate, of 10 to 30 wt% β-Si 3 N 4, 2~10
A silicon carbide refractory, characterized by being obtained by firing 1 wt% refractory clay, 1 to 10 wt% metallic aluminum and 3 to 6 wt% metallic silicon. Is the gist.
【０００９】また、本発明の炭化珪素質耐火物の製造法
は、「60〜80重量％のSiC骨材、10〜30重量％のβ-Si3N
4、2〜10重量％の耐火粘土、1〜10重量％の金属アルミ
ニウム及び3〜6重量％の金属珪素を配合し、さらにバイ
ンダ−を添加した後、混練し、所定形状に成形し、該成
形物をトンネルキルンでブリ−ズ詰めにて非酸化雰囲気
中1500〜1650℃で焼成することを特徴とする炭化珪素質
耐火物の製造方法。」を要旨とするものである。The method for producing a silicon carbide-based refractory material of the present invention is "60-80 wt% SiC aggregate, 10-30 wt% β-Si 3 N.
4 , blending 2 to 10 wt% refractory clay, 1 to 10 wt% metallic aluminum and 3 to 6 wt% metallic silicon, further adding a binder, kneading and molding into a predetermined shape, Molded products are packed in a tunnel kiln and blazed in a non-oxidizing atmosphere
A method for manufacturing a silicon carbide-based refractory material, which comprises firing at 1500 to 1650 ° C in the middle . Is the gist.
【００１０】以下、本発明を詳細に説明する。 (1) SiC骨材について 本発明におけるSiC骨材は、高炉スラグに対する耐食性
をもたせるためのものであり、その配合量は60〜80重量
％必要である。60重量％未満の場合高炉操業下での耐ス
ラグ性が劣り、また、80重量％を越える場合マトリック
ス部の結合ボンドが不足するので好ましくない。なお、
本発明において、SiC骨材の純度は90％以上が望まし
く、また、SiC骨材の粒度は6mesh以下を適度に配合する
ことが望ましい。Hereinafter, the present invention will be described in detail. (1) About SiC Aggregate The SiC aggregate in the present invention is for imparting corrosion resistance to blast furnace slag, and its content is required to be 60 to 80% by weight. If it is less than 60% by weight, the slag resistance under the operation of the blast furnace is inferior, and if it exceeds 80% by weight, the bond bond in the matrix portion becomes insufficient, which is not preferable. In addition,
In the present invention, the purity of the SiC aggregate is preferably 90% or more, and the particle size of the SiC aggregate is preferably 6 mesh or less.
【００１１】(2) β-Si3N4について 本発明におけるβ-Si3N4は、β-Si3N4含量が15重量％以
上で任意割合のものが使用でき、Si3N4源としてα-Si3N
4のような高価な原料のみを用いる必要がないものであ
る。その添加量は10〜30重量％必要であり、10％未満の
場合、不足分のマトリックス部をSiCで補うことにな
り、本発明で意図する“結合ボンドの効果”が低減され
るので好ましくない。一方、30重量％を越える場合、耐
火物自体の粒度構成が細粒構成になり、上記添加範囲内
に比して組織的に緻密化し、耐スポーリング性が劣るの
で好ましくない。また、本発明において、β-Si3N4はマ
トリックス部を形成すべく、その粒度としては65mesh以
下が好ましい。[0011] (2) β-Si 3 N β-Si 3 N 4 in the present invention for 4, β-Si 3 N 4 content can be used any ratio at 15 wt% or more, Si 3 N 4 sources As α-Si 3 N
It is not necessary to use only expensive raw materials such as 4 . The addition amount is required to be 10 to 30% by weight, and if it is less than 10%, the insufficient matrix portion will be supplemented with SiC, and the "bonding effect" intended by the present invention is reduced, which is not preferable. . On the other hand, if it exceeds 30% by weight, the refractory itself has a fine grain structure and is finely structured as compared with the above addition range, and the spalling resistance is inferior, which is not preferable. In the present invention, β-Si 3 N 4 preferably has a particle size of 65 mesh or less so as to form a matrix portion.
【００１２】(3) 耐火粘土について 本発明で使用する耐火粘土は、一般的にAl2O3、SiO2の
化合物であり、コークス中で金属Alによって還元され、
SiO2の脱酸反応が起こる作用が生じる（特開昭52-9011
号公報、特公昭56-31313号公報参照）。この反応により
活性度の高い非晶質のAl2O3が生成され、β-Si3N4に固
溶される。耐火粘土の添加量は2〜10重量％必要であ
り、2％未満の場合、前述の反応による非晶質なAl2O3の
量が少なく、Al2O3を固溶していないβ-Si3N4が存在
し、一方、10重量％を越える場合、未反応の耐火粘土が
残り、耐アルカリ性が劣るので好ましくない。(3) Refractory Clay The refractory clay used in the present invention is generally a compound of Al 2 O 3 and SiO 2 , which is reduced by metallic Al in coke,
The action of deoxidizing SiO 2 occurs (Japanese Patent Laid-Open No. 529011).
(See Japanese Patent Publication No. 56-31313). By this reaction, highly active amorphous Al 2 O 3 is generated and dissolved in β-Si 3 N 4 . The addition amount of refractory clay is required to be 2 to 10% by weight, and when it is less than 2%, the amount of amorphous Al 2 O 3 due to the above reaction is small, and β 2 that does not form a solid solution with Al 2 O 3. On the other hand, if Si 3 N 4 is present and exceeds 10% by weight, unreacted refractory clay remains and alkali resistance is poor, which is not preferable.
【００１３】(4) 金属Alについて 本発明で添加する金属Alは、耐火粘土の脱酸反応を促進
する作用が生じ、非晶質のAl2O3がβ-Si3N4に固溶する
ことになる。その添加量は1〜10重量％必要であり、1％
未満の場合、耐火粘土の脱酸反応が不充分になる。ま
た、10重量％を越える場合、金属Alが単独で存在するこ
ととなり、これがその他の酸化物と結合して3Al2O3・2S
iO2を生成し、融点を低下させるので好ましくない。(4) Metal Al The metal Al added in the present invention has a function of promoting the deoxidation reaction of refractory clay, and amorphous Al 2 O 3 forms a solid solution with β-Si 3 N 4 . It will be. Its addition amount should be 1-10% by weight, 1%
If it is less than 1, the deoxidation reaction of the refractory clay will be insufficient. Further, if it exceeds 10 wt%, it becomes the metal Al is present alone, which combines with other oxides 3Al 2 O 3 · 2S
It is not preferable because it produces iO 2 and lowers the melting point.
【００１４】(5) 金属Siについて 本発明で添加する金属Siは、耐火物の強度発現のために
添加される。添加量は3〜6重量％必要であり、3％未満
の場合、強度発現効果がみられず、一方、6重量％を越
える場合、れんがの焼結が進み過ぎ、耐スポーリング性
が劣るので好ましくない。(5) Metal Si The metal Si added in the present invention is added in order to develop the strength of the refractory. The addition amount is required to be 3 to 6% by weight. If it is less than 3%, the strength development effect is not observed, while if it exceeds 6% by weight, the brick sintering proceeds excessively and the spalling resistance is poor. Not preferable.
【００１５】(6) バインダ−について バインダ−については、本発明において特に限定するも
のではないが、素地強度の保持のため乾燥強度を得る目
的で添加するのが好ましく、例えばレジン系、燐酸系、
水ガラス、糖密及びパルプ廃液等を使用することができ
る。(6) Binder The binder is not particularly limited in the present invention, but it is preferable to add it for the purpose of obtaining dry strength in order to maintain the strength of the base material. For example, a resin type, a phosphoric acid type,
Water glass, sugar-tight, pulp waste liquid and the like can be used.
【００１６】(7) 焼成条件について 焼成温度については、1500℃以上であればβ-Si3N4中へ
のAl2O3の固溶反応が進行するが、1500℃未満ではこの
固溶反応が遅く、好ましくない。また、1700℃を越える
温度になると、サヤの耐久性に問題があるため、本発明
では、1500〜1650℃という低温焼成が望ましい。本発明
における焼成手段としては、トンネルキルンでブリ−ズ
詰めにて焼成するのが好ましい。即ち原料配合成形物を
コークスと共にサヤに挿入すること（ブリ−ズ詰め）に
より、原料であるSiC、金属Al、金属Siなどの直接酸化
を防ぎ、容易に反応させることができるので、好まし
い。(7) Firing conditions Regarding the firing temperature, the solid solution reaction of Al 2 O 3 in β- Si 3 N 4 proceeds at 1500 ° C. or higher, but at 1500 ° C., the solid solution reaction occurs. Is slow and unfavorable. Further, at temperatures exceeding 1700 ° C., there is a problem in the durability of the sheath, so in the present invention, low temperature firing of 1500 to 1650 ° C. is desirable. As the firing means in the present invention, it is preferable to perform firing in a tunnel kiln by breezing. That is, by inserting the raw material-blended molded product into the sheath together with coke (blaze filling), it is possible to prevent direct oxidation of the raw materials such as SiC, metallic Al, metallic Si, etc., and to easily react them, which is preferable.
【００１７】更に、本発明において、焼成雰囲気として
は“非酸化雰囲気”とする必要がある。酸化雰囲気で
は、原料であるSiC、金属Al、金属Siなどが直接酸化さ
れることになり、その結果、耐食性、耐アルカリ性の劣
る焼成品が得られるので好ましくない（後記比較例２参
照）。本発明では、非酸化雰囲気中、特に還元雰囲気中
で焼成するのが好ましい。なお、本発明の方法により得
られた焼成品は、Ｘ線回折法による同定の結果、骨材の
SiC間が“サイアロン相の構成相”よりなることを確認
した。Further, in the present invention, the firing atmosphere must be "non-oxidizing atmosphere". In an oxidizing atmosphere, raw materials such as SiC, metallic Al, metallic Si, etc. are directly oxidized, and as a result, a fired product having poor corrosion resistance and alkali resistance is obtained (see Comparative Example 2 below). In the present invention, firing is preferably performed in a non-oxidizing atmosphere, particularly in a reducing atmosphere. The fired product obtained by the method of the present invention was identified by X-ray diffraction, and
It was confirmed that the space between the SiC layers consisted of "the constituent phases of the sialon phase."
【００１８】[0018]
【実施例】以下、本発明の実施例を比較例と共に挙げ、
本発明をより詳細に説明する。 （実施例１） ・SiC（骨材）：70ｗｔ％ ・β-Si3N4 ：17ｗｔ％ ・金属Al ：4ｗｔ％ ・金属Si ：5ｗｔ％ ・耐火粘土 ：4ｗｔ％ 上記各原料を配合し、さらに外掛けで3重量％のフェノ
ール樹脂を添加、混練した後、常法に従って高炉シャフ
ト形状にプレス成形した。EXAMPLES Examples of the present invention will be given below together with comparative examples.
The present invention will be described in more detail. (Example 1) ・ SiC (aggregate): 70 wt% ・ β-Si 3 N 4 : 17 wt% ・ Metal Al: 4 wt% ・ Metal Si: 5 wt% ・ Refractory clay: 4 wt% After externally adding 3% by weight of phenol resin and kneading, press molding was performed into a blast furnace shaft according to a conventional method.
【００１９】次に、上記成形物をブリーズ詰めしてトン
ネルキルンにて還元雰囲気中1600℃で焼成し、炭化珪素
質れんがを得た。このれんがについて、その曲げ強さ(M
Pa)、弾性率(GPa)、耐食性、耐酸化性、耐スポ−リング
性、耐アルカリ性を夫々測定した。その結果を表１に示
す。Next, the above-mentioned molded product was breeze packed and fired in a tunnel kiln at 1600 ° C. in a reducing atmosphere to obtain a silicon carbide brick. For this brick, its bending strength (M
Pa), elastic modulus (GPa), corrosion resistance, oxidation resistance, spooling resistance, and alkali resistance were measured. Table 1 shows the results.
【００２０】（実施例２〜５）表１に示す各原料を同じ
く表１に示す配合割合で混練し、実施例１と同様に成
形、焼成して炭化珪素質れんがを得た。得られたれんが
について、実施例１と同様の試験を行い、その結果を表
１に示した。(Examples 2 to 5) The respective raw materials shown in Table 1 were kneaded at the compounding ratio shown in Table 1 and molded and fired in the same manner as in Example 1 to obtain a silicon carbide brick. The obtained brick was tested in the same manner as in Example 1, and the results are shown in Table 1.
【００２１】（比較例１）比較のため、94重量％のSiC
に6重量％の金属Siを配合したものを酸化雰囲気中1600
℃で焼成した。得られた焼成品について、実施例１と同
様の試験を行い、その結果を表１に併記した。(Comparative Example 1) For comparison, 94% by weight of SiC
1600 in an oxidizing atmosphere containing 6% by weight of metallic Si
Baked at ° C. The same test as in Example 1 was performed on the obtained fired product, and the results are also shown in Table 1.
【００２２】（比較例２、３）さらに比較のため、 ・本発明の範囲内の各原料を配合し、これを酸化雰囲気
中で1600℃で焼成した例(比較例２)、 ・金属Siについて本発明の範囲外である2重量％を配合
する点を除きその他は本発明の範囲内の各原料を配合
し、これを還元雰囲気中で1550℃で焼成した例(比較例
３)、 について、実施例１と同様の試験を行い、その結果を同
じく表１に併記した。(Comparative Examples 2 and 3) For further comparison, an example in which the respective raw materials within the scope of the present invention were mixed and the mixture was fired at 1600 ° C. in an oxidizing atmosphere (Comparative Example 2), Regarding an example (Comparative Example 3) in which each raw material within the scope of the present invention was blended except that 2% by weight, which is outside the scope of the present invention, was blended, and which was calcined at 1550 ° C. in a reducing atmosphere, The same test as in Example 1 was conducted, and the results are also shown in Table 1.
【００２３】[0023]
【表１】 [Table 1]
【００２４】表１から明らかなように、本発明の実施例
１〜５はいずれも耐食性、耐酸化性、耐アルカリ性に優
れ、しかも高強度、高弾性率のものが得られた。これに
対して、比較例１〜３では、耐スポ−リング性を除きい
ずれも上記諸特性値の劣るものが得られた。As is clear from Table 1, all of Examples 1 to 5 of the present invention were excellent in corrosion resistance, oxidation resistance and alkali resistance, and had high strength and high elastic modulus. On the other hand, in Comparative Examples 1 to 3, all of the above-mentioned characteristic values were inferior except for the spooling resistance.
【００２５】即ち、比較例１（β-Si3N4、耐火粘土及び
金属Alを配合しないもの）では、マトリックス部に本発
明が目的とする結合ボンドが存在しないため、実施例１
〜５に比し耐アルカリ性が劣るものであった。That is, in Comparative Example 1 (no blending of β-Si 3 N 4 , refractory clay and metallic Al), there is no bond bond for the purpose of the present invention in the matrix portion.
Alkali resistance was inferior compared to ~ 5.
【００２６】また、比較例２でみられるように、本発明
の範囲内の各原料を配合し、これを“酸化雰囲気中”で
焼成した場合、融点を低下させるAl2O3・SiO2系の化合
物が生成することになる。このため比較例２では、実施
例１〜５に比して耐食性、耐アルカリ性が劣るものであ
った。Also, as seen in Comparative Example 2, when each raw material within the scope of the present invention is blended and baked in an "oxidizing atmosphere", the Al 2 O 3 .SiO 2 system which lowers the melting point is obtained. Compound of
Things will be generated. Therefore, Comparative Example 2 was inferior in corrosion resistance and alkali resistance to Examples 1 to 5.
【００２７】さらに、比較例３では、金属Siが本発明の
範囲外であるため（金属Si：2ｗｔ％）、マトリックス
部において本発明が目的とする結合ボンドが不足し、ま
た、Al2O3を固溶しないβ-Si3N4が存在する。従って、
比較例３では、実施例１〜５に比して耐アルカリ性、耐
酸化性が劣るものであった。Furthermore, in Comparative Example 3, since the metal Si is outside the range of the present invention (metal Si: 2 wt%), the bond bond intended by the present invention is insufficient in the matrix portion, and Al 2 O 3 is used. There is β-Si 3 N 4 that does not form a solid solution. Therefore,
Comparative Example 3 was inferior in alkali resistance and oxidation resistance to Examples 1-5.
【００２８】[0028]
【発明の効果】本発明の炭化珪素質耐火物は、以上詳記
したとおり、骨材としてSiCを用い、マトリックス材と
して微粉のSi3N4を配し、このSi3N4に固溶させるAl2O3
源として耐火粘土を使用することを特徴とするものであ
り、これにより従来のこの種の炭化珪素質耐火物に比
し、耐アルカリ性に極めて優れた炭化珪素質耐火物が得
られる効果が生じる。また、その他の耐酸化性、高炉ス
ラグによる耐食性、耐スポ−リング性については、従来
の炭化珪素質耐火物とほぼ同等であり、これらの諸特性
について従来製品と遜色ないものが得られる効果が生じ
る。As described in detail above, the silicon carbide refractory material of the present invention uses SiC as an aggregate and finely powdered Si 3 N 4 as a matrix material to be solid-dissolved in this Si 3 N 4 . Al 2 O 3
It is characterized by using refractory clay as a source, which brings about an effect of obtaining a silicon carbide refractory having extremely excellent alkali resistance as compared with the conventional silicon carbide refractory of this kind. In addition, other oxidation resistance, corrosion resistance due to blast furnace slag, and spalling resistance are almost the same as those of the conventional silicon carbide refractory, and it is possible to obtain the effect that these characteristics are comparable to conventional products. Occurs.
【００２９】本発明の炭化珪素質耐火物の製造方法は、
サヤにブリーズ詰めしてトンネルキルンにて低温(1500
〜1650℃)で焼成することを特徴とするものであり、従
来の窒化反応による製品に比し、約1／2という低コスト
で製造することができ、また、焼成手段として、トンネ
ルキルンを使用することにより、連続焼成が可能であ
り、大量生産に優れている効果が生じる。そして、本発
明により特に高炉用内張り耐火物として極めて好適な炭
化珪素質耐火物を提供することができる。The method for producing a silicon carbide refractory material according to the present invention comprises:
Pack breeze in saya and cool in tunnel kiln (1500
It is characterized by firing at ~ 1650 ° C), and it can be manufactured at a low cost of about 1/2 compared to conventional products by nitriding reaction, and a tunnel kiln is used as a firing means. By doing so, continuous firing is possible, and an effect that is excellent in mass production occurs. Further, according to the present invention, it is possible to provide a silicon carbide refractory which is extremely suitable as a lining refractory for blast furnace.
フロントページの続き (56)参考文献 特開 昭59−121166（ＪＰ，Ａ) 特公 昭57−267（ＪＰ，Ｂ２)Continuation of front page (56) References JP-A-59-121166 (JP, A) JP-B-57-267 (JP, B2)
Claims (2)
のβ-Si3N4、2〜10重量％の耐火粘土、1〜10重量％の金
属アルミニウム及び3〜6重量％の金属珪素を焼成してな
ることを特徴とする炭化珪素質耐火物。1. 60-80% by weight SiC aggregate, 10-30% by weight
Carbonization characterized by calcining β-Si 3 N 4 , 2-10 wt% refractory clay, 1-10 wt% metallic aluminum and 3-6 wt% metallic silicon. Silicon refractory.
のβ-Si3N4、2〜10重量％の耐火粘土、1〜10重量％の金
属アルミニウム及び3〜6重量％の金属珪素を配合し、さ
らにバインダ−を添加した後、混練し、所定形状に成形
し、該成形物をトンネルキルンでブリ−ズ詰めにて非酸
化雰囲気中1500〜1650℃で焼成することを特徴とする炭
化珪素質耐火物の製造方法。2. 60-80% by weight SiC aggregate, 10-30% by weight
Β-Si 3 N 4 , 2 to 10% by weight of refractory clay, 1 to 10% by weight of metallic aluminum and 3 to 6% by weight of metallic silicon are added, and a binder is further added, followed by kneading, Molded into a shape, and the molded product is packed in a tunnel kiln and brazed to remove acid.
A method for producing a silicon carbide-based refractory material, which comprises firing at 1500 to 1650 ° C. in a chemical atmosphere .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5093937A JP2543308B2 (en) | 1993-03-30 | 1993-03-30 | Silicon carbide refractory and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5093937A JP2543308B2 (en) | 1993-03-30 | 1993-03-30 | Silicon carbide refractory and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06279116A JPH06279116A (en) | 1994-10-04 |
| JP2543308B2 true JP2543308B2 (en) | 1996-10-16 |
Family
ID=14096354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5093937A Expired - Lifetime JP2543308B2 (en) | 1993-03-30 | 1993-03-30 | Silicon carbide refractory and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2543308B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009069206A (en) * | 2007-09-10 | 2009-04-02 | Ricoh Co Ltd | Image forming apparatus |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57267A (en) * | 1980-05-31 | 1982-01-05 | Nitto Electric Ind Co | Steel plate covered roof |
| JPS6047224B2 (en) * | 1982-12-28 | 1985-10-21 | 品川白煉瓦株式会社 | Manufacturing method for carbon-silicon carbide refractories |
-
1993
- 1993-03-30 JP JP5093937A patent/JP2543308B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009069206A (en) * | 2007-09-10 | 2009-04-02 | Ricoh Co Ltd | Image forming apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06279116A (en) | 1994-10-04 |
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