JPS60145960A - Anticorrosive ceramic sintered body - Google Patents
Anticorrosive ceramic sintered bodyInfo
- Publication number
- JPS60145960A JPS60145960A JP59003246A JP324684A JPS60145960A JP S60145960 A JPS60145960 A JP S60145960A JP 59003246 A JP59003246 A JP 59003246A JP 324684 A JP324684 A JP 324684A JP S60145960 A JPS60145960 A JP S60145960A
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- chromium
- ceramic sintered
- sintering
- body according
- Prior art date
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Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、とくにＦｅＯ雰囲気中での使用に適した耐食
性エンジニアリングセラミックスに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to corrosion-resistant engineering ceramics particularly suitable for use in FeO atmospheres.
従来から、炭化珪素は窒化珪素と並び化学的に安定で耐
摩耗性、耐熱衝撃性に優れ、且つ高温での機械的特性が
良い等の点からエンジニアリングセラミックスとしての
研究開発が行われている。Silicon carbide has been researched and developed as an engineering ceramic since, like silicon nitride, it is chemically stable, has excellent wear resistance and thermal shock resistance, and has good mechanical properties at high temperatures.
炭化珪素については、共有結合性が強く難焼結性の物質
であることから、緻密な焼結体を得るためにはＢ、Ｃ，
８４Ｃ，ＡＩ、＾１Ｎ等の焼結助剤を用いるか、或いは
Ａ１２０３ 、 ＺｒＯ２等の酸化物を介して焼結する
方法が提案されている。Silicon carbide has strong covalent bonds and is difficult to sinter, so in order to obtain a dense sintered body, B, C,
Proposed methods include using sintering aids such as 84C, AI, and ^1N, or sintering via oxides such as A1203 and ZrO2.
その中でも特にＺｒＯ２のような高温で安定な酸化物と
ＳｊＣから成る焼結体は、靭性において優れていること
が最近明らかとなった。Among these, it has recently been revealed that a sintered body made of SjC and an oxide that is stable at high temperatures, such as ZrO2, has excellent toughness.
しかしながら、エンジニアリングセラミックスと呼ばれ
るものも、非酸化物セラミックスと溶融金属とくに酸化
鉄との反応が激しく、かかるエンジニアリングセラミッ
クスを金属工業、とくに製鉄業での例えばビームボタン
、ロール等に使用した場合には、侵食あるいは溶損をう
け損耗し易いという問題がある。ここに、従来の水冷部
分への金属に代わる省エネ部材としての利用が早くから
考えられていたにも拘わらず進展しなかった理由がある
。However, even in what are called engineering ceramics, the reaction between non-oxide ceramics and molten metal, especially iron oxide, is severe, and when such engineering ceramics are used in the metal industry, especially in the steel industry, for example, for beam buttons, rolls, etc. There is a problem that it is easily damaged by erosion or melting damage. Herein lies the reason why no progress has been made in spite of the idea of using it as an energy-saving member to replace metal in conventional water-cooled parts.
本発明の目的は、製鉄、製鋼プロセスにおいて溶融鉄、
酸化鉄に直接ないし間接的に接触する中で長期間使用で
きる材料としての高靭性焼結体を実現することにある。The purpose of the present invention is to produce molten iron in iron manufacturing and steel manufacturing processes.
The object of the present invention is to realize a high-toughness sintered body as a material that can be used for a long period of time in direct or indirect contact with iron oxide.
具体的には、特開昭５７−４２５７７号公報に記載の、
また、本発明者により提案された先の出願に記載のＳｉ
ＣＡ１２０３系および５ｉＣ−Ｚｒ０２系セラミツクス
構造材におけるＦｅ−０系の下での高温侵食性を向上せ
しめたもので、５ｉＣ−酸化物スピネル系、５ｉＣ−酸
化物固溶体、５ｉＣ−酸化物及び非酸化物の不定比化合
物系にまで拡大したことが含まれるものである。Specifically, as described in Japanese Patent Application Laid-Open No. 57-42577,
Moreover, the Si described in the earlier application proposed by the present inventor
It improves the high-temperature corrosion resistance under Fe-0 system in CA1203 series and 5iC-Zr02 series ceramic structural materials. This includes the expansion to non-stoichiometric compound systems.
本発明は、基本的にばＢ、Ｃ，ＡＩＮ、 ＢｅＯ等の焼
結促進剤を微量添加した拡散焼結型のＳｉＣ焼結体では
、Ｃ］’２０３添加により著しくその機械的性質が損わ
れることから、本発明者等は酸化物−非酸化物系化合物
の焼結体についてＣｒ２Ｏ３添加を試み、成功したもの
である。The present invention basically focuses on the fact that in a diffusion sintered SiC sintered body to which a small amount of sintering accelerator such as B, C, AIN, BeO, etc. is added, the mechanical properties are significantly impaired by the addition of C]'203. Therefore, the present inventors attempted to add Cr2O3 to a sintered body of an oxide-nonoxide compound, and were successful.
すなわち、ＳｉＣとＡ１２０３ 、 ＺｒＯ２等の高温
安定な金属酸化物を土量組成とする粉末配合物にクロム
またはＣｒ２Ｏ３のようなりロムを含む化合物を加えた
成形体を雰囲気加圧焼結して得たＣｒ化合物を合むＳｉ
Ｃ焼結体は、ＦｅＯ雰囲気中の高温下で著しい高耐火性
を有し損耗が極めて少なく、しかも構造材料としての機
能は低下することはないという知見に基づいて完成した
ものである。That is, a compact is obtained by atmospheric pressure sintering of a powder mixture containing SiC and high-temperature stable metal oxides such as A1203 and ZrO2, to which a chromium-containing compound such as chromium or Cr2O3 is added. Si combined with Cr compound
The C sintered body was developed based on the knowledge that it has extremely high fire resistance at high temperatures in an FeO atmosphere, exhibits extremely little wear and tear, and does not deteriorate in its function as a structural material.
高温安定な酸化物とクロムまたはクロム化合物とをＳｉ
Ｃに配合する場合、例えば、Ａ１ｚ０３とＣｒ２Ｏ３と
を配合する４合には、予めこれらを固溶体として調製し
て配合に加える事により焼結体の耐食性はさらに向上す
る。Si
When blending with C, for example, in the case where A1z03 and Cr2O3 are blended, the corrosion resistance of the sintered body is further improved by preparing these as a solid solution in advance and adding them to the blend.
クロムまたはクロム化合物の成形配合物中の含有量は、
金属クロム換算でＳｔＣに対し０．２〜４重量％の範囲
内にあることが望ましい。The content of chromium or chromium compounds in the molding compound is
It is desirable that the amount is in the range of 0.2 to 4% by weight based on StC in terms of metallic chromium.
以下の実験例はクロムまたはクロム化合物の含有量が及
ぼす影響を見たものである。The following experimental examples examine the effects of the content of chromium or chromium compounds.
（実験例）
ＳｉＣとして純度９９％、平均粒径０．３μの市販α品
１００重量部に対して、Ｚｒ０２として純度９９％以上
、平均粒径０．２μの市販単斜晶ＺｒＯ２を４５重量部
、八ＩＮ ４．７重量部、Ｙ２０３９．５重量部からな
る配合物に、クロム、クロム化合物及び含有量を種々変
えて実験した。その結果を表１，２に示す。(Experiment example) 45 parts by weight of commercially available monoclinic ZrO2 with a purity of 99% or more and an average particle size of 0.2μ as Zr02 for 100 parts by weight of a commercially available α product with a purity of 99% and an average particle size of 0.3μ as SiC. , 4.7 parts by weight of 8IN, and 39.5 parts by weight of Y20, and various chromium, chromium compounds, and contents were used in experiments. The results are shown in Tables 1 and 2.
これからクロム化合物の量が金属クロム換算で０゜２重
量％以下では効果がなく、４重量％以上では機械的強度
が劣化する事がわかる。またクロム化合物により若干の
差はあるが、耐食性の向上は全ての場合について認めら
れた。This shows that if the amount of the chromium compound is less than 0.2% by weight in terms of metallic chromium, there is no effect, and if it is more than 4% by weight, the mechanical strength deteriorates. Although there were slight differences depending on the chromium compound, improvement in corrosion resistance was observed in all cases.
以下、比較例とともに実施例を挙げて、これにより本発
明の効果を具体的に説明する。EXAMPLES Hereinafter, the effects of the present invention will be specifically explained by giving examples together with comparative examples.
実施例ｌ
ＳｉＣおよびＺｒＯ２として上記実験例と同一の粉末を
用いた。ＳｉＣ２００ｇ 、 ＺｒＯ２９０ｇ １八Ｉ
Ｎ ９．３ｇ１Ｙ２０ａ １９ｇおよびＣｒ２０３５．
５ｇを有機ハイングーとともに湿式混合、乾燥し、２
ｔｏｎ ／ ｃｎｔの圧力でラバープレスして得られた
成形体を５０気圧のＡｒ雰囲気中で１８００’ｃで１時
間加熱し雰囲気加圧焼結を行った。その結果理論密度の
９３％の焼結体が得られ、破壊靭性値は、２４ ｋｇ
ｆ ／ ｍｕ％３点曲げ強度は７０ ｋｇ ／ ｎ ２
であった。この成形体から５０、Ｘ５０Ｘ１５１１の板
状試片を切出し中央部に１０φ×５ｈＩＩＩＩのＦｅ３
Ｏ４ボタンを置いて大気中１５００°Ｃ１２，５時間の
条件で加熱した食刻寸法を測定したところ０．７ ｍに
過ぎなかった。Example 1 The same powders as in the above experimental example were used as SiC and ZrO2. SiC200g, ZrO290g 18I
N 9.3g1Y20a 19g and Cr2035.
Wet mix 5g with organic haingu, dry,
The molded body obtained by rubber pressing at a pressure of ton/cnt was heated at 1800'C for 1 hour in an Ar atmosphere of 50 atm to perform atmospheric pressure sintering. As a result, a sintered body with 93% of the theoretical density was obtained, and the fracture toughness value was 24 kg.
f/mu% 3-point bending strength is 70 kg/n2
Met. A plate-shaped specimen of 50×50×1511 was cut out from this molded body, and a 10φ×5hIII Fe3 specimen was cut out in the center.
When the etching dimension was measured by placing an O4 button and heating it in the atmosphere at 1500°C for 12.5 hours, it was only 0.7 m.
比較例１
実験例と同一の配合物に対してＣｒ２Ｏ３を添加せず、
他は同様にして、理論密度９５％の焼結体を得た。この
焼結体について、実施例１と同様の侵食テストを行った
ところ、食刻寸法は８ｆｉであった。Comparative Example 1 The same formulation as the experimental example without adding Cr2O3,
Otherwise, a sintered body with a theoretical density of 95% was obtained in the same manner. When this sintered body was subjected to the same erosion test as in Example 1, the etched size was 8fi.
実施例１と比較例１により、Ｃｒ２Ｏ３の添加は酸化鉄
の侵食を阻止する効果のある事がわかる。It can be seen from Example 1 and Comparative Example 1 that the addition of Cr2O3 is effective in inhibiting corrosion of iron oxide.
実施例２
ＳｉＣ２００ｇ、 Ａｌ１０３２０ｇ、、Ｙ２０３２
ｇ及びＣｒ２０３５ｇをバインダーとともに湿式混合、
乾燥し２ ｔｏｎ ／ ｃｒＡの圧力でラバープレスし
て得られた成形体を５０気圧のＡｒ雰囲気中で１９００
℃まで加熱し、雰囲気加圧焼結を行った。その結果理論
密度の９６％の焼結体が得られ破壊靭性値は１８ ｋｇ
ｆ ／ ｉ＋ｉ％、３点曲げ強度は５５ ｋｇ ／
ｍ ”であった。Example 2 SiC 200g, Al10320g, Y2032
Wet mixing of g and 2035g of Cr with binder,
The molded body obtained by drying and rubber pressing at a pressure of 2 ton/crA was heated at 1900 mA in an Ar atmosphere of 50 atm.
It was heated to ℃ and pressure sintered in an atmosphere. As a result, a sintered body with a theoretical density of 96% and a fracture toughness of 18 kg was obtained.
f/i+i%, 3-point bending strength is 55 kg/
m”.
この焼結体について実施例１と同様の侵食テストを行っ
たところ食刻寸法は１．２鶴であった。When this sintered body was subjected to the same erosion test as in Example 1, the etching size was 1.2 mm.
比較例２
実験例と同一の配合物に対してＣｒ２Ｏ３を添加せず他
は同様にして、理論密度の９５％の焼結体を得た。侵食
テストによる食刻寸法は８．５鰭であった。Comparative Example 2 A sintered body having a theoretical density of 95% was obtained using the same formulation as in the experimental example except that Cr2O3 was not added. The etching size according to the erosion test was 8.5 fins.
実施例３
八１２０３とＣｒ２Ｏ３の重量比が４：１の固溶体をあ
らかじめ調製し、粉砕して得た粉体２５ｇと５ｔＣ２０
０ｇ、 Ｙ２０３２ ｇをバインダーとともに湿式混合
、乾燥して得られた配合を実施例２と同様にして成形、
焼結したところ、理論密度の９６％の焼結体が得られこ
の焼結体に実施例１と同様の侵食テストを行ったところ
、食刻寸法は０．８ ｘｍであった。Example 3 A solid solution of 81203 and Cr2O3 with a weight ratio of 4:1 was prepared in advance and pulverized to obtain 25 g of powder and 5tC20.
0 g and Y2032 g were wet mixed with a binder and dried, and the resulting mixture was molded in the same manner as in Example 2.
Upon sintering, a sintered body having a theoretical density of 96% was obtained, and when this sintered body was subjected to the same erosion test as in Example 1, the etched size was 0.8 x m.
表１ 表２Table 1 Table 2
Claims (1)
とを含有する炭化珪素粉未配合物の成形体を雰囲気焼結
してなることを特徴とする耐食性を有する高靭性セラミ
ック焼結体。 ２、高温安定な金Ｂ酸化物とクロムまたはクロム化合物
と金属窒化物とを含有する炭化珪素粉未配合物の成形体
を雰囲気焼結してなることを特徴とする耐食性を有する
高靭性セラミック焼結体。 ３、高温安定な金属酸化物がＡｌ２Ｏ３である事を特徴
とする特許請求の範囲第１項または第２項に記載のセラ
ミック焼結体。 ４、高温安定な金属酸化物がＺｒＯ２および希土類金属
の酸化物である事を特徴とする特許請求の範囲第１項ま
たは第２項に記載のセラミ７り焼結体。 ５、 クロムまたはクロム化合物が金属クロム換算で配
合物中に０．２〜０．４重量％含有されていることを特
徴とする特許請求の範囲第１項または第２項に記載のセ
ラミック焼結体。 ６、Ａｌ２Ｏ３とクロムまたはクロム化合物が固溶体を
形成していることを特徴とする特許請求の範囲第３項に
記載のセラミック焼結体。 ７、雰囲気焼結が、非酸化性あるいは不活性な加圧雰囲
気下での焼結であることを特徴とする特許請求の範囲第
１項または第２項に記載のセラミック焼結体。 ８、加圧雰囲気の圧力が２〜１００気圧である事を特徴
とする特許請求の範囲第７項に記載のセラミック焼結体
。 ９、焼結が、１６００〜２１００℃での焼結であること
を特徴とする特許請求の範囲第１項または第２項に記載
のセラミック焼結体。[Claims] 1. A high-toughness ceramic having corrosion resistance characterized by being formed by atmospheric sintering of a molded body containing a high-temperature stable metal oxide and chromium or a chromium compound without silicon carbide powder. Sintered body. 2. High-toughness ceramic sintered material having corrosion resistance, characterized by being formed by atmospheric sintering of a molded body containing high-temperature stable gold B oxide, chromium or chromium compound, and metal nitride without blending silicon carbide powder. Concretion. 3. The ceramic sintered body according to claim 1 or 2, wherein the high temperature stable metal oxide is Al2O3. 4. The ceramic sintered body according to claim 1 or 2, wherein the high-temperature stable metal oxide is an oxide of ZrO2 and a rare earth metal. 5. Ceramic sintered according to claim 1 or 2, characterized in that chromium or a chromium compound is contained in the compound in an amount of 0.2 to 0.4% by weight in terms of metallic chromium. body. 6. The ceramic sintered body according to claim 3, wherein Al2O3 and chromium or a chromium compound form a solid solution. 7. The ceramic sintered body according to claim 1 or 2, wherein the atmosphere sintering is sintering in a non-oxidizing or inert pressurized atmosphere. 8. The ceramic sintered body according to claim 7, wherein the pressure of the pressurized atmosphere is 2 to 100 atmospheres. 9. The ceramic sintered body according to claim 1 or 2, wherein the sintering is performed at a temperature of 1600 to 2100°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59003246A JPS60145960A (en) | 1984-01-10 | 1984-01-10 | Anticorrosive ceramic sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59003246A JPS60145960A (en) | 1984-01-10 | 1984-01-10 | Anticorrosive ceramic sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60145960A true JPS60145960A (en) | 1985-08-01 |
| JPH0545548B2 JPH0545548B2 (en) | 1993-07-09 |
Family
ID=11552097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59003246A Granted JPS60145960A (en) | 1984-01-10 | 1984-01-10 | Anticorrosive ceramic sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60145960A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61178469A (en) * | 1985-01-31 | 1986-08-11 | 京セラ株式会社 | Manufacture of silicon carbide base sintered body |
| JPS61281070A (en) * | 1985-05-31 | 1986-12-11 | 京セラ株式会社 | Silicon carbide base sintered body |
| JPH01215774A (en) * | 1988-02-23 | 1989-08-29 | Toshiba Ceramics Co Ltd | Silicon carbide sintered porous form and production thereof |
| JP2005231985A (en) * | 2004-02-17 | 2005-09-02 | Yotai Refractories Co Ltd | Silicon carbide brick |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5446209A (en) * | 1977-09-20 | 1979-04-12 | Harima Refractories Co Ltd | Slaggresistant spout material for discharging pig iron and slag |
-
1984
- 1984-01-10 JP JP59003246A patent/JPS60145960A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5446209A (en) * | 1977-09-20 | 1979-04-12 | Harima Refractories Co Ltd | Slaggresistant spout material for discharging pig iron and slag |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61178469A (en) * | 1985-01-31 | 1986-08-11 | 京セラ株式会社 | Manufacture of silicon carbide base sintered body |
| JPS61281070A (en) * | 1985-05-31 | 1986-12-11 | 京セラ株式会社 | Silicon carbide base sintered body |
| JPH01215774A (en) * | 1988-02-23 | 1989-08-29 | Toshiba Ceramics Co Ltd | Silicon carbide sintered porous form and production thereof |
| JP2005231985A (en) * | 2004-02-17 | 2005-09-02 | Yotai Refractories Co Ltd | Silicon carbide brick |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0545548B2 (en) | 1993-07-09 |
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