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JPS59107963A - Carbon-containing refractories - Google Patents

Carbon-containing refractories

Info

Publication number
JPS59107963A
JPS59107963A JP57217058A JP21705882A JPS59107963A JP S59107963 A JPS59107963 A JP S59107963A JP 57217058 A JP57217058 A JP 57217058A JP 21705882 A JP21705882 A JP 21705882A JP S59107963 A JPS59107963 A JP S59107963A
Authority
JP
Japan
Prior art keywords
carbon
graphite
refractory
weight
parts
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.)
Pending
Application number
JP57217058A
Other languages
Japanese (ja)
Inventor
京田 洋
英昭 西尾
昌平 原
敏宏 松本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shinagawa Refractories Co Ltd
Shinagawa Shiro Renga KK
Original Assignee
Shinagawa Refractories Co Ltd
Shinagawa Shiro Renga KK
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 Shinagawa Refractories Co Ltd, Shinagawa Shiro Renga KK filed Critical Shinagawa Refractories Co Ltd
Priority to JP57217058A priority Critical patent/JPS59107963A/en
Priority to DE19833344852 priority patent/DE3344852A1/en
Priority to FR8319918A priority patent/FR2537566B1/en
Priority to GB08333238A priority patent/GB2131791B/en
Priority to AT432883A priority patent/AT384210B/en
Publication of JPS59107963A publication Critical patent/JPS59107963A/en
Pending legal-status Critical Current

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  • Ceramic Products (AREA)

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】 本発明は炭素含有耐火物の酸化防止を図り同時に熱間強
度、耐スポール性、耐食性等耐火物として重要な特性を
向上させたAl2O2− C! 、 MgO−0。
DETAILED DESCRIPTION OF THE INVENTION The present invention aims to prevent oxidation of carbon-containing refractories, and at the same time improves properties important for refractories such as hot strength, spalling resistance, and corrosion resistance. , MgO-0.

bjyo − Al2O2− 0質の焼成ならびに不焼
成耐火物に関するものである。
This invention relates to fired and unfired refractories of bjyo-Al2O2-0 quality.

発明の背景 黒鉛を含む耐火物は冶金用の耐火物として広く用いられ
て、溶銑、溶鋼、スラグ等と接する場合の化学的侵食に
対しては極めて優れた耐食性を示す。これは黒鉛自身が
スラグや溶鉄に対して濡れ難くそのため耐火物内へのス
ラグの侵入が抑えられることによる。更に黒鉛の存在に
より焼成時あるいは使用時の高温に対しても過焼結しな
いため熱的なスポーリングが起り難いことも黒鉛含有耐
火物の耐用性の高いことに寄与している。
BACKGROUND OF THE INVENTION Refractories containing graphite are widely used as refractories for metallurgy, and exhibit extremely excellent corrosion resistance against chemical attack when in contact with hot metal, molten steel, slag, and the like. This is because graphite itself is difficult to wet with slag and molten iron, which prevents slag from entering the refractory. Furthermore, due to the presence of graphite, oversintering does not occur even at high temperatures during firing or use, so thermal spalling is less likely to occur, which also contributes to the high durability of graphite-containing refractories.

しかし当然ながら黒鉛は酸素の存在下で極めて容易に酸
化する。黒鉛の酸化消失は上記黒鉛含有耐火物の優れた
特性を失うことになる。このことからこの種耐火物の一
層の耐用向上のためには黒鉛の酸化を極力おさえること
が重要であり種々の試みがなされてきてはいるが末だに
満足なものは提供されていない。
However, graphite naturally oxidizes very easily in the presence of oxygen. The loss of graphite through oxidation results in the loss of the excellent properties of the graphite-containing refractories. Therefore, in order to further improve the durability of this type of refractory, it is important to suppress the oxidation of graphite as much as possible, and although various attempts have been made, none have been satisfactory.

黒鉛の酸化を抑制する手段として例えば特開昭30−4
9106号公報には炭素成形物の表面を珪素の窒化物ま
たは炭化物で被覆し更にその上を炭化硼素および二酸化
珪素の硼珪酸ガラスで被覆する技術が示されている。し
かし溶銑、溶鋼、スラグ等に接する使用場所においては
該被覆層が侵食された後は酸化防止効果はなく好ましく
ないものである。また炭素含有成形物中に金属粉末を均
一分散させ耐酸化性とした炭素含有耐火物として例えば
特開昭A−1I−J9+ココ号公報には炭素より酸素親
和力の大きい金属粉末のAJ 、 Si 、 Or 、
 Ti 、 Mli の7種以上を添加した炭素含有耐
火物、また特開昭&&−1077グタ号公報にマグネシ
ウム粉末、アルミニウム粉末とシリコン粉末を添加した
カーボン含有耐火れんがは公知である。しかしこれらの
炭素含有耐火物は耐酸化性と熱間強度の両特性を未だ十
分満足するものではない。
As a means of suppressing the oxidation of graphite, for example, Japanese Patent Application Laid-Open No. 30-4
No. 9106 discloses a technique in which the surface of a carbon molded article is coated with silicon nitride or carbide, and then coated with borosilicate glass of boron carbide and silicon dioxide. However, in places where it is used in contact with hot metal, molten steel, slag, etc., after the coating layer is eroded, it has no oxidation-preventing effect, which is undesirable. In addition, as a carbon-containing refractory made oxidation-resistant by uniformly dispersing metal powder in a carbon-containing molded product, for example, Japanese Patent Application Laid-Open No. 1998-1-1-J9 + Coco discloses metal powders such as AJ, Si, and AJ, which have a higher affinity for oxygen than carbon. Or,
Carbon-containing refractories to which seven or more of Ti and Mli are added are known, and carbon-containing refractories to which magnesium powder, aluminum powder and silicon powder are added are disclosed in Japanese Patent Laid-Open No. 1077-1077. However, these carbon-containing refractories still do not fully satisfy both oxidation resistance and hot strength properties.

発明の概要 本発明者等は耐酸化性と熱間強度の特性を同時に発現す
る炭素含有耐火物を開発すべく種々の添加物について検
討した結果AJ −M!1合金粉末、AJ −M7− 
Si 合金粉末、AJ −M、!9− Or 合金粉末
を添加した炭素含有耐火物は耐酸化性と熱間強度の優れ
た耐火物であることを見出し本発明を完成するに至った
ものである。
Summary of the Invention The present inventors investigated various additives in order to develop a carbon-containing refractory that exhibits both oxidation resistance and hot strength properties, and as a result, AJ-M! 1 alloy powder, AJ-M7-
Si alloy powder, AJ-M,! It was discovered that a carbon-containing refractory to which 9-Or alloy powder was added is a refractory with excellent oxidation resistance and hot strength, and the present invention was completed.

本発明は黒鉛50〜3重量部、耐火骨材左。〜97重量
部からなる耐火材料にAJ −up 合金粉末、AJ 
−Np −S i 合金粉末、AJ、−My −Or 
合金粉末の7種以上を7〜10重量部含有することを特
徴とする炭素含有耐火物である。
The present invention uses 50 to 3 parts by weight of graphite and refractory aggregate. ~97 parts by weight of AJ -up alloy powder, AJ
-Np -S i alloy powder, AJ, -My -Or
The present invention is a carbon-containing refractory characterized by containing 7 to 10 parts by weight of seven or more types of alloy powder.

本発明の最も特徴とする点は耐火骨材と黒鉛に合金粉末
を添加する点にある。前述の如く金属添加に関する公知
の従来技術はAJ 、 My 、 Si。
The most distinctive feature of the present invention is that alloy powder is added to the refractory aggregate and graphite. As mentioned above, the known conventional techniques regarding metal addition are AJ, My, and Si.

Car 、 Ti  等の単体金属を単独又は組合せて
使用するものである。耐火骨材と黒鉛に金属を配し成型
した場合、不焼成れんかにあっては乾燥あるいは使用中
の加熱、焼成れんかにあっては乾燥あるいは焼成時の加
熱により揮発成分の気化が生ずる。炭素含有耐火物では
通常使用される有機、無機のバインダーの気化がioo
”cから200℃の温度範囲で生ずる。一方金属はその
溶融温度に達して後揮発物質の気化した間隙あるいは成
形時の粒子間間隙を流れる。例えばアルミニウム粉末で
はA40℃、マグネシウム粉末ではA llq’Cがそ
の溶融温度である。炭素の酸化はその使用される粒度等
によって異なるが約lIo。
Single metals such as Car and Ti are used singly or in combination. When metal is arranged and molded into refractory aggregate and graphite, volatile components vaporize due to drying or heating during use for unfired bricks and heating during drying or firing for fired bricks. The vaporization of organic and inorganic binders normally used in carbon-containing refractories is ioo
On the other hand, after the metal reaches its melting temperature, it flows through the gaps where volatile substances have vaporized or the gaps between particles during molding. C is its melting temperature.The oxidation of carbon varies depending on the particle size used, etc., but is about lIo.

℃から開始される。したがって耐火物内部は揮発物質の
気化した通路から約ti−oθ℃から酸化が進行する。
Starts from °C. Therefore, oxidation progresses inside the refractory from about ti-0.theta..degree. C. through the passage where the volatile substances have vaporized.

金属の酸化は200〜3000から開始し酸化物が生成
するがその際体積膨張するため金属の存在する場所では
外部からの酸化性物質の内部への侵入を抑える。未酸化
金属が溶融すると前述の如く付近へ流れ出すため酸化性
物質の侵入抑制効果範囲は拡大される。同時に金属酸化
物と耐火原料の間に新しい結合が生成する。
Oxidation of metal starts from 200 to 3,000 and oxide is generated, but at this time the volume expands, so in places where metal is present, oxidizing substances from the outside are prevented from entering the interior. When the unoxidized metal melts, it flows out into the vicinity as described above, so that the range of the effect of inhibiting the intrusion of oxidizing substances is expanded. At the same time, new bonds are formed between the metal oxide and the refractory raw material.

この結果酸化性と熱間強度の特性が改善される。As a result, the oxidation resistance and hot strength properties are improved.

本発明による炭素含有耐火物に合金粉末を添加する技術
も耐酸化性および熱間強度特性の発現に関する機構は前
述の機構とほぼ同等と考えられる。しかしこれら合金は
周知の如く合金を構成する端成分金属より融点が低い。
The technique of adding alloy powder to a carbon-containing refractory according to the present invention is also considered to have a mechanism similar to the above-mentioned mechanism regarding the development of oxidation resistance and hot strength properties. However, as is well known, these alloys have lower melting points than the end component metals that make up the alloy.

例えば金属アルミニウムの融点は66θ℃、金属マグネ
シウムの融点は6グ9℃であるのに対しAJ −M7 
合金の溶融開始温度は44 j / ”Cであり約20
0℃低い。
For example, the melting point of metal aluminum is 66θ℃, and the melting point of metal magnesium is 6g9℃, whereas AJ-M7
The melting onset temperature of the alloy is 44 J/”C, which is approximately 20
0℃ lower.

従来技術では酸化の始まる約yoo℃と金属が溶融し酸
化抑制効果が拡大される温度の間にアルミニウムやマグ
ネシウムの場合で約2go℃の開きがあった。すなわち
この温度の範囲では金属の使用効果が非常に低かった。
In the conventional technology, there was a gap of about 2go°C between the temperature at which oxidation begins and the temperature at which the metal melts and the oxidation suppressing effect is expanded, in the case of aluminum and magnesium. In other words, the effect of using metal was very low in this temperature range.

本発明ζこよる合金の使用はこれらの問題を一挙に解決
し得るものである。
Use of the alloy according to the present invention can solve these problems at once.

更に本発明に使用する合金粉末の場合金属酸化物化した
時A120.とMyOが極めて活性な形で共存するため
7000℃以上で極めて容易にスピネル(1jyo +
 AJ、、o、 )を生成、耐火物としての膨張を大き
くする。このことは重要な意味を有している。すなわち
炭素含有耐火物は使用中に平滑な表面の故に抜は落ちる
現象かあるが膨張によりれんが積がタイトになりこの問
題も解消することができる。
Furthermore, in the case of the alloy powder used in the present invention, when converted into a metal oxide, it has an A120. Since spinel and MyO coexist in an extremely active form, spinel (1jyo +
AJ,, o, ) is produced and expands as a refractory. This has an important meaning. That is, carbon-containing refractories have a phenomenon in which they fall off during use due to their smooth surfaces, but this problem can be solved by making the brickwork tighter due to expansion.

本発明に使用する耐火骨材としてはマグネシア、スピネ
ル、アルミナ、シリカ、ジルコン、ジルコニア等の酸化
物や炭化珪素、窒化珪素、窒化硼素等非酸化物が使用さ
れ特に限定するものではないがマグネシア、スピネル、
アルミナを主体とするものが好ましい。才だ黒鉛とじて
は土状黒鉛、鱗状黒鉛の天然黒鉛ないし電極くず、石油
コークス、カーボンブラック等の人造黒鉛が任意に使用
可能であるが不純物の少ない鱗状黒鉛の使用が好ましい
。該黒鉛の配合割合は耐火骨材の種類、該炭素含有耐火
物の使用目的によっても異なるが黒鉛と耐火骨材からな
る耐火材料ioo重量部に対して3〜SO重量部が好ま
しい。配合割合を規制する理由は黒鉛3重量部未満では
黒鉛の溶鉄やスラグに対して濡れ難いという特性が十分
発揮できないからでありgo重量部以上では強度的にも
十分なものが得られ難い。
The refractory aggregate used in the present invention includes oxides such as magnesia, spinel, alumina, silica, zircon, and zirconia, and non-oxides such as silicon carbide, silicon nitride, and boron nitride, including but not limited to magnesia, spinel,
Preferably, the material is mainly composed of alumina. As for the graphite, natural graphite such as earthy graphite, scaly graphite, or artificial graphite such as electrode scrap, petroleum coke, carbon black, etc. can be arbitrarily used, but it is preferable to use scaly graphite with few impurities. The blending ratio of graphite varies depending on the type of refractory aggregate and the purpose of use of the carbon-containing refractory, but is preferably 3 to SO parts by weight based on ioo parts by weight of the refractory material consisting of graphite and refractory aggregate. The reason for regulating the blending ratio is that if the graphite content is less than 3 parts by weight, graphite's property of not being easily wetted by molten iron or slag cannot be sufficiently exhibited, and if it is more than 5 parts by weight, it is difficult to obtain a product with sufficient strength.

本発明に使用される合金粉末としてはAJ−Mg。The alloy powder used in the present invention is AJ-Mg.

AJ−Kg−Or 、 AJ−My−8i 合金から適
宜選択することができる。これらをそれぞれ単独又は混
合して使用することもできる。いずれの合金粉末におい
てもA1を30重量%以上、7117重量%ものが好ま
しい。こめ範囲をはずれるとAJとMyが共存して得ら
れる既述の効果が十分なものにならないからである。粒
度は反応性及び均一分散性の点からθ、/2!;m以下
のものを使用するのが好ましい。該合金の配合割合は耐
火骨材と黒鉛からなる耐火材料100重量部に対し7〜
70重量部が添加されるものであるが7重量部以下では
添加する効果が小さく10重量部以上では十分緻密な成
形体を得ることが難しくまた加熱時の膨張が大きくなり
過ぎる。
It can be appropriately selected from AJ-Kg-Or and AJ-My-8i alloys. These can be used alone or in combination. In any alloy powder, A1 is preferably 30% by weight or more, preferably 7117% by weight. This is because if it is out of the range, the above-mentioned effects obtained by the coexistence of AJ and My will not be sufficient. From the viewpoint of reactivity and uniform dispersibility, the particle size is θ, /2! ; It is preferable to use one having a diameter of less than m. The blending ratio of the alloy is 7 to 100 parts by weight of the refractory material consisting of refractory aggregate and graphite.
Although 70 parts by weight is added, if it is less than 7 parts by weight, the effect of adding it is small, and if it is more than 10 parts by weight, it is difficult to obtain a sufficiently dense molded product and expansion upon heating becomes too large.

本発明の炭素含有耐火物はこれらの粒度調整した耐火材
料と合金粉末を所定の配合割合で調整しタール、ピッチ
、フェノール樹脂、フラン樹脂などの結合剤を加え常法
によって混練成形し200℃程度に乾燥すれば不焼成の
ものが得られる。またqoo−/!;00℃程度の還元
雰囲気で焼成し焼成耐火物として使用に供することがで
きる。
The carbon-containing refractory of the present invention is prepared by adjusting the particle size-adjusted refractory material and alloy powder in a predetermined blending ratio, adding a binder such as tar, pitch, phenol resin, furan resin, etc., and kneading and molding in a conventional manner at about 200°C. If dried, an unfired product can be obtained. Also qoo-/! It can be fired in a reducing atmosphere at about 00°C and used as fired refractories.

次にこの発明を実施例により具体的に示す。Next, this invention will be specifically illustrated by examples.

なお配合は重量部で示す。The formulations are shown in parts by weight.

実施例、 第1表に示す配合物にレゾール型フェノール樹脂3重量
部を添加混線後l5OOK9/crIL2 の圧で皿型
に成型してから2oo”cs時間乾燥した。
Example: 3 parts by weight of a resol type phenolic resin was added to the formulation shown in Table 1, mixed, molded into a dish shape under a pressure of 15OOK9/crIL2, and dried for 20''cs.

得られた不焼成炭素含有耐火物は第1表に示す如く本発
明品は比較品に比し耐酸化性を有しかつ熱間強度が優れ
ていることがわかる。
As shown in Table 1, the obtained unfired carbon-containing refractories show that the products of the present invention have better oxidation resistance and hot strength than the comparative products.

/′ /′ // / 、、/’ /″ 第7表/′ /′ /// / ,,/’ /″ Table 7

Claims (1)

【特許請求の範囲】[Claims] 黒鉛30〜3重量部、耐火骨材50〜97重量部からな
る耐火材料にAJ−Kg 合金粉末、AL−M1!−8
i 合金粉末、A4− M、9− Or 合金粉末07
種以上を7〜10重量部含有することを特徴とする炭素
含有耐火物
AJ-Kg alloy powder and AL-M1 are added to the fireproof material consisting of 30 to 3 parts by weight of graphite and 50 to 97 parts by weight of refractory aggregate. -8
i Alloy powder, A4-M, 9-Or Alloy powder 07
A carbon-containing refractory characterized by containing 7 to 10 parts by weight of
JP57217058A 1982-12-13 1982-12-13 Carbon-containing refractories Pending JPS59107963A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP57217058A JPS59107963A (en) 1982-12-13 1982-12-13 Carbon-containing refractories
DE19833344852 DE3344852A1 (en) 1982-12-13 1983-12-12 CARBONED FIRE-RESISTANT MATERIAL
FR8319918A FR2537566B1 (en) 1982-12-13 1983-12-13 REFRACTORY MATERIAL CONTAINING CARBON
GB08333238A GB2131791B (en) 1982-12-13 1983-12-13 Carbon-containing refractory
AT432883A AT384210B (en) 1982-12-13 1983-12-13 Carbon-containing refractory material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP57217058A JPS59107963A (en) 1982-12-13 1982-12-13 Carbon-containing refractories

Publications (1)

Publication Number Publication Date
JPS59107963A true JPS59107963A (en) 1984-06-22

Family

ID=16698165

Family Applications (1)

Application Number Title Priority Date Filing Date
JP57217058A Pending JPS59107963A (en) 1982-12-13 1982-12-13 Carbon-containing refractories

Country Status (1)

Country Link
JP (1) JPS59107963A (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57166362A (en) * 1981-04-06 1982-10-13 Tokyo Yogyo Kk Refractories containing carbonaceous matter

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57166362A (en) * 1981-04-06 1982-10-13 Tokyo Yogyo Kk Refractories containing carbonaceous matter

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