JPH0475184B2 - - Google Patents
Info
- Publication number
- JPH0475184B2 JPH0475184B2 JP59256187A JP25618784A JPH0475184B2 JP H0475184 B2 JPH0475184 B2 JP H0475184B2 JP 59256187 A JP59256187 A JP 59256187A JP 25618784 A JP25618784 A JP 25618784A JP H0475184 B2 JPH0475184 B2 JP H0475184B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- carbon
- fibers
- raw material
- short
- 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
- 239000000835 fiber Substances 0.000 claims description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 29
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 239000011449 brick Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 description 12
- 238000004901 spalling Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 2
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000011452 unfired brick Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Products (AREA)
Description
（産業上り利用分野）
本発明は、熱衝撃あるいは熱膨張応力による亀
裂が発生し難く、また亀裂が発生しても容易に剥
離しない溶融金属容器内張り用の不焼成炭素含有
煉瓦を製造する方法に関するものである。
（従来の技術）
炭素は酸化物と反応し難いこと、溶融金属に濡
れ難いことなどの性質をもつ。この炭素と他の耐
火原料を配合して製造されるなる炭素含有煉瓦
は、優れた耐用性を示し、各種の溶融金属容器の
内張り材として広く用いられている。
（発明が解決しようとする問題点）
炭素含有煉瓦は焼成品と不焼成品とに大別され
るが、不焼成品の生産量が多い。これは、不焼成
品が焼成工程を必要としないために製造コスト面
で好ましいからである。しかし、不焼成品にも次
のような欠点がある。
すなわち、タールピツチまたは熱可塑性樹脂を
結合剤にした場合は、結合剤が溶融する100〜300
℃で煉瓦の強度が低下する。結合剤に熱硬化性樹
脂を使用したものは、300℃前後で予め熱硬化さ
せているので低温域では強度低下の問題がないも
のの、500〜700℃の中温域で樹脂が炭化する過程
で強度が低下する。これらが原因で、例えば転炉
の側壁に使用されるマグネシア−炭素質の不焼成
煉瓦では、変形、亀裂、剥離などの発生が認めら
れる。
また、結合剤が炭素化する過程でクリープ変形
し易い。熱膨張でこのクリープ変形が吸収され、
冷却時に目地開きが生じると、熱衝撃によつて生
じる亀裂から容易に剥離する。このような現象
は、溶鋼の真空脱ガス処理容器あるいは取鍋で観
察される。
この対策として、成形後の煉瓦を800℃以上の
温度で焼成し、焼成品にすることも考えられる。
しかし、焼成品は製造コスト高を招く。また、熱
衝撃が厳しい使用条件の場合は、焼成品といえど
も耐亀裂、耐剥離に十分な耐久性が得られない。
亀裂、剥離を防ぐ対策として、マグネシア−黒
鉛質煉瓦などの炭素含耐火物にステンレス鋼繊維
などの鋼繊維を添加することは、既に特開昭54−
130608号で提案されている。鋼繊維の添加によ
り、熱衝撃で亀裂が発生してもそこからの剥離を
防止するものである。しかし、鋼繊維は、炭化に
よる強度劣化、酸化による酸化鉄への変化などに
より、多量の添加は煉瓦の耐食性を低下させる。
熱間強度を高める手段としては、アルミニウ
ム、シリコンなどの金属粉末の添加が知られてい
る。例えば特開昭54−163913号、特開昭55−
107749号のとおりである。これらの金属粉末の中
でもアルミニウムが最も効果的である。アルミニ
ウムと炭素と反応してアルミニウム・カーバイド
（Al4C3）を生成し、強度発現の作用を持つ。し
かし、それは900℃以上であり、300〜700℃の中
間温度域では効果がない。
（問題点を解決するための手段）
本発明は、アルミニウム短繊維の添加で従来の
炭素含有煉瓦がもつ上記の欠点を一挙に解決した
ものである。
第１発明の特徴とするところは、炭素原料５〜
50wt％、残部がマグネシアを材とする耐火原料
に、アルミニウム短繊維を外掛け１〜20wt％添
加した配合物を、有機質結合剤をもつて混練し、
成形後、熱処理する溶融金属容器内張り用の炭素
含有煉瓦の製造方法である。第２発明は、第１発
明に配合物に更に金属粉末を添加し、その効果を
高めたものである。以下に本発明を詳しく説明す
る。
本発明に使用する各種原料の具体的種類とその
好ましい配合割合は次のとおりである。
炭素原料は、鱗状黒鉛、土状黒鉛などの天然
品、ピツチコークス、電極屑、熱分解黒鉛、キツ
シユ黒鉛などの人工品などがあり、これらの何れ
でも使用できるが、充填性、品質、経済性など考
えあわせると、天然の鱗状黒鉛が最も好ましい。
耐火原料中に占める炭素の割合は、5wt％以下で
は耐食性、熱衝撃性の効果が得られず、50wt％
を超えると耐酸化性、耐摩耗性に劣る。
炭素以外の耐火原料は、マグネシアを主材にす
る。必要により、さらにドロマイト、カルシア。
スピネル、ジルコン、ジルコニア、炭化珪素、窒
化珪素、ほう化物などから選ばれる一種又は二種
以上を使用する。また、これらを主材とした煉瓦
屑も使用できる。粒度は煉瓦の用途に応じて粗
粒、中粒、微粒に適宜調整する。
有機結合剤は、高温下で炭化して上記の原料粉
末を炭素結合させる役割を持つ。例えばフエノー
ル樹脂、フラン樹脂、エポキシ樹脂、メラニン樹
脂、タールピツチ、クマロン樹脂などから選ばれ
る一種又は二種以上を使用する。中でもフエノー
ル樹脂、タールピツチが賞用される。前記耐火原
料に対する好ましい添加割合は、外掛け３〜
15wt％である。
アルミニウム短繊維の材質は、アルミニウムあ
るいはこれにMg、Si、Mnなどを組み合わせた
純度90％以上のアルミニウム合金とする。繊維の
好ましい寸法は、直径0.01〜３mm程度、長さ２〜
50mmの短繊維とする。この範囲内で長短混合して
使用してもよい。
アルミニウム短繊維の添加割合は、前記耐火原
料に対する外掛で1wt％未満では添加による効果
が得られず、20wt％を超える分散性が悪くなつ
て、煉瓦成形が困難となる。
第二発明は、更に金属粉末を添加する。金属粉
末としては、例えばアルミニウム、シリコン、ア
ルミニウム−マグネシウム合金、アルミニウム−
シリコン合金、フエロシリコン、カルシウム−シ
リコン合金などである。粒度は、0.5mm以下が好
ましい。これらの金属粉末は、低温度でアルミニ
ウム短繊維の表面に融着し、繊維のスサ効果を促
進する。
金属粉末の割合は、耐火原料に対する外掛けで
5wt％を超えると、高温下における金属粉末の反
応で、その金属が例えばアルミニウムやシリコン
の場合、炭素と反応してアルミニウム・カーバイ
ド（Al4C3）、炭化珪素（SiC）などを生成し、そ
の際の容積収縮によつて耐火物組織の強度を劣化
させる。好ましくは１〜10wt％である。
本発明は、前記の炭素、その他の耐火原料、ア
ルミニウム短繊維、必要により添加する金属粉末
などを、有機結合剤をもつて混練した後、所定の
煉瓦形状に加圧成形する。
成形後は100〜400℃程度で加熱処理し、不焼成
品とする。有機結合剤が熱可塑性の場合は、この
加熱処理によつて揮発分を除去し、強度を発現さ
せる。また熱硬化性樹脂の場合は、これによつて
熱硬化が起こり強度が発現する。
本発明において、アルミニウム短繊維は剥離防
止に効果がある。アルミニウム短繊維は高温で酸
化されると高融点のAl2O3になり、従来の鋼短繊
維を使用した場合のように耐食性の低下が著しく
ない。また、アルミニウム短繊維は高温で周囲の
炭素と反応して高融点（2200℃）のAl2O3を生成
するので高温に於いてもその効果は持続される。
これが繊維のスサ的作用を効果的に発揮し、剥離
防止効果を顕著なものにするものと思われる。
本発明において、更に金属粉末を添加した場合
は、アルミニウム短繊維の表面に金属粉末が融着
し、スサ的作用が一段と向上する。例えば、アル
ミニウム粉末ではAl4C3を生成する。アルミニウ
ム−マグネシウム合金の場合には、Al4C3と同時
にMgを生成する。これは直ちにMgOになつて繊
維の周囲を充填し繊維とマトリツクスの結合を強
めるものと推定される。シリコン、フエロシリコ
ン、カルシウムシリコンは何れもアルミニウム短
繊維と融着した後、高温で炭化珪素を生成しスサ
的作用を高める。
（実施例）
第１表に示す各例は、配合物を混練後、1000
Kg／cm2で加圧成形し、さらに200℃×24時間、熱
処理したものである。第２表に示す各例は熱処理
の温度を250℃とし、他は前記第１表の各例と同
様にした。
アルミニウム短繊維は、Al純度約99wt％、直
径0.25×８mmを使用した。アルミニウム合金短繊
維は、Mg5wt％含有し、直径0.1mm×長さ15mmを
使用した。ステンレス鋼短繊維は、SUS−430、
直径0.3mm×長さ10mmを使用した。
試験方法は次のとおりである。
曲げ強さ；40×40×160mmの試験片を切り出し、
スパン100mmで測定。熱間での測定は、不活生ガ
ス通した雰囲気下で各温度で15分保定後、測定。
耐スポーリング性；50×50×230mm試験片を高
周波誘導炉のるつぼ中で溶解した溶鋼中に浸漬
し、10分加熱した後、引出して強制空冷した。
耐食性；回転侵食試験により測定。侵食剤は鋼
片と転炉スラグを１：１の重量比で使用。温度は
1750℃。
本発明実施例はいずれも中間温度域の600℃で
の曲げ強さが大きく、しかも、耐スポーリング
性・耐食性に優れている。
比較例１は短繊維の添加がなく、中間温度域で
の曲げ強さが小さい。また、耐スポーリング性の
試験では、剥離した。
ステンレス鋼短繊維を添加した比較例２は、中
間温度域での曲げ強さが不十分であること、1400
℃での曲げ強さ小さの低下がい著しいこと、耐食
性に劣るなどの欠点がある。
比較例３は、アルミニウム短繊維の添加量が多
過ぎるため、配合物内へアルミニウム短繊維の分
散性が悪く、加圧成形できなかつた。
比較例４，５は短繊維の添加がなく、中間温度
域での曲げ強さが小さい。また、耐スポーリング
性にも劣る。
比較例６はアルミニウム短繊維を添加している
が、その割合が少ないために中間温度域での曲げ
強さ、耐スポーリング性ともに劣る。比較例７は
アルミニウム粉の添加割合が多すぎるために、耐
スポーリング性および耐食性に劣る。
(Industrial Application Field) The present invention relates to a method for manufacturing unfired carbon-containing bricks for lining molten metal containers that are less likely to crack due to thermal shock or thermal expansion stress, and do not easily peel off even if cracks occur. It is something. (Prior Art) Carbon has properties such as being difficult to react with oxides and difficult to wet with molten metal. Carbon-containing bricks manufactured by blending this carbon with other refractory raw materials exhibit excellent durability and are widely used as lining materials for various molten metal containers. (Problems to be Solved by the Invention) Carbon-containing bricks are broadly classified into fired products and unfired products, and unfired products are produced in large quantities. This is because unfired products do not require a firing process and are therefore preferable in terms of manufacturing costs. However, unfired products also have the following drawbacks. In other words, if tar pitch or thermoplastic resin is used as the binder, the binder will melt at 100 to 300
The strength of bricks decreases at ℃. Products that use thermosetting resin as a binder are heat-cured in advance at around 300℃, so there is no problem of strength loss at low temperatures, but the strength decreases in the process of carbonization in the middle temperature range of 500 to 700℃. decreases. Due to these factors, deformation, cracking, peeling, etc. are observed in magnesia-carbon unfired bricks used for the side walls of converters, for example. In addition, the binder tends to undergo creep deformation during the carbonization process. This creep deformation is absorbed by thermal expansion,
If joints open during cooling, they will easily peel off from cracks caused by thermal shock. Such a phenomenon is observed in a vacuum degassing treatment vessel or ladle for molten steel. As a countermeasure to this problem, it may be possible to bake the bricks after forming them at a temperature of 800°C or higher to create a fired product.
However, baked products result in high manufacturing costs. Furthermore, if the product is used under severe thermal shock conditions, even a fired product will not have sufficient durability to resist cracking and peeling. As a measure to prevent cracking and peeling, the addition of steel fibers such as stainless steel fibers to carbon-containing refractories such as magnesia-graphite bricks has already been reported in Japanese Patent Application Laid-Open No. 1983-1989.
Proposed in No. 130608. The addition of steel fibers prevents peeling even if cracks occur due to thermal shock. However, addition of a large amount of steel fiber reduces the corrosion resistance of bricks due to strength deterioration due to carbonization and change to iron oxide due to oxidation. Addition of metal powders such as aluminum and silicon is known as a means of increasing hot strength. For example, JP-A-54-163913, JP-A-55-
As per No. 107749. Among these metal powders, aluminum is the most effective. It reacts with aluminum and carbon to produce aluminum carbide (Al 4 C 3 ), which has the effect of developing strength. However, it is over 900℃ and has no effect in the intermediate temperature range of 300-700℃. (Means for Solving the Problems) The present invention solves all the above-mentioned drawbacks of conventional carbon-containing bricks by adding short aluminum fibers. The feature of the first invention is that the carbon raw material 5-
A mixture of 50wt% refractory raw material with the balance being magnesia and 1 to 20wt% aluminum short fibers added to the outer layer is kneaded with an organic binder,
This is a method for producing carbon-containing bricks for lining molten metal containers, which are heat-treated after forming. The second invention is the first invention in which metal powder is further added to the mixture to enhance the effect. The present invention will be explained in detail below. The specific types of raw materials used in the present invention and their preferred blending ratios are as follows. Carbon raw materials include natural products such as scaly graphite and earthy graphite, and artificial products such as pitchcoke, electrode scrap, pyrolytic graphite, and wood graphite.Any of these can be used, but there are various factors such as fillability, quality, economic efficiency, etc. All things considered, natural flaky graphite is most preferred.
If the proportion of carbon in the refractory raw material is less than 5wt%, corrosion resistance and thermal shock resistance effects cannot be obtained;
If it exceeds this, oxidation resistance and abrasion resistance will be poor. The main refractory raw material other than carbon is magnesia. Further dolomite and calcia as required.
One or more selected from spinel, zircon, zirconia, silicon carbide, silicon nitride, borides, etc. are used. Brick scraps made mainly of these materials can also be used. The particle size is adjusted to coarse, medium, or fine depending on the purpose of the brick. The organic binder carbonizes at high temperatures and has the role of carbon bonding the raw material powder. For example, one or more selected from phenol resin, furan resin, epoxy resin, melanin resin, tarpitz, coumaron resin, etc. are used. Among them, phenolic resin and tarpitz are prized. A preferable addition ratio to the refractory raw material is 3 to 3
It is 15wt%. The material of the aluminum short fibers shall be aluminum or an aluminum alloy with a purity of 90% or more, which is a combination of aluminum, Mg, Si, Mn, etc. The preferred dimensions of the fibers are approximately 0.01 to 3 mm in diameter and 2 to 3 mm in length.
Use 50mm short fibers. A mixture of long and short lengths may be used within this range. If the addition ratio of aluminum short fibers is less than 1 wt% relative to the refractory raw material, no effect will be obtained by adding the aluminum short fibers, and if it exceeds 20 wt%, the dispersibility will deteriorate and brick forming will become difficult. In the second invention, metal powder is further added. Examples of metal powders include aluminum, silicon, aluminum-magnesium alloy, and aluminum-magnesium alloy.
These include silicon alloys, ferrosilicon, calcium-silicon alloys, etc. The particle size is preferably 0.5 mm or less. These metal powders fuse to the surface of the short aluminum fibers at low temperatures, promoting the fiber's susa effect. The proportion of metal powder is multiplied by the amount of refractory raw material.
If it exceeds 5wt%, the metal powder will react at high temperatures, and if the metal is aluminum or silicon, for example, it will react with carbon to produce aluminum carbide (Al 4 C 3 ), silicon carbide (SiC), etc. The volumetric contraction at that time deteriorates the strength of the refractory structure. Preferably it is 1 to 10 wt%. In the present invention, the above-mentioned carbon, other refractory raw materials, short aluminum fibers, metal powder added if necessary, and the like are kneaded together with an organic binder, and then the mixture is press-molded into a predetermined brick shape. After molding, it is heat-treated at about 100 to 400°C to create an unfired product. When the organic binder is thermoplastic, this heat treatment removes volatile matter and develops strength. In the case of a thermosetting resin, this causes thermosetting and develops strength. In the present invention, short aluminum fibers are effective in preventing peeling. When short aluminum fibers are oxidized at high temperatures, they become Al 2 O 3 with a high melting point, so there is no significant decrease in corrosion resistance as in the case of using conventional short steel fibers. In addition, short aluminum fibers react with surrounding carbon at high temperatures to produce Al 2 O 3 with a high melting point (2200°C), so the effect is maintained even at high temperatures.
It is thought that this effectively exerts the sustenance effect of the fibers and makes the peeling prevention effect remarkable. In the present invention, when metal powder is further added, the metal powder is fused to the surface of the short aluminum fibers, further improving the suction effect. For example, aluminum powder produces Al 4 C 3 . In the case of an aluminum-magnesium alloy, Mg is produced simultaneously with Al 4 C 3 . It is presumed that this immediately turns into MgO, fills the surroundings of the fibers, and strengthens the bond between the fibers and the matrix. After silicon, ferrosilicon, and calcium silicon are fused with short aluminum fibers, they generate silicon carbide at high temperatures and enhance the susa effect. (Example) In each example shown in Table 1, after kneading the compound, 1000
It was pressure molded at Kg/cm 2 and then heat treated at 200°C for 24 hours. In each example shown in Table 2, the heat treatment temperature was 250°C, and the other conditions were the same as in each example in Table 1 above. The aluminum short fibers used had an Al purity of about 99 wt% and a diameter of 0.25 x 8 mm. The aluminum alloy short fibers contained 5wt% Mg and had a diameter of 0.1 mm and a length of 15 mm. Stainless steel short fibers are SUS−430,
A diameter of 0.3 mm x length of 10 mm was used. The test method is as follows. Bending strength: Cut out a 40 x 40 x 160 mm test piece,
Measured with a span of 100mm. For hot measurements, measure after holding each temperature for 15 minutes in an inert gas atmosphere. Spalling resistance: A 50 x 50 x 230 mm test piece was immersed in molten steel melted in a crucible of a high frequency induction furnace, heated for 10 minutes, then pulled out and forced air cooled. Corrosion resistance: Measured by rotary erosion test. As the corrosive agent, steel slabs and converter slag are used in a 1:1 weight ratio. The temperature is
1750℃. All of the examples of the present invention have high bending strength in the intermediate temperature range of 600°C, and have excellent spalling resistance and corrosion resistance. In Comparative Example 1, no short fibers were added, and the bending strength in the intermediate temperature range was low. In addition, in the spalling resistance test, peeling occurred. Comparative Example 2, in which short stainless steel fibers were added, had insufficient bending strength in the intermediate temperature range;
It has drawbacks such as a significant decrease in bending strength at ℃ and poor corrosion resistance. In Comparative Example 3, since the amount of aluminum short fibers added was too large, the dispersibility of the aluminum short fibers in the compound was poor, and pressure molding could not be performed. In Comparative Examples 4 and 5, no short fibers were added and the bending strength in the intermediate temperature range was low. It also has poor spalling resistance. In Comparative Example 6, short aluminum fibers are added, but because the proportion thereof is small, both the bending strength and spalling resistance in the intermediate temperature range are poor. Comparative Example 7 has poor spalling resistance and corrosion resistance because the proportion of aluminum powder added is too large.
【表】【table】
【表】【table】
【表】【table】
【表】
（効 果）
本発明の不焼成炭素含有煉瓦は、以上のよう
に、アルミニウム短繊維の添加によつて中間温度
域での強度低下がなく、しかも耐スポーリング性
に優れている。また、従来知られているステンレ
ス鋼短繊維を添加した材質のように、耐食性の低
下がない。
本発明の煉瓦は、転炉、取鍋、混銑炉、電気
炉、真空脱ガス槽などの特に熱衝撃条件の苛酷な
部位の内張り材として好適である。
例えば転炉内張りの煉瓦は、築造後、昇温速度
が早いと稼動面が剥離する現象があり、このため
穏やかに昇温しているが炉の稼働率を低下させる
結果となつている。これに対し、本発明の煉瓦は
耐スポーリング性に優れ、しかもその持続性が大
きいために昇温速度が早くても稼動面の剥離がな
い。
本発明において、さらに金属粉末を添加した場
合は、アルミニウム短繊維がもつ中間温度域の強
度と耐スポーリング性の効果が一段と向上する。[Table] (Effects) As described above, the unfired carbon-containing brick of the present invention has no decrease in strength in the intermediate temperature range due to the addition of short aluminum fibers, and has excellent spalling resistance. In addition, there is no reduction in corrosion resistance, unlike conventionally known materials containing short stainless steel fibers. The brick of the present invention is suitable as a lining material for areas subject to particularly severe thermal shock conditions, such as converters, ladles, mixed iron furnaces, electric furnaces, and vacuum degassing tanks. For example, the operating surface of the bricks lining the converter furnace may peel off if the temperature rises quickly after construction, and this results in a decrease in the operating rate of the furnace, even though the temperature is rising slowly. On the other hand, the brick of the present invention has excellent spalling resistance and is long lasting, so there is no peeling of the operating surface even if the temperature rise rate is fast. In the present invention, when metal powder is further added, the strength and spalling resistance in the intermediate temperature range of the short aluminum fibers are further improved.
Claims (1)
主材とする耐火原料に、アルミニウム短繊維を外
掛け１〜20wt％添加した配合物を、有機質結合
剤をもつて混練し、成形後、熱処理する溶融金属
容器内張り用の不焼成炭素含有煉瓦の製造方法。 ２ 炭素原料５〜50wt％、残部がマグネシアを
主材とする耐火原料に、アルミニウム短繊維を外
掛け１〜20wt％および金属粉末を外掛け5wt％以
下添加した配合物を、有機質結合剤をもつて混練
し、成形後、熱処理する溶融金属容器内張り用の
不焼成炭素含有煉瓦の製造方法。[Scope of Claims] 1. A refractory raw material containing 5 to 50 wt% of carbon raw material and the balance mainly magnesia, and 1 to 20 wt% of aluminum short fibers added thereto, is kneaded with an organic binder. , a method for producing an unfired carbon-containing brick for lining a molten metal container, which is heat-treated after forming. 2. A mixture containing 5 to 50 wt% of carbon raw material and a refractory raw material with the balance mainly composed of magnesia, 1 to 20 wt% of aluminum short fibers and 5 wt% or less of metal powder added to the fireproof raw material with an organic binder. A method for producing an unfired carbon-containing brick for lining a molten metal container, which comprises kneading the brick, shaping it, and then heat-treating it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59256187A JPS61136966A (en) | 1984-12-03 | 1984-12-03 | Manufacture of carbon-containing refractories |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59256187A JPS61136966A (en) | 1984-12-03 | 1984-12-03 | Manufacture of carbon-containing refractories |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61136966A JPS61136966A (en) | 1986-06-24 |
| JPH0475184B2 true JPH0475184B2 (en) | 1992-11-30 |
Family
ID=17289110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59256187A Granted JPS61136966A (en) | 1984-12-03 | 1984-12-03 | Manufacture of carbon-containing refractories |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61136966A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0735495B2 (en) * | 1986-06-12 | 1995-04-19 | 日本ペイント株式会社 | Two-component urethane coating composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60200866A (en) * | 1984-03-23 | 1985-10-11 | 黒崎窯業株式会社 | Manufacture of high endurance sliding nozzle plate |
-
1984
- 1984-12-03 JP JP59256187A patent/JPS61136966A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60200866A (en) * | 1984-03-23 | 1985-10-11 | 黒崎窯業株式会社 | Manufacture of high endurance sliding nozzle plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61136966A (en) | 1986-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6154772B2 (en) | Alumina-silicon carbide-carbon brick | |
| JP4187183B2 (en) | Magnesia-carbon brick | |
| JP2022060911A (en) | Method of producing lf-ladle magnesia-carbon brick | |
| JPH0475184B2 (en) | ||
| JPH05105506A (en) | Slide valve plate brick | |
| JP3197680B2 (en) | Method for producing unburned MgO-C brick | |
| JP2006021972A (en) | Magnesia-carbon brick | |
| JPH05262559A (en) | Unburned carbon-containing brick | |
| JP2951432B2 (en) | Unfired refractory containing magnesia | |
| JP4234804B2 (en) | Plate brick for sliding nozzle device | |
| JPS6243948B2 (en) | ||
| JP2005089271A (en) | Carbon-containing refractory, its manufacturing method and its use application | |
| JP2001192259A (en) | Spinel-carbonaceous brick for hearth of direct current electric furnace | |
| JPH0421625B2 (en) | ||
| JPH078738B2 (en) | Refractory brick for refining molten metal containing graphite | |
| JP3002296B2 (en) | Method for producing coarse aggregate blended magnesia-carbon refractory | |
| JPS5913468B2 (en) | Basic refractories | |
| JPH0925156A (en) | Refractory material containing carbon | |
| JP2000191364A (en) | Shaped magnesia-chrome refractory | |
| JPH07291710A (en) | Graphite containing refractory | |
| JPH08319151A (en) | Refractory containing carbon | |
| JPH0283250A (en) | Production of carbon-containing calcined refractory | |
| JP2002087889A (en) | Low heat conductive carbon-containing refractory | |
| JPH03205347A (en) | Magnesia-carbon brick | |
| JPH0733512A (en) | Production of carbon-containing refractory |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |