JP2574529B2 - Carbon containing refractories - Google Patents
Carbon containing refractoriesInfo
- Publication number
- JP2574529B2 JP2574529B2 JP2241265A JP24126590A JP2574529B2 JP 2574529 B2 JP2574529 B2 JP 2574529B2 JP 2241265 A JP2241265 A JP 2241265A JP 24126590 A JP24126590 A JP 24126590A JP 2574529 B2 JP2574529 B2 JP 2574529B2
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- Japan
- Prior art keywords
- weight
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- refractory
- carbon
- pitch
- 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.)
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は耐酸化性に極めて優れた炭素含有耐火物に関
する。Description: TECHNICAL FIELD The present invention relates to a carbon-containing refractory having extremely excellent oxidation resistance.
［従来の技術］ 黒鉛等の炭素質物質を含む耐火組成物は炭素のもって
いる高熱伝導性、溶融金属、スラグに対して漏れ難い性
質、耐火物の過度の焼結を防ぐ性質などにより他の耐火
骨材との共存下において、その耐火骨材の長所を補完
し、製銑用耐火物、製鋼用耐火物など幅広く冶金用耐火
物として使用されている。[Related Art] A refractory composition containing a carbonaceous material such as graphite has other properties due to its high thermal conductivity, the property of preventing leakage of molten metal and slag, and the property of preventing refractory from excessive sintering. In coexistence with refractory aggregates, it complements the advantages of refractory aggregates and is widely used as a refractory for metallurgy, such as refractories for iron making and steel making.
しかし、黒鉛等の炭素質物質は酸化性雰囲気下では極
めて容易に酸化し、前述の長所を失うことになるから炭
素含有耐火物の長所をより一層発揮するためには黒鉛等
の炭素質物質の酸化を極力少なくすること、すなわち耐
酸化性に優れた炭素含有耐火物にすることが実用上極め
て重要である。However, carbonaceous materials such as graphite are very easily oxidized in an oxidizing atmosphere, and lose the above-mentioned advantages. Therefore, in order to further demonstrate the advantages of carbon-containing refractories, carbonaceous materials such as graphite must be used. It is extremely important in practical use to minimize oxidation, that is, to provide a carbon-containing refractory having excellent oxidation resistance.
本発明者らは、炭素質物質に耐酸化性を賦与する方法
としては、特開平１−249645号公報に示すように、黒鉛
をSiO2系、Al2O3系、TiO2系及びZrO2系のコロイド溶液
によってコーティングを施すことを既に開示している。The present inventors have proposed a method for imparting oxidation resistance to a carbonaceous material, as described in JP-A-1-249645, by using graphite as an SiO 2 system, an Al 2 O 3 system, a TiO 2 system, and a ZrO 2 system. The application of a coating by a colloidal solution of the system has already been disclosed.
また、単純に窒化物、硼化物、炭化物及び金属粉末を
炭素含有耐火物に添加して耐火物中の炭素の耐酸化性向
上を図る例もある。しかし、骨材間の結合強度の低い40
0〜1000℃域では開気孔が多く、耐酸化性向上効果は小
さい。In some cases, nitrides, borides, carbides, and metal powders are simply added to carbon-containing refractories to improve the oxidation resistance of carbon in the refractories. However, the bonding strength between aggregates is low.
In the range of 0 to 1000 ° C., there are many open pores, and the effect of improving oxidation resistance is small.
また、目的は異なるが、水を用いる不定形耐火物にお
いて、水による加水分解を容易に受けるために、予め樹
脂を被覆させたアルミニウム粉を用いる不定形耐火物
（特公昭58−49511号公報）、窒化珪素の微粉にタール
ピッチを被覆したピッチコーチング窒化珪素を用いる不
定形耐火物（特開平２−80378号公報）も開示されてい
るが、これらは本発明の炭素含有耐火物とは作用効果は
異なるものである。In addition, although the purpose is different, in an amorphous refractory using water, an amorphous refractory using aluminum powder coated with a resin in advance to easily undergo hydrolysis by water (Japanese Patent Publication No. 58-49511) Amorphous refractories using pitch-coated silicon nitride in which fine pitches of silicon nitride are coated with tar pitch are also disclosed (JP-A-2-80378). These refractories have the same effect as the carbon-containing refractories of the present invention. Are different.
［発明が解決しようとする課題］ 前記特開平１−249645号公報は、コーティング材とし
て酸化物系の材質を使用しており、黒鉛粒子（以下、炭
素質粒子の代表例として黒鉛粒子を使用する）個々の耐
酸化性向上効果に優れているが、1500℃以上の高温域に
なると、コーティング材と黒鉛粒子との酸化還元反応に
よって黒鉛の一部が酸化消耗する場合があり、完全なも
のではない。[Problem to be Solved by the Invention] Japanese Patent Application Laid-Open No. 1-249645 discloses that an oxide-based material is used as a coating material, and graphite particles (hereinafter, graphite particles are used as a typical example of carbonaceous particles). ) Each is excellent in improving the oxidation resistance, but in the high temperature range of 1500 ° C or higher, part of the graphite may be oxidized and consumed by the oxidation-reduction reaction between the coating material and the graphite particles. Absent.
また、酸化防止材として単純に窒化物、硼化物、炭化
物及び金属粉末を添加して耐酸化性向上を図っている例
もあるが、バインダーにフェノールレジンを使用してい
るため、400〜1000℃の温度域での耐火物を構成する骨
材間の結合強度は低く、開気孔も多い。このため400〜1
000℃での酸化防止が十分発揮されていない。In addition, there is an example in which a nitride, a boride, a carbide, and a metal powder are simply added as an antioxidant to improve oxidation resistance.However, since phenol resin is used as a binder, 400 to 1000 ° C. The bonding strength between the aggregates constituting the refractory in the above temperature range is low and there are many open pores. For this reason 400-1
Antioxidation at 000 ° C is not sufficiently exhibited.
［課題を解決するための手段］ 本発明者らは黒鉛粒子のコーティング材について更に
開発を進め、高温（1500℃以上）での耐酸化性に優れた
コーティング材を開発した。[Means for Solving the Problems] The present inventors have further developed a coating material of graphite particles, and have developed a coating material having excellent oxidation resistance at high temperatures (1500 ° C. or higher).
更に、該コーティング材を微粉末状にして炭化含有耐
火物に添加することによって従来の単純に酸化防止材を
添加した炭素含有耐火物に比較してより優れた耐酸化防
止効果を見出した。Further, the present inventors have found that the coating material is made into a fine powder and added to the carbon-containing refractory to provide a more excellent anti-oxidation effect as compared with a conventional carbon-containing refractory simply added with an antioxidant.
即ち、本発明は予め高軟化点ピッチ100重量部当たり
窒化物、炭化硼素を除く炭化物または硼化物、金属及び
合金からなる群から選択された１種または２種以上の微
粉末10〜300重量部の添加割合をもつコーティング材で
コーティングを施した炭素質物質３〜50重量部及び耐火
材料50〜97重量部よりなることを特徴とする炭素含有耐
火物に係る。That is, the present invention relates to 10 to 300 parts by weight of one or more fine powders selected from the group consisting of nitrides, carbides or borides other than boron carbide, metals and alloys in advance per 100 parts by weight of the high softening point pitch. The present invention relates to a carbon-containing refractory comprising 3 to 50 parts by weight of a carbonaceous substance coated with a coating material having an addition ratio of 50 to 97 parts by weight.
［作用］ 高温での酸化還元反応がなく、黒鉛との漏れ性に優れ
たコーティング材の成分として残炭率50％以上、軟化温
度100〜400℃の高軟化点ピッチを選定した。残炭率を50
％以上と決めた理由として、残炭率が低いものは揮発分
が多いので昇熱中に黒鉛粒子にコーティングされたピッ
チが揮散して均一なコーティング層を形成し難く、ま
た、残炭率は高い程、均一なコーティング層を形成し易
いためである。[Action] A high softening point pitch having a residual carbon ratio of 50% or more and a softening temperature of 100 to 400 ° C. was selected as a component of a coating material having no redox reaction at high temperature and excellent in leaking properties with graphite. Residual coal rate 50
The reason why it is determined to be at least% is that the low carbon residue has a high volatile content, so that the pitch coated on the graphite particles volatilizes during the heating to form a uniform coating layer, and the residual carbon ratio is high. This is because a more uniform coating layer can be easily formed.
軟化温度を100〜400℃にした理由として軟化温度が10
0℃未満となると、昇熱中のピッチの流動性が大きくな
り、耐火物の充填性が低下し、耐酸化性、耐食性の低下
をもたらす。逆に、軟化温度が400℃を超える高軟化点
ピッチになると、流動性が悪く、均一な厚さのコーティ
ングを形成し難くなる。The reason for setting the softening temperature to 100 to 400 ° C is that the softening temperature is 10
When the temperature is lower than 0 ° C., the fluidity of the pitch during the heating increases, the filling property of the refractory decreases, and the oxidation resistance and the corrosion resistance decrease. Conversely, when the softening temperature is a high softening point pitch exceeding 400 ° C., the fluidity is poor and it is difficult to form a coating having a uniform thickness.
次に、このような高軟化点ピッチの中に窒化物（Ti
N、Si3N4等）、硼化物（BN等）、炭化物（TiC、SiC等）
及び金属並びに合金微粉末（Al、Si、Al−Si、Al−Mg
等）から選択された１種または２種以上の微粉末を混合
する効果について説明する。Next, nitride (Ti) is placed in such a high softening point pitch.
N, Si 3 N 4 etc.), boride (BN etc.), carbide (TiC, SiC etc.)
And fine powders of metals and alloys (Al, Si, Al-Si, Al-Mg
And the like, the effect of mixing one or two or more kinds of fine powders selected from the above.
これらの微粉末を添加することによって、炭化ピッチ
の残炭率及び耐酸化性が向上する。これは添加した微粉
末が外来の酸化性ガスをトラップすることによる効果と
考えられる。更に、特筆される点として、微粉末を混合
したピッチは強度発現効果が大きい。これは微粉末がガ
ス成分をトラップすることにより炭化ピッチの密度が高
くなるためと考えられる。つまり、高軟化ピッチと微粉
末の相乗効果であり、このコーティング材でコーティン
グした黒鉛を使用した炭素含有耐火物は酸化防止剤とし
ての微粉末や高軟化ピッチをそれぞれ単独に添加した耐
火物に比較して耐酸化性や耐食性に優れ、より高強度の
特性を有する。By adding these fine powders, the residual carbon ratio and oxidation resistance of the carbonized pitch are improved. This is considered to be due to the effect of the added fine powder trapping foreign oxidizing gas. Further, it should be noted that the pitch in which the fine powder is mixed has a large strength developing effect. This is considered to be because the density of the carbonized pitch is increased by the fine powder trapping the gas component. In other words, it is a synergistic effect of high softening pitch and fine powder.The carbon-containing refractory using graphite coated with this coating material is compared with the refractory to which fine powder as antioxidant and high softening pitch are individually added. It has excellent oxidation resistance and corrosion resistance, and has higher strength characteristics.
炭素質物質をコーティングするためのコーティング材
は高軟化点ピッチと前記微粉末よりなるものであるが、
その配合割合は前記高軟化点ピッチ100重量部当たり前
記微粉末10〜300重量部の範囲内である。微粉末の量が1
0重量部未満であると、微粉末の使用効果が小さいため
に好ましくなく、また、300重量部を超えると微粉末が
過多となり、良好な分散状態のコーティングを施すこと
ができないために好ましくない。The coating material for coating the carbonaceous substance is composed of the high softening point pitch and the fine powder,
The compounding ratio is in the range of 10 to 300 parts by weight of the fine powder per 100 parts by weight of the high softening point pitch. The amount of fine powder is 1
If the amount is less than 0 part by weight, it is not preferable because the effect of using the fine powder is small. On the other hand, if it exceeds 300 parts by weight, the amount of the fine powder becomes excessive, and it is not preferable because a coating in a good dispersed state cannot be applied.
また、前記コーティング材の炭素質物質へのコーティ
ング量は炭素質物質100重量部に対してコーティング材
３〜30重量部程度である。コーティング量が３重量部未
満であるとコーティング効果が少ないために好ましくな
く、また、30重量部より多ければかえって充填不良等の
品質低下をきたすために好ましくない。The coating amount of the coating material on the carbonaceous material is about 3 to 30 parts by weight based on 100 parts by weight of the carbonaceous material. A coating amount of less than 3 parts by weight is not preferable because the coating effect is small, and a coating amount of more than 30 parts by weight is unfavorable because the quality such as poor filling is rather deteriorated.
次に、前記コーティング材の炭素質物質へのコーティ
ング操作の一例を説明する。Next, an example of an operation of coating the coating material on the carbonaceous substance will be described.
炭素質物質を100〜120℃に予備加熱し、ホットミキサ
ーに投入する。The carbonaceous material is preheated to 100-120 ° C and charged into a hot mixer.
高軟化点ピッチを希釈剤例えばクレオソート油と混合
して80〜90℃で液状になるように調製し、次に、所定量
の前記微粉末を添加混合する。なお、高軟化点ピッチと
希釈剤の混合割合は高軟化点ピッチの性状に依存する
が、通常、高軟化点ピッチ／希釈剤重量比＝70/30〜95/
5の範囲とすることが好ましい。The high softening point pitch is mixed with a diluent such as creosote oil to prepare a liquid at 80 to 90 ° C., and then a predetermined amount of the fine powder is added and mixed. Although the mixing ratio of the high softening point pitch and the diluent depends on the properties of the high softening point pitch, usually, the high softening point pitch / diluent weight ratio = 70/30 to 95 /
It is preferable to set the range to 5.
で調製した混合液（高軟化点ピッチ＋微粉末＋希釈
剤）を所定量前記ホットミキサーに投入し、ミキサー内
で炭素質物質と混練することによりコーティングを施
す。A predetermined amount of the mixed solution (high softening point pitch + fine powder + diluent) prepared in the above is charged into the hot mixer and kneaded with the carbonaceous substance in the mixer to perform coating.
混練時間は特に限定されるものではないが、通常希釈
剤の添加量が多いもの程長くする必要がある。なお、希
釈剤はコーティング操作中に実質上全て揮散する。The kneading time is not particularly limited, but usually needs to be longer as the amount of the diluent added is larger. Note that substantially all of the diluent volatilizes during the coating operation.
本発明の炭素含有耐火物に作用する炭素質物質以外の
耐火材料としてはマグネシア、スピネル、カルシア、ド
ロマイト、アルミナ、シリカ、ジルコニア、ジルコン等
の酸化物や炭化珪素、窒化珪素、窒化硼素等の非酸化物
を挙げることができ、これらは特に限定されるものでは
なく、使用目的によって異なるが、マグネシア、ドロマ
イト、スピネル、アルミナを主体とするものが好まし
い。Examples of the refractory material other than the carbonaceous substance acting on the carbon-containing refractory of the present invention include oxides such as magnesia, spinel, calcia, dolomite, alumina, silica, zirconia, and zircon; Oxides can be mentioned, and these are not particularly limited and vary depending on the purpose of use, but oxides mainly composed of magnesia, dolomite, spinel, and alumina are preferable.
本発明の炭素含有耐火物はコーティングした炭素質物
質と粒度調整した耐火材料を予め定められた配合割合で
調合し、タール、ピッチ、石油ピッチ、フェノール樹脂
等の残留炭素量の多い有機樹脂の結合剤のいずれか１種
または２種以上を加え、混練後、加圧成形し、100〜500
℃程度に乾燥あるいは熱処理すれば、不焼成耐火物が得
られ、また、700〜1500℃程度の還元雰囲気で焼成して
焼成耐火物として使用に供することもできる。The carbon-containing refractory of the present invention is prepared by mixing a coated carbonaceous substance and a refractory material having a controlled particle size at a predetermined compounding ratio, and bonding an organic resin having a large residual carbon content such as tar, pitch, petroleum pitch, and phenol resin. One or two or more of the agents are added, kneaded, and then press-molded, and 100 to 500
By drying or heat-treating to about ° C, an unfired refractory can be obtained, or it can be fired in a reducing atmosphere at about 700 to 1500 ° C and used as a fired refractory.
［実 施 例］ 実施例 以下に実施例を挙げて本発明の炭素含有耐火物を更に
説明する。[Example] Example The carbon-containing refractory of the present invention will be further described below with reference to examples.
実施例１ まず、軟化温度150℃の高軟化点ピッチ93重量部とク
レオソート油７重量部を混合して液状とし、これに第１
表に記載する種類と量の微粉末を添加して混練してコー
ティング材を得た。次に、得られるコーティング材を予
めホットミキサー中で105℃に加熱された鱗状黒鉛中に
添加して混合することによりコーティング済鱗状黒鉛を
得た。なお、軟化温度320℃の高軟化点ピッチ80重量部
とクレオソート油20重量部を混合して液状としたものを
用いて同様の操作を行った。Example 1 First, 93 parts by weight of a high softening point pitch having a softening temperature of 150 ° C. and 7 parts by weight of creosote oil were mixed to form a liquid.
Fine powders of the kind and amount shown in the table were added and kneaded to obtain a coating material. Next, the obtained coating material was previously added to and mixed with scaly graphite heated to 105 ° C. in a hot mixer to obtain coated scaly graphite. The same operation was carried out using a mixture obtained by mixing 80 parts by weight of a high softening point pitch having a softening temperature of 320 ° C. and 20 parts by weight of creosote oil to form a liquid.
次に、上述のようにして得られたコーティング済鱗状
黒鉛を使用して第２表に記載する配合割合をもつ混合物
に結合剤としてフェノール樹脂を３重量部添加し、得ら
れた配合物を1500kg/cm2の圧力で230mm×114mm×65mmの
寸法に加圧成形し、200℃で24時間乾燥することにより
炭素含有耐火物を得た。得られた炭素含有耐火物の諸特
性を第２表に併記する。 Next, 3 parts by weight of a phenol resin was added as a binder to the mixture having the compounding ratio shown in Table 2 using the coated scale graphite obtained as described above, and 1500 kg of the obtained compound was added. It was press-molded to a size of 230 mm × 114 mm × 65 mm at a pressure of / cm 2 and dried at 200 ° C. for 24 hours to obtain a carbon-containing refractory. Various properties of the obtained carbon-containing refractory are also shown in Table 2.
［発明の効果］ 本発明の炭素含有耐火物は炭素質物質として高軟化点
ピッチと微粉末よりなるコーティング材でコーティング
されたものを使用するために優れた耐酸化性を提供する
ことができる。 [Effects of the Invention] The carbon-containing refractory of the present invention can provide excellent oxidation resistance because it uses a carbonaceous substance coated with a coating material comprising a high softening point pitch and a fine powder.
Claims (1)
物、炭化硼素を除く炭化物または硼化物、金属及び合金
からなる群から選択された１種または２種以上の微粉末
10〜300重量部の添加割合をもつコーティング材でコー
ティングを施した炭素質物質３〜50重量部及び耐火材料
50〜97重量部よりなることを特徴とする炭素含有耐火
物。1. One or more fine powders previously selected from the group consisting of nitrides, carbides or borides other than boron carbide, metals and alloys per 100 parts by weight of high softening point pitch
3-50 parts by weight of carbonaceous material coated with a coating material having an addition ratio of 10-300 parts by weight and a refractory material
A carbon-containing refractory comprising 50 to 97 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2241265A JP2574529B2 (en) | 1990-09-13 | 1990-09-13 | Carbon containing refractories |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2241265A JP2574529B2 (en) | 1990-09-13 | 1990-09-13 | Carbon containing refractories |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04124056A JPH04124056A (en) | 1992-04-24 |
| JP2574529B2 true JP2574529B2 (en) | 1997-01-22 |
Family
ID=17071684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2241265A Expired - Lifetime JP2574529B2 (en) | 1990-09-13 | 1990-09-13 | Carbon containing refractories |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2574529B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2592221B2 (en) * | 1993-10-29 | 1997-03-19 | 品川白煉瓦株式会社 | Carbon-containing refractory and method for producing the same |
| KR101461578B1 (en) * | 2013-02-27 | 2014-11-13 | 주식회사 포스코 | Method for preparing refractory and the refractory |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0416545A (en) * | 1990-05-09 | 1992-01-21 | Osaka Kasei Kk | Oxidation resistance graphite granulation matter for refractory |
-
1990
- 1990-09-13 JP JP2241265A patent/JP2574529B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04124056A (en) | 1992-04-24 |
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