JPH07277858A - Antioxidant for carbon-containing refractory - Google Patents
Antioxidant for carbon-containing refractoryInfo
- Publication number
- JPH07277858A JPH07277858A JP8735494A JP8735494A JPH07277858A JP H07277858 A JPH07277858 A JP H07277858A JP 8735494 A JP8735494 A JP 8735494A JP 8735494 A JP8735494 A JP 8735494A JP H07277858 A JPH07277858 A JP H07277858A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- antioxidant
- weight
- containing refractory
- silica powder
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
- C04B41/5089—Silica sols, alkyl, ammonium or alkali metal silicate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/608—Anti-oxidants
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、冶金分野における鋼の
連続鋳造用浸漬ノズルやロングノズル、ストッパ−ロッ
ド、連続測温用熱電対保護管、その他の炭素含有耐火物
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to immersion nozzles and long nozzles for continuous casting of steel in the field of metallurgy, stopper rods, thermocouple protection tubes for continuous temperature measurement, and other carbon-containing refractories.
【0002】[0002]
【従来の技術】連続鋳造用浸漬ノズル等の黒鉛含有耐火
物は、その表面に通常ガラス質の物質を塗着し、含有す
る黒鉛の酸化防止または酸化を遅延することが行われ
る。2. Description of the Related Art A graphite-containing refractory such as a dipping nozzle for continuous casting is usually coated with a vitreous substance on its surface to prevent oxidation or delay oxidation of the graphite contained therein.
【0003】[0003]
【発明が解決しようとする課題】しかし、使用温度でガ
ラス物質が高粘度で凝集力が強いと、黒鉛との接触角が
過大となり、ややもすれば凝集剥離を起こす。また、ガ
ラス物質の粘度が低すぎる場合は、溶融して流下し、そ
の目的を十分に達することができない。さらに、粘度
が、時間とともに低下することがあり、黒鉛含有耐火物
を長時間にわたって安定して使用することが著しく困難
であった。However, when the glass material has a high viscosity and a strong cohesive force at the temperature of use, the contact angle with graphite becomes excessively large, and if it does, cohesive peeling occurs. Further, if the viscosity of the glass material is too low, the glass material melts and flows down, and its purpose cannot be sufficiently achieved. Further, the viscosity may decrease with time, and it was extremely difficult to stably use the graphite-containing refractory for a long time.
【0004】[0004]
【課題を解決するための手段】本発明は、上記のような
点に鑑みたもので、上記の課題を解決するために、炭素
含有耐火物の表面に付着して熱間状態における当該炭素
含有耐火物の酸化を防止する酸化防止剤であって、上記
酸化防止剤に低融点のフリット粉末を配合し、上記酸化
防止剤に対してシリカ粉末を外掛けで5〜40重量%添
加したことを特徴とする炭素含有耐火物用酸化防止剤を
提供するにある。The present invention has been made in view of the above points, and in order to solve the above-mentioned problems, the carbon-containing refractory is adhered to the surface thereof and the carbon-containing refractory in a hot state is contained. It is an antioxidant for preventing the oxidation of refractory material, wherein a frit powder having a low melting point is blended with the above antioxidant, and silica powder is added to the above antioxidant in an amount of 5 to 40% by weight. An object is to provide a characteristic antioxidant for carbon-containing refractory materials.
【0005】[0005]
【作用】本発明の酸化防止剤を炭素含有耐火物の表面に
付着すると、酸化防止剤に低融点のフリット粉末を配合
したことによって、使用温度の500℃位でガラス層で
被覆し、低温域での炭素含有耐火物の酸化を防止でき
る。When the antioxidant of the present invention is adhered to the surface of the carbon-containing refractory material, the antioxidant is mixed with the frit powder having a low melting point so that it is coated with the glass layer at about 500 ° C. of the operating temperature, and the low temperature range is maintained. Oxidation of carbon-containing refractories can be prevented.
【0006】また、上記酸化防止剤に対してシリカ粉末
を外掛けで5〜40重量%添加したことによって、80
0〜1000℃以上の高温域にわたってガラス層を炭素
含有耐火物の表面に維持するとこができて酸化防止効果
を生じ、炭素含有耐火物を長時間にわたって使用するこ
とができる。Further, silica powder is externally added to the above antioxidant in an amount of 5 to 40% by weight to obtain 80% by weight.
When the glass layer is maintained on the surface of the carbon-containing refractory over a high temperature range of 0 to 1000 ° C. or more, an antioxidation effect is produced, and the carbon-containing refractory can be used for a long time.
【0007】[0007]
【実施例】以下、本発明を実施例にもとづいて説明す
る。本発明の連続鋳造用浸漬ノズルやロングノズル、ス
トッパ−ロッド、連続測温用熱電対保護管等の黒鉛を含
む炭素含有耐火物の酸化防止剤は、酸化防止剤に低融点
のフリット粉末を配合し、上記酸化防止剤に対してシリ
カ粉末を外掛けで5〜40重量%添加している。EXAMPLES The present invention will be described below based on examples. Antioxidants for carbon-containing refractories containing graphite such as continuous casting dipping nozzles and long nozzles, stopper rods, continuous temperature measuring thermocouple protection tubes, etc. of the present invention include a frit powder having a low melting point in the antioxidant. However, silica powder is externally added to the above antioxidant in an amount of 5 to 40% by weight.
【0008】上記フリット粉末としては、SiO2 60
〜80重量%、Al2 O3 5〜10重量%、Na2 O2
〜7重量%、CaO5〜15重量%、PbO2〜5重量
%の配合成分として、このガラス化温度を500℃位の
低融点化して、低温域で上記炭素含有耐火物の表面に均
一にガラス層を被覆できるようにしている。As the frit powder, SiO 2 60 is used.
80 wt%, Al 2 O 3 5~10 wt%, Na 2 O2
.About.7% by weight, CaO 5 to 15% by weight, PbO 2 to 5% by weight, and the vitrification temperature is lowered to about 500.degree. C. to uniformly form a glass layer on the surface of the carbon-containing refractory material in a low temperature range. To be able to cover.
【0009】また、上記シリカ粉末は、高温域にわたっ
て炭素含有耐火物の表面にガラス被覆を維持できるよう
にしているもので、添加量に対する融点の挙動について
図1に示している。Further, the above-mentioned silica powder makes it possible to maintain the glass coating on the surface of the carbon-containing refractory material in a high temperature range, and the behavior of the melting point with respect to the added amount is shown in FIG.
【0010】図1から分かるようにシリカ粉末の添加量
とともにシリカ溶融領域は高温域に広がっており、シリ
カ粉末の添加量としては5〜40重量%、好ましくは2
0〜40重量%位が実用的である。As can be seen from FIG. 1, the silica melting region spreads to a high temperature region with the addition amount of silica powder, and the addition amount of silica powder is 5 to 40% by weight, preferably 2%.
About 0 to 40% by weight is practical.
【0011】また、上記シリカ粉末について、20重量
%添加したときの各粒度の1200℃における接触角の
時間的変化を図2に示している。FIG. 2 shows the time-dependent change in contact angle at 1200 ° C. of each particle size when 20% by weight of the above silica powder was added.
【0012】シリカ粉末の粒度のガラスの接触角は、お
よそ60〜120度の間が付着性が良好な領域であり、
図2のように粒径が50μm以下のものは短時間の間に
フリットと反応し、粘性の増加が著しく、基材に対する
凝集、剥離を引き起こす。The contact angle of glass having a particle size of silica powder is in the range of about 60 to 120 degrees in which the adhesion is good,
As shown in FIG. 2, particles having a particle size of 50 μm or less react with the frit in a short time and the viscosity is remarkably increased, causing aggregation and peeling of the base material.
【0013】一方、粒径が400〜1000μmと大き
いものでは、フリットとの反応が十分でなく、粘性が低
いために、基材から流れ落ちる。On the other hand, if the particle size is as large as 400 to 1000 μm, the reaction with the frit is insufficient and the viscosity is low, so that the particles flow down from the substrate.
【0014】したがって、シリカ粉末の粒度は、50〜
400μmの粒径のものが良好な粘性を長時間維持して
有効である。Therefore, the particle size of the silica powder is 50 to 50.
Particles having a particle size of 400 μm are effective in maintaining good viscosity for a long time.
【0015】なお、上記した酸化防止剤には、珪酸ナト
リウムの水ガラスまたは有機質糊剤、水を適宜量配合
し、フリット粉末、シリカ粉末を均一状に混合して炭素
含有耐火物の表面に均一状に塗布、吹付、または浸漬付
着できるようにしている。The above-mentioned antioxidant is mixed with an appropriate amount of sodium silicate water glass or an organic sizing agent, and water, and frit powder and silica powder are mixed uniformly to obtain a uniform mixture on the surface of the carbon-containing refractory. It can be applied, sprayed, or dip-attached in the shape of a circle.
【0016】[0016]
【使用例】連続鋳造に用いられる炭素含有耐火物である
ロングノズルの表面に、表1に示す配合比率の酸化防止
剤を塗布し、実機に使用した。1ヒ−トは100分と
し、使用に際してロングノズルは500〜800℃にて
90分予熱され、その後鋳造に供した。鋳造時の表面温
度は部位により異なるが900〜1800℃であった。[Example of use] An antioxidant having a compounding ratio shown in Table 1 was applied to the surface of a long nozzle, which is a carbon-containing refractory used for continuous casting, and was used in an actual machine. One heat was 100 minutes, the long nozzle was preheated at 500 to 800 ° C. for 90 minutes before use, and then used for casting. The surface temperature at the time of casting was 900 to 1800 ° C, although it varied depending on the site.
【0017】酸化防止効果比較表Antioxidant effect comparison table
【表1】 [Table 1]
【0018】本発明No.1では、上記したフリットに対し
て50〜400μm粒径のシリカ粉末を30重量%添加
したものである。4ヒ−ト使用後、表面のガラス層の形
成が良好であったために、さらに8ヒ−ト使用したが、
表面にガラス層が光沢を持って一様に形成され、ピンホ
−ル等もなく、ノズルの酸化も認められなかった。In the present invention No. 1, 30% by weight of silica powder having a particle diameter of 50 to 400 μm was added to the above frit. After the use of 4 heats, the formation of the glass layer on the surface was good, so that 8 heats were used further,
A glass layer was uniformly formed on the surface with gloss, there was no pinhole, and no oxidation of the nozzle was observed.
【0019】比較例No.1は、シリカ粉末を含まないも
で、4ヒ−ト使用後、表面でガラス層はわずかずつ部分
的に点在し、ノズルは10mm程度に一様に酸化され、酸
化防止効果がなかった。Comparative Example No. 1 contained no silica powder, but after 4 heats were used, the glass layers were scattered little by little on the surface, and the nozzles were uniformly oxidized to about 10 mm. There was no antioxidant effect.
【0020】比較例No.2は、50μm以下の粒径のシリ
カ粉末30重量%を添加したもので、4ヒ−ト使用後、
表面でガラス層はあばた状にはじかれ、ノズルは5〜1
0mm程度に凹凸をもつ酸化層を有しており、酸化防止効
果を奏していない。Comparative Example No. 2 was obtained by adding 30% by weight of silica powder having a particle size of 50 μm or less, after using 4 heats.
The glass layer is fluttered on the surface and the nozzle is 5-1
It has an oxide layer with irregularities of about 0 mm, and does not have an antioxidant effect.
【0021】比較例No.3は、400〜1000μmの粒
径のシリカ粉末30重量%を添加したもので、4ヒ−ト
使用後、ノズル表面でガラス層はシリカ粉末を中心とし
て点在するのみで、ノズルは5〜10mm程度に凹凸をも
つ酸化層を有しており、酸化防止効果を奏していない。Comparative Example No. 3 was obtained by adding 30% by weight of silica powder having a particle diameter of 400 to 1000 μm, and after using 4 heats, the glass layer was scattered around the silica powder on the nozzle surface. Since the nozzle has an oxide layer having irregularities of about 5 to 10 mm, it has no effect of preventing oxidation.
【0022】上記では、連続鋳造用のロングノズルにつ
いて示したが、浸漬ノズル、ストッパ−ロッド等につい
ても同様である。Although the long nozzle for continuous casting has been described above, the same applies to the immersion nozzle, stopper rod and the like.
【0023】[0023]
【発明の効果】以上のように本発明にあっては、酸化防
止剤に低融点のフリット粉末を配合したので、使用温度
の500℃位でガラス層で被覆し、低温域での炭素含有
耐火物の酸化を防止できる。As described above, in the present invention, since the frit powder having a low melting point is blended with the antioxidant, it is coated with a glass layer at a temperature of about 500 ° C. to prevent the carbon-containing fire resistance in the low temperature range. It can prevent the oxidation of things.
【0024】また、上記酸化防止剤に対してシリカ粉末
を外掛けで5〜40重量%添加したので、800〜10
00℃以上の高温域にわたってガラス層を炭素含有耐火
物の表面に維持するとこができて酸化防止効果を生じ、
炭素含有耐火物を長時間にわたって使用することができ
る。Since silica powder is added to the above antioxidant in an amount of 5 to 40% by weight, 800 to 10
When the glass layer is maintained on the surface of the carbon-containing refractory over a high temperature range of 00 ° C or higher, the antioxidation effect is produced
The carbon-containing refractory can be used for a long time.
【図1】本発明のシリカ粉末の添加量とその溶融状態の
関係図、FIG. 1 is a diagram showing the relationship between the addition amount of silica powder of the present invention and its molten state,
【図2】同上のシリカ粉末の粒度の接触角の時間的な変
化状態図。FIG. 2 is a time-dependent change state diagram of the contact angle of the particle size of the silica powder.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 馬舟 倬三 兵庫県赤穂市中広字東沖1576番地の2 川 崎炉材株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuzo Mabune 2 Kawasaki Furnace Co., Ltd., 1576, East Offshore, Nakahiro, Ako City, Hyogo Prefecture
Claims (2)
態における当該炭素含有耐火物の酸化を防止する酸化防
止剤であって、 上記酸化防止剤に低融点のフリット粉末を配合し、 上記酸化防止剤に対してシリカ粉末を外掛けで5〜40
重量%添加したことを特徴とする炭素含有耐火物用酸化
防止剤。1. An antioxidant which adheres to the surface of a carbon-containing refractory and prevents oxidation of the carbon-containing refractory in a hot state, wherein a frit powder having a low melting point is added to the antioxidant, Silica powder is externally applied to the above antioxidant in an amount of 5 to 40
An antioxidant for a carbon-containing refractory, which is characterized by being added by weight%.
%、Al2 O3 5〜10重量%、Na2 O2〜7重量
%、CaO5〜15重量%、PbO2〜5重量%の配合
成分で、粒径が0.05〜0.4mmのシリカ粉末を20
〜40重量部と、珪酸ナトリウムまたは有機質糊剤と、
水を適量加えて混合したものである請求項1に記載の炭
素含有耐火物用酸化防止剤。2. The frit powder is a compounding ingredient of 60 to 80% by weight of SiO 2, 5 to 10% by weight of Al 2 O 3 , 2 to 7% by weight of Na 2 O, 5 to 15% by weight of CaO, and 2 to 5% by weight of PbO. 20 silica powder with a particle size of 0.05-0.4 mm
~ 40 parts by weight, sodium silicate or organic paste,
The antioxidant for carbon-containing refractories according to claim 1, which is obtained by adding an appropriate amount of water and mixing the mixture.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8735494A JPH07277858A (en) | 1994-03-31 | 1994-03-31 | Antioxidant for carbon-containing refractory |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8735494A JPH07277858A (en) | 1994-03-31 | 1994-03-31 | Antioxidant for carbon-containing refractory |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH07277858A true JPH07277858A (en) | 1995-10-24 |
Family
ID=13912552
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8735494A Pending JPH07277858A (en) | 1994-03-31 | 1994-03-31 | Antioxidant for carbon-containing refractory |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH07277858A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100490984B1 (en) * | 2000-11-22 | 2005-05-24 | 조선내화 주식회사 | Carbon containing refractory for continuous casting and oxidation preventing coating material thereon |
JP2012056813A (en) * | 2010-09-10 | 2012-03-22 | Nippon Crucible Co Ltd | Molded, fired product of refractory material |
CN102408244A (en) * | 2011-08-24 | 2012-04-11 | 江苏苏嘉集团新材料有限公司 | Processing method of carbon-containing refractory product |
-
1994
- 1994-03-31 JP JP8735494A patent/JPH07277858A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100490984B1 (en) * | 2000-11-22 | 2005-05-24 | 조선내화 주식회사 | Carbon containing refractory for continuous casting and oxidation preventing coating material thereon |
JP2012056813A (en) * | 2010-09-10 | 2012-03-22 | Nippon Crucible Co Ltd | Molded, fired product of refractory material |
CN102408244A (en) * | 2011-08-24 | 2012-04-11 | 江苏苏嘉集团新材料有限公司 | Processing method of carbon-containing refractory product |
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