JPH07291770A - Coating solution for forming oxidation preventing film - Google Patents
Coating solution for forming oxidation preventing filmInfo
- Publication number
- JPH07291770A JPH07291770A JP10339794A JP10339794A JPH07291770A JP H07291770 A JPH07291770 A JP H07291770A JP 10339794 A JP10339794 A JP 10339794A JP 10339794 A JP10339794 A JP 10339794A JP H07291770 A JPH07291770 A JP H07291770A
- Authority
- JP
- Japan
- Prior art keywords
- coating solution
- silica
- alumina
- glass
- composite oxide
- 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.)
- Granted
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
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- 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
- C04B41/5025—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 ceramic materials
- C04B41/5035—Silica
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、主として黒鉛などの炭
素含有耐火物の表面に酸化防止機能を持つガラス質被膜
を形成し得る塗布液に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly relates to a coating solution capable of forming a glassy film having an antioxidant function on the surface of a carbon-containing refractory material such as graphite.
【０００２】[0002]
【従来技術およびその問題点】黒鉛などの炭素含有耐火
物は、耐蝕性、耐熱スポーリング性に優れていることか
ら、鋼の連続鋳造設備等の製鋼用耐火物として用いられ
ている。しかし、炭素含有耐火物は、酸化雰囲気中で高
温に加熱されると酸化されて、その特性が低下する。2. Description of the Related Art Carbon-containing refractories such as graphite are used as steel refractories for continuous steel casting equipment because of their excellent corrosion resistance and heat-resistant spalling resistance. However, when the carbon-containing refractory is heated to a high temperature in an oxidizing atmosphere, it is oxidized and its characteristics are deteriorated.
【０００３】上記酸化防止策として、例えば、低融点ガ
ラスと水ガラスとの混合物からなる酸化防止被膜形成用
塗布液を耐火物表面にコーティングする方法が知られて
いる。しかしながら、従来の塗布液は、基材との密着性
が不充分であったり、塗布後に焼成すると、クラックが
発生するなど、未だ酸化防止機能が充分ではないという
問題点を有している。As the above-mentioned anti-oxidation measure, for example, a method is known in which a refractory surface is coated with a coating solution for forming an anti-oxidation film, which is composed of a mixture of low-melting glass and water glass. However, the conventional coating liquid has a problem that the anti-oxidation function is not yet sufficient, such as insufficient adhesion to the base material and cracking when baked after coating.
【０００４】[0004]
【発明の目的】本発明は、炭素含有耐火物等の表面にガ
ラス質被膜を形成することにより、高温下においても酸
化防止効果の高い被膜を形成し得る塗布液を提供するこ
とを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a coating solution capable of forming a coating having a high antioxidation effect even at high temperature by forming a glass coating on the surface of a carbon-containing refractory or the like. .
【０００５】[0005]
【発明の構成】本発明の酸化防止被膜形成用塗布液は、
次式を満足するシリカとアルミナを主成分とする複合酸
化物微粒子、および低融点ガラスを含む分散液からなる
ことを特徴とするものである。 Ｓ（m2/g）≧３０００／ Dp（nm） （但し、上式において、Ｓ：複合酸化物微粒子の比表面
積（m2/g）とし、Dp：複合酸化物微粒子の平均粒径（n
m）とする。）The coating liquid for forming an antioxidant coating of the present invention comprises:
It is characterized by comprising a dispersion liquid containing a composite oxide fine particle containing silica and alumina as main components and satisfying the following formula, and a low melting point glass. S (m 2 / g) ≧ 3000 / Dp (nm) (where S is the specific surface area (m 2 / g) of the composite oxide particles, and Dp is the average particle size (n
m). )
【０００６】本発明の酸化防止被膜形成用塗布液は、前
記複合酸化物微粒子１００重量部に対して、低融点ガラ
スを１０〜２００重量部含むことが好ましい。The coating solution for forming an antioxidant coating of the present invention preferably contains 10 to 200 parts by weight of a low melting point glass with respect to 100 parts by weight of the composite oxide fine particles.
【０００７】[0007]
【発明の具体的な説明】本発明の塗布液は、（ａ）特定
のシリカとアルミナの複合酸化物微粒子、および、
（ｂ）低融点ガラスの２成分を含み、これらが、水およ
び／または有機溶媒に分散した状態にある。DETAILED DESCRIPTION OF THE INVENTION The coating liquid of the present invention comprises (a) specific oxide fine particles of silica and alumina, and
(B) It contains two components of a low melting point glass, and these are in a state of being dispersed in water and / or an organic solvent.
【０００８】上記特定のシリカとアルミナの複合酸化物
は、シリカとアルミナを主成分とする複合酸化物であっ
て、それぞれの酸化物の混合物ではない。シリカとアル
ミナの複合割合は、シリカ１００重量部に対してアルミ
ナ８〜３５０重量部の範囲が適当である。８重量部未満
では後記する微粒子の比表面積が小さくなり、一方、３
５０重量部を越えると微粒子の比表面積は殆ど増加しな
くなるからである。また、３５０重量部を越えると、微
粒子が分散したゾルの安定性も劣ってくる。The above specific silica-alumina composite oxide is a composite oxide containing silica and alumina as main components, and is not a mixture of the respective oxides. The composite ratio of silica and alumina is appropriately in the range of 8 to 350 parts by weight of alumina with respect to 100 parts by weight of silica. If it is less than 8 parts by weight, the specific surface area of the fine particles to be described later becomes small, while 3
This is because if the amount exceeds 50 parts by weight, the specific surface area of the fine particles hardly increases. Further, if it exceeds 350 parts by weight, the stability of the sol in which the fine particles are dispersed becomes poor.
【０００９】この複合酸化物微粒子の比表面積Ｓ（m2/
g）は非常に大きく、具体的には微粒子の平均粒径をDp
（nm）で表した場合、不等式 Ｓ（m2/g）≧３０００／ Dp（nm） を満足するものである。The specific surface area S (m 2 /
g) is very large, specifically, the average particle size of fine particles is Dp
When expressed in (nm), the inequality S (m 2 / g) ≧ 3000 / Dp (nm) is satisfied.
【００１０】複合酸化物を製造する際のシリカの原料と
しては、アルカリ金属、アンモニウムまたは有機塩基の
珪酸塩の１種または２種以上を用いる。アルカリ金属の
珪酸塩としては、珪酸ナトリウム（水ガラス）や珪酸カ
リウムが用いられる。有機塩基としては、テトラエチル
アンモニウム塩などの第４級アンモニウム塩、モノエタ
ノールアミン、ジエタノールアミン、トリエタノールア
ミンなどのアミン類を挙げることができる。また、アン
モニウムの珪酸塩または有機塩基の珪酸塩には、珪酸液
にアンモニア、第４級アンモニウム水酸化物、アミン化
合物などを添加したアルカリ性溶液も含まれる。As a raw material of silica for producing the composite oxide, one or more kinds of silicates of alkali metal, ammonium or organic base are used. As the alkali metal silicate, sodium silicate (water glass) or potassium silicate is used. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt and amines such as monoethanolamine, diethanolamine and triethanolamine. The ammonium silicate or organic base silicate also includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.
【００１１】一方、複合酸化物のアルミナ原料として
は、アルミン酸ナトリウム、アルミノ珪酸ナトリウムな
どのアルカリ可溶のアルミニウム化合物を用いればよ
い。On the other hand, as the alumina raw material for the composite oxide, an alkali-soluble aluminum compound such as sodium aluminate or sodium aluminosilicate may be used.
【００１２】上記複合酸化物を製造するには、予め、前
記化合物のアルカリ水溶液を個別に調製するか、また
は、混合水溶液を調製しておき、この水溶液を目的とす
る複合酸化物の複合割合に応じて、ｐＨ１０以上のアル
カリ水溶液中に撹拌しながら徐々に添加する。このとき
の水溶液の添加速度には格別の制限はない。これらの水
溶液の添加と同時に同溶液のｐＨ値は変化するが、この
ｐＨ値を所定の範囲に制御するような操作は特に必要な
く、水溶液は最終的にその複合割合によって定まるｐＨ
値に落ち着く。ｐＨを所定の範囲に制御するときには、
例えば酸を添加してもよい。In order to produce the above-mentioned composite oxide, an alkaline aqueous solution of the above compound is prepared individually or a mixed aqueous solution is prepared in advance, and this aqueous solution is adjusted to a desired composite ratio of the composite oxide. Correspondingly, it is gradually added to the alkaline aqueous solution having a pH of 10 or more while stirring. There is no particular limitation on the addition rate of the aqueous solution at this time. Although the pH value of the aqueous solution changes at the same time as the addition of these aqueous solutions, the operation of controlling the pH value within a predetermined range is not particularly required, and the aqueous solution finally has a pH determined by the complex ratio thereof.
Settle down to value. When controlling the pH within a predetermined range,
For example, an acid may be added.
【００１３】本発明の複合酸化物微粒子はシード粒子の
分散液を出発原料として製造することも可能である。こ
の場合には、シード粒子として、ＳｉＯ2 、Ａｌ
2 Ｏ3 、ＴｉＯ2 またはＺｒＯ2 等の無機酸化物または
これらの複合酸化物の微粒子が用いられ、通常、これら
のゾルを用いることができる。勿論、前記した製造方法
によって得られたゾルをシード粒子分散液としてもよ
い。The composite oxide fine particles of the present invention can be produced by using a dispersion liquid of seed particles as a starting material. In this case, as seed particles, SiO 2 , Al
Fine particles of an inorganic oxide such as 2 O 3 , TiO 2 or ZrO 2 or a composite oxide of these are used, and usually, a sol thereof can be used. Of course, the sol obtained by the above-mentioned manufacturing method may be used as the seed particle dispersion liquid.
【００１４】このシード粒子分散液をｐＨ１０以上に調
整した後、該分散液中に前記原料化合物の水溶液を、上
記したアルカリ水溶液中に添加する方法と同様にして、
撹拌しながら添加する。この場合も、分散液のｐＨ制御
は行わず成り行きに任せる。このように、シード粒子を
核として複合酸化物粒子を成長させると、成長粒子の粒
径コントロールが容易であり、粒度の揃ったものを得る
ことができる。After adjusting the pH of the seed particle dispersion to 10 or more, the aqueous solution of the raw material compound is added to the dispersion in the same manner as the above-mentioned alkaline aqueous solution.
Add with stirring. In this case also, the pH of the dispersion liquid is not controlled and left to the end. As described above, when the composite oxide particles are grown with the seed particles as the nuclei, it is easy to control the particle size of the grown particles, and particles having a uniform particle size can be obtained.
【００１５】上記したシリカ原料およびアルミナ原料は
アルカリ側で高い溶解度をもっている。しかしながら、
この溶解度の大きいｐＨ領域で両者を混合すると、珪酸
イオンおよびアルミン酸イオンなどのオキソ酸イオンの
溶解度が低下し、これらの複合物が析出してコロイド粒
子に成長したり、あるいは、シード粒子上に析出して粒
子成長が起こる。従って、コロイド粒子の析出、成長に
際して、従来法のようなｐＨ制御は不要となる。The above-mentioned silica raw material and alumina raw material have a high solubility on the alkaline side. However,
If both are mixed in the pH range where the solubility is high, the solubilities of oxo acid ions such as silicate ions and aluminate ions decrease, and these compounds precipitate and grow into colloid particles, or on the seed particles. Precipitation occurs and grain growth occurs. Therefore, when precipitating and growing the colloidal particles, pH control unlike the conventional method is not necessary.
【００１６】このようにして得られた複合酸化物ゾルの
微粒子は従来法によるコロイド粒子と異なり、前記した
大きな比表面積をもっており、従って、多孔質となる。
なお、多孔性を一層高めるために、当該複合酸化物微粒
子からアルミニウム原子の一部を選択的に除去すること
も有効である。具体的な除去方法としては、複合酸化物
中のアルミニウム原子を鉱酸や有機酸を用いて溶解除去
したり、あるいは、陽イオン交換樹脂と接触させてイオ
ン交換除去する。The fine particles of the composite oxide sol thus obtained have a large specific surface area as described above, unlike the colloidal particles obtained by the conventional method, and are therefore porous.
In order to further increase the porosity, it is also effective to selectively remove a part of aluminum atoms from the composite oxide fine particles. As a specific removal method, aluminum atoms in the composite oxide are dissolved and removed by using a mineral acid or an organic acid, or ion exchange removal is performed by contacting with a cation exchange resin.
【００１７】複合酸化物ゾルを濃縮する場合には、予め
分散液中のアルカリ金属イオン、アルカリ土類金属イオ
ンおよびアンモニウムイオン等の一部を除去した後に濃
縮する方が、安定した濃縮ゾルが得られる。除去方法と
しては、限外濾過等の公知の方法を採用する。In the case of concentrating the complex oxide sol, a stable concentrated sol can be obtained by previously removing some of the alkali metal ions, alkaline earth metal ions, ammonium ions and the like in the dispersion liquid and then concentrating. To be As a removal method, a known method such as ultrafiltration is adopted.
【００１８】上記した複合酸化物微粒子は製造過程に起
因するアルカリ金属を不可避的に微粒子内部に含んでお
り、この結果、塗布液により形成される塗膜の融点が低
下し、ガラス化温度が低下するものと思われる。The above-mentioned fine particles of complex oxide inevitably contain an alkali metal resulting from the production process inside the fine particles, and as a result, the melting point of the coating film formed by the coating solution is lowered and the vitrification temperature is lowered. It seems to do.
【００１９】本発明の塗布液は、上記の如くして得られ
た複合酸化物ゾルと低融点ガラスを混合することで得ら
れる。また、該ゾルを乾燥後、上記複合酸化物微粒子と
低融点ガラスを、水、有機溶媒またはこれらの混合溶媒
中に分散してもよい。有機溶媒としては、メタノール、
エタノール等のアルコール、エチレングリコール等の多
価アルコール、または、その他の極性を有する有機溶媒
を用いることができる。塗布液中の固形分濃度は、塗工
性の点で約１０〜６０重量％の範囲が好ましい。本発明
の塗布液は、上記した複合酸化物微粒子を含有している
ので安定性が向上する。The coating solution of the present invention can be obtained by mixing the composite oxide sol obtained as described above and a low melting point glass. Further, after drying the sol, the composite oxide fine particles and the low melting point glass may be dispersed in water, an organic solvent or a mixed solvent thereof. As the organic solvent, methanol,
An alcohol such as ethanol, a polyhydric alcohol such as ethylene glycol, or another polar organic solvent can be used. The solid content concentration in the coating liquid is preferably in the range of about 10 to 60% by weight from the viewpoint of coatability. Since the coating liquid of the present invention contains the above-mentioned composite oxide fine particles, the stability is improved.
【００２０】低融点ガラスは、本発明においてガラス質
被膜の主成分を形成ものであり、ガラスフリットなどを
用いるのが好適であるが、格別の制限はない。The low melting point glass forms the main component of the vitreous coating in the present invention, and glass frit or the like is preferably used, but there is no particular limitation.
【００２１】本発明の塗布液は、基材に塗布して、乾
燥、焼成することにより、クラックのない被膜を得るこ
とができる。当該塗布液中に、さらに、増粘剤として雲
母を含有させることにより、一層、被膜の収縮によるク
ラックを防止することができる。添加する雲母として
は、白雲母、黒雲母、セリサイトなどの天然雲母や合成
雲母を用いることができる。The coating liquid of the present invention can be applied to a substrate, dried and baked to obtain a coating film without cracks. By further containing mica as a thickener in the coating solution, cracks due to shrinkage of the coating can be further prevented. As the mica to be added, natural mica such as muscovite, biotite, sericite or synthetic mica can be used.
【００２２】なお、本発明の塗布液中には酸化防止機能
を向上させる目的で、酸化鉄等を必要により混合するこ
ともできる。If necessary, iron oxide or the like may be mixed in the coating liquid of the present invention for the purpose of improving the antioxidant function.
【００２３】上記塗布液は、炭素含有耐火物の表面にス
プレー法、ディップ法、等適宜の方法で塗布した後、乾
燥し、約９００℃以上で焼成することにより、強固な酸
化防止機能をもつガラス質被膜が形成される。The above coating solution has a strong antioxidation function by being applied to the surface of a carbon-containing refractory material by an appropriate method such as a spray method or a dip method, then dried and baked at about 900 ° C. or higher. A glassy film is formed.
【００２４】[0024]
〔複合酸化物微粒子分散ゾルの調製〕実施例１ 平均粒径５nm、ＳｉＯ2 濃度２０重量％のシリカゾル２
００ｇと純水３８００ｇの混合物を８０℃に加温した。
この反応母液のｐＨは１０．５であり、同母液にＳｉＯ
2 として１．５重量％の珪酸ナトリウム水溶液１８，０
００ｇとＡｌ2Ｏ3 として０．５重量％のアルミン酸ナ
トリウム水溶液１８，０００ｇとを同時に添加した。添
加速度は５ml／分であり、その間、反応液の温度を８０
℃に保持した。反応液のｐＨは添加直後、１２．５に上
昇し、その後、殆ど変化しなかった。添加終了後、反応
液を室温まで冷却し、限外濾過膜で固形分濃度２０重量
％まで濃縮し、ＳｉＯ2 ・Ａｌ2 Ｏ3 複合酸化物ゾルを
得た。[Preparation of complex oxide fine particle dispersed sol] Example 1 Silica sol 2 having an average particle size of 5 nm and a SiO 2 concentration of 20% by weight
A mixture of 00 g and pure water 3800 g was heated to 80 ° C.
The pH of this reaction mother liquor was 10.5, and the mother liquor contained SiO
2 as a 1.5% by weight sodium silicate aqueous solution 18,0
00 g and 18,000 g of a 0.5 wt% sodium aluminate aqueous solution as Al 2 O 3 were added at the same time. The addition rate was 5 ml / min, during which the temperature of the reaction solution was 80
Hold at ℃. Immediately after the addition, the pH of the reaction solution rose to 12.5, and thereafter hardly changed. After the addition was completed, the reaction solution was cooled to room temperature and concentrated with an ultrafiltration membrane to a solid content concentration of 20% by weight to obtain a SiO 2 · Al 2 O 3 composite oxide sol.
【００２５】この複合酸化物ゾル中に分散した微粒子の
組成、比表面積および平均粒径を表１に示す。なお、比
表面積はタイトレーション法〔Analytical Chemistry V
ol.28, No.12(1956)〕により測定し、平均粒径は動的光
散乱法により測定した。Table 1 shows the composition, specific surface area and average particle size of the fine particles dispersed in this composite oxide sol. The specific surface area is determined by the titration method [Analytical Chemistry V
ol. 28, No. 12 (1956)], and the average particle size was measured by the dynamic light scattering method.
【００２６】実施例２ 実施例１において、シリカゾルを４００ｇ用いた以外は
実施例１と同様にして、複合酸化物ゾルを得た。 Example 2 A composite oxide sol was obtained in the same manner as in Example 1 except that 400 g of silica sol was used.
【００２７】実施例３ 実施例１において、平均粒径５nmのシリカ粒子の代わり
に平均粒径２０nmのシリカ粒子が分散したシリカゾルを
用いた以外は実施例１と同様にして、複合酸化物ゾルを
得た。 Example 3 A composite oxide sol was prepared in the same manner as in Example 1 except that a silica sol in which silica particles having an average particle diameter of 20 nm were dispersed was used instead of the silica particles having an average particle diameter of 5 nm. Obtained.
【００２８】実施例４ 実施例１において、Ａｌ2 Ｏ3 として０．５重量％の代
わりに１．４重量％のアルミン酸ナトリウム水溶液を用
いた以外は実施例１と同様にして、複合酸化物ゾルを得
た。 Example 4 A composite oxide was prepared in the same manner as in Example 1 except that 1.4% by weight of sodium aluminate aqueous solution was used instead of 0.5% by weight as Al 2 O 3 . I got a sol.
【００２９】[0029]
【表１】 Al2O3/SiO2 Na2O 比表面積(S) 平均粒径(Dp) S×Dp （重量比） (wt%) （m2/g） （nm） 実施例１ 33 / 100 13.1 1100 20 22000 実施例２ 29 / 100 12.2 1000 10 10000 実施例３ 33 / 100 13.1 1050 50 52500 実施例４ 84 / 100 21.7 1150 20 23000[Table 1] Al 2 O 3 / SiO 2 Na 2 O Specific Surface Area (S ) Average Particle Size (Dp) S × Dp ( Weight Ratio ) (wt% ) ( m 2 / g ) ( nm ) Example 1 33 / 100 13.1 1100 20 22000 Example 2 29/100 12.2 1000 10 10000 Example 3 33/100 13.1 1050 50 52500 Example 4 84/100 21.7 1150 20 23000
【００３０】〔塗布液の調製〕実施例５ 実施例１で得た複合酸化物ゾル２６６ｇにガラスフリッ
ト（ホウ珪酸質ガラス）４０ｇを混合して塗布液（Ａ）
を得た。塗布液の組成を表２に示すが、同表において、
塗布液の組成欄の数値は、シリカ１００重量部に対する
組成である。[Preparation of Coating Solution] Example 5 Coating solution (A) was prepared by mixing 266 g of the composite oxide sol obtained in Example 1 with 40 g of glass frit (borosilicate glass).
Got The composition of the coating liquid is shown in Table 2.
The numerical value in the composition column of the coating liquid is the composition for 100 parts by weight of silica.
【００３１】実施例６ 実施例５において、実施例１で得た複合酸化物ゾルの代
わりに実施例２で得た複合酸化物ゾルを用いた以外は同
様にして、塗布液（Ｂ）を得た。 Example 6 A coating solution (B) was obtained in the same manner as in Example 5, except that the complex oxide sol obtained in Example 2 was used instead of the complex oxide sol obtained in Example 1. It was
【００３２】実施例７ 実施例５において、実施例１で得た複合酸化物ゾルの代
わりに実施例３で得た複合酸化物ゾルを用いた以外は同
様にして、塗布液（Ｃ）を得た。 Example 7 A coating solution (C) was obtained in the same manner as in Example 5 except that the complex oxide sol obtained in Example 3 was used instead of the complex oxide sol obtained in Example 1. It was
【００３３】実施例８ 実施例５において、実施例１で得た複合酸化物ゾルの代
わりに実施例４で得た複合酸化物ゾルを用いた以外は同
様にして、塗布液（Ｄ）を得た。 Example 8 A coating solution (D) was obtained in the same manner as in Example 5, except that the complex oxide sol obtained in Example 4 was used instead of the complex oxide sol obtained in Example 1. It was
【００３４】実施例９ 実施例５において、さらに、雲母（クニミネ工業製、ス
メクトロン−ＳＡ）５ｇを添加した以外は実施例５と同
様にして、塗布液（Ｅ）を得た。 Example 9 A coating solution (E) was obtained in the same manner as in Example 5 except that 5 g of mica (Sumiktron-SA, manufactured by Kunimine Industries Co., Ltd.) was added.
【００３５】実施例１０ 実施例５において、ガラスフリットの混合量を４ｇに変
えた以外は実施例５と同様にして、塗布液（Ｆ）を得
た。 Example 10 A coating solution (F) was obtained in the same manner as in Example 5 except that the amount of glass frit mixed was changed to 4 g.
【００３６】比較例 平均粒径１８nmのシリカ粒子が水に分散したシリカゾル
（ＳｉＯ2 濃度：４０重量％）１００ｇに、純水１００
ｇおよび実施例５のガラスフリット４０ｇを添加して、
塗布液（Ｇ）を得た。 Comparative Example 100 g of silica sol (SiO 2 concentration: 40% by weight) in which silica particles having an average particle size of 18 nm are dispersed in water are mixed with 100 parts of pure water.
g and 40 g of the glass frit of Example 5 are added,
A coating liquid (G) was obtained.
【００３７】〔耐酸化能試験〕上記実施例で得られた塗
布液について、高温酸化雰囲気における炭素含有耐火物
に対する耐酸化能試験を行った。試験は各塗布液の有す
る酸化防止効果を明確化するために、以下の方法により
実施した。[Oxidation Resistance Test] The coating solutions obtained in the above examples were subjected to an oxidation resistance test on a carbon-containing refractory in a high temperature oxidizing atmosphere. The test was carried out by the following method in order to clarify the antioxidant effect of each coating solution.
【００３８】約６０〜１００μｍに粉砕した黒鉛試料
（Ｃ：３０重量％，Ａｌ2 Ｏ3 ７０重量％）の一定量を
ルツボに採取する。これに各塗布液Ａ〜Ｇを表２に示す
割合（重量比）で加えて撹拌し、黒鉛試料が充分浸るよ
うにする。この試料を１１０℃で６０分間乾燥し、水分
を蒸発させた。このようにして得られた被覆試料を９０
０℃で３０分間焼成した。A certain amount of a graphite sample (C: 30% by weight, Al 2 O 3 70% by weight) crushed to about 60 to 100 μm is sampled in a crucible. Each of the coating liquids A to G is added to this at a ratio (weight ratio) shown in Table 2 and stirred so that the graphite sample is sufficiently immersed. The sample was dried at 110 ° C. for 60 minutes to evaporate the water content. The coated sample thus obtained is
It was baked at 0 ° C. for 30 minutes.
【００３９】焼成後の試料中の炭素量を高周波燃焼法で
測定して、式１により炭素の残存率を算出し、塗布液の
耐酸化能を評価した。試験結果を表２にまとめて示す。The amount of carbon in the sample after baking was measured by the high frequency combustion method, the carbon residual rate was calculated by the formula 1, and the oxidation resistance of the coating liquid was evaluated. The test results are summarized in Table 2.
【００４０】[0040]
【式１】炭素（Ｃ）残存率＝（焼成後の炭素重量／最初
の試料中の炭素重量）×１００[Formula 1] Carbon (C) residual rate = (weight of carbon after firing / weight of carbon in first sample) × 100
【００４１】[0041]
【表２】 塗布液の組成 耐酸化能試験 ガラス 雲母 塗布液/ 試料 Ｃ残存率 塗布液 (SiO2100重量部当り) （重量比） （重量％） Ａ 100 − 25/100 15.3 Ｂ 97 − 30/100 31.1 Ｃ 100 − 50/100 50.2 Ｄ 138 − 〃 55.3 Ｅ 100 12.5 15/100 18.5 Ｆ 10 − 40/100 10.5 Ｇ 100 − 40/100 0.10 TABLE 2 coating solution having a composition the oxidation tolerance test glass mica coating solution / sample C residual ratio coating solution (SiO 2 100 parts by weight per) (weight ratio) (weight%) A 100 - 25/100 15.3 B 97 - 30 / 100 31.1 C 100-50 / 100 50.2 D 138-〃 55.3 E 100 12.5 15/100 18.5 F 10-40 / 100 10.5 G 100-40 / 100 0.10
【００４２】[0042]
【発明の効果】本発明に係る酸化防止被膜形成用塗布液
は、耐火物表面に強固なガラス質被膜を形成することに
より、優れた酸化防止機能を発揮することができる。ま
た、比較的低温でガラス質被膜を形成することができる
という効果を有している。従って、この塗布液がコーテ
ィングされた炭素含有耐火物等は酸化雰囲気中で高温に
加熱されても、酸化されることなく、その特性が低下す
ることもない。EFFECT OF THE INVENTION The coating solution for forming an antioxidant coating according to the present invention can exhibit an excellent antioxidant function by forming a strong glassy coating on the surface of a refractory material. Further, it has an effect that a glassy film can be formed at a relatively low temperature. Therefore, even if the carbon-containing refractory coated with the coating solution is heated to a high temperature in an oxidizing atmosphere, the carbon-containing refractory is not oxidized and its characteristics are not deteriorated.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 1/00 ＰＣＮ Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display area C09D 1/00 PCN
Claims (2)
分とする複合酸化物微粒子、および低融点ガラスを含む
分散液からなることを特徴とする酸化防止被膜形成用塗
布液。 Ｓ（m2/g）≧３０００／ Dp（nm） （但し、上式において、Ｓ：複合酸化物微粒子の比表面
積（m2/g）とし、Dp：複合酸化物微粒子の平均粒径（n
m）とする。）1. A coating liquid for forming an antioxidant film, which comprises a dispersion liquid containing a composite oxide fine particle containing silica and alumina as main components and satisfying the following formula, and a low melting point glass. S (m 2 / g) ≧ 3000 / Dp (nm) (where S is the specific surface area (m 2 / g) of the composite oxide particles, and Dp is the average particle size (n
m). )
して、低融点ガラスを１０〜２００重量部含む請求項１
記載の酸化防止被膜形成用塗布液。2. The low melting point glass is contained in an amount of 10 to 200 parts by weight with respect to 100 parts by weight of the composite oxide fine particles.
The coating liquid for forming an antioxidant film as described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10339794A JP3746308B2 (en) | 1994-04-18 | 1994-04-18 | Coating liquid for forming antioxidant coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10339794A JP3746308B2 (en) | 1994-04-18 | 1994-04-18 | Coating liquid for forming antioxidant coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07291770A true JPH07291770A (en) | 1995-11-07 |
| JP3746308B2 JP3746308B2 (en) | 2006-02-15 |
Family
ID=14352933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10339794A Expired - Lifetime JP3746308B2 (en) | 1994-04-18 | 1994-04-18 | Coating liquid for forming antioxidant coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3746308B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005048170A (en) * | 2003-07-14 | 2005-02-24 | Schott Ag | Use of glass composition for achieving antioxidative effect |
| JP2006036551A (en) * | 2004-07-22 | 2006-02-09 | Mitsubishi Kagaku Sanshi Corp | Anti-oxidation agent for carbon material, carbon material having excellent anti-oxidation property and method of manufacturing the same |
| WO2008066319A1 (en) * | 2006-11-28 | 2008-06-05 | Woo-Jae Lee | Inorganic pigments composition having high hardness |
| KR100838126B1 (en) * | 2006-11-28 | 2008-06-13 | 주식회사 웰쳐화인텍 | Inorganic pigments composition having high hardness |
| JP2016180526A (en) * | 2015-03-24 | 2016-10-13 | Ｊｆｅスチール株式会社 | Manufacturing method of container for high temperature |
-
1994
- 1994-04-18 JP JP10339794A patent/JP3746308B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005048170A (en) * | 2003-07-14 | 2005-02-24 | Schott Ag | Use of glass composition for achieving antioxidative effect |
| JP2006036551A (en) * | 2004-07-22 | 2006-02-09 | Mitsubishi Kagaku Sanshi Corp | Anti-oxidation agent for carbon material, carbon material having excellent anti-oxidation property and method of manufacturing the same |
| WO2008066319A1 (en) * | 2006-11-28 | 2008-06-05 | Woo-Jae Lee | Inorganic pigments composition having high hardness |
| KR100838126B1 (en) * | 2006-11-28 | 2008-06-13 | 주식회사 웰쳐화인텍 | Inorganic pigments composition having high hardness |
| JP2016180526A (en) * | 2015-03-24 | 2016-10-13 | Ｊｆｅスチール株式会社 | Manufacturing method of container for high temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3746308B2 (en) | 2006-02-15 |
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