JP2012122056A - Aqueous solution of heat resistant/oxidation resistant coating material, and coating treatment method - Google Patents
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本発明は高温雰囲気下で使用される熱電対、発電用ボイラー水管、石油精製加熱炉金属パイプ等に使用される耐熱鋳物、ステンレス、鉄、耐熱金属の金属表面に微細な空隙を持つセラミックス被膜を形成することにより金属とセラミック被膜の膨張係数によるクラックの拡大を吸収し金属の酸化防止を可能にする耐熱・耐酸化被覆材水溶液及び被覆処理方法に関するものである。 The present invention provides a heat-resistant casting used for thermocouples, power generation boiler water pipes, petroleum refining furnace metal pipes, etc. used in high-temperature atmospheres, and ceramic coatings with fine voids on the metal surfaces of stainless steel, iron and heat-resistant metals. The present invention relates to a heat-resistant / oxidation-resistant coating material aqueous solution and a coating method that absorbs the expansion of cracks due to the expansion coefficient of the metal and the ceramic coating to prevent the metal from being oxidized.
焼却炉、焼頓炉、加熱炉、リフォーマー、ボイラー、溶融炉、内燃機関、熱交換器等の熱炉の高温に曝される耐熱鋳物、ステンレス、耐熱金属等が用いられている。特にガス化溶融炉や焼却灰溶融炉では1200℃〜1350℃の高温が掛かり炉内で使用される熱電対は極めて短時間で熱劣化による不具合が発生し熱電対の取替頻度が激しく大幅なコストアップに繋がっている。又、発電用ボイラー管では高温によりボイラー水管の酸化が発生する為、水管内の蒸気温度を抑えて運転しているのが現状であり発電効率を極めて悪くしている。 Incinerators, incinerators, heating furnaces, reformers, boilers, melting furnaces, internal combustion engines, heat-resistant castings that are exposed to high temperatures of heat furnaces such as heat exchangers, stainless steel, and heat-resistant metals are used. Especially in gasification melting furnaces and incineration ash melting furnaces, high temperatures of 1200 ° C to 1350 ° C are required, and thermocouples used in the furnaces suffer from problems due to thermal degradation in a very short time, and the frequency of replacement of thermocouples is significant. This leads to cost increase. In addition, since the boiler water pipe is oxidized at a high temperature in the power generation boiler pipe, the current situation is that the steam temperature in the water pipe is suppressed and the power generation efficiency is extremely deteriorated.
又、石油精製等に用いられる加熱炉、その他熱炉である焼頓炉、ボイラー等も同様に高温雰囲気下で使用する金属の酸化防止は避けられず頻繁に補修を行っている為、稼働効率の低下に繋がっている。 In addition, heating furnaces used in oil refining, etc., incinerators, and boilers that are thermal furnaces are also inevitable to prevent oxidation of metals used in high-temperature atmospheres. Has led to a decline.
従来の特許第3399650号耐熱・耐酸化被覆材の被覆処理方法や特願2007−299829が金属の高温酸化防止被膜として有用であるが1200℃以上の温度帯で長時間に亘り連続使用すると炉内より発生する塩基性ガスと被膜構成要素のカリウムが反応し被膜表面に塩化カリウム結晶ができこれが被覆表面に細かなクラックを発生させることが判明した。これは、金属表面に高温酸化に有用なマンガンを配合し且つ、骨材となる粉末無機耐熱材料の粒子やマンガン粒子の大きさを変えることにより高温時の焼成により緻密なセラミック被膜が形成され高温ガスが被膜内部に侵入しない構造となっている。しかし1200℃以上の高温下で長時間の連続運転では緻密なセラミック被膜は金属の膨張係数を完全に吸収することは困難で被膜表面のクラック発生は避けられない問題がある。
上記目的を達成するために本発明はアルカリ金属ケイ酸塩、ホウ酸化合物、亜鉛化合物、マイカ、及び20μm〜100μmの粒子径の範囲の所定粒径であって、粒度分布は所定粒径の±10%の粒径が90%以上である粉末無機耐熱骨材を含む金属用の耐熱・耐酸化被覆材水溶液とする。粉末無機耐熱骨材の好ましい所定粒径の範囲は30μm〜70μmであり、より好ましくは40μm〜50μmである。又、粉末無機耐熱骨材の所定粒径の±10%以外の粉末無機耐熱骨材は、所定粒径の+10%を超えるものである耐熱・耐酸化被覆材水溶液とする。
アルカリ金属ケイ酸塩とはケイ酸カリウム水溶液、ケイ酸ナトリウム水溶液、ケイ酸リチウム水溶液或いはこれらにコロイダルシリカを配合しモル比調整を行ったものを指す。又はアルカリ金属ケイ酸塩とはケイ酸カリウム水溶液、ケイ酸ナトリウム水溶液、ケイ酸リチウム水溶液単体の内の1又は2以上の要素を含むものである。或いはアルカリ金属ケイ酸塩とはケイ酸カリウム水溶液、ケイ酸ナトリウム水溶液、ケイ酸リチウム水溶液にコロイダルシリカを配合したものの内の1又は2以上の要素を含むものである。更にアルカリ金属ケイ酸塩とは夫々の単体にコロイダルシリカを配合したものの混合物の内の1又は2以上の要素を含むものである。
ホウ酸化合物とはホウ酸ナトリウム、メタホウ酸塩、ラトラホウ酸塩、ピロウホウ酸塩、ホウ酸亜鉛、四ホウ酸塩、三酸化ホウ素、五ホウ酸ナトリウム、ホウ酸アンモニウムを指し、それらの内の1又は2以上の要素を含むものである。亜鉛化合物とは酸化亜鉛、水酸化亜鉛、炭酸亜鉛、三二酸化亜鉛、ホウ酸亜鉛、珪酸亜鉛を指し、それらの内の1又は2以上の要素を含むものである。
本発明は特許第3399650号耐熱・耐酸化被覆材の被覆処理方法や特願2007−299829で使用してきたマンガンを除去し従来の特許第3399650号耐熱・耐酸化被覆材の被覆処理方法や特願2007−299829で使用してきた粉末無機耐熱骨材の粒径の大きさを20μm〜100μmの範囲とし所定粒径の±10%で90%以上としてその配合割合を変えた耐熱・耐酸化被覆材水溶液である。
粉末無機耐熱骨材とは少なくとも酸化アルミニウム、無水珪酸、酸化チタンなどの無機質高融点材料を指し、これらの内1又は2以上の要素を含む粉末の材料である。
本発明は請求項1の水溶液を使用し被処理物である金属の融点より低い温度で焼成してなることを特徴とする耐熱・耐酸化被覆材水溶液の被覆処理方法である。被処理物の金属とは熱電対、溶融炉、焼却炉、焼頓炉、加熱炉、リフォーマー、ボイラーなど熱炉や高温雰囲気下で使用される耐火鋳物、鉄、ステンレス、耐熱合金等である。これら金属に耐熱・耐酸化被覆材水溶液を塗布しセラミック被膜内に形成された空隙により金属とセラミック被膜の膨張係数を吸収させ高温酸化防止を可能にすることを特徴とする耐熱・耐酸化被覆材水溶液の被覆処理方法である。
尚、粉末無機耐熱骨材の所定粒径の設定方法は被覆する膜厚によって決定される。本発明の水溶液の焼成前の膜厚の30〜50%の粒径を所定粒径の目安とする。To achieve the above object, the present invention provides an alkali metal silicate, boric acid compound, zinc compound, mica, and a predetermined particle size in the range of 20 μm to 100 μm, and the particle size distribution is ±± of the predetermined particle size. A heat-resistant / oxidation-resistant coating material aqueous solution for metal including powdered inorganic heat-resistant aggregate having a 10% particle size of 90% or more is used. The preferable range of the predetermined particle size of the powdered inorganic heat-resistant aggregate is 30 μm to 70 μm, more preferably 40 μm to 50 μm. In addition, powder inorganic heat-resistant aggregates other than ± 10% of the predetermined particle diameter of the powdered inorganic heat-resistant aggregate should be a heat-resistant / oxidation-resistant coating material aqueous solution that exceeds + 10% of the predetermined particle diameter.
The alkali metal silicate refers to an aqueous potassium silicate solution, an aqueous sodium silicate solution, an aqueous lithium silicate solution, or a mixture prepared by adding colloidal silica to these and adjusting the molar ratio. Alternatively, the alkali metal silicate includes one or more elements of a potassium silicate aqueous solution, a sodium silicate aqueous solution, and a lithium silicate aqueous solution alone. Alternatively, the alkali metal silicate includes one or more elements among those prepared by mixing colloidal silica with an aqueous potassium silicate solution, an aqueous sodium silicate solution, or an aqueous lithium silicate solution. Further, the alkali metal silicate includes one or two or more elements in a mixture of colloidal silica blended with each simple substance.
The boric acid compound means sodium borate, metaborate, ratolaborate, pyroborate, zinc borate, tetraborate, boron trioxide, sodium pentaborate, ammonium borate, and one of them Or two or more elements are included. A zinc compound refers to zinc oxide, zinc hydroxide, zinc carbonate, zinc sesquioxide, zinc borate, zinc silicate, and includes one or more elements among them.
The present invention eliminates the manganese used in Japanese Patent No. 3399650 heat-resistant / oxidation-resistant coating material and Japanese Patent Application No. 2007-299829 and removes the manganese used in Japanese Patent Application No. 2007-299829. A heat- and oxidation-resistant coating material aqueous solution in which the particle size of the powdered inorganic heat-resistant aggregate used in 2007-299829 is in the range of 20 μm to 100 μm and the blending ratio is changed to 90% or more at ± 10% of the predetermined particle size. It is.
The powdered inorganic heat-resistant aggregate refers to an inorganic high-melting-point material such as at least aluminum oxide, silicic anhydride, or titanium oxide, and is a powder material containing one or more of these elements.
The present invention is a coating treatment method for an aqueous solution of heat- and oxidation-resistant coating material, characterized in that the aqueous solution of claim 1 is used for firing at a temperature lower than the melting point of the metal to be treated. Examples of the metal to be treated include thermocouples, melting furnaces, incinerators, incinerators, heating furnaces, reformers, boilers and the like, refractory castings, iron, stainless steel, heat-resistant alloys and the like used in high-temperature atmospheres. A heat and oxidation resistant coating material characterized in that an aqueous solution of a heat and oxidation resistant coating material is applied to these metals and the expansion coefficient of the metal and the ceramic coating is absorbed by voids formed in the ceramic coating to prevent high temperature oxidation. This is a coating method for an aqueous solution.
In addition, the setting method of the predetermined particle diameter of a powder inorganic heat resistant aggregate is determined by the film thickness to coat | cover. A particle size of 30 to 50% of the film thickness of the aqueous solution of the present invention before firing is used as a guide for the predetermined particle size.
本発明によれば、アルカリ金属ケイ酸塩化合物の液相と粉末無機耐熱骨材である酸化アルミニウム、無水珪酸、酸化チタンなどの固相に熱が掛かることにより液相焼結が起こり通常の難焼結性物質も液相の助けにより極めて早く焼結する。更には触媒的な役目を果たすホウ酸化合物、亜鉛化合物を配合することにより粉末無機耐熱骨材を金属の融点以下の温度で溶融させ被処理物に被覆させる事ができる。アルカリ金属ケイ酸塩化合物水溶液は塗料化して被処理物への塗布を容易にすると共に粉末無機耐熱骨材が溶融する一定の温度帯まで接着剤として被処理物の表面にガラス状被膜として高温腐食ガスの侵入防止及び耐酸化防止の役目を果たす。マイカは高温雰囲気下に於ける耐熱・耐酸化材被覆形成時に発生しやすいクラック防止のために用いられる。セラミック化合物からなる粉末無機耐熱骨材は粒径を同じような大きさにすることにより被膜内部に微細な空隙ができ、この空隙で膨張係数の違いを吸収しクラックの拡大を防止する。 According to the present invention, liquid phase sintering occurs due to heat applied to the liquid phase of the alkali metal silicate compound and the solid phase of the powdered inorganic heat-resistant aggregate such as aluminum oxide, anhydrous silicic acid, titanium oxide, etc. Sinterable materials also sinter very quickly with the help of the liquid phase. Further, by blending a boric acid compound and a zinc compound that play a catalytic role, the powdered inorganic heat-resistant aggregate can be melted at a temperature below the melting point of the metal and coated on the object to be treated. The aqueous solution of alkali metal silicate compound is made into a paint to facilitate the application to the object to be treated, and at the same time the adhesive is heated up to a certain temperature zone where the powdered inorganic heat-resistant aggregate melts. It plays the role of preventing gas intrusion and preventing oxidation. Mica is used to prevent cracks that are likely to occur during the formation of heat and oxidation resistant coatings in a high temperature atmosphere. The powder inorganic heat-resistant aggregate made of a ceramic compound has the same particle size, thereby forming fine voids inside the coating, which absorbs the difference in expansion coefficient and prevents the expansion of cracks.
請求項3に関し、請求項1及び請求項2の耐熱・耐酸化被覆材水溶液に明記された粉末材料と所定の濃度に調整したアルカリ金属ケイ酸塩化合物を目的の被処理物に応じて配合し(表1)、耐熱・耐酸化被覆材水溶液を作成する。この時、粉末材料がダマにならないよう良く攪拌して耐熱・耐酸化被覆材水溶液を処方する。被処理物である金属に塗布する場合はスプレーガン、刷毛、ローラーなどの使用が可能だが、スプレーガン塗布が効率的である。塗布後、十分に自然乾燥するか或いは低温にて強制乾燥を行った後、耐熱・耐酸化被覆材被膜内に含まれる水分を十分乾燥させた後アルカリ金属ケイ酸塩化合物が強固なシロキサン結合となる物温200℃以上で20〜30分仮焼成する。この段階で空気中の水分を吸着してチョーキングを起こすことはなく長期保管が可能となる。又仮焼成しておくことにより、いきなり温度を上昇させても形成被覆が被処理物と剥離、割れ、クラックを生じない。 Regarding claim 3, the powder material specified in the heat-resistant and oxidation-resistant coating material aqueous solution of claim 1 and claim 2 and an alkali metal silicate compound adjusted to a predetermined concentration are blended according to the object to be treated. (Table 1) A heat-resistant / oxidation-resistant coating material aqueous solution is prepared. At this time, the heat-resistant / oxidation-resistant coating material aqueous solution is formulated by stirring well so that the powder material does not become lumps. A spray gun, brush, roller, etc. can be used when applying to the metal to be processed, but spray gun application is efficient. After coating, it is naturally dried or forcedly dried at a low temperature, and after the moisture contained in the heat and oxidation resistant coating film is sufficiently dried, the alkali metal silicate compound has a strong siloxane bond. Pre-baking is performed at a temperature of 200 ° C. or higher for 20 to 30 minutes. At this stage, moisture in the air is not adsorbed to cause choking and can be stored for a long time. Further, by pre-baking, even if the temperature is suddenly increased, the formed coating does not peel off, break or crack from the object to be processed.
本発明は高温雰囲気下で使用される耐熱金属として、耐熱鋳物、耐熱鋼管、耐熱合金などニッケル、炭素、クロム、タングステン他等の耐蝕性素材を使用しているが高価であること、元々如何なる金属であっても高温雰囲気下での酸化を止めることはできない。又、1200℃を超える高温下では如何なる金属でも耐久性に欠ける。従い本発明の耐熱・耐酸化被覆材水溶液である非酸化性のセラミック化合物被覆で且つ膨張係数を吸収する被覆材を用いれば金属表面での酸化防止することができる。従い現在使用されている耐熱金属の耐用期間を延長し使用することを可能にすると共に、これまで高温雰囲気下で使用できなかった鉄、ステンレスなどの金属も条件により使用可能となる。 The present invention uses a corrosion-resistant material such as heat-resistant casting, heat-resistant steel pipe, heat-resistant alloy such as nickel, carbon, chromium, tungsten, etc. as a heat-resistant metal used in a high-temperature atmosphere. Even so, the oxidation in a high temperature atmosphere cannot be stopped. Further, any metal lacks durability at a high temperature exceeding 1200 ° C. Therefore, if a coating material that is a non-oxidizing ceramic compound coating and is an aqueous solution of the heat-resistant / oxidation-resistant coating material of the present invention and that absorbs the expansion coefficient, oxidation on the metal surface can be prevented. Accordingly, it is possible to extend the useful life of currently used refractory metals and use metals such as iron and stainless steel that could not be used in a high temperature atmosphere until now.
以下、本発明を具体化した実施例につき説明し、本発明の理解に供する。尚、以下の実施例は本発明を具体化した一例であって、本発明の技術的範囲を限定するものではない。表1は実施例1に係わる耐熱・耐酸化被覆材水溶液を構成する材料の配合比率を示すもので、ごみのガス化溶融炉に使用する熱電対のSUS316製保護管の表面に塗布し割れ、クラック、熱電対の保護管の高温酸化による不具合発生期間を検証したものである。又、その使用方法について明記したものである。 Examples of the present invention will be described below for understanding of the present invention. It should be noted that the following example is an example embodying the present invention, and does not limit the technical scope of the present invention. Table 1 shows the blending ratio of the materials constituting the heat-resistant / oxidation-resistant coating material aqueous solution according to Example 1, which was applied to the surface of a SUS316 protective tube of a thermocouple used in a gasification melting furnace for garbage, This is a verification of the period of failure due to high temperature oxidation of cracks and thermocouple protection tubes. It also specifies how to use it.
金属用耐熱・耐酸化被覆材水溶液
表1のごとく、無機耐熱骨材他の粉末材料を所定の配合比率にて夫々計量し粉末混合機にて全体が良く混ざるように攪拌した。アルカリ金属ケイ酸塩化合物であるケイ酸カリウム液は所定の濃度に希釈調整する。粉末材料混合物が所定の濃度に調整したケイ酸カリウム液内でダマにならないように良く攪拌した。特に金属に使用する場合は水溶液中の粉末粒子同士をできるだけ分散するようにプラスチック容器に耐熱・耐酸化被覆材水溶液とアルミナビーズを入れシェーカーにて良く分散する方がよりきめ細かな被膜の形成を可能にする事が判明した。
粉末材料混合物とケイ酸カリウム液を混合して放置すると硬化現象を起こす為、施工前に混合攪拌する。As shown in Table 1, inorganic heat-resistant aggregates and other powder materials were weighed at a predetermined blending ratio and stirred by a powder mixer so that the whole was well mixed. The potassium silicate solution, which is an alkali metal silicate compound, is diluted to a predetermined concentration. The powder material mixture was stirred well so as not to become lumps in the potassium silicate solution adjusted to a predetermined concentration. In particular, when used for metals, it is possible to form a finer film by placing an aqueous solution of heat- and oxidation-resistant coating material and alumina beads in a plastic container and dispersing well with a shaker so that the powder particles in the aqueous solution are dispersed as much as possible. It turned out to be.
Mixing and stirring before construction will cause a hardening phenomenon if the powder material mixture and potassium silicate liquid are mixed and allowed to stand.
耐熱・耐酸化被覆材の被覆処理方法
表1の材料を使用して作成した耐熱・耐酸化被覆材水溶液をスプレーガン、刷毛、ローラー等で被処理物に塗布する。被覆の厚みは50μmから200μmが適当である。50μm以下では耐酸化防止には十分でなく200μm以上では冷却時に金属との膨張収縮の違いによりクラック、割れの可能性がある。試験を行った結果80μm〜120μmが最も安定した被覆厚みで金属の膨張係数の吸収及び酸化防止に最も有効な膜厚である事が判明した。塗布に際してはスプレーガンにて満遍なく塗布し表面が乾燥してから重ね塗布を4〜5回或いは所定の被覆の厚みが得られるまで塗布する。塗布後は自然乾燥か、低温強制乾燥或いは冷風にて塗布被覆内の水分を十分蒸発させてから焼成炉内で徐々に昇温させながら物温200℃で20〜30分程度仮焼成し安定化処理する。
安定化処理を施すことによりチョーキングを起こさず長期間の保存が行える。Coating method of heat and oxidation resistant coating material An aqueous solution of heat and oxidation resistance coating material prepared using the materials shown in Table 1 is applied to an object to be treated with a spray gun, brush, roller or the like. The thickness of the coating is suitably 50 μm to 200 μm. If it is 50 μm or less, it is not sufficient for preventing oxidation, and if it is 200 μm or more, there is a possibility of cracking or cracking due to the difference in expansion and contraction from the metal during cooling. As a result of testing, it was found that 80 μm to 120 μm is the most effective film thickness for absorption of metal expansion coefficient and oxidation prevention with the most stable coating thickness. In the application, it is applied evenly with a spray gun, and after the surface is dried, the application is repeated 4 to 5 times or until a predetermined coating thickness is obtained. After coating, it is naturally dried, or it is stabilized by temporarily baking at a temperature of 200 ° C for about 20 to 30 minutes while allowing the moisture in the coating to sufficiently evaporate with low-temperature forced drying or cold air, and then gradually raising the temperature in a baking furnace. To process.
By performing the stabilization treatment, it can be stored for a long time without causing choking.
「従来例との比較」
N市クリーンセンターの3系ガス化溶融炉の第一燃焼室(1200℃〜1350℃)で使用される熱電対(SUS316製保護管)に表1の通り配合した被覆材を施した熱電対と特許文献2の特願2007−299829の表2を施した熱電対を設置し、1系ガス化溶融炉の第一燃焼室には何も処理を施さなかった熱電対を設置し耐久性を比較した。
非処理熱電対は、設置後9日間で熱電対先端が溶解し不具合発生したが表2を処方した熱電対と表1を処方した熱電対は合計で36日間使用可能となった。
然し、これらの被膜表面と被膜断面を解析した結果、表2を処方した熱電対は表1を処方した被膜に比べクラック量が多く、クラック巾や深度も大きいことが判明した。炉を一旦停止し再稼働をした場合には表2を処方した熱電対は表1を処方した熱電対も同時期に不具合の発生を見たが、炉停止を行わず更に長期間の連続運転を行った場合には表2を処方した熱電対の方が表1を処方した熱電対より耐久性に欠けると思われた。
表2を処方した熱電対と表1を処方した熱電対の比較を図1〜図4に示す。
図1は被膜表面に炉内より発生した塩基性ガスと被膜内部に元より含まれるカリウムは化学結合し塩化カリウムが生成され、この塩化カリウム部分よりクラックが発生して入る。
図2は塩化カリウムの生成がきわめて少なく被膜表面にはクラックの発生が見られない。
図3は被膜断面で緻密な被膜が形成されているが被膜の中程までクラックが成長している。
図4は被膜断面内部に多くの微細な空隙が形成されており被膜にクラックは見られない。"Comparison with conventional examples"
A thermocouple with a coating material blended as shown in Table 1 in a thermocouple (SUS316 protective tube) used in the first combustion chamber (1200 ° C to 1350 ° C) of the N-system clean center system 3 gasification melting furnace; The thermocouple which gave Table 2 of Japanese Patent Application No. 2007-299829 of patent document 2 was installed, and the thermocouple which did not perform any treatment was installed in the 1st combustion chamber of 1 system gasification melting furnace, and the durability was compared. did.
The untreated thermocouple was melted at the tip of the thermocouple 9 days after installation, but the thermocouple prescribed in Table 2 and the thermocouple prescribed in Table 1 were usable for a total of 36 days.
However, as a result of analyzing the coating surface and the coating cross section, it was found that the thermocouple prescribed in Table 2 had a larger amount of cracks and a larger crack width and depth than the coating prescribed in Table 1. When the furnace was temporarily shut down and restarted, the thermocouples prescribed in Table 2 were found to have malfunctioned at the same time as the thermocouples prescribed in Table 1, but the furnace was not shut down and operated for a longer period of time. It was considered that the thermocouple formulated in Table 2 lacked durability compared to the thermocouple formulated in Table 1.
A comparison between the thermocouple prescribed in Table 2 and the thermocouple prescribed in Table 1 is shown in FIGS.
In FIG. 1, the basic gas generated from the furnace inside the coating surface and the potassium originally contained inside the coating are chemically bonded to form potassium chloride, and cracks are generated from the potassium chloride portion.
In FIG. 2, the generation of potassium chloride is very small, and no cracks are observed on the coating surface.
In FIG. 3, a dense film is formed on the film cross section, but cracks grow to the middle of the film.
In FIG. 4, many fine voids are formed inside the cross section of the film, and no cracks are seen in the film.
表1に於いて示す金属用に供する各構成材料の配合比率において、ホウ酸化合物、亜鉛化合物であるホウ酸亜鉛、マイカ、アルカリケイ酸塩化合物は置き換えることのできない材料である、使用目的である金属の高温酸化防止の対策目的により粉末無機耐熱骨材である酸化アルミニウム、無水珪酸、酸化チタンの粉末材料はこの配合内の1又は2以上の材料の要素或いはこれ以外の耐熱無機材料であっても使用できる。これ以外の耐熱無機材料とは例えば酸化ジルコニウムやマグネシウム化合物である。ホウ酸亜鉛は高温溶融材料で粉末無機耐熱骨材の酸化アルミニウム、無水珪酸、酸化チタン等の溶融点を下げる触媒として有用であり、アルカリ金属ケイ酸塩化合物であるケイ酸カリウム水溶液は液相焼結の粒子再配列や高融点材料が被処理物である耐火物と結合するまでの接着効果を発揮し温度が200℃でシロキサン結合によりガラス化することで高温腐食ガスの進入を防ぐ役目を果たしている。又アルカリ金属ケイ酸塩化合物であるケイ酸カリウム水溶液は単体のみならずケイ酸ナトリウム水溶液、ケイ酸リチウム水溶液との混合物、或いはコロイダルシリカを配合して使用することも可能である。In the compounding ratio of each constituent material used for metal shown in Table 1, boric acid compounds, zinc borate zinc borate, mica, and alkali silicate compounds are materials that cannot be replaced, and are intended for use. For the purpose of preventing high-temperature oxidation of metals, powdered inorganic heat-resistant aggregates such as aluminum oxide, silicic anhydride, and titanium oxide are one or more elements of the material in this composition or other heat-resistant inorganic materials. Can also be used. Other heat resistant inorganic materials are, for example, zirconium oxide and magnesium compounds. Zinc borate is a high-temperature melting material that is useful as a catalyst for lowering the melting point of powdered inorganic heat-resistant aggregates such as aluminum oxide, anhydrous silicic acid, and titanium oxide. It acts to prevent the invasion of high temperature corrosive gas by virtue of the effect of adhesion until the particles are rearranged and the high melting point material is bonded to the refractory material to be processed, and is vitrified by siloxane bonding at a temperature of 200 ° C. Yes. Moreover, the potassium silicate aqueous solution which is an alkali metal silicate compound can be used not only as a simple substance but also as a mixture with a sodium silicate aqueous solution, a lithium silicate aqueous solution, or colloidal silica.
アルカリ金属ケイ酸塩化合物であるケイ酸カリウム水溶液の濃度は所定の濃度(23〜28重ボーメ液)より高くしても、低くしても使用可能である。所定濃度(23〜28重ボーメ液)より高くすればするほど粉末材料との混合に於いて均一に混ざりにくく、又低くすればするほどシロキサン結合に於けるガラス被膜の厚みが薄くなり被膜形成上好ましくない。又、アルカリ金属ケイ酸塩化合物であるケイ酸カリウム水溶液と粉末無機耐熱骨材を含む粉末材料の配合比率は被処理物の性状と、使用目的、使用条件により異なるが概ねアルカリ金属ケイ酸塩化合物であるケイ酸カリウム30〜70%重量比:粉末無機耐熱骨材を含む粉末材料70〜30%重量比の範囲が適当である。 The concentration of the aqueous solution of potassium silicate that is an alkali metal silicate compound can be higher or lower than a predetermined concentration (23 to 28 double Baume solution). When the concentration is higher than a predetermined concentration (23-28 double Baume solution), it is harder to mix uniformly with the powder material, and as the concentration is lower, the thickness of the glass coating at the siloxane bond becomes thinner. It is not preferable. Moreover, the mixing ratio of the powdered material containing the potassium silicate aqueous solution, which is an alkali metal silicate compound, and powdered inorganic heat-resistant aggregate varies depending on the properties of the material to be treated, the purpose of use, and the use conditions, but it is generally an alkali metal silicate compound. A suitable range is 30 to 70% weight ratio of potassium silicate: 70 to 30% weight ratio of powder material including powdered inorganic heat-resistant aggregate.
表1に於いて示す被処理物の金属に供する各構成材料の配合比率においてアルカリ金属ケイ酸塩化合物であるケイ酸カリウム、ホウ酸化合物、マイカは置き換えることのできない材料である。ホウ酸化合物であるホウ酸亜鉛は酸化亜鉛、水酸化亜鉛、炭酸亜鉛、三二酸化亜鉛、珪酸亜鉛の内の1又は2以上の要素に置き換える事ができる、粉末無機耐熱骨材である酸化アルミニウム、無水珪酸、酸化チタンは使用条件の耐熱温度をはじめ、使用する目的により酸化アルミニウム、無水珪酸、酸化チタン等の粉末無機耐熱骨材はこの配合内の1又は2以上の材料の要素であれば使用できる。又酸化ジルコニウムやマグネシウム化合物である酸化マグネシウム、ホウ酸マグネシウム、硫酸マグネシウム、フッ化マグネシウムの内の1又は2以上の要素を追加することも可能である。ホウ酸亜鉛は粉末無機耐熱骨材である酸化アルミニウム、無水珪酸、酸化チタン等の溶融点を下げる触媒として有用であり、アルカリ金属ケイ酸塩化合物であるケイ酸カリウムは液相焼結の粒子配列により非常に速く緻密化し高融点材料が被処理物と結合するまでの接着効果を発揮しガラス化になることにより高温酸素雰囲気下で被処理物の酸化を防ぐ、又アルカリ金属ケイ酸塩化合物であるケイ酸カリウムは単体のみならずケイ酸ナトリウムとの混合物、或いはコロイダルシリカとケイ酸カリウム、又はこれにケイ酸ナトリウムなどを配合して使用することも可能である。特にシロキサン結合をより強固にするにはアルカリ金属ケイ酸塩化合物のケイ酸(シリカ)とアルカリ金属のモル比を上げる為にシリカ粉末やコロイダルシリカなどを配合する事ができる。 In the blending ratio of each constituent material used for the metal of the object to be processed shown in Table 1, the alkali metal silicate compounds potassium silicate, boric acid compound and mica are materials that cannot be replaced. Zinc borate, which is a boric acid compound, can be replaced with one or more elements of zinc oxide, zinc hydroxide, zinc carbonate, zinc sesquioxide, zinc silicate, aluminum oxide, which is a powder inorganic heat-resistant aggregate, Silicic anhydride, titanium oxide, including heat-resistant temperature of use conditions, depending on the purpose of use, powder inorganic heat-resistant aggregates such as aluminum oxide, anhydrous silicic acid, titanium oxide can be used as long as they are elements of one or more materials in this composition it can. It is also possible to add one or more elements among zirconium oxide and magnesium compounds such as magnesium oxide, magnesium borate, magnesium sulfate, and magnesium fluoride. Zinc borate is useful as a catalyst to lower the melting point of powdered inorganic heat-resistant aggregates such as aluminum oxide, anhydrous silicic acid, titanium oxide, etc., and potassium silicate, an alkali metal silicate compound, is a particle arrangement for liquid phase sintering. This prevents the oxidation of the workpiece in a high-temperature oxygen atmosphere by virtue of its vitrification and the adhesion effect until the refractory material is bonded to the workpiece by densification very quickly, and with an alkali metal silicate compound. Certain potassium silicates can be used not only as a simple substance but also as a mixture of sodium silicate, colloidal silica and potassium silicate, or sodium silicate and the like. In particular, in order to strengthen the siloxane bond, silica powder, colloidal silica, or the like can be blended in order to increase the molar ratio of silicic acid (silica) of the alkali metal silicate compound to the alkali metal.
アルカリ金属ケイ酸塩化合物であるケイ酸カリウム水溶液の濃度は所定の濃度より高くしても、低くしても使用可能である。所定濃度より高くすればするほど粉末材料との混合に於いて均一に混ざりにくく、又低くすればするほどシロキサン結合に於けるガラス被膜の厚みが薄くなり被膜形成上好ましくない。又、アルカリ金属ケイ酸塩化合物であるケイ酸カリウム水溶液と粉末無機耐熱骨材を含む粉末材料の配合比率は被処理物の性状と、使用目的、使用条件により異なるが概ねアルカリ金属ケイ酸塩化合物であるケイ酸カリウム30〜70%重量比:粉末無機耐熱骨材を含む粉末材料70〜30%重量比の範囲が適当である。 The concentration of the aqueous solution of potassium silicate that is an alkali metal silicate compound can be higher or lower than a predetermined concentration. The higher the concentration is, the more difficult it is to mix uniformly with the powder material, and the lower the concentration, the thinner the glass coating at the siloxane bond, which is not preferable for coating formation. Moreover, the mixing ratio of the powdered material containing the potassium silicate aqueous solution, which is an alkali metal silicate compound, and powdered inorganic heat-resistant aggregate varies depending on the properties of the material to be treated, the purpose of use, and the use conditions, but it is generally an alkali metal silicate compound. A suitable range is 30 to 70% weight ratio of potassium silicate: 70 to 30% weight ratio of powder material including powdered inorganic heat-resistant aggregate.
請求項1及び請求項2の組み合わせによる各材料構成とその被覆処理方法により処理されるが金属はその種類により点移転が異なり温度上昇時、或いは降下時に於いて大きな膨張収縮が起こる。この膨張係数の問題点を「実施例1」で検証している。この膨張係数を吸収するには粉末無機耐熱骨材は20μm〜100μmの粒径の範囲の所定粒径であって、粒度分布は所定粒径の±10%の粒径が90%以上であって、粉末無機骨材の所定粒径の±10%以外の粉末無機骨材は所定粒径の+10%を超えるものである粒径にすることにより被膜内部に微細な空隙を多く作り、被膜表面にクラックが入った場合でもクラックは金属表面迄達せず高温ガスの侵入を防いでいることが実証された。
尚、表4に本発明の耐熱・耐酸化被覆材水溶液の配分割合を示す。
好ましくは 粉末材料 40〜70w% ;アルカリ金属ケイ酸塩化合物 70〜30w%
より好ましくは 粉末材料 45〜65w% ;アルカリ金属ケイ酸塩化合物 55〜35w%
である。
粉末無機骨材の酸化アルミニウム(Al2O3)、無水珪酸(二酸化珪素)(SiO2)、酸化チタン(TiO2)の所定粒径は20〜100μmである。又、粒度分布は所定粒径の±10%が90%以上で、その他の粒子は所定粒径の+10%を超える粒径である。The materials are processed by the combination of claim 1 and claim 2 and the coating method, but the point transfer of the metal differs depending on the type, and large expansion and contraction occur when the temperature rises or falls. The problem of this expansion coefficient is verified in “Example 1”. In order to absorb this expansion coefficient, the powdered inorganic heat-resistant aggregate has a predetermined particle size in the range of 20 μm to 100 μm, and the particle size distribution is 90% or more with a particle size of ± 10% of the predetermined particle size. The powder inorganic aggregate other than ± 10% of the predetermined particle size of the powdered inorganic aggregate has a particle size that exceeds + 10% of the predetermined particle size, thereby creating many fine voids inside the coating, It was proved that cracks did not reach the metal surface even when cracks occurred, preventing high temperature gas from entering.
Table 4 shows the distribution ratio of the heat-resistant / oxidation-resistant coating material aqueous solution of the present invention.
More preferably, powder material 45-65 w%; alkali metal silicate compound 55-35 w%
It is.
The predetermined particle sizes of aluminum oxide (Al 2 O 3), anhydrous silicic acid (silicon dioxide) (SiO 2), and titanium oxide (TiO 2) of the powdered inorganic aggregate are 20 to 100 μm. In addition, the particle size distribution is such that ± 10% of the predetermined particle size is 90% or more, and other particles have a particle size exceeding + 10% of the predetermined particle size.
産業上の利用可能性については、特に産業廃棄物焼却炉、行政の焼却炉、焼頓炉、加熱炉、リホーマー、ボイラー等のあらゆる熱炉の高温雰囲気環境下に於いて使用される金属として例えば、熱電対、発電用ボイラー管、焼却炉の火格子、熱交換器パイプ、加熱炉のパイプ、焼頓炉釜、その他タービンケースや内燃機関等の金属材料の耐酸化防止と耐久性の向上及びそれによるコストダウン。 Regarding industrial applicability, as metals used in high-temperature atmosphere environments of all heat furnaces such as industrial waste incinerators, administrative incinerators, incinerators, heating furnaces, reformers, boilers, etc. , Anti-oxidation prevention and improvement of durability of metal materials such as thermocouples, boiler tubes for power generation, grate of incinerators, heat exchanger pipes, heating furnace pipes, incinerator furnaces, and other turbine cases and internal combustion engines Cost reduction by it.
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