JP2009120406A - Thermal spraying material - Google Patents
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本発明は、工業炉、金属溶融容器の耐火物損耗部位の補修に使用する溶射材料であり、その材料に含まれる金属粒子の酸化発熱反応により、耐火性粒子、低融点粒子を溶融し、被補修体に溶着させる溶射材料で、工業炉、金属溶融容器の中でも、特に珪石れんがを使用しているコークス炉炭化室の補修に適している。 The present invention is a thermal spray material used for repairing a refractory worn part of an industrial furnace or a metal melting container, and the refractory particles and low melting point particles are melted by an oxidation exothermic reaction of the metal particles contained in the material. It is a thermal spray material that is welded to the repair body, and is suitable for repairing coke oven carbonization chambers that use silica brick, among industrial furnaces and metal melting vessels.
製鉄所のコークス炉は、建設してから２０年以上のものが多く、特に炭化室の壁の補修が必要である。その補修に操業しながら補修する技術として溶射補修法がある。そして、溶射補修法には、プラズマ溶射、レーザー溶射、火炎溶射があるが、いずれも大掛かりな装置が必要である。 Many steelworks coke ovens have been built for over 20 years, and especially the walls of the carbonization chamber need to be repaired. There is a thermal spray repair method as a technique for repairing while operating in the repair. Thermal spray repair methods include plasma spraying, laser spraying, and flame spraying, all of which require large-scale equipment.
一方、テルミット反応等の金属粉の酸化燃焼反応熱で耐火粒子を溶融させ、補修面に溶着させる方法がある。この方法は、金属粒子と耐火粒子の混合物を酸素で高熱の補修面に吹き付け、金属粒子の酸化反応熱で耐火粒子を溶融して溶着させる方式であるため、装置が簡易である特徴を有する。 On the other hand, there is a method in which refractory particles are melted by heat of oxidation combustion reaction of metal powder such as thermite reaction and welded to the repair surface. This method has a feature that the apparatus is simple because a mixture of metal particles and refractory particles is sprayed on the repair surface heated with oxygen to heat and the refractory particles are melted and welded by heat of oxidation reaction of the metal particles.
コークス炉は珪石れんがで作られており、珪石れんがの主成分はトリジマイトであるが、炭化室は１３００℃位になるので、壁の損傷部位はクリストバライト化していることが多い。石炭を蒸し焼きにしてコークスにする炭化室の扉近くは、できたコークスを押し出す際、扉を開閉するので１３００℃位から９００℃位の温度変化がある。 The coke oven is made of silica brick, and the main component of the silica brick is tridymite, but since the carbonization chamber is around 1300 ° C, the damaged part of the wall is often cristobalite. There is a temperature change from about 1300 ° C to about 900 ° C near the door of the carbonization chamber where steamed coal is coke to make coke because the door is opened and closed when coke is made.
また、炭化室を補修する際には、扉を長時間開けておくので、４００℃近くまで冷やされることもある。炭化室壁の珪石れんがと溶射補修施工体の熱間膨張率が大幅に違うと、これらの温度変化により、溶射補修施工体が壁れんがから剥離し、耐用性が劣る。 Further, when repairing the carbonization chamber, the door is kept open for a long time, so that it may be cooled to close to 400 ° C. If the thermal expansion coefficient of the silica brick of the carbonization chamber wall and the thermal spray repair construction body are significantly different, these thermal changes cause the thermal spray repair body to peel from the wall brick, resulting in poor durability.
特開２０００−１５９５７９では、珪石またはシャモットにコーディライトを添加することにより、熱間膨張率を小さくしているが、１２００℃以上ではコーディライトが分解しはじめて、膨張率が大きくなり、剥離しやすくなる。 In Japanese Patent Laid-Open No. 2000-159579, the cordierite is added to silica stone or chamotte to reduce the hot expansion coefficient, but at 1200 ° C. or higher, the cordierite begins to decompose, the expansion coefficient increases, and it is easy to peel off. Become.
特公平５−２１８６５では、耐火性粒体の少なくともいくらかが、ケルビン温度で表した融点の０．７倍を超える温度まで前もって焼成されたものを使用する。すなわち、シリカ系ではトリジマイトやクリストバライトを使用しているが、溶射により溶融された部位はガラス化し、これが徐々に結晶化するとき、れんがと溶射補修施工体の膨張が違い、接着強度を低下させる。これを防止または抑制するためには、溶射後できるだけ早く結晶化させることが重要である。
また、特開２００５−３３６００１では、未焼成の珪石または珪砂を使用して熱膨張率の差を小さくしているが、被補修面との熱膨張率をより近づけることが望まれる。
In Japanese Examined Patent Publication No. 5-21865, at least some of the refractory particles are pre-fired to a temperature exceeding 0.7 times the melting point expressed in Kelvin temperature. That is, although tridymite and cristobalite are used in the silica system, the part melted by thermal spraying is vitrified, and when this gradually crystallizes, the expansion of the brick and the thermal spray repair construction body is different, and the adhesive strength is lowered. In order to prevent or suppress this, it is important to crystallize as soon as possible after spraying.
In JP-A-2005-336001, the difference in thermal expansion coefficient is reduced by using unfired silica or silica sand, but it is desirable to make the thermal expansion coefficient closer to the repaired surface.
また、溶融されたシリカをできるだけ早く結晶化させるために、結晶化促進剤を添加することが有効である。しかし、Ａｌ2Ｏ3が結晶化を阻害するため、溶融部位にＡｌ2Ｏ3ができるだけ入らないようにすることが望ましい。したがって、溶融しやすい微粉にＡｌ2 Ｏ3を含有したものや、燃焼してＡｌ2Ｏ3になるＡｌを含有した燃焼剤を用いない方がよく、特公平５−２１８６５、特開平５−１７２３７、特開２０００−１５９５７９では結晶化促進剤を添加していなく、金属アルミニウムやＡｌを含有する合金等を用いているので結晶化にとって好ましくない。 In order to crystallize the fused silica as soon as possible, it is effective to add a crystallization accelerator. However, since Al 2 O 3 inhibits crystallization, it is desirable to prevent Al 2 O 3 from entering the melted portion as much as possible. Therefore, it is better not to use Al 2 O 3 contained in fine powder that is easy to melt or a combustion agent containing Al that burns to become Al 2 O 3 , as disclosed in Japanese Patent Publication No. 5-21865 and Japanese Patent Laid-Open No. 5-17237. JP-A-2000-159579 is not preferable for crystallization because a crystallization accelerator is not added and metal aluminum, an alloy containing Al, or the like is used.
金属類を補修壁面の熱で着火させ、その燃焼熱で耐火物粒子を溶融させる方式の溶射では、耐火物粒子である珪石（クリストバライトの融点：１７１０℃、トリジマイトの融点：１６７０℃）等の融点が高いため、れんが目地等を溶射補修する時などの溶射速度が速い場合、耐火物粒子が溶けきらなく、リバウンドが多くなる。このため、低融点物を添加すると付着率が向上する。しかし、低融点物はそれが溶融するとき融解熱を必要とし、融点付近で吸熱する。このため、着火温度である６００〜９００℃に融点のあるものでは、着火を阻害し、かえって付着を悪くする。
近年のコークス炉は、使用条件の過酷化や炉寿命の長期延命化といった要求があり、従来の補修材より長寿命化が要求される。コークス炉の炭化室は、冷たい石炭粉を入れ、それを蒸し焼きにしてコークスにするため加熱冷却が繰り返される。 Recent coke ovens have demands such as severer use conditions and longer life of the furnace, and longer life is required than conventional repair materials. The coking oven is heated and cooled repeatedly in order to put cold coal powder and steam it into coke.
コークス炉の炭化室に使用されている珪石れんがと補修材の熱膨張を近似させることで、長期間使用時のれんが面からの剥離損耗を抑制できる。また、溶射直後は材料が溶融してガラス化しているが、これが結晶化するとき膨張があり、その膨張がれんがと補修材の接着強度を低下させる。これを防止または抑制するためには、溶射と同時に結晶化させることが重要である。 By approximating the thermal expansion of silica bricks and repair materials used in the carbonization chamber of the coke oven, it is possible to suppress delamination wear from the brick surface during long-term use. Further, although the material is melted and vitrified immediately after spraying, it expands when it crystallizes, and the expansion reduces the adhesive strength of the brick and the repair material. In order to prevent or suppress this, it is important to crystallize simultaneously with thermal spraying.
また、コークス炉の炭化室の補修は、操業上補修に要する時間が限られているため、溶射補修時間は短い方が良い。特に、れんが目地等の溶射補修は溶射遠度が速いため、耐火物粒子の融点を低くしてリバウンドを減らすことが重要である。 In addition, since the time required for repair in the coke oven in the coke oven is limited in operation, it is better that the spraying repair time is short. In particular, since the spraying repair such as brick joints has a high spraying distance, it is important to reduce the rebound by lowering the melting point of the refractory particles.
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、耐火性粒子と酸化性粉体である金属粒子との混合物を酸素と共に珪石れんがからなる被補修体に吹き付け、上記金属粒子の酸化発熱反応により混合物を溶融させて、被補修体に溶着させることを特徴とする溶射材料であって、上記耐火粒子は珪石れんがの２０００μｍ以下の粉砕粉を主成分とし、上記金属粒子は金属シリコンからなることを特徴とする溶射材料を提供するにある。 The present invention has been made in view of the above points, and in order to solve the above-described problems, a mixture of refractory particles and metal particles that are oxidizing powders is to be repaired made of silica brick with oxygen. Spraying, melting the mixture by oxidation exothermic reaction of the metal particles, and spraying the mixture to the object to be repaired, wherein the refractory particles are mainly composed of crushed powder of silica brick of 2000 μm or less, An object of the present invention is to provide a thermal spray material characterized in that the metal particles are made of metallic silicon.
また、上記耐火性粒子である珪石れんがは、ＳｉＯ2成分が９０重量％以上で、かつＡｌ2Ｏ3成分が１０重量％以下の組成の原料を使用することを特徴とし、その粒度は４２５〜２０００μｍが溶射材料の１０〜５０重量％以上で、７５μｍ以下が１０重量％以下で、７５〜４２５μｍがその残りであることを特徴とする溶射材料を提供するにある。 Further, the silica brick as the refractory particles is characterized by using a raw material having a composition in which the SiO 2 component is 90% by weight or more and the Al 2 O 3 component is 10% by weight or less. Another object of the present invention is to provide a thermal spray material characterized in that 2000 μm is 10 to 50% by weight or more of the thermal spray material, 75 μm or less is 10% by weight or less, and 75 to 425 μm is the remainder.
また、金属シリコン粒子はその添加量が溶射材料に対して１０〜３０重量％であって、その粒度は７５μｍ以上が溶射材料の５重量％以下で、２０μｍ以下が５〜１５重量％で、２０〜７５μｍがその残りであることを特徴とする溶射材料を提供するにある。 Further, the addition amount of the metal silicon particles is 10 to 30% by weight with respect to the thermal spray material, and the particle size is 75 μm or more is 5% by weight or less of the thermal spray material, and 20 μm or less is 5 to 15% by weight. The object is to provide a thermal spray material characterized in that ˜75 μm is the remainder.
また、ナトリウム塩、カリウム塩、リチウム塩の１種または複数からなり、その添加量は溶射材料に対して外掛けで０．３〜５重量％である結晶化促進剤を添加したことを特徴とする記載の溶射材料を提供するにある。 Further, it is characterized in that it comprises one or more of sodium salt, potassium salt and lithium salt, and the addition amount thereof is 0.3 to 5% by weight of crystallization accelerator added to the thermal spray material. It is in providing the thermal spray material of description.
さらに、溶融温度が９００℃以上で１５００℃以下の合金または鉱物類であって、その添加量が溶射材料に対して０．５〜５重量％であって、その粒度は１０００μｍ以下とする付着向上剤を添加することを特徴とする溶射材料を提供するにある。 Furthermore, it is an alloy or mineral having a melting temperature of 900 ° C. or higher and 1500 ° C. or lower, and its addition amount is 0.5 to 5% by weight with respect to the thermal spray material, and its particle size is 1000 μm or less. An object of the present invention is to provide a thermal spray material characterized by adding an agent.
さらにまた、発火点が３００℃以上で８００℃以下である炭素系粉末または金属粉末を溶射材料に対して外掛けで０．３〜５重量％で着火促進剤として添加することを特徴とする溶射材料を提供するにある。 Further, the thermal spraying is characterized in that a carbon-based powder or a metal powder having an ignition point of 300 ° C. or higher and 800 ° C. or lower is added as an ignition accelerator at 0.3 to 5% by weight on the outer surface of the thermal spray material. In providing materials.
またさらに、平均粒径が０．２μｍ以下であるシリカ超微粉末を溶射材料に対して外掛けで０．１〜３重量％で粉体流動化促進剤として添加することを特徴とする溶射材料を提供するにある。 Further, the thermal spray material is characterized in that an ultrafine silica powder having an average particle size of 0.2 μm or less is added as a powder fluidization accelerator in an amount of 0.1 to 3% by weight with respect to the thermal spray material. To provide.
本発明の溶射材料は、耐火性粒子と酸化性紛体である金属粒子との混合物を酸素と共に珪石れんがからなる被補修体に吹き付け、上記金属粒子の酸化発熱反応より混合物を溶融させて、被補修体に溶着させることを特徴とする溶射材料であって、上記耐火粒子は珪石れんがの２０００μｍ以下の粉砕粉を主成分とし、上記金属粒子は金属シリコンからなることを特徴とする溶射材料で、炉壁珪石れんがとの熱膨張を適合させ、かつ溶射と同時に補修材を結晶化し、れんがと補修材の接着強度を高めて、加熱冷却による補修れんが面からの剥離を抑制でき、れんが面からの剥離損耗を抑制でき、耐用性の向上をはかれる。 The thermal spray material of the present invention sprays a mixture of refractory particles and metal particles which are oxidizable powder onto a repair target made of silica brick together with oxygen, and melts the mixture by oxidation exothermic reaction of the metal particles to repair A thermal spray material characterized in that it is welded to the body, wherein the refractory particles are mainly composed of crushed powder of 2000 μm or less of silica brick, and the metal particles are made of metallic silicon. The thermal expansion with the wall silica brick is adapted, and the repair material is crystallized at the same time as the thermal spraying, the adhesion strength between the brick and the repair material is increased, and the repair brick due to heating and cooling can be prevented from peeling from the surface. Wear can be suppressed and durability can be improved.
また、上記耐火性粒子である珪石れんがは、ＳｉＯ2成分が９０重量％以上で、かつＡｌ2Ｏ3成分が１０重量％以下の組成の原料を使用することを特徴とし、その粒度は４２５〜２０００μｍが溶射材料の１０〜５０重量％以上で、７５μｍ以下が１０重量％以下で、７５〜４２５μｍがその残りとすることによって、結晶化を促進し、炉壁れんがとの熱膨張も一致して、リバウンドロスを減少できて良好な溶射ができる。 Further, the silica brick as the refractory particles is characterized by using a raw material having a composition in which the SiO 2 component is 90% by weight or more and the Al 2 O 3 component is 10% by weight or less. 2000 μm is 10 to 50% by weight or more of the sprayed material, 75 μm or less is 10% by weight or less, and 75 to 425 μm is the remainder, which promotes crystallization and coincides with the thermal expansion of the furnace wall brick. Rebound loss can be reduced and good thermal spraying can be achieved.
また、金属シリコン粒子はその添加量が溶射材料に対して１０〜３０重量％（耐火性粒子７０〜９０重量％）であって、その粒度は７５μｍ以上が溶射材料の５重量％以下で、２０μｍ以下が５〜１５重量％で、２０〜７５μｍがその残りであることによって、燃焼反応が強く、耐火性粒子が溶融して良好な溶射ができる。 Further, the addition amount of the metal silicon particles is 10 to 30% by weight (70 to 90% by weight of the refractory particles) with respect to the sprayed material, and the particle size is 75 μm or more and 5% by weight or less of the sprayed material, and 20 μm. When the following is 5 to 15% by weight and the remainder is 20 to 75 μm, the combustion reaction is strong, and the refractory particles are melted and good thermal spraying can be performed.
また、ナトリウム塩、カリウム塩、リチウム塩の１種または複数からなり、その添加量は溶射材料に対して外掛けで０．３〜５重量％である結晶化促進剤を添加することによって、溶射と同時に補修材の結晶化を促進できて付着促進効果がはかれる。 Moreover, it consists of one or more of sodium salt, potassium salt, and lithium salt, and the amount of addition is sprayed by adding a crystallization accelerator that is 0.3 to 5% by weight as an outer coating to the sprayed material. At the same time, the crystallization of the repair material can be promoted and the adhesion promoting effect is achieved.
さらに、溶融温度が９００℃以上で１５００℃以下の合金または鉱物類であって、その添加量が溶射材料に対して０．５〜１５重量％であって、その粒度は１０００μｍ以下とする付着向上剤を添加することによって、着火阻害を抑止して付着促進効果がはかれる。 Further, it is an alloy or mineral having a melting temperature of 900 ° C. or more and 1500 ° C. or less, and the addition amount is 0.5 to 15% by weight with respect to the thermal spray material, and the particle size is 1000 μm or less. By adding an agent, the inhibition of ignition is suppressed and the adhesion promoting effect is achieved.
さらにまた、発火点が３００℃以上で８００℃以下である炭素系粉末または金属粉末を溶射材料に対して外掛けで０．３〜５重量％で着火促進剤として添加することによって、確実に着火促進できて、爆発の危険なく安全に施工できる。 Furthermore, by adding a carbon-based powder or a metal powder having an ignition point of 300 ° C. or higher and 800 ° C. or lower as an ignition accelerator at 0.3 to 5% by weight as an external coating with respect to the sprayed material, ignition is ensured. It can be promoted and can be installed safely without the danger of explosion.
またさらに、平均粒径が０．２μｍ以下であるシリカ超微粉末を溶射材料に対して外掛けで０．１〜３重量％で粉体流動化促進剤として添加することによって、溶射材料のホッパータンク内での棚吊り、切出し阻害を抑止して、安定した施工ができる。 Furthermore, by adding an ultrafine silica powder having an average particle size of 0.2 μm or less as a powder fluidization accelerator at a rate of 0.1 to 3% by weight on the thermal spray material, a hopper for the thermal spray material is obtained. Stable construction can be done by preventing shelves from being hung in the tank and cutting out.
本発明の溶射材料は、耐火性粒子と酸化性粉体である金属粒子との混合物を酸素と共に珪石れんがからなる被補修体に吹き付け、上記金属粒子の酸化発熱反応により混合物を溶融させて、被補修体に溶着させることを特徴とする溶射材料であって、上記耐火粒子は珪石れんがの２０００μｍ以下の粉砕粉を主成分とし、上記金属粒子は金属シリコンからなることを特徴としている。 The thermal spray material of the present invention sprays a mixture of refractory particles and metal particles that are oxidizing powders onto a repaired body made of silica brick together with oxygen, and melts the mixture by oxidation exothermic reaction of the metal particles, A thermal spray material characterized in that it is welded to a repair body, wherein the refractory particles are mainly composed of crushed powder of 2000 μm or less of silica brick, and the metal particles are made of metallic silicon.
珪石れんがからなる被補修体の欠損部、亀裂部に溶着させ補修する溶射材料として、すなわち、珪石れんがからなる被補修体、特にコークス炉炭化室の炉壁の珪石れんがとそれを補修する溶射材料の熱膨張を、略一致させることを特徴とし、そのために補修に使用する耐火性粒子を珪石れんがの２０００μｍ以下の粉砕粉を主成分として使用することにより熱膨張を適合させ、加熱冷却による補修れんが面からの剥離を抑制し、耐用性の向上を図ることを実現した溶射材料である。 As a thermal spray material that is welded and repaired to the defect part and crack part of the repaired body made of silica brick, that is, the repaired body made of silica brick, especially the thermal spray material that repairs the silica brick on the furnace wall of the coke oven carbonization chamber The thermal expansion of the refractory particles used for the repair is adapted to the thermal expansion by using crushed powder of 2000 μm or less of silica brick as the main component, and repair brick by heating and cooling is used. It is a thermal spray material that realizes improvement in durability by suppressing peeling from the surface.
また、溶射による熱で耐火性粒子が溶融されてガラス化すると、珪石れんがとの熱膨張を適切に適合させることができない。これを防止する方法としては、溶射と同時に補修材を結晶化させる結晶化促進剤を併用することが好ましい。また、れんが目地等の溶射速度が速い補修では、耐火物粒子の融点を低くしてリバウンドを減らすことが重要であり、付着向上剤として低融点物の添加を行うことが好ましい。 Also, if the refractory particles are melted and vitrified by heat from thermal spraying, the thermal expansion with the silica brick cannot be appropriately adapted. As a method for preventing this, it is preferable to use a crystallization accelerator for crystallizing the repair material simultaneously with thermal spraying. Further, in repairing bricks with high spraying speed, it is important to lower the melting point of the refractory particles to reduce rebound, and it is preferable to add a low melting point substance as an adhesion improver.
本発明の溶射材料の耐火物粒子は、珪石れんがの粉砕粉を主成分として使用するもので、ＳｉＯ2が９０重量％以上で、かつＡｌ2Ｏ3が１０重量％以下の高ＳｉＯ2組成の原料を使用することを特徴とするもので、好ましくはＳｉＯ2が９５重量％以上で、かつＡｌ2Ｏ3が５重量％以下の高ＳｉＯ2組成の原料を使用する。Ａｌ2Ｏ3が１０重量％以上になると結晶化を阻害し、炉壁れんがとの熱膨張が一致しなくなる。 The refractory particles of the thermal spray material of the present invention use pulverized powder of silica brick as a main component, and have a high SiO 2 composition in which SiO 2 is 90% by weight or more and Al 2 O 3 is 10% by weight or less. A raw material is used. Preferably, a raw material having a high SiO 2 composition containing 95% by weight or more of SiO 2 and 5% by weight or less of Al 2 O 3 is used. When the Al 2 O 3 content is 10% by weight or more, crystallization is hindered and the thermal expansion of the furnace wall brick does not match.
さらに、この耐火物粒子の原料として、珪石れんが粉砕粉に対してこれに珪石、珪砂、溶融シリカを混合使用しても良い。混合使用量は、珪石れんが粉に対して５０重量％以下が好ましい。炭化室壁の熱で金属を発火させ、燃焼させる本方式の溶射では、耐火粒子の０．５ｍｍ以上は完全に溶融しないことが多い。このため、０．５ｍｍ以下の耐火物粒子には、Ａｌ2Ｏ3が５重量％以下の高ＳｉＯ2組成の原料を使用することが望ましい。 Further, as a raw material for the refractory particles, silica stone, silica sand, and fused silica may be mixed and used for the crushed powder of silica stone. The amount of mixing is preferably 50% by weight or less based on the silica brick powder. In this type of thermal spraying, in which metal is ignited by the heat of the carbonization chamber wall and burned, 0.5 mm or more of the refractory particles often do not completely melt. For this reason, it is desirable to use a raw material having a high SiO 2 composition containing 5% by weight or less of Al 2 O 3 for refractory particles of 0.5 mm or less.
珪石れんがの粉砕粉を主成分として使用する、あるいは珪石れんが粉砕粉、珪石、珪砂、溶融シリカを混合使用する耐火性粒子の粒度は２０００μｍ以下とし、粒度４２５〜２０００μｍが溶射材料に対して１０〜５０重量％とし、７５μｍ以下が１０重量％以下で、７５〜４２５μｍがその残りであることが望ましい。７５μｍ以下が１０重量％以上であると、材料を溶射するときに脈動し、良好な溶射ができない。４２５μｍ以上のものが５０重量％以上あると、リバウンドが大きく、リバウンドロスが多くなり好ましくない。 The particle size of the refractory particles using the pulverized powder of silica brick as the main component, or using the crushed powder of silica stone brick, silica stone, silica sand, and fused silica is 2000 μm or less, and the particle size of 425 to 2000 μm is 10 to 10 times the sprayed material. It is desirable that the amount is 50% by weight, 75 μm or less is 10% by weight or less, and 75 to 425 μm is the remainder. When 75 μm or less is 10% by weight or more, pulsation occurs when the material is sprayed, and good spraying cannot be performed. When the amount of 425 μm or more is 50% by weight or more, the rebound is large and the rebound loss increases, which is not preferable.
金属粒子の酸化発熱反応により上記耐火粒子と金属粒子の混合物を溶融させて、被補修体に溶着させる金属粒子として、本発明では金属シリコン粒子を用いる。金属シリコン粒子は、燃焼反応後はＳｉＯ2となり、ＳｉＯ2成分が９０重量％以上とする珪石れんがの２０００μｍ以下の粉砕粉を主成分として使用する耐火粒子との組合せにおいて望ましい。金属シリコン粒子は、その添加量が溶射材料に対して１０〜３０重量％であって、金属シリコン粒子の粒度は、７５μｍ以上が５重量％以下で、かつ２０μｍ以下が５〜１５重量％であることが望ましい。金属シリコン粒子の添加量が１０重量％以下であると、燃焼反応が弱く、耐火性粒子が溶融しなく良好な溶射ができない。添加量が３０重量％以上であると、材料を溶射したとき燃焼反応が強くなりすぎ、被補修体に溶射した溶射体が流れ落ち、良好な溶射ができない。 In the present invention, metal silicon particles are used as the metal particles to be melted by the oxidation exothermic reaction of the metal particles and fused to the repair target body. Metallic silicon particles become SiO 2 after the combustion reaction, and are desirable in combination with refractory particles using as a main component crushed powder of 2000 μm or less of silica brick with a SiO 2 component of 90% by weight or more. The addition amount of the metal silicon particles is 10 to 30% by weight with respect to the thermal spray material, and the particle size of the metal silicon particles is 75 μm or more to 5% by weight or less and 20 μm or less to 5 to 15% by weight. It is desirable. When the addition amount of the metal silicon particles is 10% by weight or less, the combustion reaction is weak, and the refractory particles do not melt and good thermal spraying cannot be performed. When the added amount is 30% by weight or more, the combustion reaction becomes too strong when the material is sprayed, the sprayed body sprayed on the repaired body flows down, and good spraying cannot be performed.
また、金属シリコン粒子の粒度で７５μｍ以上のものは、燃焼反応が弱く好ましくないため、５重量％以下でなければならない。２０μｍ以下が５重量％以下でも、燃焼反応が弱くなり好ましくない。２０μｍ以下が１５重量％以上では材料を溶射したとき、燃焼反応が強くなりすぎ、被補修体に溶着した溶射体が流れ落ち、良好な溶射ができない。
上記耐火性粒子は、溶射材料の７０〜９０重量％、金属シリコン粒子１０〜３０重量％の比率が上記した良好な溶射できて好ましい。
In addition, when the particle size of metal silicon particles is 75 μm or more, the combustion reaction is weak and is not preferable, so it must be 5% by weight or less. Even if 20 μm or less is 5% by weight or less, the combustion reaction becomes weak, which is not preferable. When the material is sprayed at a weight of 20 μm or less at 15% by weight or more, when the material is sprayed, the combustion reaction becomes too strong, and the sprayed body that has been welded to the repaired body flows down, and good spraying cannot be performed.
The ratio of 70 to 90% by weight of the thermal spray material and 10 to 30% by weight of the metal silicon particles is preferable for the refractory particles because the above-described good thermal spraying can be performed.
付着向上剤は、溶融温度が９００℃以上、１５００℃以下の合金類、鉱物類が用いられ、さらにそれを添加したときに、被補修体に溶着した溶射材のＡｌ2Ｏ3成分が５重量％以上になると、結晶化が著しく阻害されるため、Ａｌ2Ｏ3成分が５重量％以下になるような成分の合金類、鉱物類を用いるようにすることが望ましい。 As the adhesion improver, alloys and minerals having a melting temperature of 900 ° C. or higher and 1500 ° C. or lower are used, and when added, 5 wt.% Of the Al 2 O 3 component of the sprayed material deposited on the repair target is added. Since the crystallization is remarkably hindered when the content exceeds 5%, it is desirable to use alloys and minerals whose components make the Al 2 O 3 content 5% by weight or less.
合金類、鉱物類等では溶融するときに、融解熱として熱を吸熱する。コークス炉炭化室の壁に溶射材料を吹き付けて、その熱で着火させ、溶射材料に混合されている金属を燃焼させ、その熱で耐火粒子を溶融し、溶着する方式では、着火温度が６００〜９００℃になる。このため、この温度域に融点があるものでは着火を阻害し、溶射の火炎を引っ張ることを阻害するので好ましくなく、融点９００℃以上の合金類、鉱物類を用いることとした。また、融点が１５００℃を超えると、珪石れんが粉の主成分であるトリジマイトの溶融温度が１６７０℃であるので、付着促進効果が少なくなる。したがって鉱物類を用いることとした。 When alloys and minerals are melted, they absorb heat as heat of fusion. In the method of spraying the spray material on the wall of the coke oven carbonization chamber, igniting with the heat, burning the metal mixed in the spray material, melting the refractory particles with the heat, and welding, the ignition temperature is 600- 900 ° C. For this reason, a material having a melting point in this temperature range is not preferable because it inhibits ignition and prevents the flame of the thermal spray from being pulled, so that alloys and minerals having a melting point of 900 ° C. or higher are used. On the other hand, if the melting point exceeds 1500 ° C., the melting temperature of tridymite, which is the main component of silica brick, is 1670 ° C., and therefore the adhesion promoting effect is reduced. Therefore, we decided to use minerals.
付着向上剤の添加量としては、溶射材料に対して０．５〜５重量％添加することが望ましい。合金類としては、ケイ化カルシウム（溶融点：９８０℃）、二酸化マンガン（溶融点：１１６０℃）、フェロシリコン（溶融点：１４２０℃）、鉱物類としてはペタライト（溶融点：１３００℃）、珪酸カルシウム（溶融点：１４５０〜１５００℃）等の１種または複数を用いることが好ましい。添加量が０．５重量％未満であると、付着性向上効果がなく、５重量％より多いと溶射時に施工体が溶融しすぎて、吹き飛ばされるなどの問題が生じる。 As an addition amount of the adhesion improving agent, it is desirable to add 0.5 to 5% by weight with respect to the thermal spray material. Alloys include calcium silicide (melting point: 980 ° C.), manganese dioxide (melting point: 1160 ° C.), ferrosilicon (melting point: 1420 ° C.), minerals include petalite (melting point: 1300 ° C.), silicic acid It is preferable to use one or more of calcium (melting point: 1450 to 1500 ° C.). If the addition amount is less than 0.5% by weight, there is no effect of improving adhesion, and if it is more than 5% by weight, there is a problem that the construction body is excessively melted during spraying and blown off.
ナトリウム、カリウム、リチウムイオンをシリカ溶融物に加えると、ガラス質の結晶化が促進される。これにより結晶化促進剤としては、ナトリウム塩、カリウム塩、リチウム塩の１種または複数からなることを特徴とする。結晶化促進剤の添加量は、０．３〜５重量％が好ましく、０．３重量％より少ないと結晶化促進の効果が小さく、５重量％より多いと溶射の際に溶射体が流れ落ち、良好な施工体が得られない。ナトリウム塩としては、炭酸ナトリウム、塩化ナトリウム、カリウム塩としては塩化カリウム、リチウム塩としては炭酸リチウム等があげられる。 Addition of sodium, potassium and lithium ions to the silica melt promotes glassy crystallization. Thus, the crystallization accelerator is characterized by comprising one or more of a sodium salt, a potassium salt and a lithium salt. The addition amount of the crystallization accelerator is preferably 0.3 to 5% by weight. If the amount is less than 0.3% by weight, the effect of promoting crystallization is small. If the amount is more than 5% by weight, the sprayed material flows down during spraying. A good construction body cannot be obtained. Examples of sodium salts include sodium carbonate and sodium chloride, potassium salts include potassium chloride, and lithium salts include lithium carbonate and the like.
着火促進剤は、被溶射体、すなわちコークス炉では炭化室壁面の温度が８００℃以下である場合、溶射材料に添加される。発火点が３００〜６００℃である炭素系粉末または金属粉若しくは炭素系粉末と金属粉の混合物からなることを特徴とし、その添加量は外掛けで５重量％以下であることが好ましい。着火促進剤の発火点が６００℃超えであると、壁面温度が８００℃以下の場合、溶射開始時に発火しにくい。発火点が３００℃未満であると、爆発の危険が大きくなり、安全上好ましくない。 The ignition accelerator is added to the thermal spray material when the temperature of the carbonized chamber wall surface is 800 ° C. or less in the thermal spray body, that is, the coke oven. It is characterized by comprising a carbon-based powder or a metal powder or a mixture of a carbon-based powder and a metal powder having an ignition point of 300 to 600 ° C., and the addition amount is preferably 5% by weight or less. When the ignition point of the ignition accelerator exceeds 600 ° C, it is difficult to ignite at the start of thermal spraying when the wall surface temperature is 800 ° C or lower. If the ignition point is less than 300 ° C., the risk of explosion increases, which is not preferable for safety.
着火促進剤が金属アルミニウム粉では、溶射施工体にＡｌ2Ｏ3が入り、結晶化を阻害する割合が増大するので好ましくない。金属マグネシウム粉は、爆発の危険が大きくなり、安全上好ましくない。炭素系粉末の方が燃焼性が良く、施工体に残留しないので好ましいが、これにこだわるものではない。 When the ignition accelerator is a metal aluminum powder, Al 2 O 3 enters the thermal sprayed construction body, which is not preferable because the rate of inhibiting crystallization increases. Metal magnesium powder increases the risk of explosion and is not preferable for safety. The carbon-based powder is preferable because it has good flammability and does not remain in the construction body, but is not particular about this.
着火促進剤が外掛けで５重量％以上であると、溶射体に炭素系粉末または金属粉が残留し、ガラス化を阻害するので好ましくない。炭素系粉末としてはコークス粉（発火点：４００〜６００℃）、木炭粉（発火点：３２０〜４００℃）、コーンスターチ粉（発火点：４７０℃）等があげられ、金属粉末としては鉄粉（発火点：３１５〜３２０℃）、マンガン粉（発火点：４５０℃）、バナジウム粉（発火点：５００℃）等があげられる。 If the ignition accelerator is 5% by weight or more as an outer coating, the carbon-based powder or metal powder remains on the sprayed body, and vitrification is inhibited, which is not preferable. Examples of the carbon-based powder include coke powder (ignition point: 400 to 600 ° C.), charcoal powder (ignition point: 320 to 400 ° C.), corn starch powder (ignition point: 470 ° C.), etc. Examples thereof include ignition point: 315 to 320 ° C., manganese powder (ignition point: 450 ° C.), vanadium powder (ignition point: 500 ° C.), and the like.
被補修体に溶着させる金属粒子として本発明では金属シリコン粒子を用いるが、４５μｍ以下の金属シリコン粉を１０重量％以上添加する場合、溶射材料がホッパータンク内で棚吊りし、良好な切り出しができなくなる恐れがある。これを防止するため粉体流動化促進剤を添加することが望ましい。粉体流動化促進剤は、平均粒径が０．２μｍ以下であるシリカ超微粉末が望ましく、その添加量は０．１〜３重量％以下が望ましい。０．１重量％以上で流動化効果を発生するが、３重量％を超える添加では、高価格になる割に流動化促進の効果が増加しない。したがって、好ましくは３重量％以下の添加量として使用する。 In the present invention, metal silicon particles are used as the metal particles to be welded to the repaired body. However, when metal silicon powder of 45 μm or less is added in an amount of 10% by weight or more, the sprayed material is suspended in a hopper tank and can be cut out satisfactorily. There is a risk of disappearing. In order to prevent this, it is desirable to add a powder fluidization accelerator. The powder fluidization accelerator is desirably an ultrafine silica powder having an average particle size of 0.2 μm or less, and the addition amount is desirably 0.1 to 3% by weight or less. Although the fluidization effect is generated at 0.1% by weight or more, the addition of more than 3% by weight does not increase the effect of fluidization promotion for a high price. Therefore, it is preferably used as an addition amount of 3% by weight or less.
本発明について、実施例と比較例を表１〜表７のように構成して試験した。そのテスト結果を表１〜表７に示す。表１〜表４のように本実施例のものは、吐出性、着火性、燃焼性が良好であり、リバウンドが少なくて付着率が向上している。また、実施例１−５、実施例４−５と比較例６−９、比較例６−１０について図１のようにれんが目地充填試験を行った結果、実施例１−５、４−５は充填深さが５０ｍｍであったのに対し、比較例６−９、６−１０は充填深さが３０ｍｍ、３５ｍｍであり、実施例の方がれんが目地へも良好に充填できる。 About this invention, the Example and the comparative example were comprised as Table 1-Table 7, and tested. The test results are shown in Tables 1-7. As shown in Tables 1 to 4, the present example has good dischargeability, ignitability, and combustibility, and has low rebound and improved adhesion. Moreover, as a result of conducting a joint filling test for Example 1-5, Example 4-5, Comparative Example 6-9, and Comparative Example 6-10 as shown in FIG. 1, Examples 1-5 and 4-5 were Whereas the filling depth was 50 mm, the filling depths of Comparative Examples 6-9 and 6-10 were 30 mm and 35 mm, and the bricks could be filled better in the examples.
そして、実施例４−５と比較例６−９、６−１０について、Ａ製鉄所でコークス炉に珪石れんがを入れ、それに溶射し、サンプルを回収した。それから試料を切り出し、珪石れんがと熱間線膨張率を比較した結果を図２に示す。実施例１−５は珪石れんがと同等の熱間線膨張率を示し、加熱冷却による剥離に対し強く、大幅に溶射補修後の耐久性が向上した。 And about Example 4-5 and Comparative Examples 6-9 and 6-10, the silica brick was put into the coke oven at A steelworks, and it sprayed to it, and the sample was collect | recovered. Then, a sample is cut out, and the result of comparing the coefficient of thermal linear expansion with that of silica brick is shown in FIG. Example 1-5 showed a hot linear expansion coefficient equivalent to that of silica brick, strong against peeling by heating and cooling, and greatly improved durability after thermal spray repair.
表１ 本発明の実施例１
Table 1 Example 1 of the present invention
表２ 本発明の実施例２
Table 2 Example 2 of the present invention
表３ 本発明の実施例３
Table 3 Example 3 of the present invention
表４ 本発明の実施例４
表５ 本発明の比較例１
Table 5 Comparative Example 1 of the present invention
表６ 比較例２
Table 6 Comparative Example 2
表７ 比較例３
Table 7 Comparative Example 3
Claims (7)
上記耐火粒子は珪石れんがの２０００μｍ以下の粉砕粉を主成分とし、上記金属粒子は金属シリコンからなることを特徴とする溶射材料。 Spraying a mixture of refractory particles and metal particles, which are oxidizing powders, onto a repaired body made of silica brick together with oxygen, melting the mixture by oxidation exothermic reaction of the metal particles, and welding the repaired body to the repaired body A thermal spray material characterized by
The above-mentioned refractory particles are mainly composed of crushed powder of 2000 μm or less of silica brick, and the metal particles are made of metallic silicon.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010280848A (en) * | 2009-06-05 | 2010-12-16 | Sumitomo Metal Ind Ltd | Method for coating furnace wall in carbonization chamber of coke furnace |
| JP2012188345A (en) * | 2011-02-25 | 2012-10-04 | Shinagawa Refractories Co Ltd | Thermal spray material |
| JP5663680B1 (en) * | 2014-01-29 | 2015-02-04 | 黒崎播磨株式会社 | Thermal spray material |
| JP2015157982A (en) * | 2014-02-24 | 2015-09-03 | Ｊｆｅスチール株式会社 | Repair method by spray coating |
| JP2015218104A (en) * | 2014-05-21 | 2015-12-07 | 品川リフラクトリーズ株式会社 | Thermal spray material |
| JP2016079418A (en) * | 2014-10-10 | 2016-05-16 | 品川リフラクトリーズ株式会社 | Thermal spray material |
| KR20160056141A (en) * | 2014-11-11 | 2016-05-19 | 주식회사 포스코 | Repairing materials for blast furnace body |
| JP2017145452A (en) * | 2016-02-17 | 2017-08-24 | 品川リフラクトリーズ株式会社 | Thermal spray material |
| CN115385556A (en) * | 2021-05-25 | 2022-11-25 | 上海杰汇炉窑新技术有限公司 | Maintenance structure, method and application for sinking of silicon brick arch body of industrial furnace |
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| JP2005336001A (en) * | 2004-05-26 | 2005-12-08 | Jfe Refractories Corp | Thermal spraying material |
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| JPS63190155A (en) * | 1987-02-03 | 1988-08-05 | Nippon Steel Corp | Highly siliceous material for thermal spraying |
| JPH04118158U (en) * | 1991-04-09 | 1992-10-22 | 品川白煉瓦株式会社 | Refractory spraying equipment |
| JPH09132470A (en) * | 1995-11-10 | 1997-05-20 | Kawasaki Refract Co Ltd | Thermal spraying repairing material |
| JPH1160342A (en) * | 1997-08-05 | 1999-03-02 | Shinagawa Refract Co Ltd | Thermal spraying material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010280848A (en) * | 2009-06-05 | 2010-12-16 | Sumitomo Metal Ind Ltd | Method for coating furnace wall in carbonization chamber of coke furnace |
| JP2012188345A (en) * | 2011-02-25 | 2012-10-04 | Shinagawa Refractories Co Ltd | Thermal spray material |
| JP5663680B1 (en) * | 2014-01-29 | 2015-02-04 | 黒崎播磨株式会社 | Thermal spray material |
| JP2015157982A (en) * | 2014-02-24 | 2015-09-03 | Ｊｆｅスチール株式会社 | Repair method by spray coating |
| JP2015218104A (en) * | 2014-05-21 | 2015-12-07 | 品川リフラクトリーズ株式会社 | Thermal spray material |
| JP2016079418A (en) * | 2014-10-10 | 2016-05-16 | 品川リフラクトリーズ株式会社 | Thermal spray material |
| KR20160056141A (en) * | 2014-11-11 | 2016-05-19 | 주식회사 포스코 | Repairing materials for blast furnace body |
| KR101633472B1 (en) * | 2014-11-11 | 2016-06-24 | 주식회사 포스코 | Repairing materials for blast furnace body |
| JP2017145452A (en) * | 2016-02-17 | 2017-08-24 | 品川リフラクトリーズ株式会社 | Thermal spray material |
| CN115385556A (en) * | 2021-05-25 | 2022-11-25 | 上海杰汇炉窑新技术有限公司 | Maintenance structure, method and application for sinking of silicon brick arch body of industrial furnace |
| CN115385556B (en) * | 2021-05-25 | 2024-02-20 | 上海杰汇炉窑新技术有限公司 | Maintenance structure, method and application of sinking of industrial furnace crown block |
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