JPH07187819A - Flame spraying material and its production - Google Patents
Flame spraying material and its productionInfo
- Publication number
- JPH07187819A JPH07187819A JP5331554A JP33155493A JPH07187819A JP H07187819 A JPH07187819 A JP H07187819A JP 5331554 A JP5331554 A JP 5331554A JP 33155493 A JP33155493 A JP 33155493A JP H07187819 A JPH07187819 A JP H07187819A
- Authority
- JP
- Japan
- Prior art keywords
- cao
- clinker
- mgo
- spray material
- coating
- 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
Landscapes
- Ceramic Products (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、接着性に優れたＭｇＯ
−ＣａＯ系の火炎溶射材に関するものである。FIELD OF THE INVENTION The present invention relates to MgO having excellent adhesiveness.
-CaO-based flame spray material.
【０００２】[0002]
【従来の技術】転炉、ＡＯＤ炉、取鍋、真空脱ガス炉な
どの工業窯炉の内張り損傷を火炎溶射法をもって補修す
ることが知られている。この方法は、耐火物微粉末を高
速・高温の火炎中に通し、溶融または半溶融状態にして
損傷部分に溶射するものであり、緻密かつ高強度の補修
体組織が得られる。従来、この火炎溶射に使用される溶
射材として、ＣａＯ含有の溶射材が提案されている。例
えば特開昭６３−１０７８７２号公報には石灰質クリン
カーとマグネシアクリンカーよりなる材質、特開昭６３
−１０７８７３号公報にはさらにこれにスラグを配合し
た材質が示されている。2. Description of the Related Art It is known to repair lining damage in industrial kilns such as converters, AOD furnaces, ladles, and vacuum degassing furnaces by flame spraying. According to this method, fine refractory powder is passed through a high-speed, high-temperature flame to be in a molten or semi-molten state and sprayed onto a damaged portion, and a dense and high-strength repair body structure can be obtained. Conventionally, a CaO-containing thermal spray material has been proposed as a thermal spray material used for this flame spraying. For example, JP-A-63-107872 discloses a material comprising a calcareous clinker and a magnesia clinker.
Japanese Patent No. 107873 discloses a material in which slag is further mixed.
【０００３】[0003]
【発明が解決しようとする課題】ＣａＯ含有の溶射材は
融点が高く、耐食性に優れている。しかし反面、接着性
において十分なものではない。溶射材の接着性を向上さ
せる手段として、例えばＫ2Ｏ、Ｎａ2Ｏ、スラグなどの
低融点物質を添加することが考えられるが、十分な効果
を得るだけの量を添加すると耐食性の低下を招く。The CaO-containing thermal spray material has a high melting point and excellent corrosion resistance. However, on the other hand, the adhesiveness is not sufficient. As a means for improving the adhesiveness of the thermal spray material, it is conceivable to add a low melting point substance such as K 2 O, Na 2 O or slag. Invite.
【０００４】また、ＣａＯ含有材質は、水分と反応して
消化〔ＣａＯ＋Ｈ2Ｏ→Ｃａ（ＯＨ）2〕する。溶射材で
は粒径が一般に５００μｍ以下の微粒のために比表面積
が大きく、消化は空気中の水蒸気などによっても進行す
る。消化によって水和物を含有した溶射材は火炎溶射の
際、水和物の分解に伴う吸熱反応で雰囲気温度を低下さ
せ、溶融が不十分となって接着性および付着性に劣る。The CaO-containing material reacts with water to be digested [CaO + H 2 O → Ca (OH) 2 ]. The thermal spray material generally has a large specific surface area due to the fine particles having a particle size of 500 μm or less, and the digestion also progresses by steam in the air. During flame spraying, the thermal spray material containing the hydrate by digestion lowers the atmospheric temperature due to an endothermic reaction associated with the decomposition of the hydrate, resulting in insufficient melting and poor adhesion and adhesiveness.
【０００５】[0005]
【課題を解決するための手段及び作用】本発明は、Ｃａ
Ｏ含有の溶射材において上記従来の問題を解決すること
を目的とし、その特徴とするところは、表面にＣａＣＯ
3被膜を有する、ＣａＯ質および／またはＭｇＯ−Ｃａ
Ｏ質のＣａＯ含有クリンカーを配合した火炎溶射材とそ
の製造方法である。[Means and Actions for Solving the Problems]
The object of the present invention is to solve the above-mentioned conventional problems in the thermal spray material containing O, and the characteristic feature is that CaCO is present on the surface.
CaO and / or MgO-Ca with 3 coatings
A flame spray material containing an O-quality CaO-containing clinker and a method for producing the same.
【０００６】本発明の溶射材は、表面にＣａＣＯ3被膜
を有するＣａＯ含有クリンカーを配合したことで、接着
性が格段に向上する。これは、ＣａＣＯ3被膜が火炎溶
射の高温を受けて分解し、粒子表面が多孔質となって溶
融が促進するためと思われる。 また、ＣａＣＯ3被膜
は空気との遮断膜となってＣａＯ含有クリンカーの消化
を防止する。消化を防止したことで水和物を含有してお
らず、水和物の分解に伴う吸熱反応で付着性が低下する
といった問題もない。ＣａＣＯ3被膜の分解においても
吸熱反応を生じるが、ＣａＣＯ3被膜は厚みが０．１〜
３μｍと極めて薄く、この吸熱反応による付着性への影
響はない。In the thermal spray material of the present invention, the adhesive property is remarkably improved by incorporating the CaO-containing clinker having the CaCO 3 coating on the surface. It is considered that this is because the CaCO 3 coating is decomposed by the high temperature of flame spraying and the surface of the particles becomes porous to promote melting. In addition, the CaCO 3 film serves as a barrier film against air to prevent digestion of the CaO-containing clinker. Since the digestion is prevented, the hydrate is not contained, and there is no problem that the adhesiveness is lowered due to the endothermic reaction accompanying the decomposition of the hydrate. Although produce endothermic reactions in the degradation of CaCO 3 film, CaCO 3 coating 0.1 thickness
It is as thin as 3 μm, and the endothermic reaction does not affect the adhesiveness.
【０００７】本発明で使用するＣａＯ含有クリンカー
は、ＣａＯ質および／またはＭｇＯ−ＣａＯ質とする。
焼結品、電融品の何れでもよいが、製造コスト面から焼
結品が好ましい。ＭｇＯ−ＣａＯ質の場合、化学成分値
でＣａＯが３０ｗｔ％以上であることが好ましい。Ｃａ
Ｏがこれより少ないと耐スラグ浸透性、耐スポーリング
性に劣る。ＣａＯ、ＭｇＯ以外の成分は、５ｗｔ％以下
であることが好ましい。ＣａＯ含有クリンカーに対する
ＣａＣＯ3被膜の形成は、ＣＯ2ガス雰囲気下で加熱する
ことで行うことができる。基本的には特開昭６１−２５
６９６１号、特開昭５６−８８８２５号などで既に示さ
れる方法が利用できる。しかし、同公報に示される耐火
レンガなどの骨材に対する場合と異なり、本発明では溶
射材としての微粒のＣａＯ含有クリンカーに対するもで
ある。ＣＯ2ガス処理時の加熱温度は３８０〜８３０℃
が好ましい。The CaO-containing clinker used in the present invention is of CaO quality and / or MgO-CaO quality.
Either a sintered product or an electromelted product may be used, but a sintered product is preferred from the viewpoint of manufacturing cost. In the case of MgO-CaO, CaO is preferably 30 wt% or more in terms of chemical composition. Ca
If the O content is less than this range, the slag penetration resistance and spalling resistance are poor. Components other than CaO and MgO are preferably 5 wt% or less. The formation of the CaCO 3 coating on the CaO-containing clinker can be performed by heating in a CO 2 gas atmosphere. Basically, JP-A-61-25
The methods already disclosed in JP-A-6961 and JP-A-56-88825 can be used. However, unlike the case of an aggregate such as a refractory brick shown in the same publication, the present invention is also applied to a fine CaO-containing clinker as a thermal spray material. The heating temperature during CO 2 gas treatment is 380 to 830 ° C.
Is preferred.
【０００８】ＣＯ2ガス処理によって形成されたＣａＣ
Ｏ3被膜を顕微鏡観察すると鱗片状をしている。ＣａＣ
Ｏ3被膜が鱗片状のためにＣａＯ含有クリンカーの比表
面積が大きくなり、溶融しやすいことも接着性向上に作
用していると思われる。CaC formed by CO 2 gas treatment
Microscopic observation of the O 3 coating gives a scale-like shape. CaC
It is considered that the CaO-containing clinker has a large specific surface area due to the scale-like O 3 coating and easily melts, which also acts to improve the adhesiveness.
【０００９】ＣａＣＯ3被膜の厚さは０．１〜３μｍが
好ましい。溶射材粒子は微粒なために被膜が相当薄くて
も本発明の効果が得られる。被膜の厚さを発達させるに
は加熱処理時間が長くなる。しかも、被膜の厚さが一定
の寸法を超えると接着性においてそれ以上の効果が望め
なくなるから、生産性の面から、３μｍを超えることは
好ましくない。The thickness of the CaCO 3 coating is preferably 0.1 to 3 μm. Since the thermal spray material particles are fine particles, the effect of the present invention can be obtained even if the coating film is considerably thin. Heat treatment time increases to develop coating thickness. Moreover, if the thickness of the coating exceeds a certain dimension, no further effect can be expected in the adhesiveness, so from the viewpoint of productivity, it is not preferable to exceed 3 μm.
【００１０】本発明の溶射材は、このＣａＣＯ3被膜を
有するＣａＯ含有クリンカーだけでなく、これに他の耐
火物原料を組み合わせて配合してもよい。また、溶融助
剤を添加してもよい。他の耐火物原料としては、例えば
マグネシア、ドロマイト、ジルコン、ジルコニア、スピ
ネル、クロム鉱、アルミナ、ムライト、炭素、炭化物、
窒化物、ＣａＣＯ3被膜を有していないＣａＯ含有クリ
ンカーあるいはこれらを主材としたレンガ屑などから選
ばれる一種または二種以上である。本発明の効果を損な
わないために、その他の耐火物原料あるいは溶融助剤を
配合する場合でも、ＣａＣＯ3被膜を有するＣａＯ含有
クリンカーは少なくとも５０ｗｔ％配合することが好ま
しい。The thermal spray material of the present invention may be blended not only with the CaO-containing clinker having the CaCO 3 coating but also with other refractory raw materials in combination. Further, a melting aid may be added. Other refractory raw materials, for example, magnesia, dolomite, zircon, zirconia, spinel, chrome ore, alumina, mullite, carbon, carbide,
It is one or more selected from nitrides, CaO-containing clinker not having a CaCO 3 coating, or brick scraps containing these as main materials. In order not to impair the effects of the present invention, it is preferable to mix at least 50 wt% of the CaO-containing clinker having a CaCO 3 coating even when other refractory raw materials or melting aids are mixed.
【００１１】溶融助剤としては、例えば、スラグ、金属
鉱石、タルク、Ｋ2Ｏ、Ｎａ2Ｏ、Ｆｅ2Ｏ3、ＦｅＯ、酸
化リチウム、金属粉などから選ばれる一種または二種以
上である。溶融助剤は特に付着性に効果があるが、多量
の添加は耐食性の低下を招くので、３０ｗｔ％以下の配
合量が好ましい。The melting aid is, for example, one or more selected from slag, metal ore, talc, K 2 O, Na 2 O, Fe 2 O 3 , FeO, lithium oxide and metal powder. The melting aid is particularly effective for adhesion, but addition of a large amount thereof causes deterioration of corrosion resistance, so a blending amount of 30 wt% or less is preferable.
【００１２】溶射材の粒径は従来材質と特に変わりな
い。ノズルからの噴出性、火炎による溶融性などを考慮
して、１ｍｍ以下、好ましくは平均で１０〜５００μｍ
である。 溶射方法は従来どおり、プロパンガス、アセ
チレン、水素、灯油などの気体または液体燃料やコーク
スなどの固形燃料を熱源とする高速・高温火炎溶射装置
を用いて行う。溶射材の搬送ガスは、例えば酸素、空
気、窒素、ＣＯ、ＣＯ2、天然ガス、アルゴンなどから
選ばれる一種または二種以上が使用できる。また、転炉
ガス、熱風炉ガス、コークス炉ガスなどの、工場からの
各種の排ガスを使用することもできる。The particle size of the thermal spray material is not particularly different from that of conventional materials. Considering the jettability from the nozzle, meltability by flame, etc., 1 mm or less, preferably 10 to 500 μm on average.
Is. The thermal spraying method is performed using a high-speed, high-temperature flame spraying apparatus using a gas such as propane gas, acetylene, hydrogen, kerosene, or a solid fuel such as liquid fuel or coke as a heat source as in the conventional method. As the carrier gas for the thermal spray material, for example, one kind or two or more kinds selected from oxygen, air, nitrogen, CO, CO 2 , natural gas, argon and the like can be used. Also, various exhaust gases from the factory such as converter gas, hot stove gas, coke oven gas, etc. can be used.
【００１３】本発明の火炎溶射材は、例えば転炉、ＡＯ
Ｄ炉、取鍋、タンデッシュ、真空脱ガス炉、混銑車、電
気炉、焼却炉などの工業窯炉の内張り形成、内張りに対
する被覆または補修の他、耐火物品の形成、被覆、補修
などにも使用できる。The flame sprayed material of the present invention is, for example, a converter or AO.
D furnace, ladle, tundish, vacuum degassing furnace, mixing car, electric furnace, incinerator and other industrial kiln furnace lining formation, covering or repairing the lining, also used for forming, covering, repairing refractory articles, etc. it can.
【００１４】[0014]
【実施例】以下に本発明実施例およびその比較例を示
す。表１は各例で使用した配合原料の化学分析値と表面
性状である。ＣａＯ含有クリンカーに対してのＣＯ2ガ
ス処理は、溶射材としての粒径に予め微粉砕後、ＣＯ2
分圧９５％、加熱温度６００〜７００℃×１時間で行っ
た。ＣａＯ含有量が多いものほどＣａＣＯ3被膜の厚さ
が発達している。EXAMPLES Examples of the present invention and comparative examples thereof will be shown below. Table 1 shows the chemical analysis values and surface properties of the blended raw materials used in each example. The CO 2 gas treatment for the CaO-containing clinker is carried out by previously pulverizing to a particle size as a thermal spraying material, and then CO 2
The partial pressure was 95% and the heating temperature was 600 to 700 ° C. × 1 hour. The higher the CaO content, the more developed the thickness of the CaCO 3 coating.
【００１５】表２は本発明実施例、比較例それぞれの配
合組成と、その試験結果である。Table 2 shows the compounding compositions of the examples of the present invention and the comparative examples, and the test results thereof.
【００１６】溶射にはプロパン−酸素の火炎溶射装置を
使用した。火炎温度は最高温度部位で約２５００℃であ
る。溶射材は平均粒径１００〜１５０μｍに調整し、３
Ｋｇ／分の速度で火炎中に供給した。被溶射面は、表面
温度を１２００℃に加熱したＭｇＯ−Ｃ質レンガの垂直
面とした。A propane-oxygen flame spraying apparatus was used for the spraying. The flame temperature is about 2500 ° C. at the highest temperature part. The thermal spray material is adjusted to have an average particle size of 100 to 150 μm and 3
It was fed into the flame at a rate of Kg / min. The surface to be sprayed was a vertical surface of a MgO-C brick whose surface temperature was heated to 1200 ° C.
【００１７】付着性；溶射時のリバンドロスを差し引い
て、付着率を求めた。Adhesion: The adhesion rate was determined by subtracting the reband loss during thermal spraying.
【００１８】接着強度；１４００℃の電気炉内で被溶射
体と溶射材とのせん断強度を求めた。Adhesive strength: The shear strength between the material to be sprayed and the spray material was determined in an electric furnace at 1400 ° C.
【００１９】耐食性；溶射後の溶射材を切りだし、回転
侵食にて溶損寸法を求めた。侵食剤は鋼片と転炉スラグ
を重量比で１：１で組合せたものとした。比較例１の溶
損寸法を１とした指数で示し、数値が大きいほど溶損寸
法が大きい。Corrosion resistance: The sprayed material after thermal spraying was cut out, and the size of thermal damage was determined by rotary erosion. The erosion agent was a combination of steel slab and converter slag at a weight ratio of 1: 1. The erosion dimension of Comparative Example 1 is shown as an index, and the larger the value, the larger the erosion dimension.
【００２０】耐用性（実機試験）；３００ｔ転炉の熱間
補修を行い、耐用チャージ数を求めた。Durability (actual test): A 300 t converter was hot repaired to determine the number of durable charges.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】表２に示す試験結果からも明らかなよう
に、本発明実施例はＣａＯ質クリンカーを配合した溶射
材が本来もつ耐食性に加え、接着性が向上している。し
たがって、耐用性においても優れた効果を示している。As is clear from the test results shown in Table 2, in the examples of the present invention, in addition to the corrosion resistance originally possessed by the thermal spray material containing the CaO-based clinker, the adhesive property is improved. Therefore, it also exhibits an excellent effect in durability.
【００２４】これに対し表面にＣａＣＯ3被膜を有しな
いＣａＯ質クリンカーまたはＭｇＯ−ＣａＯ質クリンカ
ーを使用した比較例１〜３は、接着性に劣る。On the other hand, Comparative Examples 1 to 3 using the CaO-based clinker or the MgO-CaO-based clinker having no CaCO 3 coating on the surface are inferior in adhesiveness.
【００２５】[0025]
【発明の効果】溶射材においてＣａＯ含有材質は耐食性
に優れているが、接着性において十分なものではない。
本発明はＣａＣＯ3被膜を有するＣａＯ質クリンカーの
使用によって接着性の問題を解消したことにより、Ｃａ
Ｏ含有材質が本来有している耐食性の効果がいかんなく
発揮される。そして、例えば本発明の溶射材を炉の補修
材に使用すれば、補修工数および補修材の低減、さらに
は炉の稼動率向上などその効果はきわめて大きい。In the thermal spray material, the CaO-containing material is excellent in corrosion resistance, but it is not sufficient in adhesiveness.
The present invention eliminates the problem of adhesiveness by using a CaO-based clinker having a CaCO 3 coating,
The corrosion resistance originally possessed by the O-containing material can be fully exhibited. When the thermal spray material of the present invention is used as a repair material for a furnace, for example, the effect of reducing the repair man-hour and repair material, and further improving the operation rate of the furnace is extremely large.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高橋和男 兵庫県高砂市荒井町新浜１丁目３番１号 ハリマセラミック株式会社内 (72)発明者 前田一夫 富津市新富20−１ 新日本製鐵株式会社技 術開発本部内 (72)発明者 加山恒夫 富津市新富20−１ 新日本製鐵株式会社技 術開発本部内 (72)発明者 津田秀行 福岡県北九州市八幡西区東浜町１番１号 黒崎窯業株式会社内 (72)発明者 松尾正孝 福岡県北九州市八幡西区東浜町１番１号 黒崎窯業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Takahashi 1-3-1 Niihama, Arai-cho, Takasago, Hyogo Prefecture Harima Ceramic Co., Ltd. (72) Inventor Kazuo Maeda 20-1 Shintomi, Futtsu-shi Nippon Steel Corporation Technology Development Headquarters (72) Inventor Tsuneo Kayama 20-1 Shintomi, Futtsu City Nippon Steel Co., Ltd. Technology Development Headquarters (72) Inventor Hideyuki Tsuda No. 1 Higashihama-cho, Hachimansai-ku, Kitakyushu, Fukuoka Prefecture Kurosaki Kiln Industry Co., Ltd. (72) Inventor Masataka Matsuo 1-1, Higashihama-cho, Hachimansai-ku, Kitakyushu, Fukuoka Prefecture Kurosaki Ceramics Co., Ltd.
Claims (2)
質および／またはＭｇＯ−ＣａＯ質のＣａＯ含有クリン
カーを配合した火炎溶射材。1. CaO having a CaCO 3 coating on its surface
Flame spray material containing a CaO-containing clinker of high quality and / or MgO-CaO quality.
質のＣａＯ含有クリンカーをＣＯ2ガス雰囲気下で加熱
し、その表面にＣａＣＯ3被膜を形成させる火炎溶射材
の製造方法。2. CaO and / or MgO-CaO
A method for producing a flame spray material, in which a high quality CaO-containing clinker is heated in a CO 2 gas atmosphere to form a CaCO 3 coating on the surface thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5331554A JP3009580B2 (en) | 1993-12-27 | 1993-12-27 | Flame sprayed material and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5331554A JP3009580B2 (en) | 1993-12-27 | 1993-12-27 | Flame sprayed material and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07187819A true JPH07187819A (en) | 1995-07-25 |
| JP3009580B2 JP3009580B2 (en) | 2000-02-14 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5331554A Expired - Fee Related JP3009580B2 (en) | 1993-12-27 | 1993-12-27 | Flame sprayed material and manufacturing method thereof |
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| Country | Link |
|---|---|
| JP (1) | JP3009580B2 (en) |
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1993
- 1993-12-27 JP JP5331554A patent/JP3009580B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JP3009580B2 (en) | 2000-02-14 |
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