JP3389058B2 - Method for producing corrosion-resistant member and corrosion-resistant coating material - Google Patents
Method for producing corrosion-resistant member and corrosion-resistant coating materialInfo
- Publication number
- JP3389058B2 JP3389058B2 JP13673597A JP13673597A JP3389058B2 JP 3389058 B2 JP3389058 B2 JP 3389058B2 JP 13673597 A JP13673597 A JP 13673597A JP 13673597 A JP13673597 A JP 13673597A JP 3389058 B2 JP3389058 B2 JP 3389058B2
- Authority
- JP
- Japan
- Prior art keywords
- corrosion
- amorphous powder
- weight
- resistant
- coating layer
- 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.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims description 98
- 238000005260 corrosion Methods 0.000 title claims description 86
- 230000007797 corrosion Effects 0.000 title claims description 84
- 238000000576 coating method Methods 0.000 title claims description 48
- 239000011248 coating agent Substances 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000843 powder Substances 0.000 claims description 79
- 239000011247 coating layer Substances 0.000 claims description 53
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000002844 melting Methods 0.000 claims description 32
- 230000008018 melting Effects 0.000 claims description 32
- 239000011230 binding agent Substances 0.000 claims description 25
- 230000003647 oxidation Effects 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 38
- 238000000034 method Methods 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 238000007751 thermal spraying Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009689 gas atomisation Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910001068 laves phase Inorganic materials 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 238000007581 slurry coating method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005254 chromizing Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
【０００１】[0001]
【発明の属する技術分野】本発明は事業用ボイラ、産業
用ボイラ、石炭ガス化炉などにおいて、耐水蒸気酸化性
及び耐硫酸腐食性などの耐食性が要求される部位に好適
に使用できる安価な耐食性部材の製造方法、部材表面に
耐食性を付与するコーティング材料及び該コーティング
材料の原料となるアモルファス粉末に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inexpensive corrosion resistance that can be suitably used in a part for which corrosion resistance such as steam oxidation resistance and sulfuric acid corrosion resistance is required in a commercial boiler, an industrial boiler, a coal gasification furnace, etc. The present invention relates to a method for manufacturing a member, a coating material that imparts corrosion resistance to the surface of the member, and an amorphous powder that is a raw material of the coating material.
【０００２】[0002]
【従来の技術】事業用ボイラ、産業用ボイラ、石炭ガス
化炉などにおいては、水蒸気酸化及び露点による硫酸腐
食などに晒される部位が多く、従来は高Ｃｒのステンレ
ス鋼又はＮｉ基の耐食合金が大量に用いられてきた。し
かしながら、これらの材料はＣｒ、Ｎｉ、Ｍｏなどの稀
少金属を大量に含むため素材コストが高価であり、これ
らの材料を使用した装置自身の価格も必然的に高価なも
のになっていた。しかしながら近年、産業上及び環境上
の必要性から、より安価な電力の供給が要求されてお
り、これを実現するためには設備費の低減が要望される
ようになってきた。このような観点から前記のような高
級材料に代わり、より安価な材料の耐食用途への実用化
が要望されている。安価な材料の代表的なものとしては
炭素鋼などがあげられるが、これらの安価な材料の耐食
性は、前記のような耐水蒸気酸化性及び耐硫酸腐食性な
どの耐食性が要求される部位に使用するには不十分であ
り、そのままの状態で使用することはできない。そこ
で、最も現実的な対策としては前記のような安価な材料
を基材とし、耐食性が必要な表面（パイプの場合では外
面及び内面）にのみ耐食材料をコーティングする手法が
考えられる。この場合、必要な高級素材量は、従来のこ
れらの素材を用いて一体に形成されたものに比べはるか
に少なくなるため、原理的には素材コストは大幅に低減
することが期待できるが、これを実現するためのキー技
術は緻密なコーティング膜を形成するコーティング技術
とコーティング材料である。また、この場合コスト低減
が目的であるため、コーティング施工法としては高効率
で安価なものが必要である。2. Description of the Related Art In business boilers, industrial boilers, coal gasification furnaces, and the like, many parts are exposed to steam oxidation and sulfuric acid corrosion due to dew point. Conventionally, high Cr stainless steel or Ni-based corrosion-resistant alloys have been used. It has been used in large quantities. However, since these materials contain a large amount of rare metals such as Cr, Ni, and Mo, the material cost is high, and the price of the apparatus itself using these materials is inevitably high. However, in recent years, there has been a demand for cheaper power supply due to industrial and environmental needs, and in order to realize this, reduction in equipment cost has been demanded. From this point of view, there is a demand for the practical use of a cheaper material instead of the above-mentioned high-grade material for corrosion resistance. Carbon steel is a typical example of an inexpensive material, but the corrosion resistance of these inexpensive materials is used for parts that require corrosion resistance such as steam oxidation resistance and sulfuric acid corrosion resistance as described above. It is not enough to use and cannot be used as it is. Therefore, as the most practical measure, it is conceivable to use such an inexpensive material as a base material and coat the surface (outer surface and inner surface in the case of a pipe) with the corrosion resistant material with the corrosion resistant material. In this case, the amount of high-grade materials required is much smaller than that of conventional materials integrally formed using these materials, so in principle material costs can be expected to be significantly reduced. The key technologies for achieving the above are coating technology and coating materials that form a dense coating film. Further, in this case, since the purpose is cost reduction, a highly efficient and inexpensive coating method is required.
【０００３】従来、耐食性を有する材料を基材の表面に
コーティングする技術としては、肉盛り溶接、溶射及び
クロマイズ処理などがあった。これらは、いずれも次に
示すような問題があり、局部的な小領域での使用はなさ
れてきたが、大面積の素材全体に耐食性を付与するとい
う前記のような要望に答えることはできなかった。
肉盛り溶接：コーティング速度が遅く、大面積のコー
ティングを行えば施工費用が高くなるため、高級素材の
一体材と大差なくなる。また、肉盛り溶接装置が大きい
ためパイプの内面などは施工困難である。
溶射：肉盛り溶接よりはコーティング速度は早いが、
まだ不十分である。また、溶射ままではコーティング層
はポーラスであるため、耐食性は不十分である。さら
に、肉盛り溶接と同様に装置が大きいため、パイプの内
面などは施工困難である。
クロマイズ：Ｃｒなどを含む粉末中に素材を埋め込ん
で、高温に加熱することによって基材表面にＣｒを拡散
させ、表面Ｃｒ濃度を増加させる手法である。パイプ内
面などにも施工可能であるが、大面積になると非常に多
量の粉末が必要になるため、コーティングのコストは増
加する。また、Ｃｒの増加だけでは硫酸腐食に対しては
耐食性が不十分であり、適用用途も限られている。この
ように、従来の技術では大面積の部材全体に適用可能
な、安価で種々の環境での耐食性が良好なコーティング
を施すことは困難であり、高価素材の一体材を使用せざ
るを得ず、このため各種ボイラ、石炭ガス化炉、発電機
などの設備費用の高騰を招いていた。Conventionally, as techniques for coating the surface of a substrate with a material having corrosion resistance, there have been build-up welding, thermal spraying and chromizing treatment. All of these have the following problems and have been used in a small area locally, but they cannot meet the above-mentioned demand for imparting corrosion resistance to the entire large-area material. It was Overlay welding: The coating speed is slow, and the cost of coating a large area increases the construction cost. Further, since the overlay welding device is large, it is difficult to construct the inner surface of the pipe. Thermal spraying: coating speed is faster than overlay welding,
Still not enough. Moreover, since the coating layer is porous as it is as it is sprayed, the corrosion resistance is insufficient. Further, since the device is large like the build-up welding, it is difficult to construct the inner surface of the pipe. Chromize: a method of embedding a material in a powder containing Cr and the like and heating it to a high temperature to diffuse Cr on the surface of the base material and increase the surface Cr concentration. Although it can be applied to the inner surface of pipes, etc., the cost of coating increases because a large amount of powder is required in a large area. Moreover, the corrosion resistance is not sufficient for sulfuric acid corrosion only by increasing Cr, and the applications are limited. As described above, it is difficult to apply a coating that is applicable to the entire member having a large area and that is inexpensive and has good corrosion resistance in various environments by using the conventional technique. As a result, the cost of equipment such as various boilers, coal gasifiers, and generators has risen sharply.
【０００４】[0004]
【発明が解決しようとする課題】本発明はこのような従
来技術の問題を解決し、事業用ボイラ、産業用ボイラ、
石炭ガス化炉などにおける水蒸気酸化雰囲気あるいは硫
酸腐食雰囲気下でも使用可能な優れた耐食性を有し、緻
密で基材との密着性が良好で、しかも大面積部材やパイ
プ内面などの施工が難しい部位にも適用できるコーティ
ング層を形成させた耐食性部材の製造方法、該コーティ
ング層形成のためのコーティング材料及び該コーティン
グ材料の原料粉末を提供しようとするものである。SUMMARY OF THE INVENTION The present invention solves the problems of the prior art as described above, and a business boiler, an industrial boiler,
A part that has excellent corrosion resistance that can be used in steam oxidation atmosphere or sulfuric acid corrosive atmosphere in coal gasification furnace, etc., is dense and has good adhesion to the base material, and it is difficult to construct large area members or pipe inner surface The present invention also provides a method for producing a corrosion-resistant member having a coating layer formed thereon, a coating material for forming the coating layer, and a raw material powder for the coating material.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、基材とし
て安価な鋼材（炭素鋼、低合金鋼など）を前提として鋭
意検討を進め、耐食性合金相当の成分に加えてＢを含有
するコーティング材料を使用することにより前記課題を
解決できることを見出し、本発明を完成した。すなわ
ち、本発明は前記課題を解決する手段として次の（１）
〜（４）の構成を採るものである。Means for Solving the Problems The inventors of the present invention have made intensive studies on the assumption that an inexpensive steel material (carbon steel, low alloy steel, etc.) is used as a base material, and contain B in addition to a component corresponding to a corrosion resistant alloy. The present invention has been completed by finding that the above problems can be solved by using a coating material. That is, the present invention provides the following (1) as means for solving the above problems.
The configurations (4) to (4) are adopted.
【０００６】（１）金属部材の表面に、耐食性合金相当
の成分に加えてＢを含有する低融点のアモルファス粉末
をバインダ及び有機溶剤と混合してスラリ化した耐食性
コーティング材料の被覆層を形成させ、金属部材の融点
以下でアモルファス粉末の融点以上の温度に加熱して溶
融処理を行うことによって緻密な耐食性コーティング層
を形成させることを特徴とする耐食性部材の製造方法。(1) A low melting point amorphous powder containing B in addition to a component corresponding to a corrosion resistant alloy is mixed with a binder and an organic solvent to form a coating layer of a corrosion resistant coating material in the form of a slurry on the surface of a metal member. A method for producing a corrosion-resistant member, which comprises forming a dense corrosion-resistant coating layer by heating at a temperature below the melting point of the metal member and above the melting point of the amorphous powder to perform a melting treatment.
【０００７】（２）耐食性合金相当の成分に加えて２〜
４重量％のＢを含有する低融点のアモルファス粉末をバ
インダ及び有機溶剤と混合してスラリ化してなることを
特徴とする耐食性コーティング材料。(2) In addition to the components corresponding to the corrosion resistant alloy, 2 to
A corrosion-resistant coating material comprising a low melting point amorphous powder containing 4% by weight of B mixed with a binder and an organic solvent to form a slurry.
【０００８】（３）５〜３０重量％のＣｒと２〜４重量
％のＢを含有し、残部がＦｅと不可避的不純物からなる
ことを特徴とする耐水蒸気酸化性の耐食性コーティング
材料の原料となるアモルファス粉末。
（４）５〜２０重量％のＭｏと２〜４重量％のＢを含有
し、残部がＮｉ及びＣｒと不可避的不純物からなること
を特徴とする耐硫酸腐食性の耐食性コーティング材料の
原料となるアモルファス粉末。(3) A raw material of a steam oxidation resistant corrosion resistant coating material containing 5 to 30% by weight of Cr and 2 to 4% by weight of B, and the balance of Fe and inevitable impurities. Amorphous powder. (4) A raw material for a sulfuric acid-corrosion-resistant corrosion-resistant coating material characterized by containing 5 to 20% by weight of Mo and 2 to 4% by weight of B, and the balance of Ni and Cr and unavoidable impurities. Amorphous powder.
【０００９】本発明においては、耐食性コーティング層
を形成させるコーティング材料として、用途に応じて必
要な耐食性が発現できる耐食性合金相当の成分をベース
とし、これにＢ（ホウ素）を含有させることによって低
融点化したアモルファス粉末を原料としたものを使用す
る。このアモルファス粉末を金属部材（基材）表面に固
着させた後、表面温度を基材の融点以下、かつアモルフ
ァス粉末の融点以上に加熱するとアモルファス粉末のみ
が溶融して基材表面に広がり、基材との密着性が良好で
しかも緻密なコーティング層が得られる。この場合、基
材表面にアモルファス粉末を保持させる手法が必要であ
る。対象部材の形状は多岐にわたり、コーティング層形
成面が垂直あるいは下向きの場合もあることから、単に
粉末を置いただけでは保持できず、何らかの方法で固着
させる必要がある。この固着は溶射などによっても可能
であるが、前述のように溶射ではコーティング速度が遅
く、また、パイプ内面などへの適用は困難である。In the present invention, as a coating material for forming a corrosion-resistant coating layer, a component corresponding to a corrosion-resistant alloy capable of exhibiting the corrosion resistance required depending on the application is used as a base, and B (boron) is added to the base material to reduce the melting point. The raw material is made from the converted amorphous powder. After fixing this amorphous powder to the surface of the metal member (base material) and heating the surface temperature to the melting point of the base material or higher and the melting point of the amorphous powder or higher, only the amorphous powder is melted and spreads on the surface of the base material. A tight coating layer having good adhesion to and can be obtained. In this case, a method of holding the amorphous powder on the surface of the base material is necessary. Since the target member has a wide variety of shapes and the coating layer forming surface may be vertical or downward, it cannot be held merely by placing the powder, and it is necessary to fix it by some method. This fixing can be achieved by thermal spraying or the like, but as described above, thermal spraying has a low coating speed and is difficult to apply to the inner surface of the pipe.
【００１０】したがって、従来にない全く新しい手法が
必要であり、本発明ではアモルファス粉末をバインダ及
び有機溶剤でスラリ化したコーティング材料を使用して
基材表面に被覆する手法を採用した。スラリは液体状で
あるため基材表面への被覆層の形成は容易であり、例え
ば、刷毛あるいはスプレーなどにより塗布することがで
きる。また、スラリを満たした容器中に対象部材を浸漬
することによってパイプ内面などにも容易に、しかも高
効率に塗布することができる。スラリ被覆層には必要な
アモルファス粉末原料以外にも、スラリ化するために用
いたバインダ、及び有機溶剤が残留しているため、これ
らを取り除く必要があるが、これは以下のように行えば
よい。Therefore, a completely new method which has never been used is required. In the present invention, a method of coating the surface of a substrate with a coating material prepared by slurrying an amorphous powder with a binder and an organic solvent is adopted. Since the slurry is in a liquid state, it is easy to form the coating layer on the surface of the base material, and it can be applied by, for example, a brush or a spray. Further, by immersing the target member in the container filled with the slurry, it is possible to easily and highly efficiently apply it to the inner surface of the pipe or the like. In addition to the necessary amorphous powder raw material, the binder used for making slurry and the organic solvent remain in the slurry coating layer, so these need to be removed, but this can be done as follows. .
【００１１】有機溶剤の蒸発温度は通常、室温以下であ
るため、一晩程度放置するなどの方法により乾燥させる
と有機溶剤が蒸発して消失する。その後、アモルファス
粉末の融点以下でバインダの蒸発温度以上の高温（６０
０〜９００℃）に保持するとバインダが蒸発し、アモル
ファス粉末のみが基材表面に残ることとなる。なお、単
にアモルファス粉末を基材表面に載せた場合と異なり、
この場合はアモルファス粉末にとって融点以下とはいえ
比較的高温に保持されているため、アモルファス粉末間
及び粉末と基材の間には緩い固着が生じることになり、
垂直あるいは下向き面でもアモルファス粉末は落下せず
保持されることとなる。Since the evaporation temperature of the organic solvent is usually room temperature or lower, the organic solvent evaporates and disappears when it is dried by a method such as standing overnight. After that, at a temperature below the melting point of the amorphous powder and above the evaporation temperature of the binder (60
When kept at 0 to 900 ° C., the binder evaporates and only the amorphous powder remains on the surface of the base material. It should be noted that, unlike the case where the amorphous powder is simply placed on the surface of the base material,
In this case, since the amorphous powder is kept at a relatively high temperature even though it is below the melting point, loose adhesion will occur between the amorphous powder and between the powder and the base material.
The amorphous powder will be retained without falling even on the vertical or downward surface.
【００１２】[0012]
【発明の実施の形態】以下、本発明の実施の態様を作用
とともに詳述する。本発明（１）及び（２）に係る安価
な耐食性部材及び耐食性コーティング材料は以下のよう
にして得ることができる。先ず用途に応じ必要な耐食性
を有する合金組成に加えて、必要量のＢを含有するアモ
ルファス粉末を作製する。アモルファス粉末の作製方法
としては、例えば、前記合金組成の原料に必要量のＢを
添加し、高周波溶解などによって母合金を作製し、次に
ガスアトマイズ装置を用いて母合金を溶解後、粉末に急
冷することによって、Ｂが均質に固溶したアモルファス
粉末を得ることができる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail together with their functions. The inexpensive corrosion resistant member and the corrosion resistant coating material according to the present inventions (1) and (2) can be obtained as follows. First, an amorphous powder containing a required amount of B is prepared in addition to an alloy composition having a necessary corrosion resistance depending on the application. As a method for producing the amorphous powder, for example, a necessary amount of B is added to the raw material of the alloy composition, a master alloy is produced by high-frequency melting, etc., and then the master alloy is melted by using a gas atomizing device, followed by rapid cooling to powder. By doing so, an amorphous powder in which B is homogeneously solid-dissolved can be obtained.
【００１３】Ｂはコーティング材料の融点を低下させ、
原料製造時にアモルファス化を可能とすると同時に、コ
ーティング時においては基材は固相のままでコーティン
グ層のみの溶融を可能とする元素である。Ｂの添加量は
耐食性を有する合金組成などにより異なるが、通常はア
モルファス粉末中でのＢの割合が２〜４重量％程度が好
ましい。Ｂ濃度が４重量％を超える量では融点が上昇す
るため、アモルファス粉末の製造が困難となると同時
に、コーティング時の加熱温度が高くなり、基材の特性
劣化のおそれがあるため望ましくない。また、Ｂ濃度が
２重量％未満では、Ｂの添加効果が認められず、同様に
融点が上昇するため望ましくない。B lowers the melting point of the coating material,
It is an element that enables amorphization at the time of manufacturing the raw material and at the same time enables melting of only the coating layer while the substrate remains in the solid phase at the time of coating. The amount of B added varies depending on the composition of the alloy having corrosion resistance and the like, but normally, the proportion of B in the amorphous powder is preferably about 2 to 4% by weight. If the B concentration exceeds 4% by weight, the melting point increases, making it difficult to produce amorphous powder, and at the same time, the heating temperature during coating becomes high, which may deteriorate the characteristics of the base material, which is not desirable. Further, if the B concentration is less than 2% by weight, the effect of adding B is not recognized and the melting point similarly rises, which is not desirable.
【００１４】作製したアモルファス粉末に対しバインダ
及び有機溶剤を加え、混合することによってスラリ化
し、コーティング材料とする。バインダとしてはエチレ
ンビニルアセテート樹脂（ＥＶＡ樹脂）、ポリスチレ
ン、ポリブチルメタクリレートなどの高分子系バイン
ダ、メタクリル酸エステルなどのアクリル酸系バインダ
などが例示できるが、真空中やＡｒなどの不活性ガス雰
囲気中などでの加熱蒸発処理の際に蒸発しやすいことか
らメタクリル酸ブチルなどのメタクリル酸エステル系バ
インダが特に好適である。また、有機溶剤としてはメタ
ノール、エタノール、ブタノールなどのアルコール系溶
剤、トルエン、キシレンなどの芳香族系溶剤などが例示
できるが、バインダとの相性などからトルエン又はブタ
ノールが特に好適である。A binder and an organic solvent are added to the produced amorphous powder and mixed to form a slurry, which is used as a coating material. Examples of the binder include polymer binders such as ethylene vinyl acetate resin (EVA resin), polystyrene and polybutylmethacrylate, acrylic acid binders such as methacrylic acid ester, etc., but in vacuum or in an inert gas atmosphere such as Ar. A methacrylic acid ester-based binder such as butyl methacrylate is particularly suitable because it easily evaporates during the heat evaporation treatment such as. Examples of the organic solvent include alcohol solvents such as methanol, ethanol and butanol, and aromatic solvents such as toluene and xylene. Toluene or butanol is particularly preferable in view of compatibility with the binder.
【００１５】なお、これらの配合比はコーティングを施
す基材の形状やサイズ、アモルファス粉末の種類、施工
条件などによって適宜定めればよいが、一般的には、バ
インダの使用量はアモルファス粉末１重量部に対し０．
１〜０．３重量部程度とするのが好ましい。使用量が
０．１重量部未満ではスラリの流動性が不十分であり、
０．３重量部を超えると加熱時においても蒸発が遅くな
る傾向がある。また、有機溶剤の使用量はアモルファス
粉末１重量部に対し０．０５〜０．２重量部程度とする
のが好ましい。使用量が０．０５重量部未満ではスラリ
の流動性が不十分であり、０．２重量部を超えるとスラ
リ中の原料密度が小さくなり、緻密なコーティング層を
形成しにくくなるので好ましくない。The mixing ratio of these may be appropriately determined depending on the shape and size of the base material to be coated, the type of amorphous powder, the working conditions, etc. Generally, the amount of binder used is 1 weight of amorphous powder. 0 for the department.
It is preferably about 1 to 0.3 parts by weight. If the amount used is less than 0.1 part by weight, the fluidity of the slurry is insufficient,
If it exceeds 0.3 parts by weight, evaporation tends to be slow even during heating. The amount of the organic solvent used is preferably about 0.05 to 0.2 parts by weight with respect to 1 part by weight of the amorphous powder. If the amount used is less than 0.05 parts by weight, the fluidity of the slurry will be insufficient, and if it exceeds 0.2 parts by weight, the raw material density in the slurry will be small, making it difficult to form a dense coating layer, which is not preferable.
【００１６】このようにして得たスラリ（コーティング
材料）を用いて基材表面に被覆層を形成させる。被覆層
の形成方法としては、例えば刷毛、スプレーなどで基材
表面に塗布する方法が一般的である。なお、管の内面に
施工する場合、大径管ではこれらの手法も適用可能であ
るが、小径管の場合、これらの手法を適用するためには
特別の小型装置が必要となる。したがって、小径管の内
面や複雑な形状の部材に施工する場合には、塗布でなく
スラリを満たした容器の中に漬ける方法の方がコーティ
ング法としてより容易である。被覆層の厚みは１００〜
１０００μｍ（最終的な耐食性コーティング層の段階で
５０〜６００μｍ）とする。被覆層の厚みが１００μｍ
未満ではコーティング層の厚みが薄くなり、耐食性を維
持できる時間が短くなるため望ましくない。また、１０
００μｍを超えると原料費が高くなるため望ましくな
い。A coating layer is formed on the surface of the substrate by using the slurry (coating material) thus obtained. As a method of forming the coating layer, for example, a method of applying the coating layer to the surface of the base material with a brush, a spray or the like is generally used. In addition, when constructing on the inner surface of the pipe, these methods can be applied to a large-diameter pipe, but in the case of a small-diameter pipe, a special small device is required to apply these techniques. Therefore, when applying to the inner surface of a small diameter tube or a member having a complicated shape, the method of dipping in a container filled with slurry rather than coating is easier as a coating method. The thickness of the coating layer is 100-
1000 μm (50 to 600 μm at the final stage of the corrosion resistant coating layer). Thickness of coating layer is 100 μm
When it is less than 1, the thickness of the coating layer becomes thin and the time during which the corrosion resistance can be maintained becomes short, which is not desirable. Also, 10
If it exceeds 00 μm, the raw material cost becomes high, which is not desirable.
【００１７】スラリ塗布後、一晩程度大気中で放置する
などの方法によって、被覆層中の有機溶剤成分を蒸発さ
せ、被覆層をアモルファス粉末とバインダのみとする。
次に６００〜９００℃で５〜１５分間程度加熱すること
によってバインダを蒸発させる。加熱温度が６００℃未
満ではバインダの蒸発が遅く、９００℃を超えると原料
粉末とバインダ成分との反応が生じたり、酸化、炭化等
の劣化が生じる恐れがあるので好ましくない。なお、こ
のバインダ成分の加熱蒸発処理は真空中あるいはＡｒな
どの不活性ガス雰囲気中で行うのが好ましい。バインダ
蒸発後はアモルファス原料粉末のみが残るが、このバイ
ンダ蒸発のための加熱によって粉末どうし及び基材と粉
末との間でわずかな固着が生じるため、アモルファス粉
末は落下することなく、基材に固着した状態になる。After the slurry is applied, the organic solvent component in the coating layer is evaporated by a method such as leaving it in the air for about one night, so that the coating layer contains only amorphous powder and a binder.
Next, the binder is evaporated by heating at 600 to 900 ° C. for about 5 to 15 minutes. If the heating temperature is lower than 600 ° C., the evaporation of the binder is slow, and if it exceeds 900 ° C., the reaction between the raw material powder and the binder component may occur, or the deterioration such as oxidation and carbonization may occur, which is not preferable. The heating and evaporation treatment of the binder component is preferably performed in vacuum or in an atmosphere of an inert gas such as Ar. Only the amorphous raw material powder remains after the binder evaporates, but heating due to this binder evaporation causes slight adhesion between the powders and the base material and the powder, so the amorphous powder does not drop and adheres to the base material. It will be in the state of doing.
【００１８】次に、基材表面を基材の融点以下、アモル
ファス粉末の融点以上の温度に加熱することによって、
アモルファス粉末のみを溶融させる溶融処理を行う。こ
こで加熱温度、所要加熱時間は使用したアモルファス粉
末原料の種類により異なるが、通常は１１００〜１３０
０℃の温度で１〜１０分間程度の処理で十分である。こ
の場合、あまり温度を上げすぎると、基材の性質が劣化
するため、加熱は必要最小限の温度に止める必要があ
る。また、加熱の際の酸化を防止するために、局所的に
Ａｒガスなどの不活性ガス雰囲気として加熱することが
望ましい。加熱温度の例としては、例えば本発明（３）
のアモルファス粉末を使用する場合は１２５０℃以上
に、また、本発明（４）のアモルファス粉末を使用する
場合は１２００℃以上に加熱すれば粉末は溶融する。Next, by heating the surface of the base material to a temperature below the melting point of the base material and above the melting point of the amorphous powder,
A melting process is performed to melt only the amorphous powder. Here, the heating temperature and the required heating time vary depending on the type of the amorphous powder raw material used, but are usually 1100 to 130.
A treatment at a temperature of 0 ° C. for about 1 to 10 minutes is sufficient. In this case, if the temperature is raised too much, the properties of the substrate are deteriorated, so it is necessary to stop the heating at the minimum necessary temperature. Further, in order to prevent oxidation during heating, it is desirable to locally heat in an atmosphere of an inert gas such as Ar gas. Examples of the heating temperature include, for example, the present invention (3).
When the amorphous powder of No. 2 is used, it is melted at 1250 ° C. or higher, and when the amorphous powder of the present invention (4) is heated to 1200 ° C. or more, the powder is melted.
【００１９】加熱溶融処理の工程において、アモルファ
ス粉末の融点以上で基材の融点以下の温度に保持すると
アモルファス粉末のみが溶融し、コーティング材料の被
覆層を形成させた基材の表面は全て液相で覆われること
になる。その後、等温で保持するとＢが固液拡散によっ
て基材の表面から基材内部に拡散していく。そして最後
に室温まで冷却するとすべて固相の部材（本発明に係る
耐食性部材）が得られる。In the heating and melting treatment step, when the temperature is kept above the melting point of the amorphous powder and below the melting point of the base material, only the amorphous powder is melted, and the surface of the base material on which the coating material coating layer is formed is all in the liquid phase. Will be covered with. After that, when kept at the same temperature, B diffuses from the surface of the base material to the inside of the base material by solid-liquid diffusion. Finally, when cooled to room temperature, a solid phase member (corrosion resistant member according to the present invention) is obtained.
【００２０】このプロセスではいったん液相を経るた
め、最終的に固相となるコーティング層は隙間がなく緻
密である。また、基材とコーティング層とはＢの拡散に
よって原子レベルでの融合が生じるため密着性は非常に
良好となる。他の合金成分の拡散速度はＢに比べると圧
倒的に遅いため、基材へはほとんど拡散しない。したが
って、加熱溶融処理後のコーティング層の組成は原料組
成からＢのみが減少した組成となる。なお、コーティン
グ層内のＢの残存量は加熱温度と加熱保持する時間によ
ってきまり、１１００℃においても約５分間以上保持す
ると、Ｂのほとんどは基材中に拡散し、コーティング層
には残らないこととなる。In this process, since the liquid phase is passed through once, the coating layer which finally becomes a solid phase is dense with no gaps. Further, since the base material and the coating layer are fused at the atomic level by the diffusion of B, the adhesion is very good. Since the diffusion speed of other alloy components is overwhelmingly slower than that of B, it hardly diffuses into the base material. Therefore, the composition of the coating layer after the heating and melting treatment is a composition in which only B is reduced from the raw material composition. The amount of B remaining in the coating layer depends on the heating temperature and the time of heating and holding, and even if kept at 1100 ° C. for about 5 minutes or more, most of B diffuses into the base material and does not remain in the coating layer. Becomes
【００２１】本発明（３）及び（４）に係るアモルファ
ス粉末は、前記発明（１）で使用するコーティング材料
あるいは発明（２）のコーティング材料の原料として好
適なものである。本発明（３）のアモルファス粉末は、
事業用ボイラなどのパイプ内面などで耐水蒸気酸化性が
要求される部材に適用するのに特に適している。このア
モルファス粉末は５〜３０重量％のＣｒと２〜４重量％
のＢを含有し、残部がＦｅと不可避的不純物からなるこ
とを特徴とする。このアモルファス粉末において、Ｃｒ
は耐水蒸気酸化性を向上させる元素である。Ｃｒの含有
量が５重量％未満では添加効果が認められず、また、３
０重量％を超えると高温で長時間使用時にσ相と呼ばれ
る脆化相が生成し、コーティング層自身が脆化するおそ
れがある。この場合、用途によっては使用中に熱応力な
どが負荷されるため、コーティング層に割れなどが発生
し、耐食性の低い母材が直接耐食雰囲気に晒されるよう
になるので好ましくない。なお、Ｂの含有量範囲の設定
理由については前記のとおりである。The amorphous powders according to the inventions (3) and (4) are suitable as a raw material of the coating material used in the invention (1) or the coating material of the invention (2). The amorphous powder of the present invention (3) is
It is particularly suitable for application to parts that require steam oxidation resistance such as the inner surface of pipes such as commercial boilers. This amorphous powder contains 5 to 30% by weight of Cr and 2 to 4% by weight.
Of B and the balance consists of Fe and unavoidable impurities. In this amorphous powder, Cr
Is an element that improves steam oxidation resistance. If the content of Cr is less than 5% by weight, the effect of addition is not recognized, and 3
If it exceeds 0% by weight, an embrittlement phase called a σ phase is generated during long-term use at high temperature, and the coating layer itself may be embrittled. In this case, thermal stress or the like is applied during use depending on the application, so that the coating layer is cracked and the base material having low corrosion resistance is directly exposed to the corrosion resistant atmosphere, which is not preferable. The reason for setting the B content range is as described above.
【００２２】本発明（４）のアモルファス粉末は、産業
用ボイラ、石炭ガス化炉などの熱交換器、脱硫装置など
で露点による耐硫酸腐食性が要求される部材に適用する
のに特に適している。このアモルファス粉末は５〜２０
重量％のＭｏと２〜４重量％のＢを含有し、残部がＮｉ
及びＣｒと不可避的不純物からなることを特徴とする。
このアモルファス粉末において、Ｍｏは耐硫酸腐食性を
向上させる元素である。Ｍｏの含有量が５重量％未満で
は添加効果がない。また、２０重量％を超えると高温で
長時間使用時にラーベス相と呼ばれる脆化相が生成し、
コーティング層自身が脆化するため、前記σ相が生成す
る場合と同じ理由で耐食性が低下するため望ましくな
い。なお、Ｂの含有量範囲の設定理由については前記の
とおりである。The amorphous powder of the present invention (4) is particularly suitable for being applied to members such as industrial boilers, heat exchangers such as coal gasification furnaces, desulfurization devices, etc., which require sulfuric acid corrosion resistance due to dew point. There is. This amorphous powder is 5-20
% By weight Mo and 2-4% by weight B with the balance being Ni
And Cr and unavoidable impurities.
In this amorphous powder, Mo is an element that improves sulfuric acid corrosion resistance. If the content of Mo is less than 5% by weight, the effect of addition is not obtained. Further, if it exceeds 20% by weight, an embrittlement phase called a Laves phase is formed at a high temperature for a long time,
Since the coating layer itself becomes brittle, the corrosion resistance is reduced for the same reason as when the σ phase is generated, which is not desirable. The reason for setting the B content range is as described above.
【００２３】[0023]
【実施例】以下、実施例により本発明をさらに具体的に
説明する。
（実施例１）実施例１は耐水蒸気酸化性の良好な、安価
な耐食性部材の製造方法に関する例である。種々の組成
のＦｅ、Ｃｒ及びＢを含有する合金を高周波溶解によっ
て溶解し、母合金を作製した。次にガスアトマイズ装置
を用い、溶融状態から急冷することによってアモルファ
ス合金粉末を作製した。このアモルファス粉末の平均粒
径を１００μｍ程度に分級した後、アモルファス粉末１
０００ｇ、バインダとしてのメタクリル酸ブチル２００
ｇ、トルエン２００ｇ、ブタノール２０ｇを混合するこ
とによってスラリ状のコーティング材料を作製した。EXAMPLES The present invention will be described in more detail below with reference to examples. (Example 1) Example 1 is an example of a method for manufacturing an inexpensive corrosion-resistant member having good steam oxidation resistance. Alloys containing various compositions of Fe, Cr and B were melted by high frequency melting to prepare mother alloys. Next, an amorphous alloy powder was produced by rapidly cooling from a molten state using a gas atomizing device. After classifying the average particle size of the amorphous powder to about 100 μm, the amorphous powder 1
000g, butyl methacrylate 200 as a binder
g, 200 g of toluene, and 20 g of butanol were mixed to prepare a slurry-like coating material.
【００２４】次にこのコーティング材料を満たした槽中
に外径５０．８ｍｍ、板厚６．８ｍｍ、長さ３００ｍｍ
のＳＴＢ４１０チューブを漬けることによってチューブ
内面に被覆層を形成させた。なお、チューブは酸洗処理
によって内表面を洗浄したものを使用した。一晩放置し
て有機溶剤を蒸発させた後、均熱帯幅５０ｍｍの高周波
加熱装置によってチューブの内面の温度を８００℃に上
げ、１０分間保持することによってバインダを蒸発させ
た。次に引き続き同じ装置で１２５０℃に加熱後６分間
保持することによって、アモルファス粉末の溶融処理を
行った。その後、室温まで冷却し、ＳＴＢ４１０チュー
ブの内面に厚さ２００μｍの耐食性コーティング層を形
成させた本発明の耐食性部材を得た。得られた耐食性部
材を試験材として耐食性評価試験を行った。Next, in a tank filled with this coating material, the outer diameter was 50.8 mm, the plate thickness was 6.8 mm, and the length was 300 mm.
The coating layer was formed on the inner surface of the STB410 tube by immersing the STB410 tube. The tube used had its inner surface cleaned by pickling. After allowing to stand overnight to evaporate the organic solvent, the temperature of the inner surface of the tube was raised to 800 ° C. by a high frequency heating device having a soaking width of 50 mm, and the temperature was kept for 10 minutes to evaporate the binder. Next, the amorphous powder was melted by continuously heating it to 1250 ° C. and holding it for 6 minutes in the same apparatus. Then, it was cooled to room temperature to obtain a corrosion resistant member of the present invention in which a 200 μm thick corrosion resistant coating layer was formed on the inner surface of the STB410 tube. A corrosion resistance evaluation test was conducted using the obtained corrosion resistant member as a test material.
【００２５】耐食性コーティング層の耐食性評価試験と
して、チューブの内部に水蒸気を循環させる水蒸気酸化
試験を行った。酸化条件は６２５℃で２００時間保持し
た後、室温に冷却する工程の１０サイクル繰り返しであ
り、内面コーティング部（約５０ｍｍ幅）における減肉
深さの測定によって、耐水蒸気酸化性の比較を行った。
なお、この場合、コーティング部以外（基材が露出して
いるところ）の減肉深さの平均は４２０μｍであった。
検討したアモルファス粉末の組成及び耐水蒸気酸化性評
価結果をまとめて表１に示す。Corrosion resistance As a corrosion resistance evaluation test of the coating layer, a steam oxidation test was conducted in which steam was circulated inside the tube. Oxidation conditions were 10 cycles of a process of holding at 625 ° C. for 200 hours and then cooling to room temperature, and comparison of steam oxidation resistance was carried out by measuring the thickness reduction depth in the inner coating part (width of about 50 mm). .
In this case, the average thickness reduction thickness other than the coating portion (where the base material is exposed) was 420 μm.
Table 1 shows the composition of the examined amorphous powder and the evaluation result of steam oxidation resistance.
【００２６】[0026]
【表１】 [Table 1]
【００２７】試験材１はＢ添加量が１．５重量％と本発
明範囲以下のものである。Ｂ量が少ないためアモルファ
ス粉末の融点が高くなり、１２５０℃加熱では完全に液
相にならず、加熱処理後もコーティング層に欠陥が残っ
た。その結果、耐食性の低い母材が水蒸気に晒されるこ
ととなり、減肉深さが大きくなった。試験材２〜４は本
発明のアモルファス粉末を使用したものである。アモル
ファス粉末の融点は十分低くなったため、１２５０℃加
熱で完全に液相になった。その結果、緻密なコーティン
グ層が得られた。また、Ｃｒ量は適当なためコーティン
グ層の耐水蒸気酸化性は良好で、減肉深さは小さくなっ
た。Test material 1 has a B addition amount of 1.5% by weight, which is within the range of the present invention. Since the amount of B was small, the melting point of the amorphous powder was high, the liquid phase was not completely transformed by heating at 1250 ° C., and defects remained in the coating layer even after the heat treatment. As a result, the base material with low corrosion resistance was exposed to water vapor, and the metal thinning depth increased. Test materials 2 to 4 use the amorphous powder of the present invention. Since the melting point of the amorphous powder was sufficiently low, it became completely in the liquid phase by heating at 1250 ° C. As a result, a dense coating layer was obtained. Further, since the Cr content was appropriate, the steam oxidation resistance of the coating layer was good, and the thickness reduction depth was small.
【００２８】試験材５はＢ添加量が４．３重量％と本発
明範囲を超えるものである。Ｂ量が多いため１２５０℃
加熱では完全に液相にならず、加熱処理後もコーティン
グ層に欠陥が残った。その結果、耐食性の低い母材が水
蒸気に晒されることとなり、減肉深さが大きくなった。
試験材６はＣｒ添加量が３重量％と本発明範囲以下のも
のである。Ｃｒ量が少ないためコーティング層自身の耐
水蒸気酸化性が低くなり、減肉深さが大きくなった。The test material 5 has a B addition amount of 4.3% by weight, which exceeds the range of the present invention. 1250 ° C due to the large amount of B
Upon heating, the liquid phase was not completely formed, and defects remained in the coating layer even after the heat treatment. As a result, the base material with low corrosion resistance was exposed to water vapor, and the metal thinning depth increased.
The test material 6 has a Cr addition amount of 3% by weight and is within the range of the present invention. Since the amount of Cr was small, the steam oxidation resistance of the coating layer itself was low, and the thinning depth was large.
【００２９】試験材７〜９は本発明のアモルファス粉末
を使用したものである。耐水蒸気酸化性の良好な緻密な
コーティング層が得られたため、減肉深さは小さくなっ
た。試験材１０はＣｒ添加量が３３重量％と本発明範囲
を超えるものである。Ｃｒ量が多いため水蒸気酸化試験
中に脆いσ相が生成し、コーティング相を脆化させた。
水蒸気酸化試験は高温と室温を繰り返すサイクル試験で
行ったため、その過程での熱応力によってσ相の生成に
よって脆くなったコーティング層が破壊し、耐食性の低
い母材が水蒸気に晒されることとなり、減肉深さが大き
くなった。Test materials 7 to 9 use the amorphous powder of the present invention. Since a dense coating layer having good steam oxidation resistance was obtained, the metal thinning depth was small. The test material 10 has a Cr addition amount of 33% by weight, which exceeds the range of the present invention. Due to the large amount of Cr, a brittle σ phase was generated during the steam oxidation test, and the coating phase was embrittled.
Since the steam oxidation test was conducted as a cycle test in which high temperature and room temperature were repeated, the coating layer that became brittle due to the formation of the σ phase due to the thermal stress in the process was destroyed, and the base material with low corrosion resistance was exposed to steam. The meat depth has increased.
【００３０】（実施例２）実施例２は耐硫酸腐食性の良
好な、安価な耐食性部材の製造方法に関する例である。
Ｎｉ−Ｃｒをベースに種々の組成のＭｏ及びＢを含有す
る合金を高周波溶解によって溶解し、母合金を作製し
た。次にガスアトマイズ装置を用い、溶融状態から急冷
することによってアモルファス合金粉末を作製した。こ
のアモルファス粉末の平均粒径を１００μｍ程度に分級
した後、アモルファス粉末１２０ｇ、バインダとしての
メタクリル酸ブチル２５ｇ、トルエン９ｇ、ブタノール
１ｇを混合することによってスラリ状のコーティング材
料を作製した。(Example 2) Example 2 is an example of a method for manufacturing an inexpensive corrosion-resistant member having good sulfuric acid corrosion resistance.
Alloys containing Mo and B having various compositions based on Ni-Cr were melted by high frequency melting to prepare a mother alloy. Next, an amorphous alloy powder was produced by rapidly cooling from a molten state using a gas atomizing device. After classifying the average particle size of the amorphous powder to about 100 μm, 120 g of the amorphous powder, 25 g of butyl methacrylate as a binder, 9 g of toluene, and 1 g of butanol were mixed to prepare a slurry-like coating material.
【００３１】基材は外径５０．８ｍｍ、板厚６．８ｍ
ｍ、長さ３００ｍｍのＳＴＢ４１０チューブであり、酸
洗によって外表面を洗浄した後、外面に刷毛塗りでスラ
リ状のコーティング材料を塗布した。一晩放置して有機
溶剤を蒸発させた後、均熱帯幅５０ｍｍの高周波加熱装
置によってチューブ外面の温度を８００℃に上げ、１０
分間保持することによってバインダを蒸発させた。次に
引き続き同じ装置で１２００℃に加熱後６分間保持する
ことによって、アモルファス粉末の溶融処理を行った。
その後、室温まで冷却し、ＳＴＢ４１０チューブの外面
に厚さ２００μｍの耐食性コーティング層を形成させた
本発明の耐食性部材を得た。さらに実機での長時間使用
状況を模擬するため、７００℃で１００時間保持した
後、室温に冷却する工程を１０サイクル繰り返す時効処
理を施した後、耐食性評価試験を行った。The substrate has an outer diameter of 50.8 mm and a plate thickness of 6.8 m.
A STB410 tube having a length of m and a length of 300 mm, the outer surface was washed by pickling, and then a slurry coating material was applied to the outer surface by brushing. After allowing to stand overnight to evaporate the organic solvent, the temperature of the outer surface of the tube is raised to 800 ° C. by a high-frequency heating device having a soaking width of 50 mm, and 10
The binder was evaporated by holding it for a minute. Next, the amorphous powder was melted by continuously heating it to 1200 ° C. and holding it for 6 minutes in the same apparatus.
Then, it was cooled to room temperature to obtain a corrosion resistant member of the present invention in which a 200 μm thick corrosion resistant coating layer was formed on the outer surface of the STB410 tube. Furthermore, in order to simulate a long-term use condition in an actual machine, after holding at 700 ° C. for 100 hours and then cooling to room temperature, an aging treatment was repeated 10 cycles, and then a corrosion resistance evaluation test was performed.
【００３２】耐食性コーティング層の耐食性評価試験と
して、コーティング部から試験片を切り出し、硫酸中に
浸漬する硫酸腐食試験を行った。硫酸濃度は５０重量％
であり、５０℃で２４時間浸漬後の重量減によって耐食
性を比較した。なお、試験片のコーティング面以外は樹
脂でマスキングすることによって腐食を完全に防止し
た。検討したアモルファス粉末の組成及び耐硫酸腐食性
評価結果をまとめて表２に示す。Corrosion Resistance As a corrosion resistance evaluation test of the coating layer, a sulfuric acid corrosion test was carried out by cutting out a test piece from the coated portion and immersing it in sulfuric acid. Sulfuric acid concentration is 50% by weight
The corrosion resistance was compared by weight reduction after immersion at 50 ° C. for 24 hours. In addition, corrosion was completely prevented by masking with resin other than the coated surface of the test piece. Table 2 shows the composition of the examined amorphous powder and the evaluation result of sulfuric acid corrosion resistance.
【００３３】[0033]
【表２】 [Table 2]
【００３４】試験材１１はＢ添加量が１．５重量％と本
発明範囲以下のものである。Ｂ量が少ないためコーティ
ング材料の融点が高くなり、１２００℃加熱では完全に
液相にならず、加熱処理後もコーティング層に欠陥が残
った。その結果、耐食性の低い母材が硫酸に晒されるこ
ととなり、重量減が大きくなった。試験材１２、１３は
本発明のアモルファス粉末を使用したものである。Ｂ量
が適当なためアモルファス粉末の融点は十分低くなり、
１２００℃加熱で完全に液相になった。その結果、緻密
なコーティング層が得られた。また、Ｍｏ量も適当であ
るためコーティング層の耐硫酸腐食性は良好で、重量減
は小さくなった。The test material 11 has a B addition amount of 1.5% by weight, which is within the range of the present invention. Since the amount of B was small, the melting point of the coating material was high, and when heated at 1200 ° C., the liquid phase was not completely formed, and defects remained in the coating layer after the heat treatment. As a result, the base material with low corrosion resistance was exposed to sulfuric acid, and the weight loss was large. The test materials 12 and 13 use the amorphous powder of the present invention. Since the amount of B is appropriate, the melting point of the amorphous powder is sufficiently low,
The liquid phase was completely turned on by heating at 1200 ° C. As a result, a dense coating layer was obtained. Further, since the amount of Mo is also appropriate, the sulfuric acid corrosion resistance of the coating layer was good, and the weight loss was small.
【００３５】試験材１４はＢ添加量が４．４重量％と本
発明範囲を超えるものである。Ｂ量が多いため１２００
℃の加熱では完全に液相にならず、加熱処理後もコーテ
ィング層に欠陥が残った。その結果、耐食性の低い母材
が硫酸に晒されることとなり、重量減が大きくなった。
試験材１５はＭｏ添加量が３重量％と本発明範囲以下の
ものである。Ｍｏ量が少ないためコーティング層自身の
耐硫酸腐食性が低くなり、重量減は大きくなった。The test material 14 has a B addition amount of 4.4% by weight, which exceeds the range of the present invention. 1200 due to the large amount of B
Heating at ℃ did not completely turn into a liquid phase, and defects remained in the coating layer even after the heat treatment. As a result, the base material with low corrosion resistance was exposed to sulfuric acid, and the weight loss was large.
The test material 15 has a Mo addition amount of 3% by weight, which is within the range of the present invention. Since the amount of Mo was small, the sulfuric acid corrosion resistance of the coating layer itself was low, and the weight loss was large.
【００３６】試験材１６、１７は本発明のアモルファス
粉末を使用したものである。耐硫酸腐食性の良好な緻密
なコーティング層が得られたため、重量減は小さくなっ
た。試験材１８はＭｏ添加量が２３重量％と本発明範囲
を超えるものである。Ｍｏ量が多いため７００℃の時効
処理中に脆いラーベス相が生成し、コーティング層を脆
化させた。時効処理は高温と室温を繰り返すサイクルで
行ったため、その過程での熱応力によってラーベス相の
生成によって脆くなったコーティング層が破壊し、耐食
性の低い母材が硫酸に晒されることとなり、重量減が大
きくなった。The test materials 16 and 17 use the amorphous powder of the present invention. Since a dense coating layer having good sulfuric acid corrosion resistance was obtained, the weight loss was small. The test material 18 had a Mo addition amount of 23% by weight, which exceeds the range of the present invention. Due to the large amount of Mo, a brittle Laves phase was generated during the aging treatment at 700 ° C, and the coating layer was embrittled. Since the aging treatment was performed in a cycle of repeating high temperature and room temperature, the coating layer which became brittle due to the generation of Laves phase due to the thermal stress in the process was destroyed, and the base material with low corrosion resistance was exposed to sulfuric acid, resulting in weight loss. It got bigger.
【００３７】[0037]
【発明の効果】以上詳述したように、本発明の方法によ
れば事業用ボイラ、産業用ボイラ、石炭ガス化炉などに
おける水蒸気酸化雰囲気あるいは硫酸腐食雰囲気下で使
用可能な優れた耐食性を有し、緻密で基材との密着性が
良好で、しかも大面積部材やパイプ内面などの施工が難
しい部位にも適用できるコーティング層を形成させた耐
食性部材を製造することができる。また、本発明のコー
ティング材料は前記耐食性部材の製造に好適なものであ
り、さらに本発明のアモルファス粉末は前記コーティン
グ材料の原料粉末として優れた特性を有するものであ
る。As described above in detail, according to the method of the present invention, it has excellent corrosion resistance that can be used in a steam boiler, industrial boiler, coal gasifier, etc. in a steam oxidizing atmosphere or a sulfuric acid corrosive atmosphere. Further, it is possible to manufacture a corrosion-resistant member that is dense and has good adhesion to a base material, and that has a coating layer formed that can be applied to a site such as a large area member or the inner surface of a pipe that is difficult to construct. Further, the coating material of the present invention is suitable for the production of the corrosion resistant member, and the amorphous powder of the present invention has excellent characteristics as a raw material powder of the coating material.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭57−26165（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 24/10 B22F 1/00 C22C 45/02 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-57-26165 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C23C 24/10 B22F 1/00 C22C 45 / 02
Claims (4)
分に加えてＢを含有する低融点のアモルファス粉末をバ
インダ及び有機溶剤と混合してスラリ化した耐食性コー
ティング材料の被覆層を形成させ、金属部材の融点以下
でアモルファス粉末の融点以上の温度に加熱して溶融処
理を行うことによって緻密な耐食性コーティング層を形
成させることを特徴とする耐食性部材の製造方法。1. A coating layer of a corrosion-resistant coating material is formed by mixing a low melting point amorphous powder containing B in addition to a component corresponding to a corrosion-resistant alloy with a binder and an organic solvent on the surface of a metal member, A method for producing a corrosion-resistant member, comprising forming a dense corrosion-resistant coating layer by heating at a temperature not higher than the melting point of a metal member and at a temperature not lower than the melting point of amorphous powder to perform a melting treatment.
量％のＢを含有する低融点のアモルファス粉末をバイン
ダ及び有機溶剤と混合してスラリ化してなることを特徴
とする耐食性コーティング材料。2. A corrosion-resistant coating material comprising a low melting point amorphous powder containing 2 to 4% by weight of B in addition to a component corresponding to a corrosion-resistant alloy, mixed with a binder and an organic solvent to form a slurry.
Ｂを含有し、残部がＦｅと不可避的不純物からなること
を特徴とする耐水蒸気酸化性の耐食性コーティング材料
の原料となるアモルファス粉末。3. A raw material of a steam oxidation resistant corrosion resistant coating material, characterized by containing 5 to 30% by weight of Cr and 2 to 4% by weight of B, and the balance of Fe and inevitable impurities. Amorphous powder.
Ｂを含有し、残部がＮｉ及びＣｒと不可避的不純物から
なることを特徴とする耐硫酸腐食性の耐食性コーティン
グ材料の原料となるアモルファス粉末。4. A raw material for a sulfuric acid-corrosion-resistant corrosion-resistant coating material, characterized by containing 5 to 20% by weight of Mo and 2 to 4% by weight of B, and the balance of Ni and Cr and inevitable impurities. Amorphous powder that becomes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13673597A JP3389058B2 (en) | 1997-05-27 | 1997-05-27 | Method for producing corrosion-resistant member and corrosion-resistant coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13673597A JP3389058B2 (en) | 1997-05-27 | 1997-05-27 | Method for producing corrosion-resistant member and corrosion-resistant coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10324976A JPH10324976A (en) | 1998-12-08 |
| JP3389058B2 true JP3389058B2 (en) | 2003-03-24 |
Family
ID=15182288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13673597A Expired - Fee Related JP3389058B2 (en) | 1997-05-27 | 1997-05-27 | Method for producing corrosion-resistant member and corrosion-resistant coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3389058B2 (en) |
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|---|---|---|---|---|
| CN114981374B (en) * | 2020-01-16 | 2023-04-04 | 可隆工业株式会社 | Heat resistant coating composition |
| EP4092309A4 (en) | 2020-01-17 | 2023-05-24 | Kolon Industries, Inc. | Pipe and manufacturing method therefor |
| CN111455376B (en) * | 2020-04-23 | 2022-09-30 | 上海海事大学 | Cr for enhancing corrosion resistance of 45# steel 7 C 3 -Mo 2 NiB 2 Preparation method of complex phase ceramic coating |
| CN113026013B (en) * | 2021-03-05 | 2022-09-02 | 中国工程物理研究院材料研究所 | Preparation method of corrosion-resistant zirconium-based amorphous alloy composite material coating |
| CN114054743B (en) * | 2021-12-17 | 2023-07-21 | 武汉苏泊尔炊具有限公司 | Corrosion-resistant material, method for producing the same, and corrosion-resistant coating formed therefrom |
-
1997
- 1997-05-27 JP JP13673597A patent/JP3389058B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10324976A (en) | 1998-12-08 |
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