JP6646493B2 - Iron-based metal member having a metal spray coating layer - Google Patents
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Description
本発明は、表面に金属溶射によって形成された耐熱性に優れた溶射被覆層を有する鉄系金属部材、より詳細には鋳鉄管に関する。 The present invention relates to an iron-based metal member having a thermally sprayed coating layer formed on the surface by metal spraying and having excellent heat resistance, and more particularly to a cast iron pipe.
表面に金属溶射によって形成された溶射被覆層を有する鉄製または鋼製の溶射被覆部材は幅広く使用されており、特に耐食性が要求される用途などによく用いられている。 Iron or steel spray-coated members having a spray-coated layer formed by metal spray on the surface are widely used, and are often used particularly for applications requiring corrosion resistance.
溶射に用いる金属としては、特に、犠牲防食作用を有する亜鉛が利用されており、溶射材料としては、亜鉛または亜鉛合金が用いられ、亜鉛合金には、例えば、亜鉛スズ合金や亜鉛アルミニウム合金などがある。その他に、亜鉛と亜鉛合金、または亜鉛とその他金属材料とを溶射材料として用いた擬合金溶射も用いられている。例えば、亜鉛ワイヤとアルミニウムワイヤを用いたアーク溶射による擬合金溶射などが挙げられる。 As a metal used for thermal spraying, zinc having a sacrificial anticorrosive action is used in particular, and as a thermal spraying material, zinc or a zinc alloy is used.For the zinc alloy, for example, a zinc tin alloy or a zinc aluminum alloy is used. is there. In addition, pseudo alloy spraying using zinc and a zinc alloy or zinc and other metal materials as a spraying material is also used. For example, pseudo alloy spraying by arc spraying using a zinc wire and an aluminum wire, and the like can be mentioned.
これらの亜鉛系合金溶射や亜鉛系擬合金溶射は、亜鉛溶射よりも耐食性が高いため、より高い耐食性が要求される場合などに用いられている。近年、ライフサイクルコストの低減のため、例えば水道管などにおいて、長期間の腐食に耐えることが要求され、亜鉛溶射よりむしろ亜鉛系合金溶射や亜鉛系擬合金溶射が用いられることが多くなってきている。現在、水道用ダクタイル鋳鉄管の外面溶射に用いられる亜鉛系擬合金溶射には、主に、亜鉛と亜鉛スズマグネシウム合金、または亜鉛とアルミニウム合金が用いられている（特許文献１および２）。 These zinc-based alloy spraying and zinc-based pseudo-alloy spraying have higher corrosion resistance than zinc spraying, and are therefore used when higher corrosion resistance is required. In recent years, in order to reduce life cycle costs, for example, in water pipes and the like, it is required to withstand long-term corrosion, and zinc-based alloy spraying and zinc-based pseudo-alloy spraying are increasingly used rather than zinc spraying. I have. At present, zinc and zinc tin magnesium alloys or zinc and aluminum alloys are mainly used for zinc-based pseudo-alloy spraying used for the outer surface spraying of ductile cast iron pipes for waterworks (Patent Documents 1 and 2).
しかし、広く金属溶射に用いられている亜鉛は、加熱すると酸化し、耐食性能が低下するという問題がある。 However, zinc, which is widely used for metal spraying, oxidizes when heated, and has a problem in that its corrosion resistance deteriorates.
そこで、新たに、２００〜３００℃程度の加熱により耐食性能が低下しない亜鉛系擬合金溶射被膜を提供することを目的とする。 Accordingly, it is an object of the present invention to newly provide a zinc-based pseudo-alloy sprayed coating in which the corrosion resistance is not reduced by heating at about 200 to 300 ° C.
本発明者らは、上記課題を解決するために鋭意検討した結果、亜鉛と亜鉛ニッケル合金とを用いた、亜鉛−亜鉛ニッケル擬合金溶射被膜とすることにより、２００〜３００℃程度の加熱によっても耐食性能が低下しない亜鉛系擬合金溶射被膜が得られることを見出し、本発明を完成した。 The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result of using a zinc-zinc-nickel alloy to form a zinc-zinc-nickel pseudo-alloy thermal sprayed coating, it is possible to perform heating at about 200 to 300 ° C. The present inventors have found that a zinc-based pseudo-alloy sprayed coating that does not reduce the corrosion resistance can be obtained, and completed the present invention.
すなわち、本発明は、
［１］表面に金属溶射被覆層を有する鉄系金属部材であって、該金属溶射被覆層が、亜鉛と亜鉛ニッケル合金とが混合した擬合金層であることを特徴とする鉄系金属部材、
［２］前記金属溶射被覆層におけるニッケルの含有量が０．４〜２．５質量％である上記［１］記載の鉄系金属部材、
［３］前記金属溶射被覆層の表面に封孔処理層および樹脂塗料被膜層を有する上記［１］または［２］記載の鉄系金属部材、および
［４］前記鉄系金属部材が鋳鉄管である上記［１］〜［３］のいずれかに記載の鉄系金属部材
に関する。
That is, the present invention
[1] An iron-based metal member having a metal spray coating layer on a surface, wherein the metal spray coating layer is a pseudo-alloy layer in which zinc and a zinc-nickel alloy are mixed.
[2] The iron-based metal member according to [1], wherein the content of nickel in the metal spray coating layer is 0.4 to 2.5% by mass.
[3] The iron-based metal member according to the above [1] or [2], wherein the metal-sprayed coating layer has a sealing treatment layer and a resin paint coating layer on the surface thereof, and [4] the iron-based metal member is a cast iron tube. The present invention relates to the iron-based metal member according to any one of the above [1] to [3].
本発明によれば、２００〜３００℃程度の加熱によっても耐食性能が低下しない溶射被膜を備えた鉄系金属部材を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the iron-based metal member provided with the thermal spray coating which corrosion resistance performance does not fall by heating at about 200-300 degreeC can be provided.
本発明の鉄系金属部材は、その表面に亜鉛と亜鉛ニッケル合金とが混合した擬合金層である金属溶射被覆層が設けられていることを特徴とする。この金属溶射被覆層は、亜鉛およびニッケルが共に腐食膨張しないため、溶射被覆層の上に合成樹脂塗装などを施しても塗膜の膨れを生じるリスクがない。 The iron-based metal member of the present invention is characterized in that a metal spray coating layer, which is a pseudo-alloy layer in which zinc and a zinc-nickel alloy are mixed, is provided on the surface thereof. In this metal spray coating layer, both zinc and nickel do not corrode and expand, so there is no risk of swelling of the coating film even if a synthetic resin coating or the like is applied on the spray coating layer.
本発明にかかる金属溶射被覆層におけるニッケルの含有量は、０．４質量％以上が好ましい。ニッケルの含有量を０．４質量％以上とすることにより、ニッケルを加えた本発明の効果が十分に発揮される傾向がある。また、本発明に係る金属溶射被覆層におけるニッケルの含有量は、２．５質量％以下が好ましい。ニッケルの含有量を２．５質量％以下とすることにより、アーク溶射とする場合に材料とする亜鉛ニッケル合金の伸線加工が容易となる傾向がある。 The content of nickel in the metal spray coating layer according to the present invention is preferably 0.4% by mass or more. When the content of nickel is 0.4% by mass or more, the effect of the present invention to which nickel is added tends to be sufficiently exhibited. Further, the content of nickel in the metal spray coating layer according to the present invention is preferably 2.5% by mass or less. By setting the content of nickel to 2.5% by mass or less, there is a tendency that the wire drawing of a zinc-nickel alloy used as a material for arc spraying becomes easy.
また、本発明にかかる金属溶射被覆層は、亜鉛およびニッケル以外に、他の元素を添加することを特に予定するものではないが、１質量％未満程度の添加は許容される。特にスズを含有する場合には、その含有量は１質量％未満とすることが好ましい。 Further, the metal spray coating layer according to the present invention is not particularly intended to add other elements other than zinc and nickel, but addition of less than about 1% by mass is permissible. In particular, when tin is contained, its content is preferably less than 1% by mass.
本発明において、鉄系金属部材の素地金属としては、亜鉛系の溶射が有効である、鉄系の金属、例えば、鋳鉄、鋼などが挙げられる。本発明の鉄系金属部材としては、特に限定されるものではなく、管体、バルブ、橋梁などが挙げられる、特に鋳鉄管、鋼管などの鉄系金属管が好ましく使用され、管外面に本発明にかかる金属溶射被覆層が設けられる。 In the present invention, examples of the base metal of the iron-based metal member include iron-based metals, such as cast iron and steel, for which zinc-based thermal spraying is effective. The iron-based metal member of the present invention is not particularly limited, and examples thereof include a pipe, a valve, and a bridge. In particular, an iron-based metal pipe such as a cast iron pipe and a steel pipe is preferably used, and the present invention Is provided.
本発明の鉄系金属部材は、公知の金属溶射方法により、亜鉛と亜鉛ニッケル合金とを溶射することにより製造することができ、例えば一方の電極を純亜鉛、もう一方の電極を亜鉛ニッケル合金としたアーク溶射によって、その表面に亜鉛と亜鉛ニッケル合金が微細に混合した擬合金溶射被覆層を形成することにより製造することができる。擬合金層における亜鉛と亜鉛ニッケル合金とは微細に混合していることが好ましく、その程度は、亜鉛と亜鉛ニッケル合金とが２層に分離していないことが好ましい。両方の電極を亜鉛ニッケル合金とした合金溶射でも良好な耐食性が得られると考えられる。 The iron-based metal member of the present invention can be manufactured by spraying zinc and a zinc-nickel alloy by a known metal spraying method.For example, one electrode is made of pure zinc, and the other electrode is made of a zinc-nickel alloy. It can be manufactured by forming a pseudo-alloy spray coating layer in which zinc and a zinc-nickel alloy are finely mixed by the arc spraying. It is preferable that zinc and the zinc-nickel alloy in the pseudo alloy layer are finely mixed, and to that extent, it is preferable that the zinc and the zinc-nickel alloy are not separated into two layers. It is considered that good corrosion resistance can be obtained even by alloy spraying using both electrodes as a zinc-nickel alloy.
亜鉛と亜鉛ニッケル合金とを用いて溶射を行う際、使用する亜鉛ニッケル合金中のニッケルの含有量は、０．８質量％以上が好ましい。ニッケルの含有量を０．８質量％以上とすることにより、形成される本発明の金属溶射被覆層の耐食性が十分に発揮される傾向がある。また、亜鉛ニッケル合金中のニッケルの含有量は、５質量％以下が好ましい。ニッケルの含有量を５質量％以下とすることにより、亜鉛ニッケル合金を伸線加工することが容易となる傾向がある。さらに、使用する亜鉛および亜鉛ニッケル合金には０．０２質量％程度であれば、不純物が含まれていてもよい。例えば、０．０１質量％の銅、０．０２質量％の鉄、０．０１５質量％のマンガン、０．０１５質量％のケイ素を含む亜鉛ニッケル合金などを使用することができる。 When performing thermal spraying using zinc and a zinc-nickel alloy, the content of nickel in the zinc-nickel alloy used is preferably 0.8% by mass or more. When the content of nickel is 0.8% by mass or more, the corrosion resistance of the formed metal spray coating layer of the present invention tends to be sufficiently exhibited. Further, the content of nickel in the zinc-nickel alloy is preferably 5% by mass or less. By setting the content of nickel to 5% by mass or less, there is a tendency that the zinc nickel alloy can be easily drawn. Further, impurities may be contained in the zinc and the zinc-nickel alloy used as long as they are about 0.02% by mass. For example, a zinc-nickel alloy containing 0.01% by mass of copper, 0.02% by mass of iron, 0.015% by mass of manganese, and 0.015% by mass of silicon can be used.
また、使用する亜鉛ニッケル合金への添加元素としては１質量％未満での添加が許容される。例えば、０．３質量％程度のマグネシウムを添加した場合も、良好な耐食性を発揮する。 Further, as an additive element to the zinc nickel alloy to be used, addition of less than 1% by mass is permissible. For example, even when about 0.3% by mass of magnesium is added, good corrosion resistance is exhibited.
本発明の鉄系金属部材においては、亜鉛ニッケル合金の溶融開始温度は４１８．５℃以上であり、純亜鉛の融点である４１９．５８℃と同等以上であるため、亜鉛溶射と同様の温度履歴を与えても溶融することはない。また本発明の鉄系金属部材は、２００〜３００℃程度の熱を数十分加えても、耐食性能の低下はみられない。したがって、水道用ダクタイル鋳鉄管とした場合には、管外面に本発明にかかる金属溶射被覆層を設け、外面塗装を行った後、２００℃〜３００℃程度の管の予熱を必要とする粉体塗装を管内面に施工しても、耐食性能に影響を及ぼすことはなく、また溶融して外観を損ねることもない。 In the iron-based metal member of the present invention, the melting start temperature of the zinc-nickel alloy is 418.5 ° C. or higher, which is equal to or higher than the melting point of pure zinc, 419.58 ° C. Does not melt. In addition, the iron-based metal member of the present invention does not show a decrease in corrosion resistance even when heat of about 200 to 300 ° C. is applied for tens of minutes. Therefore, in the case of ductile cast iron pipe for water supply, the metal spray coating layer according to the present invention is provided on the outer surface of the pipe, and after the outer surface is coated, the powder that requires preheating of the pipe at about 200 ° C. to 300 ° C. Even if the coating is applied to the inner surface of the pipe, it does not affect the corrosion resistance and does not melt and impair the appearance.
本発明の鉄系金属部材には、上述した金属溶射被覆層の表面に通常の封孔処理による封孔処理層を設けることができ、これにより金属溶射被覆層の気孔を封鎖し、防食効果をさらに高めることができる。 The iron-based metal member of the present invention can be provided with a sealing treatment layer by a normal sealing treatment on the surface of the above-mentioned metal spray coating layer, whereby the pores of the metal spray coating layer are blocked and the anticorrosion effect is obtained. Can be even higher.
封孔処理としては、特に限定されるものではなく、一般に本技術分野において使用されているものを用いることができる。例えば、金属塗装に用いられるアクリル樹脂、エポキシ樹脂、アクリルシリコーン樹脂などの樹脂成分に、コロイダルシリカなどの無機化合物、表面調整剤などの添加剤を含む水系処理液による処理が挙げられる。 The sealing treatment is not particularly limited, and those generally used in this technical field can be used. For example, treatment with an aqueous treatment liquid containing an additive such as an inorganic compound such as colloidal silica and a surface conditioner in a resin component such as an acrylic resin, an epoxy resin, and an acrylic silicone resin used for metal coating can be given.
また、本発明の鉄系金属部材には、上述の金属溶射被覆層の表面に、または封孔処理が施されている場合には封孔処理層の表面に樹脂塗料による被膜層を設けることができる。樹脂塗料被膜層は、単層としてもよいが、下塗り層および上塗り層の２層としてもよい。本発明の鉄系金属部材に施された金属溶射は、上述したとおり、亜鉛およびニッケルが共に腐食膨張しないため、合成樹脂塗料等による樹脂塗料被膜層を設けても膨れ等のリスクがなく、樹脂塗料被膜層による耐久性を十分に発揮することができる。 In the iron-based metal member of the present invention, a coating layer of a resin paint may be provided on the surface of the metal spray coating layer described above, or on the surface of the sealing layer when the sealing process is performed. it can. The resin coating film layer may be a single layer, or may be two layers of an undercoat layer and an overcoat layer. Metal spraying applied to the iron-based metal member of the present invention, as described above, because zinc and nickel do not corrode and expand, there is no risk of swelling even if a resin coating layer such as a synthetic resin coating is provided. The paint film layer can sufficiently exhibit durability.
樹脂塗料としては、特に限定されるものではなく、通常金属管の外面塗装に使用されているアクリル系樹脂塗料、エポキシ系樹脂塗料などが挙げられる。また、水道用の鋳鉄管については、日本水道協会規格のＪＷＷＡ Ｋ １３９「水道用ダクタイル鋳鉄管合成樹脂塗料」に規定される合成樹脂塗料を用いることができる。 The resin paint is not particularly limited, and examples thereof include an acrylic resin paint and an epoxy resin paint which are usually used for coating the outer surface of a metal tube. As for the cast iron pipe for water supply, a synthetic resin paint specified in JWWA K139 “Ductile cast iron pipe for water supply synthetic resin paint” of the Japan Water Works Association standard can be used.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
実施例１
サンドブラスト処理された圧延鋼板ＳＰＣＣ（１５０×７０×２．０ｍｍ）に、陽極を亜鉛−ニッケル（４．２質量％）合金ワイヤ（直径１．６ｍｍ）、陰極を亜鉛ワイヤ（直径１．６ｍｍ）とするアーク溶射によって、付着量４１２ｇ／ｍ2のＺｎ／Ｚｎ−４．２Ｎｉ擬合金溶射被覆層を有する試験板４枚を作製した。このうちの２枚については電気炉を用いて大気中で加熱した（２６０℃×２０分間）。
Example 1
On a rolled steel plate SPCC (150 × 70 × 2.0 mm) subjected to sandblasting, an anode was formed of a zinc-nickel (4.2 mass%) alloy wire (diameter 1.6 mm), and a cathode was formed of a zinc wire (diameter 1.6 mm). By arc spraying, four test plates having a Zn / Zn-4.2Ni pseudo-alloy spray coating layer having an adhesion amount of 412 g / m 2 were produced. Two of these were heated in the air using an electric furnace (260 ° C. × 20 minutes).
実施例２
陽極の亜鉛−ニッケル（４．２質量％）合金ワイヤ（直径２．０ｍｍ）を、亜鉛−ニッケル（０．９７質量％）合金ワイヤ（直径２．０ｍｍ）とし、溶射付着量を３５２ｇ／ｍ2とした以外は、実施例１と同様にして試験板４枚を作製した。このうちの２枚については、実施例１と同様にして加熱処理した。
Example 2
The zinc-nickel (4.2 mass%) alloy wire (diameter 2.0 mm) of the anode was changed to a zinc-nickel (0.97 mass%) alloy wire (diameter 2.0 mm), and the thermal spray adhesion amount was 352 g / m 2. Four test plates were prepared in the same manner as in Example 1, except that Two of them were heat-treated in the same manner as in Example 1.
比較例１
陽極の亜鉛−ニッケル（４．２質量％）合金ワイヤ（直径１．６ｍｍ）を、亜鉛ワイヤ（直径１．６ｍｍ）とし、溶射付着量を３５６ｇ／ｍ2とした以外は、実施例１と同様にして試験板４枚を作製した。このうちの２枚については、実施例１と同様にして加熱処理した。
Comparative Example 1
Same as Example 1 except that a zinc-nickel (4.2% by mass) alloy wire (diameter 1.6 mm) of the anode was changed to a zinc wire (diameter 1.6 mm) and a thermal spray coating amount was set to 356 g / m 2. Thus, four test plates were prepared. Two of them were heat-treated in the same manner as in Example 1.
試験例：複合サイクル試験
実施例１および２ならびに比較例１で得られた試験片の中央に、試験片の対角線に沿ったＸ字状に鉄地まで達する幅０．３ｍｍ×長さ５０ｍｍの切れ込みを入れ、複合サイクル試験（ＪＩＳ Ｋ ５６００−７−９、附属書ＣのサイクルＡ）を実施した。赤錆が発生したときの試験サイクル数を比較し、耐食性を評価した。結果を表１に示す。ただし、試験片端１０ｍｍの範囲は赤錆の評価範囲外とした。また、一般に耐食性は溶射付着量に比例するため、表１の結果を付着量３５０ｇ／ｍ2に換算したものを表２に示す。表２において耐食性指数は、比較例１のサイクル数を１として指数表示したものである。
Test example: Combined cycle test A 0.3 mm wide x 50 mm long notch reaching the center of the test piece obtained in Examples 1 and 2 and Comparative Example 1 in an X-shape along the diagonal line of the test piece. , And a combined cycle test (JIS K 5600-7-9, Annex C, cycle A) was performed. The corrosion resistance was evaluated by comparing the number of test cycles when red rust occurred. Table 1 shows the results. However, the range of the test piece end of 10 mm was outside the evaluation range of red rust. In addition, since corrosion resistance is generally proportional to the amount of thermal spray adhesion, Table 2 shows the result of Table 1 converted to the amount of adhesion of 350 g / m 2 . In Table 2, the corrosion resistance index is shown as an index with the number of cycles in Comparative Example 1 being 1.
実施例１および２のいずれにおいても加熱処理による耐食性の低下は見られなかった。また、実施例１においては、比較例１の平均約６倍もの耐食性能を発揮し、亜鉛／亜鉛−０．９７質量％ニッケル擬合金溶射である実施例２においても比較例１の平均約４倍以上の耐食性を発揮した。 In each of Examples 1 and 2, no decrease in corrosion resistance due to the heat treatment was observed. Further, in Example 1, the corrosion resistance was about six times as large as that of Comparative Example 1, and in Example 2 in which zinc / zinc-0.97 mass% nickel pseudoalloy was sprayed, the average of about 4 times that of Comparative Example 1 was obtained. Demonstrated more than twice the corrosion resistance.
これらの結果から、亜鉛と亜鉛ニッケル合金とが混合した擬合金層である金属溶射被覆層が、亜鉛溶射被覆層よりも耐食性能が非常に優れており、さらに２００〜３００℃程度の加熱によっても耐食性能が低下しないという優れた効果を奏することがわかる。 From these results, the metal spray coating layer, which is a pseudo-alloy layer in which zinc and a zinc-nickel alloy are mixed, has much better corrosion resistance than the zinc spray coating layer, and even when heated at about 200 to 300 ° C. It can be seen that there is an excellent effect that the corrosion resistance does not decrease.
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