JP2013136798A - Surface corrosion-protected body - Google Patents
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Abstract
Description
本発明は外面防食体に関し、たとえば鋳鉄管や橋梁やその他の構造物などの鉄系材料で構成された部材の表面に溶射被膜により防食層が形成された外面防食体に関する。 The present invention relates to an outer surface anticorrosive body, for example, an outer surface anticorrosive body in which an anticorrosive layer is formed on a surface of a member made of an iron-based material such as a cast iron pipe, a bridge, and other structures by a thermal spray coating.
地下埋設物として実用に供せられる金属管は、腐食防止のため、古くからタール系やビチュメン系の塗装が施されている。しかしながら塗装に傷が付いた場合は、傷部から金属管の腐食が進行することとなる。こうした腐食問題を解決するため、金属管素材よりイオン化傾向の大きな金属性被膜を金属管の表面に形成し、イオン化傾向の差異によって犠牲陽極作用を発生せしめ、傷部からの腐食を防止することが広く行われるようになっている。こうした犠牲陽極作用を持つ金属としては、亜鉛が代表的で、メッキや溶射によって被膜形成が行われている。この被膜は、そのまま用いられたり、あるいはさらに上塗り塗装が施されて用いられたりしている。亜鉛はイオン化傾向が高く、例えば鉄系金属と組み合わせて用いられる場合、鉄と亜鉛との電気化学的な電位差が大きいので、塗覆装に多少の傷が生じても犠牲陽極作用が発揮され、傷部での腐食を抑制することが出来る。また、上下水道管路として広く用いられている鋳鉄管の場合には、塗覆装の上からポリエチレンスリーブと呼ばれるポリエチレンシートで覆い、外部環境から遮断することにより、更に防食効果を高めることが行われている。 Metal pipes that are practically used as underground buried objects have been tar-based or bitumen-based for a long time to prevent corrosion. However, when the coating is scratched, the corrosion of the metal tube proceeds from the scratched portion. In order to solve these corrosion problems, a metallic coating with a greater ionization tendency than the metal pipe material is formed on the surface of the metal pipe, and a sacrificial anodic action is generated due to the difference in ionization tendency to prevent corrosion from scratches. It has become widely used. A typical metal having such sacrificial anodic action is zinc, and a film is formed by plating or thermal spraying. This coating is used as it is or after being further overcoated. Zinc has a high tendency to ionize, for example, when used in combination with an iron-based metal, the electrochemical potential difference between iron and zinc is large, so even if some scratches occur in the coating, the sacrificial anodic action is exhibited, Corrosion at the scratch can be suppressed. Also, in the case of cast iron pipes widely used as water and sewage pipes, the anticorrosion effect is further enhanced by covering with a polyethylene sheet called a polyethylene sleeve over the coating and blocking from the external environment. It has been broken.
しかし、亜鉛はイオン化傾向が高いので、犠牲陽極作用を長期的に保持することが難しい。この問題の解決策としては、亜鉛塗着量の増大が有効な手段であるが、その場合は、材料コストのアップだけでなく施工時間が長くなり、生産能率も低下することになる。 However, since zinc has a high ionization tendency, it is difficult to maintain the sacrificial anodic action for a long time. As a solution to this problem, an increase in the zinc coating amount is an effective means, but in this case, not only the material cost is increased, but also the construction time is lengthened and the production efficiency is also lowered.
また、他の方法としてＺｎ−Ｓｎ−Ｍｇ系合金を用いる場合もある（特許文献１）。 As another method, a Zn—Sn—Mg alloy may be used (Patent Document 1).
本発明は、外面防食体において、特許文献１に記載された亜鉛−錫−マグネシウム合金の溶射被膜と同等の性能を、これよりも安価な材料で達成できるようにすることを目的とする。 An object of the present invention is to enable an outer surface anticorrosive body to achieve performance equivalent to that of a spray coating of a zinc-tin-magnesium alloy described in Patent Document 1 with a material cheaper than this.
この目的を達成するため本発明の外面防食体は、鉄系材料で構成された部材の表面に防食層が形成され、この防食層は、Ｓｎが０．１質量％以上かつ２０質量％以下であり、Ａｌが５質量％以上かつ５０質量％以下であり、残部がＺｎであるＺｎ−Ｓｎ−Ａｌ系合金溶射被膜を含有することを特徴とする。 In order to achieve this object, in the outer surface anticorrosive body of the present invention, an anticorrosion layer is formed on the surface of a member made of an iron-based material, and the anticorrosion layer has an Sn content of 0.1% by mass or more and 20% by mass or less. In addition, it is characterized by containing a Zn-Sn-Al alloy sprayed coating in which Al is 5 mass% or more and 50 mass% or less, and the balance is Zn.
本発明によれば、鉄系材料で構成された部材の一例として、鋳鉄管を挙げることができる。 According to this invention, a cast iron pipe can be mentioned as an example of the member comprised with the iron-type material.
本発明の外面防食体によれば、鉄系材料で構成された部材の外面の防食層が、Ｚｎ−Ｓｎ−Ａｌ系合金溶射被膜を含有するため、単なる亜鉛溶射被膜を用いたものに比べて防食性能を格段に向上させることができる。またＭｇを用いないので、これを用いた場合に比べて防食層を安価に構成することができる。 According to the outer surface anticorrosive body of the present invention, the anticorrosion layer on the outer surface of the member made of an iron-based material contains a Zn-Sn-Al-based alloy sprayed coating, so that it is compared with a simple zinc sprayed coating. The anticorrosion performance can be remarkably improved. Moreover, since Mg is not used, the anticorrosion layer can be constructed at a lower cost than when this is used.
本発明の外面防食体は、鉄系材料で構成された部材の表面に、合金溶射被膜を含有した防食層が形成されたものである。 In the outer surface anticorrosive body of the present invention, an anticorrosion layer containing an alloy spray coating is formed on the surface of a member made of an iron-based material.
合金溶射被膜は、Ｓｎが０．１質量％以上かつ２０質量％以下であり、Ａｌが５質量％以上かつ５０質量％以下であり、残部がＺｎであるＺｎ−Ｓｎ−Ａｌ系合金にて形成されている。このように主体とするＺｎにＳｎとＡｌとが加えられたものであることにより、Ｚｎだけを用いた溶射被膜に比べて防食性能を向上させることができる。その防食性能は、Ｚｎ−Ｓｎ−Ｍｇ系合金と同程度とすることができる。Ｓｎの含有量が０．１質量％未満である場合や２０質量％を超える場合には、Ｓｎを加えることによる実質的な防食性能の向上効果を得ることができない。同様に、Ａｌの含有量が５質量％未満である場合や５０質量％を超える場合には、Ａｌを加えることによる実質的な防食性能の向上効果を得ることができない。 The alloy sprayed coating is formed of a Zn—Sn—Al alloy in which Sn is 0.1% by mass to 20% by mass, Al is 5% by mass to 50% by mass, and the balance is Zn. Has been. Thus, by adding Sn and Al to the main Zn, the anticorrosion performance can be improved as compared with the thermal spray coating using only Zn. The anticorrosion performance can be comparable to that of a Zn—Sn—Mg alloy. When the content of Sn is less than 0.1% by mass or exceeds 20% by mass, it is not possible to obtain a substantial effect of improving the anticorrosion performance by adding Sn. Similarly, when the Al content is less than 5% by mass or exceeds 50% by mass, it is not possible to obtain a substantial effect of improving the anticorrosion performance by adding Al.
またＳｎを含有することで、白錆すなわちＺｎの腐食生成物が発生しにくいという利点もある。すなわち、Ｓｎを添加することにより白錆の溶出が抑制され、鉄系材料で構成された部材に対する犠牲陽極作用を長期にわたって持続させることができる。かつ合金溶射被膜の上面に塗料による塗装を行う場合には、その塗膜における「ふくれ」の発生を低減することができる。 Further, by containing Sn, there is an advantage that white rust, that is, a corrosion product of Zn is hardly generated. That is, by adding Sn, the elution of white rust is suppressed, and the sacrificial anodic action on the member made of the iron-based material can be maintained for a long time. In addition, when the upper surface of the alloy sprayed coating is coated with a paint, the occurrence of “blowing” in the coating can be reduced.
Ｚｎ−Ｓｎ−Ａｌ系合金であることにより、Ｚｎ−Ｓｎ−Ｍｇ系合金に比べて経済的に有利であり、かつＺｎ−Ｓｎ−Ｍｇ系合金と同等の防食性能を達成することができる。しかも、軟らかい材料であるＳｎを含有することで、溶射のための材料としてのＺｎ−Ｓｎ−Ａｌ合金線材を作製しやすいという利点もある。 By being a Zn—Sn—Al-based alloy, it is economically advantageous as compared with a Zn—Sn—Mg-based alloy, and corrosion resistance equivalent to that of a Zn—Sn—Mg-based alloy can be achieved. In addition, the inclusion of Sn, which is a soft material, has the advantage that it is easy to produce a Zn—Sn—Al alloy wire as a material for thermal spraying.
本発明の外面防食体は、防食層が上記したＺｎ−Ｓｎ−Ａｌ系合金溶射被膜を含有するものであるが、この防食層は、合金溶射被膜に加えて、上塗り塗装などの他の被膜が積層されたものであることが特に好ましい。上塗り塗装は、アクリル樹脂系塗料やエポキシ樹脂系塗料などの合成樹脂塗料や、ビチュメン系塗料などによって施すことができる。 In the outer surface anticorrosive body of the present invention, the anticorrosion layer contains the above-described Zn-Sn-Al-based alloy sprayed coating. In addition to the alloy sprayed coating, this anticorrosive layer has another coating such as a top coat. It is particularly preferred that they are laminated. The top coat can be applied with a synthetic resin paint such as an acrylic resin paint or an epoxy resin paint, or a bitumen paint.
本発明の外面防食体を製造する際には、公知の溶射方法、すなわちＺｎ−Ｓｎ−Ａｌ線材を用いて、アーク溶射を行う方法を挙げることができる。あるいは、線材に代えて合金粉末を用いた溶射を行うこともできる。 When manufacturing the outer surface anticorrosive body of this invention, the method of performing an arc spraying using the well-known thermal spraying method, ie, a Zn-Sn-Al wire, can be mentioned. Alternatively, thermal spraying using an alloy powder can be performed instead of the wire.
また、Ｚｎ−Ｓｎ−Ａｌ合金溶射被膜は、Ｚｎ−Ｓｎ−Ａｌ線材を第１の線材として用いるとともに、Ｚｎ線材を第２の線材として用いて、同時にアーク溶射を行うことによって得ることもできる。 In addition, the Zn—Sn—Al alloy sprayed coating can be obtained by simultaneously performing arc spraying using a Zn—Sn—Al wire as the first wire and a Zn wire as the second wire.
たとえばＺｎ−１０Ｓｎ−２０Ａｌ（Ｓｎ：１０質量％、Ａｌ：２０質量％、Ｚｎ：残部、以下、同様に表記することがある）の合金溶射被膜を得るために、Ｚｎ−１０Ｓｎ−２０Ａｌ線材を２本用いて同時にアーク溶射することに代えて、Ｚｎ−２０Ｓｎ−４０Ａｌ線材とＺｎ線材とを等量ずつ用いて同時にアーク溶射することができる。 For example, in order to obtain an alloy sprayed coating of Zn-10Sn-20Al (Sn: 10% by mass, Al: 20% by mass, Zn: balance, hereinafter may be similarly expressed), Zn-10Sn-20Al wire 2 Instead of arc spraying simultaneously using this, arc spraying can be performed simultaneously using equal amounts of Zn-20Sn-40Al wire and Zn wire.
このようにすると、防食性能をよりいっそう向上させることができる。またＺｎ−Ｓｎ−Ａｌ線材の使用量を半減させることができるため、その調合に要するコストを削減することができる。 If it does in this way, anticorrosion performance can be improved further. Moreover, since the usage-amount of a Zn-Sn-Al wire can be halved, the cost required for the preparation can be reduced.
このような溶射方法を採用することで、防食性能をよりいっそう向上させることができる理由は、明らかではないが、以下の（ａ）（ｂ）のそれぞれ、あるいはそれらの相乗効果によるものと考えることができる。 The reason why the anticorrosion performance can be further improved by adopting such a thermal spraying method is not clear, but it is considered to be due to each of the following (a) and (b) or their synergistic effect. Can do.
（ａ）たとえばＺｎ−Ｓｎ−Ａｌ合金線材とＺｎ線材とを用いて同時にアーク溶射を行った場合には、それによって形成される溶射被膜中には、Ｚｎ−Ｓｎ−Ａｌ合金とＺｎとがそれぞれ分布することになる。このとき、Ｚｎ−Ｓｎ−Ａｌ合金はＺｎよりも電位が低いため、これらが犠牲陽極として働く場合には、Ｚｎ−Ｓｎ−Ａｌ合金が優先的に溶け出す。この溶け出したＺｎ−Ｓｎ−Ａｌ合金が被膜の表面に比較的安定した別の被膜を形成することで、それが、残りのＺｎ−Ｓｎ−Ａｌ合金とＺｎとの消耗または溶解を抑制しているためであると考えることができる。 (A) For example, when arc spraying is simultaneously performed using a Zn—Sn—Al alloy wire and a Zn wire, the Zn—Sn—Al alloy and Zn are respectively formed in the sprayed coating formed thereby. Will be distributed. At this time, since the potential of the Zn—Sn—Al alloy is lower than that of Zn, when these act as a sacrificial anode, the Zn—Sn—Al alloy preferentially melts. This dissolved Zn—Sn—Al alloy forms another relatively stable coating on the surface of the coating, which suppresses the consumption or dissolution of the remaining Zn—Sn—Al alloy and Zn. It can be considered that this is because.
（ｂ）被膜中に存在しているＺｎが物理的な障害となってＺｎ−Ｓｎ−Ａｌ合金の溶解を抑制し、またＺｎ−Ｓｎ−Ａｌ合金が溶解した場合はその腐食生成物がＺｎの溶解を抑制しているためであると考えることができる。 (B) Zn present in the coating becomes a physical obstacle to suppress the dissolution of the Zn-Sn-Al alloy, and when the Zn-Sn-Al alloy is dissolved, the corrosion product is Zn. It can be considered that this is because dissolution is suppressed.
本発明の外面防食体を製造する際には、鉄系の部材に合金溶射被膜を形成したうえで、これを合金の共晶温度（３５０℃）以上かつ融点未満の温度で熱処理することが好ましい。このように熱処理を施すことで、防食性能をより向上させることができる。これは、Ｚｎ−Ｓｎ−Ａｌ合金の共晶温度を超える温度で熱処理することでＳｎだけが溶解し、これによって溶射被膜中に生じていた微細な空隙が埋められることになって、部材をたとえば地中に埋設したときに被膜中に電解質が浸入することを抑制可能となるためであると推定される。 When producing the outer surface anticorrosive body of the present invention, it is preferable to form an alloy spray coating on an iron-based member and then heat-treat it at a temperature equal to or higher than the eutectic temperature (350 ° C.) of the alloy and lower than the melting point. . By performing the heat treatment in this way, the anticorrosion performance can be further improved. This is because heat treatment is performed at a temperature exceeding the eutectic temperature of the Zn—Sn—Al alloy, so that only Sn is melted, thereby filling the fine voids generated in the sprayed coating. It is estimated that it is possible to suppress the infiltration of the electrolyte into the coating when buried in the ground.
したがって、共晶温度未満の温度で熱処理したのでは、Ｓｎが実質的に溶解せず、上記した効果が得られないことになる。反対に熱処理温度が合金溶射被膜の融点以上であると、合金の酸化が進んで本来の防食性能が失われることになる。 Therefore, if heat treatment is performed at a temperature lower than the eutectic temperature, Sn is not substantially dissolved, and the above-described effects cannot be obtained. On the other hand, if the heat treatment temperature is equal to or higher than the melting point of the alloy sprayed coating, the oxidation of the alloy proceeds and the original anticorrosion performance is lost.
熱処理の時間は、特に制限はないが、１秒〜６０分であることが好適である。熱処理の時間がこの範囲よりも短いと、処理時間が不足して、必要な熱処理を行うことができなくなる。 The heat treatment time is not particularly limited, but is preferably 1 second to 60 minutes. If the heat treatment time is shorter than this range, the treatment time is insufficient and the necessary heat treatment cannot be performed.
上述した上塗り塗装を行う場合は、合金溶射被膜が形成されたあとの施工とする。 When performing the above-described top coating, the construction is performed after the alloy sprayed coating is formed.
以下、本発明の実施例について説明する。なお、以下の実施例、比較例において、耐食性の評価は、次のようにして行った。 Examples of the present invention will be described below. In the following examples and comparative examples, the corrosion resistance was evaluated as follows.
下記の要領で耐食試験を行い評価した。すなわち、１５０ｍｍ×７０ｍｍ×２ｍｍのサンドブラスト鋼板を試験片として用い、これに、φ１．６ｍｍの線材を用いた電気式アーク溶射方法によって、溶射量１３０ｇ／ｍ２で、厚さ２０〜３０μｍの溶射被膜を形成して供試サンプルとした。耐食試験の方法およびその評価方法は、次の通りとした。 The corrosion resistance test was performed and evaluated as follows. That is, a 150 mm × 70 mm × 2 mm sandblasted steel plate is used as a test piece, and an electric arc spraying method using a wire of φ1.6 mm is used, and a sprayed coating is 130 g / m 2 and a thickness of 20 to 30 μm. To form a test sample. The corrosion resistance test method and its evaluation method were as follows.
すなわち、ＪＩＳ Ｚ２３７１に規定される塩水噴霧試験を実施した。すなわち、上記のサンプルに所定の条件で塩水を噴霧し続けて、赤錆が発生するまでの期間を測定した。そして、上記と同様の条件でＺｎのみを溶射したサンプルについての赤錆が発生するまでの期間を「１」としたときの値を求めた。 That is, the salt spray test prescribed | regulated to JISZ2371 was implemented. That is, salt water was continuously sprayed on the above sample under predetermined conditions, and the period until red rust was generated was measured. And the value when the period until red rust generate | occur | produces about the sample which sprayed only Zn on the conditions similar to the above was set to "1" was calculated | required.
また溶射被膜の上に、アクリル樹脂系塗料を用いて、塗布量２５０ｇ／ｍ２、塗布厚さ１００μｍの条件で塗装を施した。そのうえで所定の条件で塩水を噴霧し続けたときの塗膜における「ふくれ」の発生状況について調査し、所定の面積の範囲における「ふくれ」が発生した部分の面積比を求めた。 On the sprayed coating, coating was performed using an acrylic resin-based paint under the conditions of a coating amount of 250 g / m 2 and a coating thickness of 100 μm. In addition, the occurrence of “blowing” in the coating film when the salt water was continuously sprayed under predetermined conditions was investigated, and the area ratio of the portion where “blowing” occurred in a predetermined area range was determined.
各実施例、比較例の詳細は、下記の通りである。
（参考例１）
表１に示すように、試験片にＺｎのみを溶射して供試サンプルとした。その評価結果を表１に示す。
Details of each example and comparative example are as follows.
(Reference Example 1)
As shown in Table 1, a test sample was prepared by spraying only Zn on the test piece. The evaluation results are shown in Table 1.
（参考例２）
表１に示すように、試験片にＺｎ−２０．５Ｓｎ−０．１５Ｍｇ合金を溶射して供試サンプルとした。塗料による上塗り塗装も行った。その評価結果を表１に示す。
(Reference Example 2)
As shown in Table 1, Zn-20.5Sn-0.15Mg alloy was sprayed on the test piece to prepare a test sample. Top coating with paint was also performed. The evaluation results are shown in Table 1.
（実施例１〜１２、比較例１〜４）
表１に示す成分組成のＺｎ−Ｓｎ-Ａｌ合金を試験片に溶射して、実施例１〜１２、比較例１〜４の供試サンプルを得た。これらの供試サンプルについての評価結果を表１に示す。
(Examples 1-12, Comparative Examples 1-4)
A sample sample of Examples 1 to 12 and Comparative Examples 1 to 4 was obtained by spraying a Zn—Sn—Al alloy having a component composition shown in Table 1 on a test piece. The evaluation results for these test samples are shown in Table 1.
表１から明らかな通り、実施例１〜１２の供試サンプルは、いずれも耐食性にすぐれており、赤錆発生までの期間、塗膜の「ふくれ」の範囲とも、Ｚｎ−２０．５Ｓｎ−０．１５Ｍｇ合金と同等の性能を達成することができた。すなわち、Ｍｇを含有せず、それに代えてＭｇよりも安価なＡｌを含有したものでありながら、Ｍｇを含有したものと同等の性能を達成することができた。 As is clear from Table 1, all of the test samples of Examples 1 to 12 have excellent corrosion resistance, and the period until the occurrence of red rust and the range of “blowing” of the coating film are both Zn-20.5Sn-0. The performance equivalent to 15Mg alloy could be achieved. That is, although it did not contain Mg and instead contained Al that was cheaper than Mg, it was possible to achieve the same performance as that containing Mg.
これに対し、比較例１は、Ｓｎの含有量が本発明の規定の範囲を下回っていたため、赤錆発生までの期間、塗膜の「ふくれ」の範囲とも、各実施例よりも劣っていた。また、比較例２はＳｎの含有量が本発明の規定の範囲を上回っていたため、比較例３はＡｌの含有量が本発明の規定の範囲を下回っていたため、比較例４はＡｌの含有量が本発明の規定の範囲を上回っていたため、いずれも、比較例１と同様に、各実施例よりも耐食性能が劣るものであった。 On the other hand, in Comparative Example 1, since the Sn content was below the specified range of the present invention, both the period until the occurrence of red rust and the range of “blowing” of the coating film were inferior to those of the Examples. In Comparative Example 2, the Sn content exceeded the specified range of the present invention. Therefore, Comparative Example 3 had an Al content lower than the specified range of the present invention. Therefore, Comparative Example 4 had an Al content. However, the corrosion resistance was inferior to each of the examples as in Comparative Example 1.
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| IT202200010391A1 (en) * | 2022-05-19 | 2023-11-19 | Kofler Srl | IMPROVED TYPE METAL ALLOY FOR HOT GALVANIZING OF FERROUS MATERIALS |
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