JP2002069606A - Anticorrosion spraying film member and its production method - Google Patents
Anticorrosion spraying film member and its production methodInfo
- Publication number
- JP2002069606A JP2002069606A JP2000268231A JP2000268231A JP2002069606A JP 2002069606 A JP2002069606 A JP 2002069606A JP 2000268231 A JP2000268231 A JP 2000268231A JP 2000268231 A JP2000268231 A JP 2000268231A JP 2002069606 A JP2002069606 A JP 2002069606A
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- JP
- Japan
- Prior art keywords
- aluminum
- sprayed
- spraying
- steel
- 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.)
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Links
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- Coating By Spraying Or Casting (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、海水、塩分などに
対して優れた耐食性を示すアルミニウム系の防食溶射被
覆部材およびその製造方法に関するものである。本発明
の技術は、重工業地帯、田園地帯、都市などに建設され
る鋼構造物や産業機械用部材あるいはアルミニウムやそ
の合金部材の耐食性を保障するための被覆としても利用
できるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum-based anti-corrosion sprayed member having excellent corrosion resistance to seawater, salt and the like, and a method for producing the same. The technology of the present invention can also be used as a coating for ensuring the corrosion resistance of steel structures, industrial machine members, or aluminum and its alloy members that are constructed in heavy industrial areas, countryside areas, cities, and the like.
【０００２】[0002]
【従来の技術】橋梁、建築用鉄骨、塔槽類などに用いら
れる鋼材の多くは、自然環境下において赤さびを発生し
て損耗する。特に、大気中に硫黄酸化物(SOx) や窒素酸
化物(NOx) の含有量が多い重工業地帯に建設される鋼構
造物は、酸性雨などによる腐食作用を強く受けるもので
あり、また海洋気象地域に構築されている鋼構造物は、
海水や海塩粒子による腐食により著しく損耗することが
知られている。そのため、これらの鋼構造物には通常、
何らかの防食表面処理を施して、腐食を抑制する工夫が
されている。その代表的なものとして、塗装処理あるい
は溶融亜鉛めっき処理や溶融アルミニウムめっき処理な
どがある。その他の防食法としては、炭素鋼の表面に溶
射法によって、電気化学的に卑な電位を示す亜鉛やアル
ミニウムまたはそれらの合金類の溶射皮膜を形成する方
法もある。例えば、JIS H8300 (1999)亜鉛・アルミニウ
ムおよびそれらの合金溶射として制定されている。2. Description of the Related Art Many steel materials used for bridges, architectural steel frames, towers, and the like generate red rust in a natural environment and are worn. In particular, steel structures constructed in heavy industrial areas that have a high content of sulfur oxides (SOx) and nitrogen oxides (NOx) in the atmosphere are highly corrosive due to acid rain, etc. Steel structures built in the region
It is known that it is significantly worn by corrosion by seawater or sea salt particles. As such, these steel structures are usually
Some anti-corrosion surface treatments have been devised to suppress corrosion. Typical examples include a coating process, a hot-dip galvanizing process, and a hot-dip aluminum plating process. As another anticorrosion method, there is a method of forming a sprayed coating of zinc, aluminum, or an alloy thereof having an electrochemically low potential on the surface of carbon steel by a spraying method. For example, JIS H8300 (1999) has been established as thermal spraying of zinc and aluminum and their alloys.
【０００３】こうした溶射による防食技術は、そもそも
Zn, Alおよびそれらの合金類の皮膜それ自身が優れた耐
食性を発揮することと、たとえ皮膜の一部が損耗して基
材が露出したとしても、残存する皮膜金属が電気化学的
に鋼基材を保護する性質 (犠牲陽極作用) を有すること
を利用したものである。なお、これらの溶射皮膜の表面
に対しては、さらに塗装を施して長期間にわたる耐久性
を保持させる、いわゆる重防食処理を施す例が多い。し
かしながら、最近の鋼構造物については、新しく建築さ
れるものに加え、既存の鋼構造物の保守点検にも莫大な
人手と経費を必要とするようになっており、従来の上述
した考え方による鋼構造物への防食技術だけでは対処で
きなくなっているのが実情である。[0003] Such anti-corrosion technology by thermal spraying, in the first place
The films of Zn, Al and their alloys themselves exhibit excellent corrosion resistance, and even if a part of the film is worn away and the substrate is exposed, the remaining film metal is electrochemically steel-based. It utilizes the property of protecting the material (sacrificial anode action). In many cases, the surface of these thermal spray coatings is subjected to a so-called heavy-corrosion treatment, in which the surface is further coated to maintain long-term durability. However, with recent steel structures, maintenance and inspection of existing steel structures, in addition to those newly constructed, require enormous manpower and costs. The fact is that it is no longer possible to deal with corrosion prevention techniques for structures alone.
【０００４】[0004]
【発明が解決しようとする課題】鋼構造物に施されてい
る塗装や、ZnやAlなどの金属溶射皮膜による従来防食技
術は、ある程度の防食作用は認められるものの、周期的
な塗り替えや、溶射皮膜の場合、多孔質であることか
ら、再施工を行う必要がある他、次のような問題点もあ
った。 (1) 基材に対して電気化学的に卑な電位をもつZn, Alお
よびそれらの合金などを用いた溶融皮膜は、犠牲陽極作
用によって鋼構造物を保護する方法であり、鋼構造物基
材の腐食をある程度抑制できるものの、一方でZn, Al金
属皮膜の側から見れば、これらが早く損耗することを意
味しており、再溶射を頻繁に行わねばならないという問
題点があった。 (2) とくに溶射皮膜の場合、多孔質となるため、重工業
が多いことに加え海岸線の長い我が国のよな地域では、
SOx, NOxの腐食作用に加え、塩害の影響をうけやすく、
そのために鋼構造物の腐食損耗速度が大きいという問題
点があった。The conventional anti-corrosion technology using a coating applied to a steel structure or a metal spray coating such as Zn or Al has a certain anti-corrosion effect. In the case of a film, since it is porous, it is necessary to perform reconstruction, and there are also the following problems. (1) Melt coating using Zn, Al and their alloys, which have an electrochemically low potential with respect to the substrate, is a method of protecting steel structures by sacrificial anodic action. Although corrosion of the material can be suppressed to some extent, on the other hand, when viewed from the side of the Zn and Al metal coatings, it means that these are worn away quickly, and there has been a problem that re-spraying must be performed frequently. (2) Especially in the case of thermal sprayed coatings, since they are porous, in areas such as Japan where there are many heavy industries and the coastline is long,
In addition to the corrosive action of SOx and NOx, it is easily affected by salt damage,
Therefore, there is a problem that the corrosion wear rate of the steel structure is high.
【０００５】本発明の目的は、海水や塩分、さらにはNO
x やSOx などの腐食性ガスに対する耐久性に優れた溶射
被覆部材を提供することにある。本発明の他の目的は、
耐塩水特性等に優れた溶射被覆部材を安価にかつ確実に
製造する方法を提案することにある。It is an object of the present invention to provide a method for treating seawater, salt, and NO.
An object of the present invention is to provide a thermal spray coating member having excellent durability against corrosive gases such as x and SOx. Another object of the present invention is to
An object of the present invention is to propose a method for reliably and inexpensively producing a thermal spray coated member having excellent salt water resistance and the like.
【０００６】[0006]
【課題を解決するための手段】本発明は、上述した課題
を次のような技術的手段の採用によって解決するもので
あり、とくに、Al, Al−Zn, Al−Mg合金のように、純Al
もしくはAlを含む合金からなる溶射材料を、熱源温度の
高い電気アーク溶射法によって、さらに溶融微粒子の飛
行速度を制御 (抑制) することによって、溶射粒子の少
なくともその一部をその溶射処理の過程で酸化させ、酸
化物を多く含む粒子が分散した状態の溶射皮膜を形成す
る技術である。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems by employing the following technical means. In particular, the present invention relates to pure metals such as Al, Al-Zn, and Al-Mg alloys. Al
Alternatively, by spraying a sprayed material made of an alloy containing Al using an electric arc spraying method with a high heat source temperature and further controlling (suppressing) the flying speed of the molten fine particles, at least a part of the sprayed particles during the spraying process. This is a technique for forming a thermal spray coating in a state in which particles containing a large amount of oxides are dispersed by oxidation.
【０００７】このようにして形成された溶射皮膜は次に
示すような特徴を発揮する。 (1) 酸化された多くのAl酸化物溶射粒子を含むので、酸
化物を含まない溶射皮膜に比較すると、耐食性に優れて
いる。 (2) 酸化された多くのAl酸化物溶射粒子を含むので、酸
化物含有量の少ない皮膜に比較すると、腐食電位が貴側
にある。しかし、鋼鉄製基材に対しては卑な電位を示す
性質は維持している。 (3) 上記の酸化物を多く含むAlもしくはAl合金溶射皮膜
は、鋼鉄製基材を電気化学的に保護 (犠牲陽極作用) す
るが、従来技術による酸化物含有量の少ない溶射皮膜に
比較すると、鋼鉄製基材との電位差が小さいので、犠牲
陽極反応によって溶解する皮膜量が少なく、同一の膜厚
であれば、保護作用を長期間にわたって維持する。[0007] The sprayed coating thus formed exhibits the following characteristics. (1) Since it contains many oxidized Al oxide spray particles, it has excellent corrosion resistance as compared with a thermal spray coating containing no oxide. (2) Since it contains many oxidized Al oxide spray particles, the corrosion potential is on the noble side as compared with a coating having a low oxide content. However, the property of showing a low potential with respect to the steel base material is maintained. (3) The above-mentioned Al or Al alloy thermal spray coating containing a large amount of oxides electrochemically protects the steel base material (sacrificial anode action), but compared with the thermal spray coating having a low oxide content according to the prior art. Since the potential difference from the steel base material is small, the amount of the film dissolved by the sacrificial anodic reaction is small, and if the film thickness is the same, the protective action is maintained for a long time.
【０００８】このような知見の下に開発した本発明の要
旨構成は次のとおりである。 (1) 鋼鉄製基材の表面に、1.2 〜3.0 wt％の酸素を含む
アルミニウムもしくはアルミニウム合金溶射被膜が、40
〜2000μm の厚さで被覆されていることを特徴とする防
食溶射被覆部材である。 (2) 鋼鉄製基材の表面に、1.2 〜3.0 wt％の酸素を含む
アルミニウムもしくはアルミニウム合金溶射被膜と、1.
2 wt％未満の酸素を含むアルミニウムもしくはアルミニ
ウム合金溶射被膜とが交互に積層被覆されていることを
特徴とする防食溶射被覆部材である。 (3) 鋼鉄製基材の表面にアルミニウムもしくはアルミニ
ウム合金の溶射材料の間に電気アークを発生させること
により、該溶射材料を溶融微粒化すると同時に、その溶
融微粒子を、圧縮空気あるいは圧縮酸素によって60〜15
0 m/s の速度で飛行させることで少なくともその一部が
酸化する雰囲気下で付着させ、Al２O３粒子を含む全酸
素量が1.2 〜3.0 wt％であるアルミニウムもしくはアル
ミニウム合金溶射皮膜を40〜2000μm の厚さに形成する
ことを特徴とする防食溶射被覆部材の製造方法である。 (4) なお、本発明において、上記アルミニウムもしくは
アルミニウム合金溶射皮膜には、アルミニウム酸化物を
含有すると共に、そのアルミニウム酸化物は溶射処理の
過程で生成させたものであることが好ましい。The gist configuration of the present invention developed based on such knowledge is as follows. (1) A sprayed aluminum or aluminum alloy coating containing 1.2 to 3.0 wt% oxygen is applied to the surface of a steel base material.
An anticorrosion spray-coated member coated with a thickness of 20002000 μm. (2) An aluminum or aluminum alloy thermal spray coating containing 1.2 to 3.0 wt% oxygen on the surface of a steel base material;
An anti-corrosion spray coated member characterized by being alternately laminated and coated with an aluminum or aluminum alloy sprayed coating containing less than 2 wt% oxygen. (3) By generating an electric arc between the sprayed material of aluminum or aluminum alloy on the surface of the steel base material, the sprayed material is melted and atomized, and at the same time, the molten fine particles are cooled by compressed air or compressed oxygen. ~ 15
By flying at a speed of 0 m / s, at least a part of the aluminum or aluminum alloy sprayed coating having an overall oxygen content of 1.2 to 3.0 wt% containing Al 2 O 3 particles of 40 to 40 wt% is deposited. A method for producing an anticorrosion spray-coated member, characterized in that the member is formed to a thickness of 20002000 μm. (4) In the present invention, the aluminum or aluminum alloy sprayed coating preferably contains aluminum oxide, and the aluminum oxide is formed during the thermal spraying process.
【０００９】[0009]
【発明の実施の形態】一般に、亜鉛やアルミニウムある
いはこれらの合金の溶射皮膜は、鋼構造部材の防食用表
面処理被覆として使用されている。これらが防食被覆と
して用いられる理由は、これらの皮膜が次のような作用
機構を有するからである。その第一は、亜鉛やアルミニ
ウムあるいはこれらの合金の溶射皮膜は、自然界の清浄
な大気中では、その表面に緻密で耐食性に優れた塩基性
炭酸塩の薄膜を形成して、溶射皮膜の損耗を防ぐ作用を
有するからである。その第二は、例えば溶射皮膜が局部
的に損耗して鋼基材面が露出したり、皮膜の気孔部を通
して雨水や海水が内部へ浸入した場合、電気化学的に卑
な亜鉛やアルミニウムあるいはこれらの合金皮膜が犠牲
陽極となって溶出し、鋼基材の腐食損耗を積極的に防ぐ
ところにある。DESCRIPTION OF THE PREFERRED EMBODIMENTS In general, a sprayed coating of zinc, aluminum or an alloy thereof is used as a surface treatment coating for corrosion protection of steel structural members. These are used as anticorrosion coatings because these films have the following action mechanism. The first is that sprayed coatings of zinc, aluminum or their alloys form a thin film of a basic carbonate with excellent corrosion resistance in the clean air of nature to reduce wear of the sprayed coating. This is because it has an action of preventing. The second is that, for example, when the sprayed coating is locally worn and the steel substrate surface is exposed, or when rainwater or seawater infiltrates through the pores of the coating, zinc or aluminum which is electrochemically basic or Is eluted as a sacrificial anode to actively prevent corrosion and abrasion of the steel substrate.
【００１０】このような知見の下に開発した本発明の特
徴を要約して説明すると、アルミニウムおよびアルミニ
ウム合金 (アルミニウムを含むもの）の溶射皮膜中に、
空気もしくは酸素雰囲気下の溶射熱源中で溶射粒子 (溶
滴) を酸化して得られるAl酸化物微粒子を分散含有させ
ることにより、アルミニウムおよびアルミニウム合金皮
膜の電極電位を上げて (貴な方向へ移動) 、該溶射皮膜
そのものの耐食性を向上させた点の構成にある。このよ
うに、溶射粒子の表面の少なくとも一部が酸化性雰囲気
中での溶射処理によって酸化した微粒子を含む該溶射皮
膜中には、主としてAl２O３が生成しているが、この酸
化物はそれ自体耐食性に優れているため、重工業地帯で
の腐食原因となっているNOｘ, SOｘをはじめこれらの成
分を含む (溶解した）酸性雨に対しても強い耐食性を発
揮する。[0010] The features of the present invention developed on the basis of the above findings will be briefly described as follows. Thermal spray coatings of aluminum and aluminum alloys (including aluminum) include:
By dispersing and containing Al oxide fine particles obtained by oxidizing spray particles (droplets) in a spray heat source under air or oxygen atmosphere, the electrode potential of aluminum and aluminum alloy film is raised (moving in noble direction) ), In that the corrosion resistance of the sprayed coating itself is improved. As described above, Al 2 O 3 is mainly generated in the thermal spray coating containing fine particles in which at least a part of the surface of the thermal spray particles is oxidized by the thermal spray treatment in an oxidizing atmosphere. excellent for use in its own corrosion resistance, including NO x, SO x that is the corrosion caused in heavy industry area (dissolved) containing these ingredients exhibit strong corrosion resistance against acid rain.
【００１１】一方で、Al２O３の微粒子を分散含有する
溶射皮膜が、もし何らかの原因で、鋼基材に達する損傷
を受けた場合や、皮膜の気孔部を通して海水などが浸入
してきたときには、該溶射皮膜中の金属Alが犠牲陽極作
用によって鋼基材を防食する作用を発揮する。On the other hand, if the thermal spray coating containing dispersed Al 2 O 3 fine particles is damaged for some reason and reaches the steel base material, or if seawater or the like enters through the pores of the coating, The metal Al in the thermal spray coating exerts an action of preventing corrosion of the steel base material by a sacrificial anode action.
【００１２】ただ、本発明に係る溶射皮膜については、
マトリックスであるAl、Al合金中にAl２O３等のアルミ
ニウム酸化物の微粒子を分散含有しているため、純Alと
比較すると、貴な電位を示すため、鋼基材との電位差は
必然的に小さくなる。しかし、鋼基材より卑であるか
ら、犠牲陽極作用は十分に発揮できる状態にある。例え
ば、５wt％ NaCl 水溶液中で銀／塩化銀電極を参照電極
としてそれぞれの腐食電位を測定すると、次の通りであ
る。 (1) Al溶射皮膜＝−0.7V (2) Al溶射皮膜 (Al２O３を多量に含む本発明皮膜) −
0.65V (3) 鋼基材 −4.5VHowever, with regard to the thermal spray coating according to the present invention,
Since aluminum oxide fine particles such as Al 2 O 3 are dispersed and contained in the matrix Al and Al alloy, they show a noble potential compared to pure Al, so the potential difference from the steel substrate is inevitable. Become smaller. However, the sacrificial anode function is in a state where it can be sufficiently exerted because it is more base than the steel base material. For example, when the corrosion potential of each of the silver / silver chloride electrodes is measured in a 5 wt% NaCl aqueous solution using the silver / silver chloride electrode as a reference electrode, the results are as follows. (1) Al thermal spray coating = -0.7 V (2) Al sprayed coating (Al 2 O 3 present invention film containing a large amount) -
0.65V (3) Steel substrate −4.5V
【００１３】この測定結果から明らかなように、従来技
術の場合、鋼基材とAl溶射皮膜との間には、2.5Vの電位
差があるので、Al溶射皮膜がアノードとなって、鋼基材
を防食する。一方、本発明に係る上記溶射皮膜も、鋼基
材とAl２O３酸化物微粒子入りAl溶射皮膜との間には2.0
Vの電位差があるので、十分な防食作用を発揮する。こ
の点、本発明に係る溶射皮膜を使用すると、上記従来溶
射皮膜に比較して電位差が小さい値を示すので、むしろ
アノードとしての溶出速度が小さくなり、鋼基材を長期
間にわたって安定して防食することができるようにな
る。As is clear from the measurement results, in the case of the prior art, since there is a potential difference of 2.5 V between the steel base and the Al sprayed coating, the Al sprayed coating becomes an anode and To prevent corrosion. On the other hand, the thermal sprayed coating according to the present invention also has a distance between the steel substrate and the Al thermal sprayed coating containing Al 2 O 3 oxide fine particles of 2.0.
Since there is a potential difference of V, it exerts a sufficient anticorrosive action. In this regard, when the thermal spray coating according to the present invention is used, since the potential difference shows a smaller value than the conventional thermal spray coating, the elution rate as an anode is rather low, and the steel substrate is stably protected for a long period of time. Will be able to
【００１４】要するに、本発明の考え方の一端は、鋼基
材表面に被覆する溶射皮膜について、それが基材の電位
に比較して卑であることが必要な条件となるものの、両
者の電位差を必要最小限にとどめることで、その分だけ
長期間にわたって安定した防食作用を発揮するように工
夫することにある。In short, one aspect of the concept of the present invention is that the sprayed coating that coats the surface of the steel base material needs to have a base that is lower than the potential of the base material. It is an object of the invention to exhibit a stable anticorrosion effect over a long period of time by keeping it to the minimum necessary.
【００１５】次に、本発明において、溶射皮膜中にAl２
O３等の酸化物微粒子を分散含有させる方法としては、
次に示すような手段を採用することが好ましい。それ
は、AlまたはAl合金の溶射材料を用いて、この材料が溶
射熱源中を飛行する際に、Al２O３酸化物が多く含まれ
るような溶射条件を採用することによって成膜すること
である。この点について、一般に、Al２O３微粒子を予
め添加した溶射材料をつくり、この材料を溶射して成膜
する方法もあるが、本発明は、前者の、いわゆる溶射処
理中にAl２O３等の酸化物微粒子を生成させる方法を採
用する。その理由は、AlまたはAl合金溶射材料は市販さ
れているため、入手が容易であるうえ、安価だからであ
る。以下、その本発明に適合する溶射処理の方法につい
て説明する。Next, in the present invention, Al 2 is contained in the thermal spray coating.
The oxide fine particles O 3 or the like as a method of dispersing contained,
It is preferable to employ the following means. That is, a film is formed by using a thermal spraying material of Al or an Al alloy and adopting thermal spraying conditions such that when the material flies through a thermal spraying heat source, a large amount of Al 2 O 3 oxide is contained. . In this regard, in general, making a thermal spray material with addition in advance of Al 2 O 3 fine particles, there is a method of forming a film by thermal spraying of this material, the present invention is, in the former, Al 2 O 3 in a so-called thermal spraying And the like. The reason is that, because the Al or Al alloy sprayed material is commercially available, it is easily available and inexpensive. Hereinafter, a method of the thermal spraying process suitable for the present invention will be described.
【００１６】プラズマ溶射法と言われる溶射法は、理論
的には数万度に達する熱源をもっているが、この方式で
溶射しても、Al皮膜中に含まれる酸化物含有量はせいぜ
い0.5 〜0.8 wt％程度である。発明者らは、この原因に
ついて研究した。その結果、溶射用として市販されてい
る装置が発生するプラズマジェットの温度は、5000〜70
00℃の高温環境にあるが、プラズマジェットの速度が非
常に大きいため (通常350 〜700m/s) ため、溶射粒子が
空気と接触する時間が極めて短く、そのために酸化物を
生成するに十分な時間が与えられていないのである。そ
のうえ、プラズマジェット中には多数の電子が存在して
いるため、還元環境も構成されており、酸化が抑制され
る傾向にある。Although the thermal spraying method called the plasma spraying method theoretically has a heat source reaching tens of thousands of degrees, the oxide content contained in the Al film is at most 0.5 to 0.8 even when spraying by this method. It is about wt%. The inventors have studied this cause. As a result, the temperature of the plasma jet generated by a device commercially available for thermal spraying is 5000-70.
Despite the high temperature environment of 00 ° C, due to the very high speed of the plasma jet (typically 350-700 m / s), the time for the sprayed particles to come into contact with air is very short, which is not enough to generate oxides. Time is not given. In addition, since a large number of electrons are present in the plasma jet, a reducing environment is also formed, and oxidation tends to be suppressed.
【００１７】これに対し、可燃性ガスの燃料エネルギー
を熱源とするフレーム溶射法では、フレームの速度は遅
くなるが熱源温度が低くなるため (1800〜2200℃) 酸化
物含有量の少ない溶射皮膜となり、本発明が求めている
ような溶射皮膜とはならないのが普通である。On the other hand, in the flame spraying method using the fuel energy of the flammable gas as a heat source, the flame speed is slow but the heat source temperature is low (1800 to 2200 ° C.). Usually, the thermal spray coating does not become as required by the present invention.
【００１８】そこで、本発明では、熱源温度は高くする
一方で、その中を飛行して鋼基材の表面に衝突する溶射
粒子の飛行速度を遅くすることにより、この飛行期間中
に粒子の酸化が容易に進行する条件を検討した。具体的
には、溶射材料を線状とし、この２本の線状溶射材料間
に直流を印加してアークを発生させ、そのアーク熱によ
って材料を溶融させる。ここで、溶融した材料は微粒子
(溶滴) となるので、これを圧縮空気または圧縮酸素等
からなる酸化性雰囲気に保持したまま鋼基材表面に吹き
付け、溶射皮膜を形成するのである。Therefore, in the present invention, while the temperature of the heat source is increased, the flying speed of the spray particles which fly through the heat source and impinge on the surface of the steel base material is reduced, thereby oxidizing the particles during the flight. The conditions under which the process proceeds easily were studied. Specifically, the sprayed material is linear, an arc is generated by applying a direct current between the two linear sprayed materials, and the material is melted by the arc heat. Here, the molten material is fine particles
This is sprayed onto the surface of the steel base material while maintaining it in an oxidizing atmosphere composed of compressed air or compressed oxygen to form a thermal spray coating.
【００１９】本発明は、このような溶射方法 (一般に、
アーク溶射法と呼ばれている方法)について、直流電圧3
0V 以上を印加し、粒子の飛行速度を60〜160m/sに制御
することによって、酸化物の含有量が高い溶射皮膜を形
成する方法である。なお、近年の溶射技術は、高速フレ
ーム溶射法に代表されるように、熱源や溶射粒子の飛行
速度を高温・高速化することによって、粒子の基材表面
への衝突エネルギーを増大させ、それによって緻密で密
着力の強い溶射皮膜とする傾向にあるが、これに対して
本発明に係る溶射方法は、溶射粒子の飛行速度をむしろ
遅くすることが特徴となっている。The present invention relates to such a spraying method (generally,
DC voltage 3)
This method forms a thermal spray coating with a high oxide content by controlling the flight speed of particles to 60 to 160 m / s by applying 0 V or more. In recent years, thermal spraying technology, as represented by the high-speed flame spraying method, increases the collision energy of particles to the base material surface by increasing the flight speed of heat sources and spray particles to high temperatures and high speeds. In contrast, the thermal spraying method according to the present invention is characterized in that the flying speed of the thermal spray particles is rather slowed down.
【００２０】本発明において重要なことは、上述したよ
うに、特定雰囲気中での溶射材料の溶融粒子の飛行速度
を制御することである。即ち、その速度が60m/s よりも
遅くなると、粒子の酸化反応はよく進むものの、皮膜に
なったときの、粒子間結合力が弱く、しかも鋼鉄製基材
との密着力が低下するので好ましくない。一方、粒子の
飛行速度が160m/sを超えると、溶射皮膜は緻密となり、
粒子間結合力や基材との密着性は向上するが、酸化物含
有量が少なくなるので、本発明で求めるような皮膜には
ならない。What is important in the present invention, as described above, is to control the flying speed of the molten particles of the thermal spray material in a specific atmosphere. That is, when the speed is lower than 60 m / s, although the oxidation reaction of the particles proceeds well, when the film is formed, the bonding force between the particles is weak, and the adhesion to the steel base material is reduced, which is preferable. Absent. On the other hand, when the flying speed of the particles exceeds 160 m / s, the thermal spray coating becomes dense,
Although the interparticle bonding force and the adhesion to the substrate are improved, the oxide content is reduced, so that the film does not become the film required in the present invention.
【００２１】上述したような方法の実施によって形成さ
れる本発明に係る溶射皮膜中は、Al ２O３等の酸化物特
徴粒子 (0.01〜0.1 μｍ程度) が含まれることになる
が、その含有量は、全酸素量に換算して1.2 〜3.0 wt％
の範囲がよい。この理由は、全酸素量が1.2 wt％未満の
溶射皮膜では、従来の皮膜に比較して貴な電位を示すも
のの、その差が僅かであるため (0.01〜0.02V)、本発明
の機能を十分に発揮することができないからであり、一
方、全酸素量が3.0 wt％以上の溶射皮膜を形成させるこ
とは、上述したアーク溶射法の下では困難を伴う。Formed by performing a method as described above.
Al in the thermal spray coating according to the present invention 2O3Oxide characteristics such as
Includes particles (about 0.01 to 0.1 μm)
However, its content is 1.2 to 3.0 wt% in terms of total oxygen.
Range is good. The reason is that the total oxygen content is less than 1.2 wt%
Sprayed coatings show a more noble potential than conventional coatings.
However, since the difference is small (0.01 to 0.02 V), the present invention
This is because the functions of
On the other hand, it is not possible to form a thermal spray coating with a total oxygen content of 3.0 wt% or more.
Is difficult under the arc spraying method described above.
【００２２】なお、溶射皮膜中の酸素は、金属Al溶射材
料を用いた場合は、Al２O３、Zn−Al合金の場合はZnO
、Al２O３、Al−Mg合金の場合はAl２O３、MgO 、Al−S
i合金ではAl２O３とSiO２などが主成分であるが、防食
技術上酸化物を区別する必要がないため、本発明では全
酸素含有量として表示することとした。また、本発明に
係る溶射皮膜は、鋼鉄製基材の表面に対し、40〜2000μ
ｍの厚さ、特に80〜300 μｍ厚さに施工することが好ま
しい。それは、40μｍ以下の厚さでは、均等で緻密を皮
膜が得られにくいうえ、腐食損耗による寿命が短くな
り、一方、その厚さを2000μｍ以上にしても、効果が飽
和する一方でコスト高となるからである。The oxygen in the thermal spray coating is Al 2 O 3 when a metal Al thermal spray material is used, and ZnO when a Zn-Al alloy is used.
, Al 2 O 3 , and Al 2 O 3 , MgO, Al-S for Al-Mg alloy
In the i-alloy, Al 2 O 3 and SiO 2 are the main components, but it is not necessary to distinguish oxides in terms of anticorrosion technology. Therefore, in the present invention, the total oxygen content is indicated. Further, the thermal spray coating according to the present invention, the surface of the steel substrate, 40 ~ 2000μ
m, particularly preferably 80 to 300 μm. It is difficult to obtain a uniform and dense film at a thickness of 40 μm or less, and the life due to corrosion and wear is shortened. On the other hand, even if the thickness is 2000 μm or more, the effect is saturated and the cost increases. Because.
【００２３】さて、本発明に係る酸素含有量の多い溶射
皮膜は、鋼鉄製基材の表面に直接施工することを原則と
するが、全酸素含有量の異なるAl、Al−Zn、Al−Mg合
金、Al−Si合金などの溶射皮膜を、二層以上に亘って積
層することもできる。The sprayed coating having a high oxygen content according to the present invention is basically applied directly to the surface of a steel base material, but Al, Al-Zn, Al-Mg having different total oxygen contents. Thermal spray coatings such as alloys and Al-Si alloys can be laminated in two or more layers.
【００２４】さらに、本発明では、電気アーク溶射する
際に、２本の線状溶射材料を用いて直流を通電する。こ
のとき、一方の線をAl、他の線をZnのように異質な溶射
材料を用いて形成される溶射皮膜についても、Al−Zn合
金または不完全な合金の集合体から構成されるが、この
ような溶射皮膜であっても、全酸素量が1.2 〜3.0 wt％
の範囲であれば、本発明に適合する溶射皮膜としての特
性を発揮することができる。Further, in the present invention, when performing electric arc spraying, a direct current is applied using two linear sprayed materials. At this time, one of the lines is Al, and the other line is also formed of an Al-Zn alloy or an incomplete alloy aggregate, even for a thermal spray coating formed using a different thermal spray material such as Zn. Even with such a sprayed coating, the total oxygen content is 1.2 to 3.0 wt%
Within this range, the properties as a thermal spray coating conforming to the present invention can be exhibited.
【００２５】[0025]
【実施例】この実施例は、溶射条件を調整することによ
って、皮膜中の酸素含有量として、1.2 〜2.5 wt％を含
む本発明に適合する溶射皮膜を、SS400 基材 (幅50mm×
長さ100mm ×厚さ５mm) の表面に、250 μｍの厚さに形
成した後、JIS Z 2371制定の塩水噴霧試験を連続5000時
間実施して、その耐食性を調査した結果の説明である。
比較例の溶射皮膜として、無処理のままのSS400 基材の
例、および同じ溶射材料を用いて通常の条件、すなわち
溶射皮膜中の全酸素含有量が 0.5〜1.0 wt％となる溶射
条件で成膜した溶射皮膜を250 μｍの厚さに形成した例
について、塩水噴霧試験を行った。表１は、これらの結
果をまとめたものである。比較例である無処理のSS400
基材は、24時間の塩水噴霧試験によって全面赤さびが発
生したが、その他の比較例の皮膜は、白さびの発生は認
められるものの赤さびは見られず優れた耐食性を発揮し
た。これに対し本発明の皮膜 (No. １，２，３）も、酸
化物を多量に含んでいるが5000時間の塩水噴霧試験によ
っても、赤さびの発生は認められず、JIS H8661 −(199
9)制定の耐食性試験では従来の方法で形成された溶射皮
膜と同等の耐食性を有し、両者間に差は認められなかっ
た。EXAMPLE In this example, by adjusting the spraying conditions, a sprayed coating conforming to the present invention containing an oxygen content of 1.2 to 2.5 wt% in a coating was applied to an SS400 substrate (width 50 mm × width).
This is a description of the results of examining the corrosion resistance of a 250-μm-thick (100 mm long × 5 mm thick) surface formed by conducting a salt spray test for 5,000 hours continuously according to JIS Z 2371.
As the sprayed coating of the comparative example, an untreated SS400 substrate was used, and the same sprayed material was used under normal conditions, that is, a spraying condition in which the total oxygen content in the sprayed coating was 0.5 to 1.0 wt%. A salt spray test was performed on an example in which the formed thermal spray coating was formed to a thickness of 250 μm. Table 1 summarizes these results. Untreated SS400 as a comparative example
Red rust was generated on the entire surface of the substrate by a salt spray test for 24 hours, but the other comparative films exhibited excellent corrosion resistance, although white rust was observed but no red rust was observed. On the other hand, the coating of the present invention (Nos. 1, 2, and 3) also contained a large amount of oxides, but no rust was observed even after 5000 hours of salt spray test, and JIS H8661- (199)
9) In the established corrosion resistance test, it had the same corrosion resistance as the thermal sprayed coating formed by the conventional method, and there was no difference between the two.
【００２６】[0026]
【表１】 [Table 1]
【００２７】実施例２ この実施例では、実施例１の要領で作製した溶射皮膜試
験片を用いて、３wt％NaCl、30℃、空気飽和の条件の食
塩水溶液を満たした容量１リットルのビーカ中に90日間
浸漬し、水溶液中の溶出したAl量を化学分析法によって
求めるとともに試験片の表面の変化を観察した。表２は
これらの結果をまとめたものである。この結果から明ら
かなように、３wt％NaCl水溶液中に90日間 (2160h)浸漬
しても、何れも白さびの発生は認められるものの、赤さ
びの発生は全く見られず、優れた耐食性を発揮している
ことがわかった。ただ、食塩水溶液中へのAl溶出量には
明瞭な差が見られ、比較例の皮膜が90〜110g/m２であっ
たのに対し、本発明適合例は、８〜15g/m２の範囲にと
どまっており、非常に溶出しにくいことが判明した。す
なわち、本発明適合例はSS400 基材を防食しつつ、溶出
はするものの、その量が非常に少ないため、比較例より
も長期間にわたって防食作用を維持することができると
推定される。Example 2 In this example, a test piece of the thermal spray coating prepared in the same manner as in Example 1 was used in a 1-liter beaker filled with a saline solution of 3 wt% NaCl, 30 ° C. and air saturation. For 90 days, the amount of eluted Al in the aqueous solution was determined by a chemical analysis method, and changes in the surface of the test piece were observed. Table 2 summarizes these results. As is evident from these results, even when immersed in a 3 wt% NaCl aqueous solution for 90 days (2160 h), white rust was observed in any case, but no red rust was observed at all, and excellent corrosion resistance was exhibited. I understood that. However, a clear difference was seen in the amount of Al eluted in the saline solution, and the film of the comparative example was 90 to 110 g / m 2 , whereas the conforming example of the present invention was 8 to 15 g / m 2 . It was found that it was within the range, and it was very difficult to elute. That is, it is presumed that the conforming examples of the present invention elute while eluting the SS400 substrate, but the amount is very small, so that the anticorrosion action can be maintained for a longer period of time than in the comparative example.
【００２８】[0028]
【表２】 [Table 2]
【００２９】実施例３ この実施例では、全酸素含有量の異なる複数層からなる
アルミニウム、アルミニウム合金溶射皮膜を積層したSS
400 試験片を用いて、JIS Z 2371規定の塩水噴霧試験を
5000時間連続して実施し皮膜の外観変化を調査した。供
試溶射皮膜試験片（皮膜厚さアンダーコート100 μｍ／
トップコート100 μｍ) は以下のものを用いた。 アンダーコートAl (酸素含有量2.3 ％) ／トップコー
トAl（酸素含有量0.6％) アンダーコートAl−５Mg (酸素含有量2.2 ％) ／トッ
プコートAl−５Mg（酸素含有量0.7 ％) アンダーコートAl (酸素含有量2.3 ％) ／トップコー
トAl−５Mg（酸素含有量2.2 ％) 上記の5000時間経過後の溶射皮膜の表面は、何れも白さ
びの発生は認められるものの赤さびは全く見られず、酸
素含有量の異なる複数種の溶射皮膜を積層した場合も、
耐食性には全く影響を与えないことが判明した。Example 3 In this example, an aluminum or aluminum alloy sprayed coating composed of a plurality of layers having different total oxygen contents was laminated.
Using a 400 specimen, the salt spray test specified in JIS Z 2371 was performed.
The test was performed continuously for 5000 hours, and the appearance change of the film was investigated. Specimen sprayed coating test piece (film thickness undercoat 100 μm /
The following was used for the top coat (100 μm). Undercoat Al (oxygen content 2.3%) / Topcoat Al (oxygen content 0.6%) Undercoat Al-5Mg (oxygen content 2.2%) / Topcoat Al-5Mg (oxygen content 0.7%) Undercoat Al ( Oxygen content 2.3%) / Topcoat Al-5Mg (oxygen content 2.2%) On the surface of the above-mentioned thermal sprayed coating after 5,000 hours, white rust was observed, but no red rust was observed at all. Even when multiple types of thermal spray coatings with different contents are laminated,
It was found that it had no effect on corrosion resistance.
【００３０】[0030]
【発明の効果】以上説明したように、本発明によれば、
アルミニウム、アルミニウム−亜鉛合金、アルミニウム
−マグネシウム合金溶射皮膜中に、全酸素量にして1.2
wt％〜3.0 wt％に当る酸化物微粒子を含有させることで
皮膜が鋼鉄製基材に対して卑な電位を示すように調整し
てある。従って、該基材が電気化学的に効果的に保護さ
れるとともに、皮膜それ自体も耐食性を発揮して食塩水
溶液中への溶出量が非常に少なくなり、それ故に基材の
腐食を長期間にわたって防止することができる。その結
果として、本発明に適合する溶射皮膜を施工した鋼鉄製
基材は、メンテナンスフリーの期間を延長することがで
き、ひいては設備、補修費の節減に寄与するところが大
きいと言える。As described above, according to the present invention,
Aluminum, aluminum-zinc alloy, aluminum-magnesium alloy spray coating, total oxygen content 1.2
The coating is adjusted so as to show a base potential with respect to the steel base material by containing the oxide fine particles corresponding to wt% to 3.0 wt%. Therefore, the base material is effectively protected electrochemically, and the film itself also exhibits corrosion resistance, so that the amount of elution into the saline solution is very small, and therefore, the corrosion of the base material can be prevented for a long period of time. Can be prevented. As a result, it can be said that the steel base material on which the thermal spray coating conforming to the present invention has been applied can extend the maintenance-free period, and greatly contributes to the reduction of equipment and repair costs.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4K031 AA01 AA08 AB02 AB03 AB09 CB08 CB12 CB37 CB39 CB43 DA03 EA09 EA12 4K060 AA02 BA08 BA13 BA19 BA33 DA07 EA08 EB01 EB05 FA03 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4K031 AA01 AA08 AB02 AB03 AB09 CB08 CB12 CB37 CB39 CB43 DA03 EA09 EA12 4K060 AA02 BA08 BA13 BA19 BA33 DA07 EA08 EB01 EB05 FA03
Claims (4)
酸素を含むアルミニウムもしくはアルミニウム合金溶射
被膜が、40〜2000μm の厚さで被覆されていることを特
徴とする防食溶射被覆部材。An anti-corrosion spray coated member characterized in that a steel base material is coated with a sprayed aluminum or aluminum alloy film containing 1.2 to 3.0 wt% of oxygen in a thickness of 40 to 2000 μm. .
酸素を含むアルミニウムもしくはアルミニウム合金溶射
被膜と、1.2 wt％未満の酸素を含むアルミニウムもしく
はアルミニウム合金溶射被膜とが交互に積層被覆されて
いることを特徴とする防食溶射被覆部材。2. An aluminum or aluminum alloy thermal spray coating containing 1.2 to 3.0 wt% oxygen and an aluminum or aluminum alloy thermal spray coating containing less than 1.2 wt% oxygen are alternately laminated on the surface of a steel substrate. An anticorrosion sprayed coating member characterized in that:
合金溶射皮膜には、アルミニウム酸化物を含有すると共
に、そのアルミニウム酸化物は溶射処理の過程で生成さ
せたものであることを特徴とする、請求項１または２に
記載の防食溶射被覆部材。3. The sprayed aluminum or aluminum alloy film contains an aluminum oxide, and the aluminum oxide is formed during a thermal spraying process. 3. The anticorrosion sprayed coating member according to 1.
はアルミニウム合金の溶射材料の間に電気アークを発生
させることにより、該溶射材料を溶融微粒化すると同時
に、その溶融微粒子を、圧縮空気あるいは圧縮酸素によ
って60〜150m/s の速度で飛行させることで少なくとも
その一部が酸化する雰囲気下で付着させ、Al２O３粒子
を含む全酸素量が1.2 〜3.0 wt％であるアルミニウムも
しくはアルミニウム合金溶射皮膜を40〜2000μm の厚さ
に形成することを特徴とする防食溶射被覆部材の製造方
法。4. An electric arc is generated between a sprayed material of aluminum or an aluminum alloy on the surface of a steel base material to melt and atomize the sprayed material and simultaneously melt the fine particles with compressed air or compressed oxygen. at least a so partially deposited in an atmosphere of oxidizing, aluminum or aluminum alloy sprayed coating total amount of oxygen containing Al 2 O 3 particles are 1.2 to 3.0 wt% by to fly at a speed of 60~150m / s by Is formed to a thickness of 40 to 2000 .mu.m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000268231A JP3866911B2 (en) | 2000-09-05 | 2000-09-05 | Corrosion-proof spray-coated member and method for manufacturing the same |
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| JP2000268231A JP3866911B2 (en) | 2000-09-05 | 2000-09-05 | Corrosion-proof spray-coated member and method for manufacturing the same |
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| JP2002069606A true JP2002069606A (en) | 2002-03-08 |
| JP3866911B2 JP3866911B2 (en) | 2007-01-10 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007191800A (en) * | 2007-04-04 | 2007-08-02 | Nisshin Steel Co Ltd | Welded plated steel pipe having excellent weld zone corrosion resistance |
| JP2011094170A (en) * | 2009-10-27 | 2011-05-12 | Kobe Steel Ltd | Heat exchange member |
| US8007178B2 (en) | 2004-09-29 | 2011-08-30 | Mahle Engine Systems Ltd. | Bearing materials and method for the production thereof |
| JP2013213446A (en) * | 2012-04-02 | 2013-10-17 | Toyota Motor Corp | Internal combustion engine and method for manufacturing the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0578801A (en) * | 1991-09-19 | 1993-03-30 | Tocalo Co Ltd | Member for molten zinc bath |
| JPH07188891A (en) * | 1993-12-27 | 1995-07-25 | Toyota Motor Corp | Formation of metal oxide dispersed layer |
| JPH08225912A (en) * | 1995-02-20 | 1996-09-03 | Fujikura Ltd | Formation of oxide ceramic thermal-sprayed coating |
| JPH0967661A (en) * | 1995-08-31 | 1997-03-11 | Toshiba Corp | High temperature resistant coated member by thermal spraying and its production |
| JPH10509770A (en) * | 1994-11-26 | 1998-09-22 | グリコ−メタル−ウエルケ・グリコ・ベー・ファウ・ウント・コンパニー・コマンディトゲゼルシャフト | Multilayer material and manufacturing method thereof |
| JPH11140616A (en) * | 1997-11-12 | 1999-05-25 | Tocalo Co Ltd | Member with high temperature resistant spray coating, and its production |
-
2000
- 2000-09-05 JP JP2000268231A patent/JP3866911B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0578801A (en) * | 1991-09-19 | 1993-03-30 | Tocalo Co Ltd | Member for molten zinc bath |
| JPH07188891A (en) * | 1993-12-27 | 1995-07-25 | Toyota Motor Corp | Formation of metal oxide dispersed layer |
| JPH10509770A (en) * | 1994-11-26 | 1998-09-22 | グリコ−メタル−ウエルケ・グリコ・ベー・ファウ・ウント・コンパニー・コマンディトゲゼルシャフト | Multilayer material and manufacturing method thereof |
| JPH08225912A (en) * | 1995-02-20 | 1996-09-03 | Fujikura Ltd | Formation of oxide ceramic thermal-sprayed coating |
| JPH0967661A (en) * | 1995-08-31 | 1997-03-11 | Toshiba Corp | High temperature resistant coated member by thermal spraying and its production |
| JPH11140616A (en) * | 1997-11-12 | 1999-05-25 | Tocalo Co Ltd | Member with high temperature resistant spray coating, and its production |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8007178B2 (en) | 2004-09-29 | 2011-08-30 | Mahle Engine Systems Ltd. | Bearing materials and method for the production thereof |
| JP2007191800A (en) * | 2007-04-04 | 2007-08-02 | Nisshin Steel Co Ltd | Welded plated steel pipe having excellent weld zone corrosion resistance |
| JP2011094170A (en) * | 2009-10-27 | 2011-05-12 | Kobe Steel Ltd | Heat exchange member |
| JP2013213446A (en) * | 2012-04-02 | 2013-10-17 | Toyota Motor Corp | Internal combustion engine and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3866911B2 (en) | 2007-01-10 |
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