JPH05195241A - Heat resistant and corrosion resistant superposedly coated steel product - Google Patents
Heat resistant and corrosion resistant superposedly coated steel productInfo
- Publication number
- JPH05195241A JPH05195241A JP18441892A JP18441892A JPH05195241A JP H05195241 A JPH05195241 A JP H05195241A JP 18441892 A JP18441892 A JP 18441892A JP 18441892 A JP18441892 A JP 18441892A JP H05195241 A JPH05195241 A JP H05195241A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- layer
- nickel
- chromic acid
- black
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、例えば内燃機関におけ
る機関周囲での各種部品或いはこれら部材として250
℃程度以下の加温雰囲気状態にあって使用される板、
管、棒或いは線材等からなる鉄鋼材の表面に施して成る
耐熱・耐食性を同時に要求される重合被覆鋼材に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various parts around an engine in an internal combustion engine or members thereof.
A plate that is used in a heated atmosphere below about ℃,
The present invention relates to a polymer-coated steel material that is required to have heat resistance and corrosion resistance at the same time, which is formed on the surface of a steel material such as a pipe, a rod, or a wire material.
【0002】[従来の技術]従来、機関周囲に使用され
る各種部品或いはこれら部材として耐熱・耐食性の被覆
構造を有する鉄鋼材としては、一般に電鍍法或いは浸漬
法によって形成した鉄鋼材表面の亜鉛の鍍金層上に、単
に通常のクロメート被膜を有して成るか、或いは外観で
の品質価値の要求に関連して、鉄鋼材表面の前記亜鉛の
鍍金層上に、黒色クロメート被膜を形成するかして実用
に供していた。2. Description of the Related Art Conventionally, as various parts used around the engine or as a steel material having a heat-resistant and corrosion-resistant coating structure as these members, zinc on the surface of a steel material formed by an electroplating method or a dipping method is generally used. On the plating layer, either a normal chromate coating may be simply provided, or a black chromate coating may be formed on the zinc plating layer on the surface of the steel material in connection with the requirement of quality value in appearance. And put it to practical use.
【0003】[0003]
【発明が解決しようとする課題】しかしながらこれら従
来のものにあっては、長時間の走行等による機関からの
連続した或いは断続繰返しによる熱影響によって、前記
クロメート被膜或いは黒色クロメート被膜ともいずれも
概して短時間に変色し、強いては消失、剥離等を生ずる
等、未だ耐熱性の要求を充分に満足できない状況にあ
り、同時に耐熱性の劣化に起因して耐食性をも損ってそ
の低下を招く問題を有し、従って広くその改善が望まれ
る現状にある。However, in these prior arts, both the chromate coating and the black chromate coating are generally short due to the thermal effect of continuous or intermittent repetition from the engine due to running for a long time. There is a problem that heat resistance is still not fully satisfied, such as discoloration with time, strong disappearance, peeling, etc., and at the same time, deterioration of heat resistance also deteriorates corrosion resistance and causes deterioration. Therefore, the present situation is such that improvement is widely desired.
【0004】本発明は、従来の前記問題を、特に亜鉛−
ニッケル合金による鍍金層と黒色ニッケルの電鍍層との
なす相互の被着重合面での密着性を著しく向上し、更に
外側表面にクロム酸被膜を形成し、それぞれの前記鍍金
層、電鍍層およびクロム酸被膜の有する耐食性に関連し
て効果的に解決せしめ、前記温度以下の加温雰囲気にお
ける使用状態下にあっても、耐熱性と耐食性とを共に満
足することのできる耐熱・耐食性重合被覆鋼材を提供す
ることを目的とするものである。The present invention addresses the above-mentioned problems of the prior art, especially zinc-
Adhesion between the plating layer of nickel alloy and the electroplating layer of black nickel on the surface to be adhered to each other is remarkably improved, and a chromic acid film is further formed on the outer surface to form each of the plating layer, electroplating layer and chromium layer. A heat-resistant / corrosion-resistant polymer-coated steel material that can be effectively solved in relation to the corrosion resistance of an acid coating and can satisfy both heat resistance and corrosion resistance even under use in a heating atmosphere at a temperature lower than the above temperature. It is intended to be provided.
【0005】[0005]
【課題を解決するための手段】本発明は、鉄鋼材の表面
に亜鉛−ニッケル合金の鍍金層を下層とし、該鍍金層の
表面に黒色ニッケルの電鍍層を上層として被着重合し、
更に該電鍍層の表面にクロム酸被膜を有する耐熱・耐食
性重合被覆鋼材を要旨とするものである。According to the present invention, a zinc-nickel alloy plating layer is formed on a surface of a steel material as a lower layer, and an electroplating layer of black nickel is formed on the surface of the plating layer as an upper layer to perform polymerization.
Further, the gist is a heat-resistant and corrosion-resistant polymer coated steel material having a chromic acid coating on the surface of the electroplated layer.
【0006】[0006]
【作用】本発明に係る耐食性重合被覆鋼材の重合被覆を
形成するには、予め脱脂、脱錆等の前処理を施した鉄鋼
材の表面に電鍍法による亜鉛−ニッケル合金の鍍金層を
形成し、更に該亜鉛−ニッケル合金の鍍金層の表面に、
電鍍法による黒色ニッケルの電鍍層を形成せしめ、次い
で該黒色ニッケルの電鍍層の表面に、クロム酸水溶液に
よる浸漬、水洗及び乾燥のこれら一連からなるクロム酸
処理を1回以上施してクロム酸被膜を形成する。或いは
前記クロム酸処理を、クロム酸水溶液による浸漬、乾燥
及び加熱からなるこれら一連の処理を1回以上施してク
ロム酸被膜を形成する。更に或いはクロム酸処理をクロ
ム酸水溶液による浸漬、水洗及び乾燥のこれら一連から
なるクロム酸処理を1回以上施すとともに、更に再度ク
ロム酸水溶液による浸漬、乾燥及び加熱からなるこれら
一連の処理を1回以上施してクロム酸被膜を形成する。In order to form the polymer coating of the corrosion-resistant polymer-coated steel material according to the present invention, a zinc-nickel alloy plating layer is formed by electroplating on the surface of a steel material that has been pretreated by degreasing, derusting, etc. , Further on the surface of the zinc-nickel alloy plating layer,
A black nickel electroplating layer is formed by an electroplating method, and then the surface of the black nickel electroplating layer is subjected to a chromic acid treatment consisting of a series of dipping with a chromic acid aqueous solution, water washing and drying once or more to form a chromic acid film. Form. Alternatively, the chromic acid coating is formed by performing the above-mentioned chromic acid treatment one or more times of these series of treatments including immersion in a chromic acid aqueous solution, drying and heating. Furthermore, the chromic acid treatment is performed by chromic acid treatment consisting of a series of dipping in chromic acid aqueous solution, washing and drying at least once, and then once again in the series consisting of dipping in chromic acid aqueous solution, drying and heating. The above process is performed to form a chromic acid film.
【0007】[0007]
【実施例】以下本発明を図面に基づいて説明すれば次の
通りである。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings.
【0008】図1及び図2はいずれも本発明によって構
成された耐熱・耐食性重合被覆鋼材として板材(図1)
及び管材(図2)にそれぞれ施した要部の一部切欠によ
る拡大断面図であって、(1) は予め脱脂、脱錆等の前処
理を施した表面(1')に電鍍法によって亜鉛−ニッケル合
金からなる鍍金層(2) を形成した鉄鋼材、(3) は亜鉛−
ニッケル合金からなる鍍金層(2) の表面(2')に電鍍法に
より被着重合した黒色ニッケルの電鍍層、(4) は更に黒
色ニッケルの電鍍層(3) の表面(3')に形成したクロム酸
被膜である。1 and 2 are both plate materials as heat-resistant and corrosion-resistant polymer-coated steel materials constructed according to the present invention (FIG. 1).
FIG. 2 is an enlarged cross-sectional view of a main part of the pipe and the pipe material (FIG. 2) partially cut away, in which (1) is a zinc-plated surface (1 ′) that has been pretreated by degreasing, rusting, or the like. − A steel material with a plating layer (2) made of a nickel alloy, (3) is zinc −
A black nickel electroplating layer deposited and polymerized on the surface (2 ') of the nickel alloy plating layer (2) by the electroplating method, and (4) is further formed on the surface (3') of the black nickel electroplating layer (3). It is a chromic acid coating.
【0009】尚前記亜鉛−ニッケル鍍金層は、塩化亜
鉛、塩化ニッケル及び塩化アンモニウムを主成分とする
pH5.8乃至6.8の電鍍浴によって施されるもの
で、又ニッケルを7重量%乃至15重量%の範囲に含有
した状態で形成されるもので、当然ニッケルのこれら含
有によって耐熱・耐食性を効果的となすものである。一
方前記黒色ニッケルの電鍍層(3) の被着重合に際して
は、硫酸ニッケル、硫酸亜鉛、硫酸ニッケルアンモニウ
ム及びチオシアン化カリウムからなるpH5.6乃至
5. 9の電鍍浴をもって使用できることとなり、且つ亜
鉛を30重量%乃至50重量%の範囲に含有したニッケ
ル−亜鉛の合金層からなる外観黒色を呈して形成される
もので、前記下層の亜鉛−ニッケルの鍍金層に類似した
同種金属の組成によって被着重合してなるため、相互の
被着重合面での密着性を著しく向上することとなる。又
同時に被着重合に際して使用する前記pH5.6乃至
5.9の範囲にある電鍍浴を使用するため、その中間で
の前処理に制限をうけることなく、これら処理作業を簡
易とし、密着性と充分な耐熱性を有して被着重合し、更
に又黒色ニッケルの電鍍層(3) の表面(3')に構成したク
ロム酸被膜(4) に相乗して耐食性をも充分に発揮するこ
とができるのである。The zinc-nickel plating layer is applied by an electroplating bath containing zinc chloride, nickel chloride and ammonium chloride as the main components and having a pH of 5.8 to 6.8, and 7% by weight to 15% of nickel. It is formed in a state of being contained in the range of wt%, and naturally, heat resistance and corrosion resistance are made effective by containing these nickel. On the other hand, for the deposition polymerization of the black nickel electroplating layer (3), it is possible to use an electroplating bath comprising nickel sulfate, zinc sulfate, nickel ammonium sulfate and potassium thiocyanate and having a pH of 5.6 to 5.9, and zinc is used in an amount of 30 A nickel-zinc alloy layer contained in an amount of 50% by weight to 50% by weight, which is formed to have a black appearance and is deposited by a similar metal composition similar to that of the lower zinc-nickel plating layer. Therefore, the adhesion between the surfaces to be adhered and polymerized is significantly improved. At the same time, since the electroplating bath having a pH in the range of 5.6 to 5.9, which is used for the deposition polymerization, is used, pretreatment in the middle thereof is not limited, and these treatment operations are simplified, and adhesion is improved. Adhesive polymerization with sufficient heat resistance, and synergistic effect with the chromic acid film (4) formed on the surface (3 ') of the black nickel electroplating layer (3) to exert sufficient corrosion resistance. Can be done.
【0010】尚クロム酸被膜(4) の形成に際しては、無
水クロム酸の水溶液に前記被着重合した鉄鋼材(1) を約
20秒乃至60秒間浸漬し、水洗した後に常温乃至15
0℃の範囲で乾燥を行い、これら浸漬、水洗及び乾燥の
一連の処理を1回以上施すか、或いは無水クロム酸の水
溶液に前記鉄鋼材(1) を同様に浸漬し、引き上げた後そ
のままの状態で乾燥せしめ、その後約300℃以下にお
いて1分乃至5分間の加熱を行い、これら浸漬、乾燥及
び加熱からなる一連の処理を1回以上施すか、或いは
又、前記浸漬、水洗及び乾燥の一連の処理を1回以上施
した後に、更に再度前記浸漬、乾燥及び加熱からなる一
連の処理を1回以上施すかして形成されるものである。In forming the chromic acid film (4), the adhered and polymerized steel material (1) is immersed in an aqueous solution of chromic anhydride for about 20 to 60 seconds, washed with water and then at room temperature to 15
Drying is performed in the range of 0 ° C., and a series of treatments of dipping, washing with water and drying is performed once or more, or the steel material (1) is similarly dipped in an aqueous solution of chromic anhydride, and after pulling up, it is left as it is. It is dried in the state, and then heated at about 300 ° C. or lower for 1 minute to 5 minutes, and then subjected to a series of treatments of dipping, drying and heating one or more times, or alternatively, dipping, washing and drying. After the treatment (1) is performed once or more, the series of treatments including the dipping, drying and heating is performed once or more again.
【0011】又無水クロム酸の濃度としては、20g/
l乃至900g/lの範囲が望まれるところであり、2
0g/l未満では被膜効果に乏ぼしく、又900g/l
を越えると水溶液の粘度を増して著しく作業性を低下せ
しめ、同時に不経済となす理由によるものである。The concentration of chromic anhydride is 20 g /
A range of 1 to 900 g / l is desired, and 2
If it is less than 0 g / l, the coating effect is poor, and 900 g / l
The reason for this is that the viscosity of the aqueous solution increases and the workability is remarkably lowered, and at the same time, it becomes uneconomical.
【0012】以上の通り、本発明は、前記の重合被覆構
造を要旨とするため、亜鉛−ニッケル合金からなる鍍金
層(2) に、硫化ニッケル中に金属亜鉛が共析した黒色ニ
ッケルの電鍍層(3) を被着重合して優れた密着性を発揮
し、更に上層の黒色ニッケル電鍍層(3) によって250
℃以下の加温雰囲気状態下での耐熱性を、又下層の亜鉛
−ニッケル合金からなる鍍金層(2) によって耐熱性と同
時に耐食性をそれぞれ発揮せしめる結果となり、更に黒
色ニッケルの電鍍層(3) の被着重合に際しての前記電鍍
浴のpH値の範囲で処理するため、その中間での前処理
が至極簡単で、従って生産性を向上して廉価に形成する
ことは勿論のこと、特に黒色ニッケルの電鍍層(3) の表
面(3')に前記一連の処理を施すことに関連したクロム酸
被膜(4)によって白錆の発生を抑制し、亜鉛とクロム酸
との反応によって生ずるクロム化合物により、存在する
ピンホールを封孔するとともに、表面に不働態被膜を形
成して安定化させる作用を発揮して一層耐食性を向上さ
せ、同時にクロム酸被膜(4) での変色、消失或いは剥離
等をも軽減、防止する結果となるのである。 実施例1 ・鉄鋼材…材質STPG38、外径10.0m/m、肉
厚0.7m/m、長さ500m/mの管材を常法により
脱脂、脱錆の前処理を行う。As described above, the present invention is based on the above-mentioned polymerized coating structure. Therefore, the electroplating layer of black nickel in which metallic zinc is co-deposited in nickel sulfide is added to the plating layer (2) made of a zinc-nickel alloy. (3) is adhered and polymerized to exhibit excellent adhesiveness, and the black nickel electroplating layer (3), which is the upper layer, is used to form 250
As a result, the heat resistance under a heating atmosphere of ℃ or below and the corrosion resistance at the same time as the heat resistance and the corrosion resistance can be exhibited by the lower plating layer (2) made of zinc-nickel alloy. Since the treatment is carried out within the range of the pH value of the electroplating bath during the deposition polymerization of, the pretreatment in the middle thereof is extremely simple, and therefore the productivity can be improved and the cost can be reduced. The surface (3 ') of the electroplated layer (3) of (1) suppresses the generation of white rust by the chromic acid coating (4) related to the above series of treatments, and the chromium compound generated by the reaction between zinc and chromic acid In addition to sealing the existing pinholes, it also forms a passivation film on the surface to stabilize and improve the corrosion resistance, and at the same time discolor, disappear or peel off the chromic acid film (4). Results that also reduce or prevent It is made of. Example 1-Steel material ... A material having a material of STPG38, an outer diameter of 10.0 m / m, a wall thickness of 0.7 m / m, and a length of 500 m / m is subjected to a pretreatment for degreasing and derusting by a conventional method.
【0013】・亜鉛−ニッケル合金鍍金処理…塩化亜鉛
45g/l、塩化ニッケル75g/l、塩化アンモニウ
ム250g/l、硼酸20g/lの組成からなるpH
5.8の鍍金浴を使用し、前記管材を陰極とし、一方ニ
ッケル板を陽極として浴温38℃で陰極電流密度2A/
dm2で10分間通電した後、水洗を行い、層厚5μか
らなる亜鉛−ニッケル合金の鍍金層を得た。· Zinc-nickel alloy plating treatment: pH of zinc chloride 45 g / l, nickel chloride 75 g / l, ammonium chloride 250 g / l, boric acid 20 g / l
Using a plating bath of 5.8, using the tube material as a cathode, while using a nickel plate as an anode, and a bath temperature of 38 ° C. and a cathode current density of 2 A /
After energizing at dm 2 for 10 minutes, it was washed with water to obtain a zinc-nickel alloy plating layer having a layer thickness of 5 μm.
【0014】・中間での前処理…10%の硫酸水溶液に
5秒間浸漬した後、水洗を行う。Pretreatment in the middle: Immersed in a 10% sulfuric acid aqueous solution for 5 seconds and then washed with water.
【0015】・黒色ニッケル電鍍処理…硫酸ニッケル7
5g/l、硫酸亜鉛38g/l、硫酸ニッケルアンモニ
ウム45g/l、チオシアン化カリウム15g/lの組
成からなるpH5.6の電鍍浴を使用し、前記亜鉛−ニ
ッケル合金の鍍金層を有した管材を陰極とし、一方ニッ
ケル板を陽極として浴温50℃、陰極電流密度1A/d
m2で5分間通電した後、水洗を行った結果、前記鍍金
層上に層厚4μからなる黒色ニッケルの電鍍層を被着重
合して得た。・ Black nickel electroplating process ... Nickel sulfate 7
Using a galvanizing bath having a composition of 5 g / l, zinc sulfate 38 g / l, nickel ammonium sulfate 45 g / l, and potassium thiocyanate 15 g / l and having a pH of 5.6, the tube material having the zinc-nickel alloy plating layer was used as a cathode. On the other hand, with a nickel plate as the anode, the bath temperature was 50 ° C, and the cathode current density was 1 A / d.
After energizing at m 2 for 5 minutes, washing with water was carried out. As a result, a black nickel electroplating layer having a thickness of 4 μm was deposited and polymerized on the plating layer.
【0016】・クロム酸処理…無水クロム酸750g/
lの水溶液に前記被着重合した管材を30秒間浸漬し、
水洗した後、50℃で乾燥し、これら一連の処理により
クロム酸被膜を形成した。 実施例2 ・鉄鋼材…実施例1に同じ。Chromic acid treatment: Chromic anhydride 750 g /
immersing the adhered and polymerized tubing in an aqueous solution of 1 for 30 seconds,
After washing with water, it was dried at 50 ° C., and a chromic acid film was formed by these series of treatments. Example 2 • Steel material ... Same as in Example 1.
【0017】・亜鉛−ニッケル合金鍍金処理…塩化亜鉛
60g/l、塩化ニッケル85g/l、塩化アンモニウ
ム200g/l、アンモニア水50ml/l、硼酸20
g/lの組成からなるpH6.5の鍍金浴を使用し、前
記管材を陰極とし、一方ニッケル板を陽極として浴温4
0℃で陰極電流密度2.5A/dm2で8分間通電した
結果層厚5μからなる亜鉛−ニッケル合金の鍍金層を得
た。Zinc-nickel alloy plating treatment: zinc chloride 60 g / l, nickel chloride 85 g / l, ammonium chloride 200 g / l, ammonia water 50 ml / l, boric acid 20
A plating bath having a composition of g / l and having a pH of 6.5 was used, and the tube material was used as a cathode, while a nickel plate was used as an anode and the bath temperature was 4
After applying current for 8 minutes at 0 ° C. and a cathode current density of 2.5 A / dm 2 , a zinc-nickel alloy plating layer having a layer thickness of 5 μ was obtained.
【0018】・中間での前処理…実施例1に同じ。Pretreatment in the middle ... Same as in the first embodiment.
【0019】・黒色ニッケル電鍍処理…実施例1に同
じ。Black nickel electroplating process: Same as in Example 1.
【0020】・クロム酸処理…無水クロム酸50g/l
の水溶液に前記被着重合した管材を40秒間浸漬し、水
洗した後、120℃で炉中乾燥し、これら一連の処理を
2回行ってクロム酸被膜を形成した。 実施例3 鉄鋼材、亜鉛−ニッケル合金鍍金処理、中間での前処理
及び黒色ニッケル電鍍処理は、いずれも実施例1に同
じ。Chromic acid treatment: Chromic anhydride 50 g / l
The tube material subjected to the adhesion polymerization was dipped in the aqueous solution for 40 seconds, washed with water, dried in an oven at 120 ° C., and a series of these treatments was performed twice to form a chromic acid film. Example 3 The steel material, zinc-nickel alloy plating treatment, intermediate pretreatment, and black nickel electroplating treatment were all the same as in Example 1.
【0021】・クロム酸処理…無水クロム酸500g/
lの水溶液に前記被着重合した管材を30秒間浸漬し、
90℃で乾燥した後、260℃で5分間加熱し、これら
一連の処理によりクロム酸被膜を形成した。 実施例4 鉄鋼材、亜鉛−ニッケル合金鍍金処理、中間での前処理
及び黒色ニッケル電鍍処理は、いずれも実施例1に同
じ。Chromic acid treatment: Chromic anhydride 500 g /
immersing the adhered and polymerized tubing in an aqueous solution of 1 for 30 seconds,
After drying at 90 ° C., it was heated at 260 ° C. for 5 minutes, and a chromic acid film was formed by these series of treatments. Example 4 The steel material, zinc-nickel alloy plating treatment, intermediate pretreatment, and black nickel electroplating treatment were all the same as in Example 1.
【0022】・クロム酸処理…無水クロム酸250g/
lの水溶液に前記被着重合した管材を25秒間浸漬し、
常温で乾燥した後、230℃で5分間加熱し、これら一
連の処理を2回行ってクロム酸被膜を形成した。 実施例5 鉄鋼材、亜鉛−ニッケル合金鍍金処理、中間での前処理
及び黒色ニッケル電鍍処理は、いずれも実施例1に同
じ。Chromic acid treatment: Chromic anhydride 250 g /
immersing the coating-polymerized tubing in an aqueous solution of 1 for 25 seconds,
After drying at room temperature, it was heated at 230 ° C. for 5 minutes, and a series of these treatments was performed twice to form a chromic acid film. Example 5 The steel material, zinc-nickel alloy plating treatment, intermediate pretreatment, and black nickel electroplating treatment were all the same as in Example 1.
【0023】・クロム酸処理…無水クロム酸750g/
lの水溶液に前記被着重合した管材を30秒間浸漬し、
水洗した後、60℃で乾燥し、更に再度無水クロム酸2
50g/lの水溶液に30秒間浸漬し、60℃で乾燥し
た後、250℃で3分間加熱してクロム酸被膜を形成し
た。 比較例 実施例1と同じ鉄鋼材を用いて酸化亜鉛30g/l、青
化ソーダ50g/l、苛性ソーダ60g/lの組成から
なる鍍金浴を使用し、前記管材を陰極とし、一方亜鉛板
を陽極として常温下で陰極電流密度3A/dm2で15
分間通電した後、水洗を行って層厚9μからなる亜鉛の
鍍金層を得た後に、黒色クロメート浴に常温下で20秒
間浸漬し、その後水洗、乾燥して黒色クロメート被膜を
得た。Chromic acid treatment: Chromic anhydride 750 g /
immersing the adhered and polymerized tubing in an aqueous solution of 1 for 30 seconds,
After washing with water, drying at 60 ° C and chromic anhydride 2 again
It was immersed in an aqueous solution of 50 g / l for 30 seconds, dried at 60 ° C., and then heated at 250 ° C. for 3 minutes to form a chromic acid film. Comparative Example Using the same steel material as in Example 1, a plating bath having a composition of 30 g / l of zinc oxide, 50 g / l of soda blue and 60 g / l of caustic soda was used, and the tube was used as a cathode, while the zinc plate was used as an anode. As a cathode current density of 3 A / dm 2 at room temperature for 15
After energizing for a minute, it was washed with water to obtain a zinc-plated layer having a layer thickness of 9 μ, immersed in a black chromate bath at room temperature for 20 seconds, then washed with water and dried to obtain a black chromate film.
【0024】尚前記本発明品(実施例1乃至5)と従来
品(比較例)との耐熱・耐食性試験に係る比較特性結果
については、下記の表1及び表2に記載するところであ
る。The results of comparative characteristics of the products of the present invention (Examples 1 to 5) and the conventional product (Comparative Example) in the heat and corrosion resistance tests are shown in Tables 1 and 2 below.
【0025】・耐熱性試験結果 加温雰囲気200℃で24時間連続一定加熱した後、大
気中に放冷して大気温度まで温度降下し、その後再び2
50℃の昇温雰囲気で24時間連続一定加熱してそれぞ
れの外観状態を目視により観察した結果を表1に示す。Results of heat resistance test: After constant heating at 200 ° C. in a heating atmosphere for 24 hours, the temperature is allowed to cool to the atmospheric temperature and the temperature is lowered to the atmospheric temperature.
Table 1 shows the results obtained by visually observing the appearance states of each of the samples, which were continuously heated at a constant temperature of 50 ° C. for 24 hours under constant heating.
【0026】[0026]
【表1】 ・耐食性試験結果 前記耐熱性試験の200℃、24時間経過後の試料につ
いて、JISZ−2371による塩水噴霧試験法の規定
によって行った結果を表2に示す。[Table 1] -Corrosion resistance test results Table 2 shows the results obtained by the salt spray test method according to JIS Z-2371 for the samples after the heat resistance test at 200 ° C for 24 hours.
【0027】[0027]
【表2】 尚表2中Wは白錆斑点、Rは赤錆斑点、WWは流状白
錆、RRは流状赤錆をそれぞれ示し、又前記発生物に付
された数字は、記録時での発生個数の平均値と発生部の
表面積%をそれぞれ示すと共に、Rが発生していれば、
W、WWの発生に拘らずRのみを、又RRが発生してい
ればRの発生に拘らずRRのみを記録した。[Table 2] In Table 2, W indicates white rust spots, R indicates red rust spots, WW indicates flow white rust, RR indicates flow red rust, and the numbers attached to the above-mentioned products are the average number of occurrences at the time of recording. The value and the surface area% of the generated part are shown respectively, and if R is generated,
Only R was recorded regardless of occurrence of W and WW, and if RR was generated, only RR was recorded regardless of occurrence of R.
【0028】[0028]
【発明の効果】前記したように本発明による耐熱・耐食
性重合被覆鋼材は、前記相互の亜鉛−ニッケル合金の鍍
金層(2) と黒色ニッケルの電鍍層(3) とをもって、それ
ぞれに前記加温雰囲気状態下での耐熱性と耐食性とを同
時に満足することができ、且つこれら相互の被着重合面
での密着性を著しく良好とし、更に前記黒色ニッケル電
鍍層(3) の表面(3')に一連の処理を施すことに関連して
成るクロム酸被膜(4) によって白錆発生を抑制し、亜鉛
とクロム酸との反応によって生ずるクロム化合物により
存在するピンホールでの封孔を促進すると共に、表面に
不働態被膜を形成して安定化するこれら相乗効果によっ
て耐食性を一層向上させることとなり、同時にクロム酸
被膜自体での変色、消失或いは剥離等をも軽減、防止す
ることができ、更に重合被覆処理に際して、前記電鍍浴
のpH値の使用範囲に関連した中間での前処理の簡素化
により、生産性を向上して比較的廉価とすることがで
き、更に第2層として施した黒色ニッケル電鍍層によっ
て鋼材表面の重合被覆が黒色を呈するため放熱性も改善
される等、多くの特徴を有する極めて有用な耐熱・耐食
性重合被覆鋼材である。As described above, the heat-resistant and corrosion-resistant polymer-coated steel material according to the present invention has the mutual zinc-nickel alloy plating layer (2) and black nickel electroplating layer (3), and each of them is heated. Heat resistance and corrosion resistance under atmospheric conditions can be satisfied at the same time, and the adhesion between these adhered polymerization surfaces is remarkably good, and the surface (3 ') of the black nickel electroplated layer (3) is further improved. The chromic acid film (4) associated with a series of treatments suppresses the generation of white rust and promotes the sealing of pinholes existing by the chromium compound generated by the reaction between zinc and chromic acid. By the synergistic effect of forming and stabilizing a passivation film on the surface, the corrosion resistance is further improved, and at the same time, discoloration, disappearance or peeling of the chromic acid film itself can be reduced or prevented. In the covering treatment, the productivity can be improved and the manufacturing cost can be made relatively low by simplifying the intermediate pretreatment related to the use range of the pH value of the electroplating bath, and the black nickel applied as the second layer. It is a very useful heat-resistant and corrosion-resistant polymer-coated steel material having many features, such as that the electro-plated layer causes the polymer coating on the surface of the steel material to appear black, which improves heat dissipation.
【図1】本発明の一実施例に係る耐熱・耐食性重合被覆
を板材に施した要部の一部切欠による拡大断面図であ
る。FIG. 1 is an enlarged cross-sectional view of a plate member with a heat-resistant and corrosion-resistant polymerized coating according to an embodiment of the present invention, with a partial cutout.
【図2】同じく管材に施した要部の一部切欠による拡大
断面図である。FIG. 2 is an enlarged cross-sectional view of a main part of the pipe material, which is partially cut away.
1 鉄鋼材 1′ 表面 2 亜鉛−ニッケル合金の鍍金層 2′ 表面 3 黒色ニッケルの電鍍層 3′ 表面 4 クロム酸被膜 1 Steel material 1'Surface 2 Zinc-nickel alloy plating layer 2'Surface 3 Black nickel electroplating layer 3'Surface 4 Chromic acid coating
Claims (1)
ル合金からなる鍍金層(2) を下層とし、該鍍金層の表面
(2')に黒色ニッケルの電鍍層(3) を上層として被着重合
し、更に黒色ニッケルの電鍍層(3) の表面(3')にクロム
酸被膜(4) を有して成ることを特徴とする耐熱・耐食性
重合被覆鋼材。1. A surface (1 ') of a steel material (1) having a plating layer (2) made of a zinc-nickel alloy as a lower layer, and a surface of the plating layer.
The black nickel electroplating layer (3) is deposited and polymerized on (2 ') as the upper layer, and the chromic acid coating (4) is further formed on the surface (3') of the black nickel electroplating layer (3). Characteristic heat resistant and corrosion resistant polymer coated steel.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4184418A JPH0718020B2 (en) | 1992-06-18 | 1992-06-18 | Heat resistant / corrosion resistant polymer coated steel |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4184418A JPH0718020B2 (en) | 1992-06-18 | 1992-06-18 | Heat resistant / corrosion resistant polymer coated steel |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11800484A Division JPS60262976A (en) | 1984-06-08 | 1984-06-08 | Heat and corrosion resistant multiply coated steel material and formation of multilayered coat |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05195241A true JPH05195241A (en) | 1993-08-03 |
JPH0718020B2 JPH0718020B2 (en) | 1995-03-01 |
Family
ID=16152821
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4184418A Expired - Lifetime JPH0718020B2 (en) | 1992-06-18 | 1992-06-18 | Heat resistant / corrosion resistant polymer coated steel |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0718020B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002167692A (en) * | 2000-11-29 | 2002-06-11 | Nippon Seisen Co Ltd | Coated stainless steel wire and manufacturing method |
JP2019127629A (en) * | 2018-01-25 | 2019-08-01 | 木田精工株式会社 | High corrosion-resistance plating article and high corrosion-resistance plating method |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5638495A (en) * | 1979-09-04 | 1981-04-13 | Kobe Steel Ltd | Surface-treated steel material with high corrosion resistance |
JPS586995A (en) * | 1981-07-03 | 1983-01-14 | Kawasaki Steel Corp | Zinc-nickel alloy plated steel plate of superior adhesive strength after working |
-
1992
- 1992-06-18 JP JP4184418A patent/JPH0718020B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5638495A (en) * | 1979-09-04 | 1981-04-13 | Kobe Steel Ltd | Surface-treated steel material with high corrosion resistance |
JPS586995A (en) * | 1981-07-03 | 1983-01-14 | Kawasaki Steel Corp | Zinc-nickel alloy plated steel plate of superior adhesive strength after working |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002167692A (en) * | 2000-11-29 | 2002-06-11 | Nippon Seisen Co Ltd | Coated stainless steel wire and manufacturing method |
JP4585108B2 (en) * | 2000-11-29 | 2010-11-24 | 日本精線株式会社 | Coated stainless steel wire and its manufacturing method |
JP2019127629A (en) * | 2018-01-25 | 2019-08-01 | 木田精工株式会社 | High corrosion-resistance plating article and high corrosion-resistance plating method |
JP2022023231A (en) * | 2018-01-25 | 2022-02-07 | 木田精工株式会社 | High corrosion resistance plating method |
Also Published As
Publication number | Publication date |
---|---|
JPH0718020B2 (en) | 1995-03-01 |
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