JPH0747827B2 - Method for forming molybdenum film on steel materials - Google Patents
Method for forming molybdenum film on steel materialsInfo
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- JPH0747827B2 JPH0747827B2 JP15722990A JP15722990A JPH0747827B2 JP H0747827 B2 JPH0747827 B2 JP H0747827B2 JP 15722990 A JP15722990 A JP 15722990A JP 15722990 A JP15722990 A JP 15722990A JP H0747827 B2 JPH0747827 B2 JP H0747827B2
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- aqueous solution
- ammonium molybdate
- molybdenum film
- molybdenum
- forming
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は鉄鋼材料あるいは鉄鋼製品をモリブデン化合物
を含有する水溶液に浸漬して短時間でその表面に耐食性
に優れたモリブデン皮膜を形成する鉄鋼材料のモリブデ
ン皮膜形成方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention is a steel material for forming a molybdenum film excellent in corrosion resistance on the surface by immersing a steel material or steel product in an aqueous solution containing a molybdenum compound. Of the molybdenum film.
一般的に鉄鋼材料の防錆には表面の塗装やメッキが用い
られる。このメッキ法の一つに比較的容易に耐食性のよ
いクロム皮膜を生成するクロメート処理法が知られてい
る。しかしクロムは人体に悪影響を及ぼすので公害規制
物質であり、メッキ液は使用後に廃水処理をしなければ
ならないという問題があった。Generally, surface coating or plating is used for rust prevention of steel materials. As one of the plating methods, a chromate treatment method is known, which relatively easily forms a chromium film having good corrosion resistance. However, since chromium has a harmful effect on the human body, it is a pollution control substance, and there is a problem that the plating solution must be treated with waste water after use.
そこでクロムに匹敵する防錆力をもつことが知られてい
るモリブデンの適用が鉄鋼材料の防錆のために考えられ
てきた。モリブデンの皮膜形成については、“電析Fe-M
o合金皮膜の非晶質化条件と腐食挙動”金属表面技術協
会、第77回講演大会要旨集第８−９頁、金属表面技術協
会（1988）に記載されているように、次のような処理液
及び処理条件を用いて電気メッキが行われている。すな
わち 電解浴：Fe(SO4)・7H2O 18〜70g/l Na2MoO4・2H2O 41.5g/l PHは2.5〜6.5でNaOHとH2SO4を用いて調整 陽極液：Na2SO4 浴温度:20〜60℃ 陰極電流密度:0.2〜3.0A/cm2 しかし、このモリブデンの電気メッキ方法によれば、処
理液の組成が複雑で、その濃度やPHの管理が難しく、ま
た処理液に流す電流をコントロールする必要があるとい
う難点があった。Therefore, application of molybdenum, which is known to have an anticorrosive power comparable to that of chromium, has been considered for the anticorrosion of steel materials. For molybdenum film formation, refer to "Electrodeposited Fe-M
o Amorphization conditions and corrosion behavior of alloy coatings "As described in Metal Surface Technology Society of Japan, 77th Annual Meeting, Proceedings, pp. 8-9, Metal Surface Technology Society (1988), Electroplating is carried out using the treatment liquid and treatment conditions: Electrolytic bath: Fe (SO 4 ) ・ 7H 2 O 18〜70g / l Na 2 MoO 4・ 2H 2 O 41.5g / l PH is 2.5〜 Adjusted with NaOH and H 2 SO 4 at 6.5 Anolyte: Na 2 SO 4 Bath temperature: 20-60 ℃ Cathode current density: 0.2-3.0A / cm 2 However, according to this electroplating method of molybdenum, treatment The composition of the solution is complicated, it is difficult to control its concentration and PH, and it is necessary to control the current flowing through the processing solution.
上記のように従来技術のモリブデン電気メッキ方法は処
理液の組成および処理条件が複雑であるという問題があ
った。As described above, the conventional molybdenum electroplating method has a problem that the composition of the processing liquid and the processing conditions are complicated.
本発明の目的は、鉄鋼材料にモリブデン皮膜を形成する
に処理液及び処理条件が簡単な鉄鋼材料のモリブデン皮
膜形成方法を提供することにある。An object of the present invention is to provide a method for forming a molybdenum film on a steel material, in which a treatment liquid and a treatment condition for forming the molybdenum film on the steel material are simple.
上記目的を達成するために、本発明の鉄鋼材料のモリブ
デン皮膜形成方法は、鉄鋼材料をモリブデン酸アンモニ
ウム水溶液に浸漬し、その後乾燥させることを特徴とし
ている。またモリブデン酸アンモニウム水溶液はモリブ
デン酸アンモニウムを0.5〜40％含有したものがよい。
さらにモリブデン酸アンモニウム水溶液には硝酸銅を添
加するのがよく、その添加量はその水溶液当り30〜170m
gにするとよい。さらに硝酸銅の代りに硫酸銅を用いて
もよく、その添加量はその水溶液１当り50〜200mgに
するとよい。In order to achieve the above object, the method for forming a molybdenum film of a steel material of the present invention is characterized by immersing the steel material in an aqueous solution of ammonium molybdate and then drying it. The ammonium molybdate aqueous solution preferably contains 0.5 to 40% ammonium molybdate.
Furthermore, it is preferable to add copper nitrate to the ammonium molybdate aqueous solution, and the addition amount is 30 to 170 m per aqueous solution.
It should be g. Further, copper sulfate may be used in place of copper nitrate, and the addition amount thereof may be 50 to 200 mg per 1 aqueous solution thereof.
本発明の鉄鋼材料のモリブデン皮膜形成方法において、
モリブデン酸アンモニウム水溶液は弱酸性を呈し、その
中に浸漬された鉄鋼材料はFe2+を溶出し、モリブデン酸
アンモニウム水溶液中のモリブデン酸イオンはFe2+の溶
出の置換反応として鉄鋼材料の表面に吸着して、酸化モ
リブデンとして皮膜を形成する。In the molybdenum film forming method of the steel material of the present invention,
The ammonium molybdate aqueous solution exhibits weak acidity, the steel material immersed in it elutes Fe 2+ , and the molybdate ion in the ammonium molybdate aqueous solution elutes Fe 2+ on the surface of the steel material as a substitution reaction. Adsorbs and forms a film as molybdenum oxide.
またモリブデン酸アンモニウム水溶液に添加された硝酸
銅または硫酸銅はCu++イオンを溶出し、このCu++イオン
がCuとFeのイオン化傾向の差により鉄鋼材料の表面に付
着してカソード面を形成し、Fe2+の溶出を速め、モリブ
デンの吸着を加速する。Cu++は安定で均一な皮膜を形成
するのに役立つ。Also, copper nitrate or copper sulfate added to the ammonium molybdate solution elutes Cu ++ ions, and these Cu ++ ions adhere to the surface of the steel material due to the difference in the ionization tendency of Cu and Fe to form the cathode surface. Then, the elution of Fe 2+ is accelerated and the adsorption of molybdenum is accelerated. Cu ++ helps to form a stable and uniform film.
以下、本発明の実施例を説明する。 Examples of the present invention will be described below.
実施例１ まず前処理として、被処理材の炭素鋼（SPCC）を脱脂し
て水洗し、さらに酸洗して水洗した。前処理された炭素
鋼は次に示す処理液と処理条件を用いてメッキ処理し
た。Example 1 First, as a pretreatment, carbon steel (SPCC) as a material to be treated was degreased, washed with water, further pickled and washed with water. The pretreated carbon steel was plated using the treatment liquid and treatment conditions shown below.
処理液:0.1〜40wt％モリブデン酸アンモニウム水溶液 処理温度:45℃ 処理時間:15分 それからメッキ処理した炭素鋼を水洗して乾燥させた。Treatment liquid: 0.1-40 wt% ammonium molybdate aqueous solution Treatment temperature: 45 ° C. Treatment time: 15 minutes The plated carbon steel was washed with water and dried.
このように炭素鋼にメッキされたモリブデン皮膜の性能
を調べるために、テスト方法（１）として、18wt％HCl
を滴下してモリブデン皮膜からH2が発生するまでの時間
を測定した。またテスト方法（２）として、0.1NのNaOH
（pH13）溶液中にモリブデン皮膜の分極を行った。In order to investigate the performance of the molybdenum coating plated on carbon steel in this way, 18 wt% HCl was used as the test method (1).
Was dropped and the time until H 2 was generated from the molybdenum film was measured. As a test method (2), 0.1N NaOH
A molybdenum film was polarized in a (pH13) solution.
テスト（１）の結果は第１表に示すとおりで、0.1wt％
モリブデン酸アンモニウム水溶液でメッキされたモリブ
デン皮膜は18％HClを滴下すると直ぐに剥離し、布切れ
でこすってとれる程度の密着強さであった。The result of the test (1) is shown in Table 1, 0.1wt%
The molybdenum film plated with the ammonium molybdate aqueous solution peeled off immediately when 18% HCl was dropped, and the adhesion strength was such that it could be scraped off with a piece of cloth.
また、モリブデン酸アンモニウム0.5〜40％の各種水溶
液によりメッキされたモリブデン皮膜は、18％HCl滴下
後H2が発生するまで約200秒またはそれ以上であって、
良好な皮膜であることを示した。 In addition, a molybdenum film plated with various aqueous solutions of ammonium molybdate 0.5 to 40% takes about 200 seconds or more until H 2 is generated after dropping 18% HCl,
It was shown to be a good film.
テスト（２）においては、1wt％モリブデン酸アンモニ
ウムでモリブデン皮膜が形成された炭素鋼なる処理材を
NaOH水溶液に浸漬し、基準電極（Ag/AgCl）に対する電
圧Ｅをスキャンレート５分/Vで負荷し、その時に流れる
溶解電流を測定した。同様にして比較のために未処理の
裸の炭素鋼なる未処理材をテストした。その結果は第１
図に示すように、この処理材は電圧Ｅが＋3.5〜4.0V（v
sAg/AgCl）になるまでモリブデン皮膜の剥離が認められ
ず、溶解電流は100μＡ程度で極め小さく、電圧Ｅが＋
4.0V（vsAg/AgCl）でモリブデン皮膜が剥離して溶解電
流が1000倍程度に急増する。一方、未処理材は電圧Ｅが
0.5Vで、溶解電流が急激に増加する。またモリブデン皮
膜の剥離後、電圧Ｅを−0.5〜＋0.5（vsAg/AgCl）に降
下させた場合、処理材の溶解電流は、同様に電圧降下さ
せた未処理材の溶解電流に比べて１桁小さい値を示して
おり、このモリブデン皮膜の有効性は顕著である。In test (2), a carbon steel treated material with a molybdenum coating formed with 1 wt% ammonium molybdate was used.
The sample was dipped in an aqueous solution of NaOH, a voltage E for the reference electrode (Ag / AgCl) was applied at a scan rate of 5 minutes / V, and the dissolution current flowing at that time was measured. Similarly, an untreated untreated bare carbon steel was tested for comparison. The result is first
As shown in the figure, this treated material has a voltage E of +3.5 to 4.0V (v
No peeling of the molybdenum film was observed until the sAg / AgCl), the melting current was about 100 μA, and the voltage E was +
At 4.0V (vsAg / AgCl), the molybdenum film peels off, and the melting current increases about 1000 times. On the other hand, the untreated material has a voltage E
At 0.5V, the melting current increases rapidly. When the voltage E is lowered to -0.5 to +0.5 (vsAg / AgCl) after the molybdenum film is peeled off, the dissolution current of the treated material is 1 compared to the dissolution current of the untreated material which is also subjected to the voltage reduction. The values are orders of magnitude smaller, and the effectiveness of this molybdenum coating is remarkable.
実施例２ 前処理として、被処理材の炭素鋼（SPCC）を脱脂して水
洗し、さらに酸洗して水洗した。前処理された炭素鋼は
次に示す処理液と処理条件を用いてメッキ処理した。Example 2 As a pretreatment, carbon steel (SPCC) as a material to be treated was degreased, washed with water, further pickled and washed with water. The pretreated carbon steel was plated using the treatment liquid and treatment conditions shown below.
処理液:5wt％モリブデン酸アンモニウム水溶液＋その水
溶液１当り100gの硝酸銅 処理温度:45℃ 処理時間:15分 それからメッキ処理した炭素鋼（試料Ａ）を水洗して乾
燥させた。Treatment liquid: 5 wt% ammonium molybdate aqueous solution + 100 g of copper nitrate per 1 aqueous solution Treatment temperature: 45 ° C. Treatment time: 15 minutes The plated carbon steel (Sample A) was washed with water and dried.
このようにメッキ処理された炭素鋼のモリブデン皮膜の
性能を調べるために、18wt％HClを滴下してモリブデン
皮膜からH2が発生するまでの時間を測定した。このテス
トでは比較のために実施例１で5wt％モリブデン酸アン
モニウム水溶液で処理した炭素鋼（試料Ｂ）と、未処理
の炭素鋼をあわせて試験した。In order to investigate the performance of the molybdenum film of the carbon steel plated as described above, 18 wt% HCl was dropped and the time until H 2 was generated from the molybdenum film was measured. In this test, for comparison, a carbon steel treated in Example 1 with a 5 wt% ammonium molybdate aqueous solution (Sample B) and an untreated carbon steel were tested together.
テストの結果は、第２表に示すように、5wt％モリブデ
ン酸アンモニウム水溶液で処理した炭素鋼及び（5wt％
モリブデン酸アンモニウム＋硝酸銅100mg/l）水溶液で
処理した炭素鋼は、未処理材のH2発生までの時間３秒に
対し、それぞれH2発生までの時間が135秒、270秒と大幅
に増加し、モリブデン皮膜は耐酸性に優れていることを
示している。 As shown in Table 2, the test results show that carbon steel treated with 5 wt% ammonium molybdate aqueous solution and (5 wt%
Carbon steel treated with ammonium molybdate + copper nitrate 100 mg / l) aqueous solution has a significantly increased time of H 2 generation of 135 seconds and 270 seconds, respectively, compared to 3 seconds of H 2 generation of untreated material. However, it shows that the molybdenum film has excellent acid resistance.
なお、硝酸銅の添加量はモリブデン酸アンモニウム水溶
液１当り30〜170mgの範囲でモリブデン皮膜形成を加
速する効果があった。この添加量の範囲はCu++イオンで
みると、モリブデン酸アンモニウム水溶液１当り10〜
50mgCu++に当たる。また硝酸銅の代りに硫酸銅を用いる
ことができ、硫酸銅の添加量はモリブデン酸アンモニウ
ム水溶液１当り50〜200mgがよい。The amount of copper nitrate added was in the range of 30 to 170 mg per 1 aqueous ammonium molybdate solution, which had the effect of accelerating the formation of the molybdenum film. Looking at Cu ++ ions, the range of this addition amount is 10 to 10 per 1 ammonium ammonium molybdate aqueous solution.
It corresponds to 50mgCu ++ . Further, copper sulfate can be used instead of copper nitrate, and the addition amount of copper sulfate is preferably 50 to 200 mg per ammonium ammonium molybdate aqueous solution.
実施例３ 前処理として、被処理材の炭素鋼（SPCC）を脱脂して水
洗し、さらに酸洗して水洗した。前処理された炭素鋼は
次に示す処理液と処理条件を用いてメッキ処理した。Example 3 As a pretreatment, carbon steel (SPCC) as a material to be treated was degreased, washed with water, further pickled and washed with water. The pretreated carbon steel was plated using the treatment liquid and treatment conditions shown below.
処理液:1wt％モリブデン酸アンモニウム水溶液＋その水
溶液１当り100gの硝酸銅 処理温度:45℃ 処理時間:15分 それからメッキ処理した炭素鋼（試料Ｃ）を水洗して室
温で乾燥させた。Treatment liquid: 1 wt% ammonium molybdate aqueous solution + 100 g of copper nitrate per 1 aqueous solution Treatment temperature: 45 ° C. Treatment time: 15 minutes The plated carbon steel (Sample C) was washed with water and dried at room temperature.
このようにメッキ処理した炭素鋼のモリブデン皮膜を腐
食抑制剤として0.1NのLiOH及び500mg/lのLi2MoO4を含有
する60wt％臭化リチウム水溶液中に160℃で500時間浸漬
して、モリブデン皮膜の腐食量と水素ガス発生量を測定
して、耐食性をテストした。The molybdenum film of carbon steel plated in this way is immersed in a 60 wt% lithium bromide aqueous solution containing 0.1N LiOH and 500 mg / l Li 2 MoO 4 as a corrosion inhibitor at 160 ° C for 500 hours, and molybdenum The corrosion resistance was tested by measuring the amount of corrosion of the film and the amount of hydrogen gas generated.
第３表のテスト結果に示すように、（1wt％モリブデン
酸アンモニウム＋100mg/l硝酸銅）水溶液でメッキ処理
した炭素鋼は、未処理の炭素鋼と比較して腐食量で1/25
0程度、水素発生量で1/150程度の値を示し、耐食性が極
めて優れていることを証明している。なお実施例３の耐
食性試験で用いた60wt％臭化リチウム水溶液は、吸収式
冷凍機に一般に用いられる冷媒吸収液である。また、こ
の実施例で用いた硝酸銅の代りに硫酸銅を用いることが
でき、硝酸銅及び硫酸銅の添加量は実施例２におけると
同じである。 As shown in the test results in Table 3, carbon steel plated with an aqueous solution of (1 wt% ammonium molybdate + 100 mg / l copper nitrate) has a corrosion rate of 1/25 compared to untreated carbon steel.
The hydrogen generation rate is about 0, which is about 1/150, demonstrating excellent corrosion resistance. The 60 wt% lithium bromide aqueous solution used in the corrosion resistance test of Example 3 is a refrigerant absorbing liquid generally used in the absorption refrigerator. Further, copper sulfate can be used in place of the copper nitrate used in this example, and the addition amounts of copper nitrate and copper sulfate are the same as in Example 2.
以上説明したように、本発明によれば次のような効果が
得られる。すなわち、鉄鋼材料をモリブデン酸アンモニ
ウム水溶液に浸漬するだけでモリブデン皮膜を形成でき
るので従来の電気メッキ法などのような難しい調整が必
要なく、処理液の組成および処理条件を簡単にできる。
また、モリブデン酸アンモニウム水溶液に硝酸銅または
硫酸銅を加えることによりモリブデン皮膜の形成を加速
し、かつ均一な皮膜を形成することができる。As described above, according to the present invention, the following effects can be obtained. That is, since the molybdenum film can be formed simply by immersing the steel material in the ammonium molybdate aqueous solution, it is possible to simplify the composition of the processing liquid and the processing conditions without requiring difficult adjustments such as the conventional electroplating method.
Further, by adding copper nitrate or copper sulfate to the ammonium molybdate aqueous solution, formation of the molybdenum film can be accelerated and a uniform film can be formed.
第１図は本発明の実施例により形成されたモリブデン皮
膜をNaOH溶液中で分極した時の負荷電圧−溶解電流の関
係を示す図である。FIG. 1 is a diagram showing a relationship between a load voltage and a dissolution current when a molybdenum film formed according to an example of the present invention is polarized in a NaOH solution.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 乙部 博昭 静岡県浜松市東町740 矢崎資源株式会社 内 (72)発明者 橘 孝二 神奈川県津久井郡城山町若葉台３―15―５ ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Hiroaki Otobe 740 Higashimachi, Hamamatsu City, Shizuoka Prefecture Yazaki Resources Co., Ltd. (72) Inventor Koji Tachibana 3-15-5 Wakabadai, Shiroyama Town, Tsukui County, Kanagawa Prefecture
Claims (6)
液に浸漬させ、その後乾燥させて、前記鉄鋼材料表面に
モリブデン皮膜をメッキする鉄鋼材料のモリブデン皮膜
形成方法。1. A method for forming a molybdenum film of a steel material, which comprises immersing the steel material in an aqueous solution of ammonium molybdate, and then drying it to plate a molybdenum film on the surface of the steel material.
デン酸アンモニウムを0.5〜40重量％含有することを特
徴とする請求項１記載の鉄鋼材料のモリブデン皮膜形成
方法。2. The method for forming a molybdenum film on a steel material according to claim 1, wherein the ammonium molybdate aqueous solution contains 0.5 to 40% by weight of ammonium molybdate.
を加えたことを特徴とする請求項１記載のモリブデン皮
膜形成方法。3. The method for forming a molybdenum film according to claim 1, wherein copper nitrate is added to the aqueous solution of ammonium molybdate.
を加えたことを特徴とする請求項１記載のモリブデン皮
膜形成方法。4. The method for forming a molybdenum film according to claim 1, wherein copper sulfate is added to the ammonium molybdate aqueous solution.
デン酸アンモニウムを0.5〜40重量％含有し、硝酸銅は
前記モリブデン酸アンモニウム水溶液１当り30〜170m
g添加することを特徴とする請求項３記載の鉄鋼材料の
モリブデン皮膜形成方法。5. The ammonium molybdate aqueous solution contains 0.5 to 40% by weight of ammonium molybdate, and the copper nitrate is 30 to 170 m per 1 said ammonium molybdate aqueous solution.
The method for forming a molybdenum film on a steel material according to claim 3, wherein g is added.
デン酸アンモニウムを0.5〜40重量％含有し、硫酸銅は
前記モリブデン酸アンモニウム水溶液１当り50〜200m
g添加することを特徴とする請求項４記載の鉄鋼材料の
モリブデン皮膜形成方法。6. The ammonium molybdate aqueous solution contains 0.5 to 40% by weight of ammonium molybdate, and the copper sulfate is 50 to 200 m per 1 said ammonium molybdate aqueous solution.
The method for forming a molybdenum film on a steel material according to claim 4, wherein g is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15722990A JPH0747827B2 (en) | 1990-06-15 | 1990-06-15 | Method for forming molybdenum film on steel materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15722990A JPH0747827B2 (en) | 1990-06-15 | 1990-06-15 | Method for forming molybdenum film on steel materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0448081A JPH0448081A (en) | 1992-02-18 |
| JPH0747827B2 true JPH0747827B2 (en) | 1995-05-24 |
Family
ID=15645055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15722990A Expired - Lifetime JPH0747827B2 (en) | 1990-06-15 | 1990-06-15 | Method for forming molybdenum film on steel materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0747827B2 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4654089B2 (en) | 2004-12-03 | 2011-03-16 | 新日本製鐵株式会社 | Chromate-free resin composite vibration damping material with excellent durability adhesion |
| JP2007196550A (en) * | 2006-01-27 | 2007-08-09 | Toppan Printing Co Ltd | Gas barrier film laminate resistant to heat treatment |
| JP4978066B2 (en) * | 2006-06-13 | 2012-07-18 | 凸版印刷株式会社 | Method for evaluating manufacturing conditions of gas barrier film laminate |
| JP5103801B2 (en) * | 2006-06-14 | 2012-12-19 | 凸版印刷株式会社 | Solar cell backsheet and solar cell module |
| JP4984702B2 (en) * | 2006-07-18 | 2012-07-25 | 凸版印刷株式会社 | High moisture barrier film |
| JP2009154449A (en) * | 2007-12-27 | 2009-07-16 | Toppan Printing Co Ltd | Barrier film |
| JP4755289B1 (en) * | 2010-03-23 | 2011-08-24 | 尾池工業株式会社 | Method for producing gas barrier film having hot water resistance and gas barrier film having hot water resistance |
| JP4755290B1 (en) * | 2010-03-23 | 2011-08-24 | 尾池工業株式会社 | Method for producing gas barrier film having hot water resistance and gas barrier film having hot water resistance |
| JP4731630B1 (en) * | 2010-03-23 | 2011-07-27 | 尾池工業株式会社 | Gas barrier film manufacturing method and gas barrier film |
| JP6077318B2 (en) * | 2013-01-29 | 2017-02-08 | Koa株式会社 | Electroless plating bath, method for producing molybdenum trioxide film, and method for producing chemical sensor |
| CN103205739B (en) * | 2013-04-28 | 2015-04-08 | 东南大学 | Surface chemical treatment method for improving abrasive resistance of steel material |
| CN105369236A (en) * | 2015-12-17 | 2016-03-02 | 山东建筑大学 | Non-chrome passivating agent for brown zinc coating |
| CN105369237A (en) * | 2015-12-17 | 2016-03-02 | 山东建筑大学 | Brown passivant |
| CN112011790A (en) * | 2019-05-29 | 2020-12-01 | 北京铂阳顶荣光伏科技有限公司 | Stainless steel foil blackening liquid for photovoltaic and blackening treatment method of stainless steel foil |
-
1990
- 1990-06-15 JP JP15722990A patent/JPH0747827B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0448081A (en) | 1992-02-18 |
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