JPH0448081A - Formation of molybdenum film on steel material - Google Patents
Formation of molybdenum film on steel materialInfo
- Publication number
- JPH0448081A JPH0448081A JP15722990A JP15722990A JPH0448081A JP H0448081 A JPH0448081 A JP H0448081A JP 15722990 A JP15722990 A JP 15722990A JP 15722990 A JP15722990 A JP 15722990A JP H0448081 A JPH0448081 A JP H0448081A
- Authority
- JP
- Japan
- Prior art keywords
- ammonium molybdate
- molybdenum film
- aqueous solution
- steel material
- molybdenum
- 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
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 41
- 239000011733 molybdenum Substances 0.000 title claims abstract description 41
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 31
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 26
- 239000010959 steel Substances 0.000 title claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 title description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 37
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 37
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 37
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 37
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000007747 plating Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 15
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- 229910000975 Carbon steel Inorganic materials 0.000 description 18
- 239000010962 carbon steel Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229940125368 controlled substance Drugs 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- -1 molybdate ions Chemical class 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
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] [Field of Industrial Application] The present invention provides a steel material or a steel product that is immersed in an aqueous solution containing a molybdenum compound to form a molybdenum film with excellent corrosion resistance on its surface in a short period of time. The present invention relates to a method for forming a 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ヰ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 painting or plating is used to prevent rust on steel materials. As one of the plating methods, a chromate treatment method is known which relatively easily produces a chromium film with good corrosion resistance. However, chromium is a pollution-controlled substance because it has an adverse effect on the human body, and there was a problem in that the plating solution had to be treated as wastewater 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Ｆ
ｅ −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（Ｓｏ、）７Ｈ，０１８〜７０ｇ／ＱＮ
ａ ２Ｍ Ｏ０４・２ Ｈｚ Ｏ３１−５ｇ ／ ＱＰ
Ｈは２．５〜６．５でＮａＯＨとＨ２ＳＯ４を用いて調
整
陽極液：Ｎａ、ＳＯ４
浴温度：２０〜６０℃
陰極電流密度： ０．２〜３．ＯＡ／ 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, the application of molybdenum, which is known to have rust-preventing properties comparable to chromium, has been considered for rust-preventing steel materials. Regarding molybdenum film formation, 'electrodeposition F
As described in "Amorphization conditions and corrosion behavior of e-Mo alloy film", Metal Surface Technology Association, 77th Lecture Conference Abstracts, pp. 8-9, Metal Surface Technology Association (1988),
Electroplating is performed using the following processing solution and processing conditions. That is, electrolytic bath: Fe(So,)7H, 018~70g/QN
a 2M O04・2 Hz O31-5g / QP
H is 2.5-6.5 adjusted using NaOH and H2SO4 Anolyte: Na, SO4 Bath temperature: 20-60°C Cathode current density: 0.2-3. OA/Cm2 However,
This molybdenum electroplating method has disadvantages in that the composition of the treatment solution is complex, it is difficult to control its concentration and pH, and it is necessary to control the current flowing through the treatment 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 in that the composition of the treatment liquid and the treatment 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 using a simple processing solution and processing conditions.
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
〜１７０ｍｇにするとよい。さらに硝酸銅の代りに硫酸
鋼を用いてもよく、その添加量はその水溶液１ｌ当り５
０〜２００ｍｇにするとよい。In order to achieve the above object, the method for forming a molybdenum film on a steel material of the present invention is characterized by immersing the steel material in an aqueous ammonium molybdate solution and then drying it. The ammonium molybdate aqueous solution preferably contains 0.5 to 40% ammonium molybdate. Furthermore, it is recommended to add copper nitrate to the ammonium molybdate aqueous solution, and the amount added is 30% per the aqueous solution.
It is recommended that the amount be ~170 mg. Furthermore, sulfuric acid steel may be used instead of copper nitrate, and the amount added is 5 ml per liter of the aqueous solution.
It is recommended to use 0 to 200 mg.
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Ｕ性を呈し、その中
に浸漬された鉄鋼材料はＦｅ”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Ｆｅ”＋
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 method for forming a molybdenum film on a steel material of the present invention,
The ammonium molybdate aqueous solution exhibits U properties, and the steel material immersed therein elutes Fe'', and the molybdate ions in the ammonium molybdate aqueous solution exhibit Fe''+
It adsorbs to the surface of steel materials as a displacement reaction of elution, forming 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
鋼または硫酸銅は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、Ｆｅ”＋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。In addition, steel nitrate or copper sulfate added to ammonium molybdate aqueous solution elutes Cu"+ ions, and this Cu+
Due to the difference in ionization tendency between Cu and Fe, + ions adhere to the surface of steel materials and form a cathode surface, accelerating the elution of Fe"+ and accelerating the adsorption of molybdenum. *Cu"+ forms a stable and uniform film. It helps to form.
以下、本発明の詳細な説明する。 The present invention will be explained in detail below.
実施例１
まず前処理として、被処理材の炭素！（ＳＰＣＣ）を脱
脂して水洗し、さらに酸洗して水洗した。Example 1 First, as a pretreatment, carbon of the material to be treated! (SPCC) was degreased, washed with water, and further acid-washed and washed with water.
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。The pretreated carbon steel was plated using the treatment solution 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 = 0.1-40wt% ammonium molybdate aqueous solution Treatment temperature = 45°C Treatment time: 15 minutes Then, 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％
ＨＣＩ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
．ＩＮのＮａ０Ｈ（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 film plated on carbon steel, as test method (1), 18wt%
HCI was dropped and the time until H2 was generated from the molybdenum film was measured. In addition, as test method (2), 0
．． Polarization of the molybdenum film was carried out in a solution of IN in NaOH (pH 13).
テスト（１）の結果は第１表に示すとおりで、０．１ｗ
ｔ％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％ＨＣＩを滴下すると直ぐに剥離し
、布切れでこす２てとれる程度の密着強さであった。The results of test (1) are shown in Table 1, and 0.1w
The molybdenum film plated with t% ammonium molybdate aqueous solution peeled off immediately when 18% HCI was dropped, and the adhesion strength was such that it could be rubbed 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％Ｈ
ＣＩ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, molybdenum films plated with various aqueous solutions containing ammonium molybdate from 0.5 to 40% are 18%H
It took about 200 seconds or more for H2 to occur after dropping CI, indicating 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／ＡｇＣ１
）に対する電圧Ｅをスキャンレート５分／■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。In test (2), a carbon steel treated material on which a molybdenum film was formed with 1 wt% ammonium molybdate was immersed in a NaOH aqueous solution, and a reference electrode (Ag/AgC1
) with a scan rate of 5 minutes/■,
The dissolution current flowing at that time was measured. Similarly, untreated bare carbon steel was tested for comparison.
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 、 ＯＶ （ｖ ｓ Ａ ｇ ／
Ａ ｇ Ｃｌ ） Ｌ：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 、 ＯＶ （ｖ ｓ Ａ ｇ ／ Ａ
ｇ Ｃｌ ）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 （ｖｓ
Ａｇ／ＡｇＣ１）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。As shown in Fig. 1, the results show that this treated material has a voltage E of +3, 5~4, OV (vs A g /
A g Cl ) L: No peeling of the molybdenum film was observed until the dissolution current was extremely small at about 100 μA, and the voltage E was +4, OV (v s A g / A
g Cl ), the molybdenum film is peeled off and the dissolution current increases rapidly by about 1000 times. On the other hand, in the case of untreated material, the voltage E is 0.5V, and the melting current increases rapidly. In addition, after peeling off the molybdenum film, the voltage E was set to -0.5 to +0.5 (vs
When the voltage was lowered to Ag/AgC1), the dissolution current of the treated material was one order of magnitude smaller than that of the untreated material that was similarly lowered, indicating the effectiveness of this molybdenum film. be.
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 and washed with water, and then pickled and washed with water. The pretreated carbon steel was plated using the treatment solution 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１ｌ当り１００
ｇ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: 5wt% ammonium molybdate aqueous solution +
100 g of copper nitrate per liter of the aqueous solution Treatment temperature: 45° C. Treatment time: 15 minutes Then, 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％ＨＣＩ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。In order to investigate the performance of the molybdenum film on the carbon steel plated in this manner, 18 wt % HCI was dropped and the time until H2 was generated from the molybdenum film was measured.
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 this test, carbon steel (sample B) treated with a 5 wt% ammonium molybdate aqueous solution in Example 1 was used for comparison.
and untreated carbon steel were also tested.
第２表
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（５ｗ
ｔ％モリブデン酸アンモニウム＋硝酸銅１００ ｍ
ｇ ／ Ｑ ）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。Table 2 The results of the test are as shown in Table 2.
t% ammonium molybdate + copper nitrate 100 m
g/Q) For carbon steel treated with an aqueous solution, the time until H2 generation increases significantly to 135 seconds and 270 seconds, respectively, compared to 3 seconds for untreated material, and the molybdenum film becomes acid resistant. It shows that it is excellent.
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１ｌ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
ｌ当り１０〜５０ｍｇＣｕ”＋に当たる、また硝酸銅の
代りに硫酸鋼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１ｌ当り５０〜２００ｍ
ｇがよい。The amount of copper nitrate added in the range of 30 to 170 mg per liter of ammonium molybdate aqueous solution was effective in accelerating the formation of a molybdenum film. The range of this addition amount is Cu”
In terms of + ions, ammonium molybdate aqueous solution 1
This corresponds to 10 to 50 mg Cu"+ per liter, and sulfuric acid steel can be used instead of copper nitrate, and the amount of copper sulfate added is 50 to 200 mg per liter of ammonium molybdate aqueous solution.
g is good.
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 and washed with water, and then pickled and washed with water. The pretreated carbon steel was plated using the treatment solution 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１２当り１００
ｇ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: 1wt% ammonium molybdate aqueous solution +
100 g of copper nitrate per 12 of the aqueous solution Treatment temperature: 45° C. Treatment time: 15 minutes The plated carbon steel (sample C) was then 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．ＩＮのＬｉＯＨ及び５００ ｍｇ
／ Ｑ （’） Ｌ ｘ ｚ Ｍ ｏ Ｏ＋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 on the carbon steel plated in this way is used as a corrosion inhibitor. IN LiOH and 500 mg
/ Q (') L x z M o Corrosion resistance was tested by immersing it in a 60 wt% lithium bromide aqueous solution containing O+ at 160°C for 500 hours and measuring the amount of corrosion of the molybdenum film and the amount of hydrogen gas generated. .
第３表
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＋１００■／Ｑ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１／２５０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。As shown in the test results in Table 3, carbon steel plated with an aqueous solution of (1wt% ammonium molybdate + 100μ/Q copper nitrate) has a corrosion rate of 1/2 compared to untreated carbon steel. 250, and the amount of hydrogen generated was about 1/150, proving that the corrosion resistance is extremely excellent.
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。Note that the 60 wt % lithium bromide aqueous solution used in the corrosion resistance test of Example 3 is a refrigerant absorption liquid commonly used in absorption refrigerators. Further, copper sulfate can be used in place of the copper nitrate used in this example, and the amounts of copper nitrate and copper sulfate added 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。As explained above, according to the present invention, the following effects can be obtained. That is, since a molybdenum film can be formed simply by immersing a steel material in an ammonium molybdate aqueous solution, there is no need for difficult adjustments as in conventional electroplating methods, and the composition of the treatment liquid and treatment conditions can be simplified.
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。Further, by adding copper nitrate or copper sulfate to the ammonium molybdate aqueous solution, the formation of a 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 the relationship between load voltage and dissolution current when a molybdenum film formed according to an example of the present invention is polarized in a NaOH solution.
Claims (6)
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 on a steel material, which comprises immersing the steel material in an ammonium molybdate aqueous solution, then drying it, and plating a molybdenum film on the surface of the steel material.
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. 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.
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. 2. The method for forming a molybdenum film according to claim 1, wherein copper nitrate is added to the ammonium molybdate aqueous solution.
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. 2. The method for forming a molybdenum film according to claim 1, wherein copper sulfate is added to the ammonium molybdate aqueous solution.
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１ｌ当り３０〜１７０
ｍｇ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 content is 30 to 170% per liter of the ammonium molybdate aqueous solution.
4. The method for forming a molybdenum film on a steel material according to claim 3, wherein mg of molybdenum is added.
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１ｌ当り５０〜２００
ｍｇ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 content is 50 to 200% per liter of the ammonium molybdate aqueous solution.
5. The method for forming a molybdenum film on a steel material according to claim 4, wherein mg of molybdenum 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 true JPH0448081A (en) | 1992-02-18 |
| JPH0747827B2 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) |
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|---|---|---|---|---|
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| JP2007196550A (en) * | 2006-01-27 | 2007-08-09 | Toppan Printing Co Ltd | Gas barrier film laminate resistant to heat treatment |
| JP2007331157A (en) * | 2006-06-13 | 2007-12-27 | Toppan Printing Co Ltd | Gas barrier film laminate |
| JP2007331187A (en) * | 2006-06-14 | 2007-12-27 | Toppan Printing Co Ltd | Backseat for solar cell and solar-cell module |
| JP2008023729A (en) * | 2006-07-18 | 2008-02-07 | Toppan Printing Co Ltd | Barrier film having high moistureproof properties |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH0747827B2 (en) | 1995-05-24 |
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