JPH01246398A - Production of composite dispersive particles and composite plating method - Google Patents
Production of composite dispersive particles and composite plating methodInfo
- Publication number
- JPH01246398A JPH01246398A JP63073921A JP7392188A JPH01246398A JP H01246398 A JPH01246398 A JP H01246398A JP 63073921 A JP63073921 A JP 63073921A JP 7392188 A JP7392188 A JP 7392188A JP H01246398 A JPH01246398 A JP H01246398A
- Authority
- JP
- Japan
- Prior art keywords
- composite
- ions
- plating
- dispersed particles
- plating bath
- 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.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000002245 particle Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- 230000002378 acidificating effect Effects 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 239000010452 phosphate Substances 0.000 claims abstract description 16
- 238000009713 electroplating Methods 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract 3
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- 229910052725 zinc Inorganic materials 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- 229910001297 Zn alloy Inorganic materials 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 229910052750 molybdenum Inorganic materials 0.000 abstract 1
- 229910052721 tungsten Inorganic materials 0.000 abstract 1
- 229910052720 vanadium Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 17
- 235000021317 phosphate Nutrition 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 15
- 229940021013 electrolyte solution Drugs 0.000 description 13
- 239000011701 zinc Substances 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910007567 Zn-Ni Inorganic materials 0.000 description 2
- 229910007614 Zn—Ni Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910007564 Zn—Co Inorganic materials 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum ion Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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、めっき皮膜中に金属酸化物の微小粒子を共析
させたいわゆる複合めっきに係わり、特に、めっき浴中
で凝集し沈澱することが少ない複合分散粒子の製造方法
とこの複合分散粒子を用いて行う複合めっき方法に関す
るものである。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to so-called composite plating in which fine particles of metal oxide are eutectoided in a plating film, and in particular, to prevent coagulation and precipitation in a plating bath. The present invention relates to a method for producing composite dispersed particles with a small amount of carbon dioxide, and a composite plating method using the composite dispersed particles.
（従来の技術）
例えば、亜鉛めっき鋼板の耐食性を高める方法に、亜鉛
と他の元素との合金をめっきする方法がある０代表的な
ものはＺｎ−Ｆｅ、 Ｚｎ−Ｎｉ、 Ｚｎ−Ｇｏ等のＺ
ｎ系合金めっきである。(Prior art) For example, one method of increasing the corrosion resistance of galvanized steel sheets is to plate them with an alloy of zinc and other elements. Typical examples include Zn-Fe, Zn-Ni, Zn-Go, etc. Z
This is n-based alloy plating.
他方、このような合金をめっきするのではなく、めっき
皮膜中にマトリックスの金属とは異なる金属酸化物の微
小粒子を共析させたいわゆる複合めっきする方法がある
。そして、この複合めっきに関する特許も多く出願され
ている０例えば、特開昭６１−４７９１９号公報には亜
鉛めっき皮膜中にアルミナを複合共析させたものが、同
５４−１５９３４２号公報には同様にシリカ、酸化チタ
ン、酸化ジルコニウムの１種以上を複合共析させたもの
が、また、同５６−４９９９９号公報にはＳｉＯ□を複
合共析させた電気亜鉛めっき鋼板がそれぞれ開示されて
いる。On the other hand, instead of plating such an alloy, there is a method of so-called composite plating in which fine particles of a metal oxide different from the matrix metal are eutectoided into the plating film. Many patents related to this composite plating have been filed. For example, JP-A No. 61-47919 discloses a composite eutectoid of alumina in a zinc plating film, and JP-A No. 54-159342 discloses a similar method. 56-49999 discloses an electrogalvanized steel sheet in which one or more of silica, titanium oxide, and zirconium oxide are compositely eutectoided, and SiO□ is compositely eutectoided in Japanese Patent Publication No. 56-49999.
確かに、亜鉛めっき或いは亜鉛系合金めっきに上記のよ
うな複合めっき方法を適用することで耐食性が改善され
るが、従来の複合めっきには下記に述べるような問題点
がある。It is true that corrosion resistance can be improved by applying the above composite plating method to zinc plating or zinc-based alloy plating, but conventional composite plating has the following problems.
複合めっきにおいて、耐食性の向上効果を充分得るには
、分散粒子をめっき皮膜中に均一に且つ多量に取り込む
ことが肝要である。しかし、従来の複合めっき方法では
めっき浴中で分散粒子が凝集し、沈澱を起こすために均
一に且つ多量に取り込むことができず、耐食性の向上に
限界がある。In composite plating, in order to sufficiently improve corrosion resistance, it is important to incorporate dispersed particles uniformly and in large quantities into the plating film. However, in the conventional composite plating method, the dispersed particles aggregate and precipitate in the plating bath, making it impossible to incorporate them uniformly and in large quantities, which limits the improvement in corrosion resistance.
さらには、品質の安定したものを長期にわたって製造す
ることができない。Furthermore, it is not possible to manufacture products with stable quality over a long period of time.
複合めっきにおける上記のような問題点を解消するため
の特許も種々提案されている。Various patents have been proposed to solve the above-mentioned problems in composite plating.
例えば、■特開昭４９−２１３３２号公報には、陽イオ
ン型もしくは非イオン型界面活性剤を含有する水溶液で
電気泳動法により導電性基板にアルミニウムを電着させ
る方法が、■同５９−３１８９５号公報には、不溶性粒
子として陽イオン吸着処理されたもの、例えば、ＮＨ４
”イオン吸着処理して電着させる方法が、■同６１−１
２７９００号公報には、めっき金属とＡ ｌ ＊Ｏｓ、
ＳｉＯ□を同時に電着させるに際して、負に帯電したシ
リカコロイドの表面に正に帯電したアルミナコロイドま
たはアルミニウムイオンと、電荷が２価以上の金属陽イ
オンを吸着したものを用いて電着させる方法が、それぞ
れ開示されている。For example, Japanese Patent Application Laid-Open No. 49-21332 describes a method of electrodepositing aluminum on a conductive substrate by electrophoresis using an aqueous solution containing a cationic or nonionic surfactant. The publication describes insoluble particles that have been treated with cation adsorption, such as NH4
``The method of ion adsorption treatment and electrodeposition is ■ 61-1
No. 27900 discloses that plating metal and A l *Os,
When simultaneously electrodepositing SiO□, there is a method of electrodepositing using a positively charged alumina colloid or aluminum ion and a metal cation with a charge of two or more adsorbed on the surface of a negatively charged silica colloid. , respectively, are disclosed.
しかし、■の方法は、めっき金属マトリックス内に不要
な或いは有害な有機化合物が混入してめっき品質を阻害
するおそれがある。■の方法は、イオン吸着処理だけで
は電析量の増加に十分な効果が得られない、■の方法は
、還元反応により正電荷を失い、皮膜中に取り込まれな
いものは沈澱を起こす。また、皮膜中に取り込まれたも
のについても本来の金属マトリックスの性質を変える可
能性がある。However, in method (2), there is a risk that unnecessary or harmful organic compounds may be mixed into the plating metal matrix and impair the plating quality. In the method (2), the ion adsorption treatment alone does not have a sufficient effect on increasing the amount of electrodeposition, and in the method (2), positive charges are lost due to the reduction reaction, and those that are not incorporated into the film cause precipitation. Furthermore, substances incorporated into the film may also change the properties of the original metal matrix.
（発明が解決しようとする課題）
本発明の課題は、めっき浴中で凝集して沈澱を起こすこ
とが少ない金属酸化物の分散粒子を提供すること、およ
びこの分散粒子を均一に且つ多量にめっき皮膜中に取り
込んで品質に優れたものを安定して長期にわたって製造
することができる複合めっき方法を提供することにある
。(Problems to be Solved by the Invention) An object of the present invention is to provide dispersed particles of a metal oxide that are less likely to aggregate and cause precipitation in a plating bath, and to plate these dispersed particles uniformly and in large quantities. It is an object of the present invention to provide a composite plating method that can be incorporated into a film to stably produce products of excellent quality over a long period of time.
（課題を解決するための手段）
上記するように複合めっきにおける最も大きな問題点は
、めっき浴中で分散粒子が凝集を起こし、安定して保持
することができないことにある。(Means for Solving the Problems) As mentioned above, the biggest problem in composite plating is that the dispersed particles agglomerate in the plating bath and cannot be stably maintained.
凝集を少なくするのは、それぞれの粒子に同一極性を付
与し、電気的に反発させてやることで可能である。Ａ
ｆｆｉ 、０．、ＳｉＯ２およびＺｒ（ｈ等の金属酸化
物の分散粒子はめっき浴中ではｐｕにより異なるが、弱
く正に、或いは負に帯電しており、このままでは陰極と
なるめっき面に共析させることが困難である。このため
、電着については分散粒子のそれぞれをより強く正に帯
電させてやる必要がある。Aggregation can be reduced by giving each particle the same polarity and making them electrically repel. A
ffi, 0. Dispersed particles of metal oxides such as , SiO2, and Zr(h) are weakly positively or negatively charged in the plating bath, depending on the pu, and it is difficult to eutectoid them on the plating surface that will become the cathode. Therefore, for electrodeposition, it is necessary to charge each dispersed particle more strongly and positively.
前掲の特開昭５４−１５９３４ｉ号、同５９−３１８９
５号および同６１−１２７９００号、特公昭６２−６７
６０号等に開示されている複合めっき方法は、このよう
な考え方に基づいたものである。JP-A-54-15934i and JP-A No. 59-3189 mentioned above
No. 5 and No. 61-127900, Special Publication No. 62-67
The composite plating method disclosed in No. 60 and the like is based on this idea.
本発明者らも分散粒子に陽イオン吸着処理する方法を考
えたが、１価の金属イオンでは充分な電析量の増加が得
られず、２価以上の金属イオンでは還元反応により電荷
が失われて不安定なものとなり沈澱が起こる。そこで、
本発明者らは次のような方法で分散粒子を製造して複合
めっきする方法を試みた。The present inventors also considered a method of adsorbing cations on dispersed particles, but monovalent metal ions did not result in a sufficient increase in the amount of electrodeposition, and divalent or higher valent metal ions lost charge due to reduction reaction. It becomes unstable and precipitation occurs. Therefore,
The present inventors attempted a method of manufacturing dispersed particles and performing composite plating using the following method.
Ａｊｌ！ｇｏｓ、Ｓｉｎｇおよび／又はＺｒＯｚの分散
粒子に金属イオンを吸着させ、これをめっき浴とは別の
酸性電解質液で電解し、金属イオンを酸化物の形に変え
、この酸化物が分散粒子の表面に吸着した複合分散粒子
を製造し、この複合分散粒子をめっき浴に含ませて電気
めっきした。その結果、下記のことが判明した。Ajl! Metal ions are adsorbed onto the dispersed particles of gos, Sing and/or ZrOz, and electrolyzed with an acidic electrolyte solution different from the plating bath to convert the metal ions into oxides, which form on the surface of the dispersed particles. Composite dispersed particles adsorbed on the substrate were produced, and the composite dispersed particles were included in a plating bath for electroplating. As a result, the following was found.
吸着させる金属イオンとして電解で酸化物となり、しか
も正電荷をもつものを選べば、めっき浴中で凝集の少な
い複合分散粒子を得ることができる。凝集が起こらなく
なる理由は、正電荷を帯びた酸化物を吸着した複合酸化
物が正電荷を帯び、これが還元反応により電荷を失うこ
とのない安定なものであるからである。By selecting a metal ion to be adsorbed that becomes an oxide through electrolysis and has a positive charge, composite dispersed particles with little agglomeration in the plating bath can be obtained. The reason why aggregation does not occur is that the composite oxide that has adsorbed a positively charged oxide is positively charged and is stable because it does not lose its charge due to a reduction reaction.
ここに、本発明の要旨は下記の（ｉ）および（ｉｉ ）
にある。Here, the gist of the present invention is as follows (i) and (ii)
It is in.
（ｉ）Ａｊ！ｇｏｓ、ＳｉｎｇおよびＺｒ０１よりなる
群から選ばれた１種以上の酸化物と、Ｔｉイオン、Ｍｏ
イオン、Ｃｒイオン、■イオン、ＭｎイオンおよびＷイ
オンよりなる群から選ばれた１種以上の金属イオンを含
む酸性電解質液を電解することを特徴とする複合分散粒
子の製造方法。(i)Aj! one or more oxides selected from the group consisting of gos, Sing and Zr01, Ti ions, Mo
1. A method for producing composite dispersed particles, which comprises electrolyzing an acidic electrolyte solution containing one or more metal ions selected from the group consisting of ions, Cr ions, ■ ions, Mn ions, and W ions.
（ｉｉ ）Ａ ｌ ｚＯｓ、ＳｉｎｇおよびＺｒＯ２よ
りなる群から選ばれた１種以上の酸化物の表面にＴｉイ
オン、門。イオン、Ｃｒイオン、■イオン、ｉｎイオン
およびＷイオンよりなる群から選ばれた１種以上の金属
イオンから生じた酸化物を吸着させた複合分散粒子を含
むめっき浴を用いて電気め４きすることを特徴とする複
合めっき方法。(ii) Ti ions and gates on the surface of one or more oxides selected from the group consisting of Al zOs, Sing, and ZrO2. Electroplating using a plating bath containing composite dispersed particles adsorbing oxides generated from one or more metal ions selected from the group consisting of ions, Cr ions, ■ ions, in ions, and W ions. A composite plating method characterized by:
本願の第１発明において、好ましい態様は、上記酸化物
と金属イオンとを含む酸性電解質液に、更に０．０５〜
１．０ ｗｔ％の縮合リン酸塩を添加して電解し、複合
分散粒子を製造することである。In the first invention of the present application, in a preferred embodiment, the acidic electrolyte solution containing the above oxide and metal ions further contains 0.05 to 0.05%
1.0 wt% of condensed phosphate is added and electrolyzed to produce composite dispersed particles.
また、第２発明の好ましい態様は、上記複合分散粒子を
含むめっき浴に、更に０．０５〜Ｌ、０ｗｔ％の縮合リ
ン酸塩を添加して電気めっきし、めっき金属と複合分散
粒子を共析電着させることである。Further, in a preferred embodiment of the second invention, electroplating is performed by further adding 0.05 to 0 L, 0 wt% of condensed phosphate to the plating bath containing the composite dispersed particles, and the plating metal and the composite dispersed particles are combined. It is electrodeposition.
複合分散粒子の製造に際して、酸性電解液に縮合リン酸
塩を添加して行えば生成した酸化物自身の凝集を防止す
ることができる。When producing composite dispersed particles, adding a condensed phosphate to the acidic electrolyte can prevent the produced oxides from agglomerating themselves.
また、めっき浴に添加して複合めっきすれば、大きな界
面活性効果が得られるので、複合分散粒子を長期間安定
して保持することができる。その結果、均一に且つ多量
に電着させることができるとともに、品質のよいめっき
を安定して長期にわたって施すことが可能となる。Moreover, if it is added to the plating bath for composite plating, a large surface active effect can be obtained, so that the composite dispersed particles can be stably maintained for a long period of time. As a result, it is possible to electrodeposit uniformly and in a large amount, and it is also possible to stably apply high-quality plating over a long period of time.
（作用）
以下、本発明の複合分散粒子の製造方法と複合めっき方
法について詳細に説明する。(Function) Hereinafter, the method for producing composite dispersed particles and the composite plating method of the present invention will be explained in detail.
まず、本発明の複合分散粒子の製造方法について述べる
。First, the method for producing composite dispersed particles of the present invention will be described.
ＡＸ、Ｏ，，５ｔ（ｈおよびＺｒＯ２よりなる群から選
ばれた１種以上の酸化物と、Ｔｉイオン、門。イオン、
Ｃｒイオン、■イオン、ＭｎイオンおよびＷイオンより
なる群から選ばれた１種以上の金属イオンを含む酸性電
解質液を電解すると、浴中で、まず金属イオンがイオン
の状態で酸化物の表面に吸着し、電解により酸化されて
酸化物となる。AX, O,, 5t (h and one or more oxides selected from the group consisting of ZrO2, Ti ions, gate ions,
When an acidic electrolyte solution containing one or more metal ions selected from the group consisting of Cr ions, ■ ions, Mn ions, and W ions is electrolyzed, the metal ions first reach the surface of the oxide in an ionic state in the bath. It is adsorbed and oxidized by electrolysis to become an oxide.
金属イオンがＴｉの場合はＴｔＯ□に、同じ＜Ｍｏの場
合はＭｏｏｔに、Ｃｒの場合はＣｒＯ３に、■の場合ば
ＶｔＯ。If the metal ion is Ti, set it to TtO□, if the same <Mo, set it to Moot, if it is Cr, set it to CrO3, and if it is ■, set it to VtO.
に、Ｍｎの場合はＭｎＯ□におよびＷの場合は６０．の
酸化物になる。その結果、Ａ２□０ツ、５ｉ（ｈおよび
／又はＺｒＯ□の粒子に金属イオンから生じた酸化物が
吸着された状態の複合分散粒子が形成される。In the case of Mn, it is MnO□, and in the case of W, it is 60. becomes an oxide. As a result, composite dispersed particles are formed in which oxides generated from metal ions are adsorbed on A2□0, 5i(h and/or ZrO□ particles).
本発明において、この複合分散粒子の製造に使用する金
属イオンを上記するような金属イオンに限定する理由は
、これら金属イオンは電解で酸化物となるとともに、酸
化物状態でＡｊ！ｇｏｓ、５ｉｆｔおよび／又はＺｒ０
１よりも強く正に帯電するからである。このような正電
荷を帯びた粒子を吸着している複合分散粒子は、帯電力
が強（めっき浴中でおこる還元反応によっても容易に電
荷を失うことがなく安定なものとなる。In the present invention, the reason why the metal ions used in the production of the composite dispersed particles are limited to those mentioned above is that these metal ions become oxides by electrolysis, and in the oxide state Aj! gos, 5ift and/or Zr0
This is because it is positively charged more strongly than 1. Composite dispersed particles adsorbing such positively charged particles have a strong electrostatic charge (they do not easily lose charge even in the reduction reaction that occurs in the plating bath, making them stable).
また、複合分散粒子の製造を酸性電解質液から行う理由
は、中性およびアルカリ性の液では、金属イオンが安定
に存在せず、単体で酸化物となり沈澱を起こし、Ａ Ｉ
！、ｚＯｓ、Ｓｉｎｇおよび／又はＺｒ０１に吸着され
ないからである。酸性電解質液ではこのようなことがな
い。In addition, the reason why composite dispersed particles are manufactured from an acidic electrolyte solution is that metal ions do not exist stably in neutral or alkaline solutions, and become oxides and precipitate when used alone.
! , zOs, Sing and/or Zr01. This does not happen with acidic electrolyte solutions.
酸性電解質液に更にＯ，ＯＳ〜１．０ｗｔ％の縮合リン
酸塩を添加して複合分散粒を製造すれば、前記するよう
な効果が得られるが、０．０５ｗｔ％未満ではその効果
が小さく、１．０ｗｔ％を超えると効果が飽和し、添加
が無意味で経済的に不利を招く。If composite dispersion particles are produced by further adding O,OS to 1.0 wt% of condensed phosphate to the acidic electrolyte solution, the above-mentioned effect can be obtained, but if it is less than 0.05 wt%, the effect is small. If the amount exceeds 1.0 wt%, the effect will be saturated, and the addition will be meaningless and economically disadvantageous.
縮合リン酸塩は、ＮａａＰｔＯｔ、Ｎａ５ＰｓＯ＋ｏ、
Ｎａ４Ｐ４０＋ｓおよびＮａ６ＰｉＯ＋ｗの化学式もつ
縮合リン酸塩を使用するのが好ましく、このような化学
式の縮合リン酸塩であれば上記の効果がより多く得られ
る。Condensed phosphates include NaaPtOt, Na5PsO+o,
It is preferable to use condensed phosphates having the chemical formulas Na4P40+s and Na6PiO+w, and condensed phosphates having such chemical formulas can provide more of the above effects.
本発明において、前記金属イオンは次のような形で酸性
電解浴に添加することができる。In the present invention, the metal ions can be added to the acidic electrolytic bath in the following form.
即ち、金属イオンがＴｉの場合は、Ｔｉｔ（Ｓｏｎ）ｓ
、ＴｉＣｆｆ１ｓとして、Ｍｏの場合は、ＮａＪｏＯ，
として、Ｃｒの場合は、ＣｒＣ１２ｓとして、■の場合
はＶＣｌ３として、Ｍｎ場合は、ＭｎＣｌ ｚ、ＭｎＣ
ｌ ３としておよびＷの場合は、ＷＣＬ、ＷＣＺ、とし
て添加することができる。そして、これらの中から１種
以上をおよそ０．１〜３０ｇ／ ｌ添加するのが望まし
い、これら金属イオンの違いによる作用効果には大きな
差はない。That is, when the metal ion is Ti, Tit(Son)s
, TiCff1s, in the case of Mo, NaJoO,
For Cr, use CrC12s, for ■, use VCl3, for Mn, use MnCl z, MnC
It can be added as 13 and in the case of W as WCL, WCZ. It is desirable to add one or more of these metal ions in an amount of approximately 0.1 to 30 g/l; there is no significant difference in the effects due to the differences in these metal ions.
次に、この複合分散粒子を用いて行う複合めっき方法に
ついて説明する。Next, a composite plating method using these composite dispersed particles will be explained.
複合めっきは、酸性電解質液で電解して得られた前記複
合分散粒子を濾過等により一旦この浴から取り出したも
のをめっき浴に添加するか、酸性電解質液から複合分散
粒子を取り出すことなく、複合分散粒子を含んだままの
酸性電解質液をめっき浴に添加するか、或いは酸性電解
質液で複合分散粒子を生成させた後、この浴にめっきす
べき金属イオンを添加して、めっき条件を整えてめっき
するか、いずれかの方法で行うことができる。Composite plating can be carried out either by removing the composite dispersed particles obtained by electrolysis with an acidic electrolyte solution from the bath by filtration or the like and adding them to the plating bath, or by adding them to the plating bath without taking out the composite dispersed particles from the acidic electrolyte solution. Either add the acidic electrolyte solution containing the dispersed particles to the plating bath, or after generating the composite dispersed particles with the acidic electrolyte solution, add the metal ions to be plated to this bath and adjust the plating conditions. It can be done by plating or by any of the following methods.
複合分散粒子をめっき浴に少量含ませることによって耐
食性の改善されためっき皮膜が得られるが、その添加量
が少ないと効果が小さく、また、多すぎるとめっき皮膜
中に取り込まれる量が多くなりすぎて、加工性が損なわ
れる。好ましい量は０．１〜３０ｇ／ ｊ！である。A plating film with improved corrosion resistance can be obtained by adding a small amount of composite dispersed particles to the plating bath, but if the amount added is small, the effect will be small, and if it is too large, the amount incorporated into the plating film will be too large. As a result, workability is impaired. The preferred amount is 0.1-30g/j! It is.
この複合めっきをするに際しても、上記するような縮合
リン酸塩を同量添加して行うのがよい。When carrying out this composite plating, it is also preferable to add the same amount of condensed phosphate as described above.
縮合リン酸塩の含有量が０．０５ｗｔ％未満では効果が
小さく、１．０ｗｔ％を超えると効果が飽和し、添加が
無意味で経済的に不利を招く。If the content of the condensed phosphate is less than 0.05 wt%, the effect will be small, and if it exceeds 1.0 wt%, the effect will be saturated, making the addition pointless and economically disadvantageous.
適量の縮合リン酸塩であれば、例えば亜鉛および亜鉛系
合金めっき浴では、縮合リン酸塩が亜鉛と難溶性塩を生
成することなく、安定して浴中に存在し、大きな界面活
性効果が得られるので、複合分散粒子をめっき浴中で長
期間安定して分散した状態に保持することができる。If an appropriate amount of condensed phosphate is used, for example, in a zinc and zinc-based alloy plating bath, the condensed phosphate will stably exist in the bath without forming poorly soluble salts with zinc, and will have a large surfactant effect. Therefore, the composite dispersed particles can be stably maintained in a dispersed state for a long period of time in the plating bath.
ｆ、ＫｉＢ、本発明の複合めっき方法において、７１分
散粒子とめっき金属とを共析電着させるためのめっき浴
は、一般には亜鉛めっき浴或いはＺｎ −Ｆｅ、Ｚｎ
Ｎｉ、 Ｚｎ−Ｃｏ、 Ｚｎ−Ｍｒ＋等の亜鉛系合金
めっき浴である。f, KiB, In the composite plating method of the present invention, the plating bath for eutectoid electrodeposition of the 71 dispersed particles and the plating metal is generally a zinc plating bath or a Zn-Fe, Zn
This is a zinc-based alloy plating bath such as Ni, Zn-Co, Zn-Mr+, etc.
以下、実施例により本発明をさらに説明する。The present invention will be further explained below with reference to Examples.
（実施例１）
酸性電解質液としてＮａ、ＳＯ，溶液を用い、これにＡ
Ｉ ＪｓとＴｉイオンをＴｉｔ（ＳＯＪｉの形で添加
して下記（１）に示す条件でＡｆ、Ｏ，の表面に正に帯
電したＴｉ０ｆを吸着した複合分散粒子を製造した。(Example 1) A Na, SO, solution was used as the acidic electrolyte solution, and A
IJs and Ti ions were added in the form of Tit (SOJi) to produce composite dispersed particles in which positively charged Ti0f was adsorbed on the surfaces of Af, O, and under the conditions shown in (1) below.
（１）複合分散粒子製造条件
ＮａｔＳＯａ： ｌｏｏｇ／ １
ｐＨ： １．０〜３．０
浴温：５０〜６０°Ｃ
′ｃｌｆＬ密度： ６０〜１００Ａ／ｄａ”Ａｊ！ｇｏ
ｓ： ２０ｇ／Ｉ
Ｔｉｔ（Ｓｏｎ）ｚ： ３．Ｏｇ／ １使用電極：Ｐｔ
次いで、複合分散粒子を含んだままの上記酸性電解質液
をめっき浴に添加し、下記（２）に示す複合めっき条件
で電気めっきして皮膜中のＮｉ含有量が１１．５〜１２
．５ｗｔ％で付着量が２０ｇ／ｍ”のＺｎ−Ｎｉ合金め
っきを施した評価サンプル（１０ｈｍ幅Ｘ １ｏｏｓ＋
＊長さ）を連続して作製した。(1) Composite dispersed particle production conditions NatSOa: loog/ 1 pH: 1.0-3.0 Bath temperature: 50-60°C'clfL density: 60-100A/da"Aj!go
s: 20g/I Tit(Son)z: 3. Og/1 Electrode used: Pt Next, the acidic electrolyte solution containing the composite dispersed particles was added to the plating bath, and electroplating was performed under the composite plating conditions shown in (2) below until the Ni content in the film was 11 .5-12
．． Evaluation sample coated with Zn-Ni alloy plating with 5wt% and coating weight of 20g/m (10hm width x 1oos+
*Length) were produced continuously.
なお、複合分散粒子の製造および複合めっきは１２ビー
カーの中のスターラー攪拌により行った。Note that the production of composite dispersed particles and composite plating were performed by stirring with a stirrer in a 12-beaker.
（２）複合めっき条件
ＺｎＳＯ４・７ＨｔＯ： １４０ｇ／ ｊ！Ｎ１５Ｏａ
・６ＨｘＯ： ２６０ｇ／ ｊ！ｐＨ： １．０〜３．
０
浴温：５０〜６０℃
電流密度：６０〜１００Ａ／ｃ１ｍ”
複合分散粒：Ａ２□０ ： １０ｇ／ ｌに対してＴｉ
１ｔ ：１、ＯＯｇ／ｆの割合で付着したもの。(2) Composite plating conditions ZnSO4/7HtO: 140g/j! N15Oa
・6HxO: 260g/j! pH: 1.0-3.
0 Bath temperature: 50~60℃ Current density: 60~100A/c1m'' Composite dispersed grains: A2□0: Ti for 10g/l
1t:1, deposited at a ratio of OOg/f.
得られた評価サンプルについて、加工性と耐食性の経時
劣化を調査した。その結果を第１表に示す、なお、縮合
リン酸塩を複合分散粒子の製造および／又は複合めっき
時に添加したものについては、その種類と量を併せて同
表に示した。The obtained evaluation samples were investigated for deterioration over time in workability and corrosion resistance. The results are shown in Table 1. For those in which condensed phosphate was added during the production of composite dispersed particles and/or composite plating, the type and amount thereof are also shown in the same table.
第１表において、評価１はめっき浴建浴直後にめっきし
た評価サンプル、評価２は評価サンプル５枚相当分を連
続通電後にめっきした評価サンプル、評価３は同じ＜１
００枚相当分連続通電後にめっきした評価サンプル、評
価４は同じり２００枚通電後にめっきした評価サンプル
に対する特性を意味するものである。In Table 1, evaluation 1 is an evaluation sample plated immediately after preparing the plating bath, evaluation 2 is an evaluation sample plated after continuous energization of the equivalent of 5 evaluation samples, and evaluation 3 is the same <1
The evaluation sample was plated after continuous energization for 00 sheets, and the rating 4 means the characteristics for the evaluation sample plated after 200 sheets were energized.
耐食性は、５％の塩水による塩水噴霧試験を行い、赤錆
発生までの日数により評価した。Corrosion resistance was evaluated by conducting a salt spray test using 5% salt water and determining the number of days until red rust appeared.
加工性は、評価サンプルから９０ｍｍφの円板のブラン
クを採取し、これを５０ｍｍ＋φ、２８ｒａｔａ深さの
円筒状に深絞り成形して、その側壁面のめっき皮膜を粘
着テープで剥離させる試験を行い、その剥離量を目視調
査し、５段階で評価した。評価は、５：全く剥離無し、
４：テープの全面積に対して剥離片の付着しているテー
プ面積が１０％未満、３：同じ＜１０％以上〜３０％未
満、２：同じ＜３０％以、上〜５０％未満、１：同じ＜
５０％以上、としてランク付けした。Processability was tested by taking a 90mmφ disc blank from the evaluation sample, deep drawing it into a cylindrical shape of 50mm+φ and 28ra depth, and peeling off the plating film on the side wall surface with adhesive tape. The amount of peeling was visually inspected and evaluated on a five-point scale. Rating: 5: No peeling at all.
4: The tape area to which the peeling piece is attached is less than 10% of the total area of the tape, 3: Same <10% or more and less than 30%, 2: Same <30% or more, above and less than 50%, 1 ：same＜
Ranked as 50% or more.
第１表から明らかなように、Ｎαｌへ１１の本発明例の
ものは、従来の複合めっきに相当するＡ２□０゜および
Ｔｉ０１を単独にめっき浴に添加してめっきした比較例
Ｎα１２のものと比べて、高い加工性と耐食性を示す、
また、本発明例の中でも阻２〜１１の複合分散粒子の製
造および／又は複合めっきの際に縮合リン酸塩を添加し
て行ったものは、その効果が充分に発渾されている。As is clear from Table 1, Nαl of Inventive Example 11 is different from Comparative Example Nα12, which is plated by adding A2□0° and Ti01, which corresponds to conventional composite plating, to the plating bath. In comparison, it shows high workability and corrosion resistance.
Moreover, among the examples of the present invention, those in which condensed phosphate was added during the production of composite dispersed particles and/or composite plating according to Inhibitions 2 to 11 exhibited sufficient effects.
比較例ｋ１３〜Ｎα１５は、複合分散粒子の製造成いは
複合めっきの際に縮合リン酸塩を添加したものであるが
、その添加量が本発明で規定する量より少ない場合は縮
合リン酸塩の効果がなく、一方、多すぎても効果が飽和
していることがわかる。In Comparative Examples k13 to Nα15, condensed phosphate was added during the production of composite dispersed particles during composite plating, but if the amount added was less than the amount specified in the present invention, condensed phosphate was added. It can be seen that there is no effect, and on the other hand, even if the amount is too high, the effect is saturated.
（実施例２）
酸性電解液としてＨｘＳＯ４溶液を用い、これに第２表
に示す１種もしくは２種以上の酸化物と金属イオンを添
加して同表に示す条件で複合分散粒子を製造し、この複
合分散粒子を第３表に示す浴組成のめっき浴に添加して
同表に示す条件で複合めっきを施し、付着量が２０ｇ／
ｍ”の評価サンプルを作製した。(Example 2) Using HxSO4 solution as the acidic electrolyte, one or more oxides and metal ions shown in Table 2 were added to it to produce composite dispersed particles under the conditions shown in the same table, The composite dispersed particles were added to a plating bath having the bath composition shown in Table 3, and composite plating was performed under the conditions shown in Table 3, with a coating weight of 20 g/
An evaluation sample of "m" was prepared.
得られた評価サンプルの耐食性および加工性を実施例１
と同じ方法で評価した。なお、亜鉛めっきは加工性が良
（評価点が５となり、めっき皮膜複合化による差が認め
られないため、耐食性のみを評価した。The corrosion resistance and workability of the obtained evaluation samples were evaluated in Example 1.
was evaluated using the same method. Note that zinc plating has good workability (the evaluation score was 5, and no difference was observed due to the composite plating film, so only the corrosion resistance was evaluated.
同じく第３表に耐食性と加工性の評価結果と複合分散粒
子の製造および／又は複合めっき時に縮合リン酸塩を添
加したものについては、その種類と量を示す。Similarly, Table 3 shows the evaluation results of corrosion resistance and workability, and the type and amount of condensed phosphates added during production of composite dispersed particles and/or composite plating.
第３表から明らかなように、Ｎα１６〜２４の本発明例
のものは、従来の複合めっきに相当するＡ ｌ ｔ（ｈ
およびＴｉＯｘを単独にめっき浴に添加してめっきした
比較例ＮＣＬ１２のものと比べて、高い加工性と耐食性
を示す、Ｎα５〜Ｎα９の合金系のマトリックスのもの
でも橿めて良好な加工性を示し、複合分散粒子の均一な
電着性を示している。As is clear from Table 3, the inventive examples with Nα16 to 24 have Al t(h
Also, compared to Comparative Example NCL12, which was plated by adding TiOx alone to the plating bath, it showed higher workability and corrosion resistance, and even the alloy matrix of Nα5 to Nα9 showed better workability. , indicating uniform electrodeposition of the composite dispersed particles.
Ｎα２５の比較例はＮｏ、２６の従来例の浴に縮合リン
酸塩を入れただけの条件であるが、初期に耐食性がわず
かに上昇するもののその効果は不十分で、本発明方法に
基づいた添加のみで効果が得られることがわかる。The comparative example of Nα25 is a condition in which condensed phosphate is simply added to the conventional bath of No. 26, but although the corrosion resistance increases slightly at the initial stage, the effect is insufficient. It can be seen that the effect can be obtained only by addition.
（発明の効果）
以上説明した如く、本発明方法で得られた複合分散粒子
は強い正電荷を有するためにめっき浴中で凝集し、沈澱
することが少ない、また、複合めっき方法は、このよう
な利点をもつ複合分散粒子を用いて行うから均一に且つ
多量にめっき皮膜中に電着させることができるので耐食
性および加工性に優れたものを長期にわたり安定して製
造することができる。(Effects of the Invention) As explained above, since the composite dispersed particles obtained by the method of the present invention have a strong positive charge, they are less likely to aggregate or precipitate in the plating bath. Since composite dispersion particles are used, which have the following advantages, they can be electrodeposited uniformly and in large quantities into the plating film, and products with excellent corrosion resistance and workability can be stably produced over a long period of time.
Claims (4)
りなる群から選ばれた１種以上の酸化物と、Ｔｉイオン
、Ｍｏイオン、Ｃｒイオン、Ｖイオン、Ｍｎイオンおよ
びＷイオンよりなる群から選ばれた１種以上の金属イオ
ンを含む酸性電解質液を電解することを特徴とする複合
分散粒子の製造方法。(1) One or more oxides selected from the group consisting of Al_2O_3, SiO_2, and ZrO_2 and one or more oxides selected from the group consisting of Ti ions, Mo ions, Cr ions, V ions, Mn ions, and W ions. A method for producing composite dispersed particles, comprising electrolyzing an acidic electrolyte solution containing metal ions.
、更に０．０５〜１．０ｗｔ％の縮合リン酸塩を添加し
て電解することを特徴とする特許請求の範囲第１項記載
の複合分散粒子の製造方法。(2) Claim 1, characterized in that 0.05 to 1.0 wt% of condensed phosphate is further added to the acidic electrolyte solution containing the oxide and metal ions for electrolysis. A method for producing composite dispersed particles.
りなる群から選ばれた１種以上の酸化物の表面にＴｉイ
オン、Ｍｏイオン、Ｃｒイオン、Ｖイオン、Ｍｎイオン
およびＷイオンよりなる群から選ばれた１種以上の金属
イオンから生じた酸化物を吸着させた複合分散粒子を含
むめっき浴を用いて電気めっきすることを特徴とする複
合めっき方法。(3) One or more oxides selected from the group consisting of Ti ions, Mo ions, Cr ions, V ions, Mn ions, and W ions on the surface of one or more oxides selected from the group consisting of Al_2O_3, SiO_2, and ZrO_2. A composite plating method characterized by electroplating using a plating bath containing composite dispersed particles adsorbing oxides generated from the above metal ions.
５〜１．０ｗｔ％の縮合リン酸塩を添加して電気めっき
することを特徴とする特許請求の範囲第３項記載の複合
めっき方法。(4) Add 0.0% to the plating bath containing the above composite dispersed particles.
4. The composite plating method according to claim 3, wherein electroplating is carried out by adding 5 to 1.0 wt% of condensed phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63073921A JPH01246398A (en) | 1988-03-28 | 1988-03-28 | Production of composite dispersive particles and composite plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63073921A JPH01246398A (en) | 1988-03-28 | 1988-03-28 | Production of composite dispersive particles and composite plating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01246398A true JPH01246398A (en) | 1989-10-02 |
Family
ID=13532103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63073921A Pending JPH01246398A (en) | 1988-03-28 | 1988-03-28 | Production of composite dispersive particles and composite plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01246398A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01294897A (en) * | 1988-05-20 | 1989-11-28 | Nkk Corp | Surface-treated steel sheet excellent in suitability for chemical treatment and coating and excellent in corrosion resistance |
| JPH03243795A (en) * | 1990-02-20 | 1991-10-30 | Kawasaki Steel Corp | Production of silicon steel sheet having fine appearance of coating film |
| JPH03249183A (en) * | 1990-02-28 | 1991-11-07 | Nippon Steel Corp | Galvanized steel sheet having excellent press formability and chemical conversion treatability |
| JPH03287786A (en) * | 1990-04-03 | 1991-12-18 | Nippon Steel Corp | Zinc plated steel sheet having superior press formability, chemical convertibility and weldability |
| JP2018135554A (en) * | 2017-02-21 | 2018-08-30 | 株式会社Ｊｃｕ | Electrolyte and electrolytic deposition method using the same |
| WO2023090234A1 (en) * | 2021-11-18 | 2023-05-25 | Dic株式会社 | Composite hard chromium plating |
-
1988
- 1988-03-28 JP JP63073921A patent/JPH01246398A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01294897A (en) * | 1988-05-20 | 1989-11-28 | Nkk Corp | Surface-treated steel sheet excellent in suitability for chemical treatment and coating and excellent in corrosion resistance |
| JPH03243795A (en) * | 1990-02-20 | 1991-10-30 | Kawasaki Steel Corp | Production of silicon steel sheet having fine appearance of coating film |
| JP2709172B2 (en) * | 1990-02-20 | 1998-02-04 | 川崎製鉄株式会社 | Manufacturing method of silicon steel sheet with excellent coating appearance |
| JPH03249183A (en) * | 1990-02-28 | 1991-11-07 | Nippon Steel Corp | Galvanized steel sheet having excellent press formability and chemical conversion treatability |
| JPH0696781B2 (en) * | 1990-02-28 | 1994-11-30 | 新日本製鐵株式会社 | Galvanized steel sheet with excellent press formability and chemical conversion treatment |
| JPH03287786A (en) * | 1990-04-03 | 1991-12-18 | Nippon Steel Corp | Zinc plated steel sheet having superior press formability, chemical convertibility and weldability |
| JPH0696783B2 (en) * | 1990-04-03 | 1994-11-30 | 新日本製鐵株式会社 | Galvanized steel sheet with excellent press formability, chemical conversion treatment and weldability |
| JP2018135554A (en) * | 2017-02-21 | 2018-08-30 | 株式会社Ｊｃｕ | Electrolyte and electrolytic deposition method using the same |
| WO2023090234A1 (en) * | 2021-11-18 | 2023-05-25 | Dic株式会社 | Composite hard chromium plating |
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