EP1301655B1 - Verfahren zur elektrolytischen verzinkung aus alkansulfonsäurehaltigen elektrolyten - Google Patents

Verfahren zur elektrolytischen verzinkung aus alkansulfonsäurehaltigen elektrolyten Download PDF

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Publication number
EP1301655B1
EP1301655B1 EP01971759A EP01971759A EP1301655B1 EP 1301655 B1 EP1301655 B1 EP 1301655B1 EP 01971759 A EP01971759 A EP 01971759A EP 01971759 A EP01971759 A EP 01971759A EP 1301655 B1 EP1301655 B1 EP 1301655B1
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EP
European Patent Office
Prior art keywords
zinc
electrolyte
acid
reaction
metals
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Expired - Lifetime
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EP01971759A
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German (de)
English (en)
French (fr)
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EP1301655A2 (de
Inventor
Gregor Brodt
Jens Haas
Werner Hesse
Hans-Ulrich JÄGER
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc

Definitions

  • the invention relates to a method for the electrolytic coating of metals Zinc or a zinc alloy, an electrolytic composition for an electrolytic Coating steel or iron with zinc or zinc alloys as well Use of additives to improve the surface roughness and avoid it of dendritic edge growth in the electrolytic coating of metals with zinc or a zinc alloy.
  • Zinc coatings offer very good protection against atmospheric influences and are used to protect metals from corrosion. Galvanizing metals, especially iron or steel, is used on a large scale, e.g. for the Automotive industry. In addition, wires, e.g. for the electronics industry, tapes and pipes galvanized on a large scale.
  • Galvanizing can be carried out in both acidic and alkaline or alkaline cyanide Electrolytes are made. Cyanide zinc electrolytes provide smooth, fine crystalline precipitation. The spreadability is very good in these baths However, current yield is poor, which means that it can only be used with relatively low current densities be electrolyzed. However, the current density is proportional to Coating speed. It is therefore desirable for economic reasons Electroysing at the highest possible current densities and thus the fastest possible zinc deposition to obtain.
  • acidic electrolytes are preferred because, due to the applicability of high current densities up to 200 A / dm 2 with sufficient movement of the electrolyte and an almost 100% current efficiency rapid zinc deposition is possible.
  • Electrolytes based on chloride or sulfate are usually used.
  • US 4,207,150 discloses aqueous cyanide-free electrolytes for electrolytic galvanizing, which contain a water-soluble zinc salt and in which a quaternary butyl nicotinate salt is used as a shine-forming and scatter-improving additive.
  • Be next to it preferably additionally polyether as brightener and methanesulfonic acid and their salts used as a spreading improver.
  • the benefits of the additives used can be at pH values from 2 to 7.5 can be observed.
  • US 5,616,232 relates to a method for the electrolytic deposition of zinc-chromium alloys in an acidic electrolyte.
  • Polyethyleneoxyphenol derivatives are used as additives used to promote the deposition of the zinc-chromium alloy.
  • EP-A 0 727 512 relates to the electrolytic deposition of zinc at high current densities.
  • An electrolyte is used, containing zinc sulfate in an aqueous, acidic Electrolysis bath. In this electrolysis bath, dendrite formation and "combustion" are the Edges of the workpiece and the roughness of the zinc surface are reduced and the Grain size is checked.
  • the electrolyte becomes highly molecular as additives Polyoxyalkylene glycols as grain refiners in combination with sulfonated Condensation products of naphthalene and formaldehyde as antidendritic Added reagents.
  • EP-A 0 807 697 relates to electrolytes for the galvanic deposition of zinc at high Current densities and a pH of 2 to 5, which are the common problems with these Current densities should occur.
  • These electrolytes essentially consist of a.
  • Zinc salt selected from zinc sulfate and / or a zinc organosulfonate, as well a low molecular weight polyoxyalkylene glycol based on Alkylene oxides with 2 to 4 carbon atoms, an aromatic sulfonate and one Conductivity-increasing salt, preferably a potassium salt.
  • EP-A 0 786 539 also relates to electrolytes for the galvanic deposition of zinc at high current densities which are the common problems that occur at these current densities should decrease.
  • This additive is a polyoxyalkylene glycol homo or copolymer, based on alkylene oxides with 2 to 4 carbon atoms.
  • water-soluble boron oxide compounds, lignin compounds and / or a sulfonated Condensation product of naphthalene and formaldehyde may be included.
  • a suitable electrolyte system for the deposition of zinc or Zinc alloys at high current densities desirable that the disadvantages of high speed deposition are simple Reduced in a wide pH range and current density range or entirely avoids
  • the object of the present invention is to provide a method for electrolytic deposition of zinc or zinc alloys at high current densities, that the disadvantages occurring in the prior art such as increased edge roughness galvanized workpieces due to dendrite growth and "burns" of the edges, increased roughness of the entire zinc layer and problems in controlling the Grain growth of the zinc layer is reduced or avoided.
  • the metals to be galvanized are iron or metals containing iron, especially steel.
  • the method according to the invention also includes the deposition of zinc alloys possible by adding appropriate metal salts to the electrolyte.
  • suitable metal salts are chromium and nickel salts, which are preferably in the form of their sulfates and / or alkanesulfonates are used.
  • the Electrolyte an alkanesulfonic acid.
  • Alkanesulfonic acids in the context of the present invention are understood to mean aliphatic sulfonic acids. Their aliphatic radicals can optionally be substituted with functional groups or heteroatoms, for example hydroxyl groups. Alkanesulfonic acids of the general formulas are preferred R-SO 3 H or HO-R'-SO 3 H used.
  • R is a hydrocarbon radical, which can be branched or unbranched, with 1 to 12 carbon atoms, preferably with 1 to 6 carbon atoms, particularly preferably one unbranched hydrocarbon radical with 1 to 3 carbon atoms, very special preferably with 1 carbon atom, ie methanesulfonic acid.
  • R ' is a hydrocarbon residue that can be branched or unbranched, with 2 to 12 Carbon atoms, preferably having 2 to 6 carbon atoms, particularly preferably one unbranched hydrocarbon radical with 2 to 4 carbon atoms, the Hydroxy group and the sulfonic acid group can be bound to any carbon atoms can, with the restriction that they are not bound to the same carbon atom.
  • methanesulfonic acid is very particularly preferred as alkanesulfonic acid used.
  • the alkanesulfonic acid used especially methanesulfonic acid, enables a good one Conductivity of the electrolyte, high possible current densities and a very good spread in the deposition of zinc or zinc alloys.
  • the Electrolyte either as the only acid an alkane sulfonic acid or a mixture of Sulfuric acid and alkanesulfonic acid.
  • the electrolyte preferably contains 10 to 100 parts by weight an alkanesulfonic acid and 90 to 0 parts by weight of sulfuric acid, the sum of alkanesulfonic acid and sulfuric acid is 100 parts by weight and a concentration from 0 to 5% by weight, preferably 0.5 to 3% by weight, of the electrolyte.
  • the electrolyte preferably contains 10 to 90 parts by weight of an alkanesulfonic acid and 90 to 10 parts by weight of sulfuric acid, very particularly preferred are 20 to 80 parts by weight of one Alkanesulfonic acid and 80 to 20 parts by weight of sulfuric acid.
  • alkanesulfonic acid as the only acid in the electrolyte is also possible.
  • the electrolytes used in the process according to the invention are broad pH range of generally ⁇ 0.5 to 5 can be used.
  • the one according to the invention is preferred Process at pH values from about 2.7 to 4, particularly preferably from 3 to 3.5 carried out. Even at low pH values, there is an optimal surface roughness and no or little dendritic edge growth is observed.
  • the Electrolyte at least one zinc alkanesulfonate. It is also possible to use a mixture from an alkane sulfonate of zinc and zinc sulfate.
  • Soluble anodes can be the zinc salt or the zinc alloy salt during the Electrolysis can be simulated.
  • Alkanesulfonates for the purposes of the present invention are understood to mean aliphatic sulfonates. Their aliphatic radicals can optionally be substituted with functional groups or heteroatoms, for example hydroxyl groups. Alkanesulfonates of the general formulas are preferred R-SO 3 - or HO-R'-SO 3 ' used.
  • R is a hydrocarbon radical, which can be branched or unbranched, with 1 to 12 carbon atoms, preferably with 1 to 6 carbon atoms, particularly preferably one unbranched hydrocarbon radical with 1 to 3 carbon atoms, very special preferably with 1 carbon atom, ie methanesulfonate
  • R ' is a hydrocarbon residue that can be branched or unbranched, with 2 to 12 Carbon atoms, preferably having 2 to 6 carbon atoms, particularly preferably one unbranched hydrocarbon radical with 2 to 4 carbon atoms, the Hydroxy group and the sulfonate group can be attached to any carbon atoms can, with the restriction that they are not bound to the same carbon atom.
  • Zinc methanesulfonate is very particularly preferred in the invention Process used.
  • the zinc salt selected from zinc sulfate and / or an alkanesulfonate, preferably methanesulfonate, is generally present in an amount of> 5 g / l up to the saturation concentration of the corresponding zinc salt (or mixture) in the corresponding electrolyte.
  • the corresponding zinc salt (or mixture) is preferably present in an amount of 10 to 250 g / l, preferably 30 to 250 g / l, particularly preferably 50 to 150 g / l, very particularly preferably 75 to 100 g / l, based on the Weight of zinc, calculated as g Zn 2+ per liter of electrolyte used.
  • the inventive method is particularly suitable for an electrolytic Zinc deposition at high current densities, i.e. for high-speed deposition of zinc, preferred for continuous galvanizing.
  • the method according to the invention is suitable for a current density range of 10 to 500 A / dm 2 , preferably 20 to 400 A / dm 2 , particularly preferably 20 to 300 A / dm 2 .
  • the current densities used depend, among other things, on the area of application.
  • Pipes are generally coated at current densities of 10 to 75 A / dm 2 , and a layer thickness of the zinc surface of 0.2 to 20 ⁇ m is obtained.
  • the workpiece is continuously guided through the electrolysis bath.
  • the wire coating is generally carried out similarly to the coating of pipes.
  • the current density is generally 10 to 100 A / dm 2 and the layer thickness of the zinc surface is 10 to 100 ⁇ m.
  • the high speed deposition of zinc is generally at temperatures from room temperature (25 ° C.) to 75 ° C., preferably from 40 to 70 ° C.
  • the additives used in the process according to the invention to improve the Surface roughness and avoidance of dendritic edge growth are selected from nitrogen-containing surface-active compounds which are ionic or cannot be ionic, sulfur-containing anionic surfactants Compounds as well as surface-active compounds, starting from multifunctional Alcohols with at least three hydroxyl groups.
  • surface active compounds are both for use in electrolytes containing sulfuric acid as the only acid in the electrolyte suitable, as well as for the Use in electrolytes containing alkanesulfonic acid, preferably methanesulfonic acid and for use in electrolytes containing an alkanesulfonic acid, preferred Methanesulfonic acid, as the only acid.
  • the additives in electrolytes are preferred used that contain an alkanesulfonic acid, either in a mixture with sulfuric acid or as the only acid.
  • the surface-active compounds used according to the invention can be used individually or can be used as a mixture of two or more surface-active compounds.
  • other commonly used additives such as Conductive salts are used.
  • the surface-active compounds used in accordance with the invention also stand out the positive influences in particular on the surface roughness of the zinc surface and on the dendritic edge growth further by only one have a low tendency to foam. This property is for large-scale implementation electrolytic galvanizing of great importance.
  • An optimal surface roughness (R a ) of generally 0.3 to 3 ⁇ m, preferably 1 to 2 ⁇ m, can be set by the surface-active compounds used according to the invention. Uniformly thick, well-adhering zinc layers are obtained.
  • the layer thickness of the zinc surfaces obtained with the method according to the invention is variable depending on the desired application. Usual layer thicknesses are generally 0.1 to 100 ⁇ m, preferably 1 to 20 ⁇ m, particularly preferably 5 to 10 ⁇ m.
  • the layer thicknesses to be produced depend on the field of application, the particularly preferred embodiment being for continuous strip galvanizing.
  • the additives used according to the invention are used in an amount of 0.1 to 20 g / l, preferably from 0.5 to 10 g / l, particularly preferably from 1 to 6 g / l.
  • the are as Additives used nitrogen-containing surface-active compounds that ionic (although the nitrogen itself can be quaternized) or non-ionic can be selected from polyethyleneimines and reaction products of amines with Epichlorohydrin.
  • the polyethyleneimines can be both high molecular weight and low molecular weight, with average molecular weights of 400 to 1,000,000, the low molecular weight Polyethyleneimines with average molecular weights of 600 to 5000 are preferred. She are generally produced by customary methods. especially the Polyethyleneimines are preferred in electrolytes containing an alkanesulfonic acid, preferably methanesulfonic acid used. Suitable types are polyethyleneimines Lugalvan® G 15000 as well as Lugalvan® G 20 and Lugalvan® G 35.
  • Suitable amines are heterocyclic Amines, in particular heterocyclic 5-rings such as pyrrole, pyrazole and imidazole, amines, those with aliphatic residues, or optionally with hydrogen (if primary or secondary amines), where the aliphatic radicals are the same as or can be different, branched or unbranched, saturated or unsaturated and by further heteroatoms can be substituted.
  • additives are the reaction products of imidazole with epichlorohydrin used.
  • the reaction products with epichlorohydrin can with after their reaction suitable crosslinkers.
  • these additives are the products that are used in a 0.3: 1 to 1: 0.3% by weight conversion, preferably in a 0.5: 1 to 1: 0.5% by weight conversion obtained from imidazole and epichlorohydrin, particularly preferred.
  • reaction products of dimethylaminopropylamine with epichlorohydrin preferred, which in particular after the implementation e.g. crosslinked with bisdichloroethane ether become.
  • reaction products from an amine with epichlorohydrin already have an effect as the only additives in that used in the process according to the invention Electrolytes an improvement of the surface roughness and a reduction or Avoiding dendritic edge growth.
  • Suitable commercially available Products are the types Lugalvan® IZE 2 and Lugalvan® IZE 3 from BASF AG as well MIRAPOL® WT from Rhodia.
  • Preferred anionic surface-active sulfur-containing additives Compounds are selected from sulfates, preferably ether sulfates or alkyl sulfates with at least 5 carbon atoms, e.g. Ethyl hexyl sulfate (e.g. Lutensit® TC-EHS der BASF AG), sulfonates, preferably reaction products of propane sultone (e.g. the Ralufon® grades from Raschig) and isethionates (e.g. Lutensit® A-IS from BASF AG).
  • sulfates preferably ether sulfates or alkyl sulfates with at least 5 carbon atoms, e.g. Ethyl hexyl sulfate (e.g. Lutensit® TC-EHS der BASF AG), sulfonates, preferably reaction products of propane sultone (e.g. the Ralufon® grades from
  • Preferred ether sulfates are C 5 to C 12 phenol polyglycol ether sulfates and fatty alcohol polyglycol ether sulfates.
  • Preferred reaction products of propane sultone are sulfopropyl ether with 6 up to 20 carbon atoms in the alkyl chain or an aryl group with an alkyl radical can be alkylated with 6 to 15 carbon atoms.
  • These sulfopropyl ethers can have a further 3 to 20 ethylene oxide units.
  • These additives are preferably used in electrolytes containing alkanesulfonic acid.
  • Suitable devices and electrodes for electrolytic galvanizing with the Methods according to the invention are generally dependent on the particular Field of application (e.g. pipe, strip, wire galvanizing). Basically, it can The inventive method in all the usual devices and with all the usual Electrodes are performed.
  • Another object of the present invention is an electrolyte composition for electrolytic coating of metals with zinc or zinc alloys, containing a zinc salt and optionally further metal salts, an acid selected from Sulfuric acid or an alkanesulfonic acid or a mixture of the two acids and at least one additive selected from nitrogen-containing surfactants Compounds that can be ionic or non-ionic containing sulfur anionic surface-active compounds and surface-active compounds, starting from multifunctional alcohols with at least three hydroxyl groups.
  • This electrolyte composition is particularly suitable for high-speed deposition of zinc or zinc alloys on metals, which at high Current densities take place.
  • Electrolyte compositions can have the disadvantages known from the prior art high-speed deposition, in particular high surface roughness and dendritic edge growth can be reduced or avoided.
  • Suitable metals, Electrolysis conditions, acids and zinc salts have already been mentioned above.
  • An electrolyte composition containing additives is preferably used selected from polyethyleneimines and reaction products of amines with Epichlorohydrin, sulfates, preferably ether sulfates or alkyl sulfates with at least 5 Carbon atoms, e.g. Ethyl hexyl sulfate, sulfonates, preferably reaction products of propane sultone, and isethionates.
  • Another object of the present invention is the use of Compounds selected from nitrogen-containing surface-active compounds, which can be ionic or non-ionic, sulfur-containing anionic surface-active compounds and surface-active compounds, starting from multifunctional alcohols with at least three hydroxyl groups as additives for Improve surface roughness and avoid dendritic Edge growth in the electrolytic coating of metals with zinc or a Zinc alloy in an electrolyte containing alkanesulfonic acid. Suitable metals, Electrolysis conditions, zinc salts and preferred additives are already in place mentioned above.
  • the electrolyte compositions containing these additives are used in particular high speed electrolytic continuous deposition of zinc or Zinc alloys on metals containing iron, especially on steel, are used.
  • Preferred areas of application are strip galvanizing, e.g. for making one or double-sided galvanized steel sheets for the automotive industry, the production of galvanized Steel pipes and strips as well as the production of galvanized wires.
  • Zinc sulfate and zinc methanesulfonate were used as zinc salts, the latter being obtained by reacting zinc carbonate with methanesulfonic acid. All tests were carried out at 55 ° C., the deposition time was 84 s, the average current density was 20 A / dm 2 , which resulted in current densities of> 100 A / dm 2 in the edge region of the sheet to be coated.
  • Lugalvan® IZE 2 a drastically reduced dendrite growth, better scattering and one significantly more uniform and closed zinc layer even in the high current density range, where the Layer thickness was about 40 microns.
  • Example 2 is compared to Example 1 better dispersion and less edge burning even without the addition.
  • the Addition of Lugalvan® IZE 3 effectively avoids dendritic growth and further improves the spread.
  • Fig. 6a in middle current density range an approximately 7 ⁇ m thick zinc layer was obtained with the additive appears even and smooth (Fig. 6a), while without addition an uneven Layer is obtained which partially has pores up to the steel substrate (Fig. 6b).
  • Example 1 The base electrolyte from Example 1 was mixed with 2 g / l Lugalvan® G20. There were comparable results as in Example 1 with the addition of Lugalvan® IZE 3 receive.
  • Example 2 The base electrolyte from Example 2 was mixed with 2 g / l Mirapol® WT. There were comparable results as in Example 2 with the addition of Lugalvan® IZE 3 receive.
  • Example 3 The base electrolyte from Example 3 was treated with 4 g / l ethoxylated sorbitol (24 Ethylene oxide units) added. The results were comparable to those with the addition obtained from Lugalvan® IZE 2 in Example 3. Burning and dendrite growth were very low and the spread was very good.
  • Example 14 shows the dendrite growth in an electrolyte according to Example 3 with the addition of to recognize ethoxylated sorbitol.
  • the base electrolyte from Example 3 was mixed with 4 g / l Lutensit® A-IS (isethionate). The burn was very low and the dendrite growth was moderate and the deposition very evenly.
  • the base electrolyte from Example 3 was 2 g / l Lugalvan® IZE 2 and 4 g / l Lutensit® TC-EHS offset. The results were comparable to the addition of Receive Lugalvan® IZE 2. The burn was compared to Lugalvan® IZE 2 alone less, and no dendrite growth was discernible, the scatter was very good and the Deposition very evenly.
  • Example 18 shows the dendrite growth in an electrolyte according to Example 3 with the addition of Lugalvan® IZE 2 and Lutensit® TC-EHS.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
EP01971759A 2000-07-10 2001-07-09 Verfahren zur elektrolytischen verzinkung aus alkansulfonsäurehaltigen elektrolyten Expired - Lifetime EP1301655B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10033433A DE10033433A1 (de) 2000-07-10 2000-07-10 Verfahren zur elektrolytischen Verzinkung aus alkansulfonsäurehaltigen Elektrolyten
DE10033433 2000-07-10
PCT/EP2001/007876 WO2002004713A2 (de) 2000-07-10 2001-07-09 Verfahren zur elektrolytischen verzinkung aus alkansulfonsäurehaltigen elektrolyten

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EP1301655A2 EP1301655A2 (de) 2003-04-16
EP1301655B1 true EP1301655B1 (de) 2004-05-26

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EP01971759A Expired - Lifetime EP1301655B1 (de) 2000-07-10 2001-07-09 Verfahren zur elektrolytischen verzinkung aus alkansulfonsäurehaltigen elektrolyten

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US (1) US6811673B2 (pt)
EP (1) EP1301655B1 (pt)
JP (1) JP2004502876A (pt)
CN (1) CN1188550C (pt)
AT (1) ATE267895T1 (pt)
AU (2) AU9166701A (pt)
BR (1) BR0112349A (pt)
CA (1) CA2415341A1 (pt)
DE (2) DE10033433A1 (pt)
ES (1) ES2220806T3 (pt)
MX (1) MXPA03000018A (pt)
PL (1) PL359778A1 (pt)
TW (1) TWI229151B (pt)
WO (1) WO2002004713A2 (pt)

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DE60233979D1 (de) * 2002-06-25 2009-11-19 Applied Intellectual Capital L Zink-luft-batterie mit säureelektrolyt
DE102005040964A1 (de) * 2005-08-30 2007-03-01 Dr. M. Kampschulte Gmbh & Co. Kg Matte Zinkbeschichtung und Verfahren zur Abscheidung matter Zinkschichten
DE102006042076A1 (de) * 2006-09-05 2008-03-20 Goldschmidt Tib Gmbh Ein neues Additiv für Chromelektrolyte
JP5497261B2 (ja) * 2006-12-15 2014-05-21 ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． インジウム組成物
EP2123799B1 (en) * 2008-04-22 2015-04-22 Rohm and Haas Electronic Materials LLC Method of replenishing indium ions in indium electroplating compositions
JP5299994B2 (ja) * 2008-07-30 2013-09-25 株式会社ブリヂストン 銅−亜鉛合金電気めっき浴および銅−亜鉛合金めっき付きスチールコード用ワイヤ
MY157126A (en) * 2009-07-30 2016-05-13 Basf Se Composition for metal plating comprising suppressing agent for void free submicron feature filling
US8497359B2 (en) * 2010-02-26 2013-07-30 Ppg Industries Ohio, Inc. Cationic electrodepositable coating composition comprising lignin
US9234291B2 (en) 2010-09-09 2016-01-12 Globalfoundries Inc. Zinc thin films plating chemistry and methods
JP5467374B2 (ja) * 2011-08-25 2014-04-09 ユケン工業株式会社 軸体に電気めっきを形成するための装置、めっき皮膜を有する軸体の製造方法および軸体上に亜鉛系めっき皮膜を形成するためのめっき液
CN106757189A (zh) * 2015-11-23 2017-05-31 湖南衡阳新澧化工有限公司 一种含硫酸盐的添加剂及其制备方法
JP6948053B2 (ja) * 2017-01-12 2021-10-13 上村工業株式会社 フィリングめっきシステム及びフィリングめっき方法
CN114597386B (zh) * 2022-02-22 2023-05-12 浙江大学 一种锌金属电极及其制备方法和应用

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AU9166701A (en) 2002-01-21
JP2004502876A (ja) 2004-01-29
BR0112349A (pt) 2003-07-01
CN1188550C (zh) 2005-02-09
CN1446272A (zh) 2003-10-01
AU2001291667B2 (en) 2005-07-14
EP1301655A2 (de) 2003-04-16
US6811673B2 (en) 2004-11-02
ATE267895T1 (de) 2004-06-15
CA2415341A1 (en) 2003-01-09
WO2002004713A2 (de) 2002-01-17
DE10033433A1 (de) 2002-01-24
PL359778A1 (en) 2004-09-06
US20030141195A1 (en) 2003-07-31
DE50102424D1 (de) 2004-07-01
TWI229151B (en) 2005-03-11
ES2220806T3 (es) 2004-12-16
WO2002004713A3 (de) 2002-08-15
MXPA03000018A (es) 2003-07-14

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