EP2184384A1 - Bain galvanique et procédé pour la déposition de couches contenant du zinc - Google Patents

Bain galvanique et procédé pour la déposition de couches contenant du zinc Download PDF

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Publication number
EP2184384A1
EP2184384A1 EP09014111A EP09014111A EP2184384A1 EP 2184384 A1 EP2184384 A1 EP 2184384A1 EP 09014111 A EP09014111 A EP 09014111A EP 09014111 A EP09014111 A EP 09014111A EP 2184384 A1 EP2184384 A1 EP 2184384A1
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EP
European Patent Office
Prior art keywords
zinc
anolyte
galvanic bath
deposition
cell space
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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
Application number
EP09014111A
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German (de)
English (en)
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EP2184384B1 (fr
Inventor
Axel Dr. Fuhrmann
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MacDermid Enthone Inc
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Enthone Inc
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Priority to PL09014111T priority Critical patent/PL2184384T3/pl
Publication of EP2184384A1 publication Critical patent/EP2184384A1/fr
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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
    • C25D3/22—Electroplating: Baths therefor from solutions 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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002—Cell separation, e.g. membranes, diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/22—Regeneration of process solutions by ion-exchange
    • 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

Definitions

  • the present invention relates to a galvanic bath and a method for the deposition of zinc-containing layers on substrate surfaces.
  • the present invention relates to a galvanic bath and a method for the deposition of zinciferous layers from an acidic deposition electrolyte.
  • Zinc-containing layers are characterized in particular by their high corrosion resistance. Due to the appearance of the resulting zinc coatings, zinc layers or zinc-containing layers are used less in the field of decorative coatings than in the field of functional coatings. Thus, for example, it is common to coat small parts such as screws, nuts, washers, prefabricated structural elements such as angle plates or connecting plates and the like in large numbers. In many cases, the small parts are immersed in so-called drum baskets in appropriate Abscheidebäder and it is created between the Abscheidekorb and an anode a Abscheidestrom.
  • the obtained properties of the deposited zinc-containing layer can be influenced.
  • the appearance, the corrosion resistance and the mechanical properties of the deposited layers can be influenced by appropriate alloying depositions. So it is for example from the DE 103 06 823 A1 known to deposit zinc-manganese alloys. In the DE 101 46 559 describes the galvanic deposition of zinc-nickel alloys.
  • a problem with the electrodeposition of zinc-containing layers on substrate surfaces of acidic zinc-containing electrolytes is that the use of dissolving zinc anodes leads to the formation of deposits on the anode surface, which passivate them and adversely affect the production cycle. By these deposits and the effectiveness of the electrodeposition can be reduced.
  • a galvanic bath for depositing a zinc-containing layer on a substrate surface comprising a first cell space, which receives an acidic deposition electrolyte, and a second cell space, which receives a neutral or acidic anolyte, wherein the first cell space of the second Cell space is separated by a cation-permeable membrane and wherein in the anolyte receiving cell space a dissolving zinc anode is arranged, which is characterized in that the anolyte receiving cell space is in hydraulic communication with a device which contains any in the anolyte Exchange foreign metal ions for zinc ions and / or protons.
  • the object is achieved by a method for electrodeposition of a zinc-containing layer on a substrate surface, wherein the substrate to be coated is brought into contact with an acidic, at least zinc ion-containing deposition electrolyte in a galvanic bath and between the substrate and at least one An anode current is applied, which is suitable to induce the deposition of a zinc-containing layer on the substrate surface, wherein the galvanic bath is divided into at least two cells and the cells separated from one another by a membrane permeable to cations, wherein one cell receives the acidic deposition electrolyte and the second cell a neutral or acid zinc ion-containing anolyte and wherein a dissolving zinc anode is disposed in the cell receiving the anolyte, which is characterized in that the acid anolyte is at least partially removed from the cell space receiving it and passed through a device in which any foreign metal ions are exchanged for zinc ions and / or protons.
  • the device in which any foreign metal ions contained in the anolyte are exchanged can be, for example, a precipitation compartment or a cation exchanger.
  • the pH of the anolyte will be increased to a value at which the foreign metal ions possibly contained in the anolyte precipitate out as hydroxides.
  • the resulting precipitate can be separated off by means of sedimentation, filtration, centrifugation or the like, and the anolyte, depleted of any foreign metal ions, can then be returned to the cell space accommodating the anode.
  • the pH is adjusted to a corresponding acidic pH by addition of an acid. As a result, foreign metal ions are finally exchanged for protons.
  • the device in which any foreign metal ions contained in the anolyte are exchanged for other cations is a cation exchanger which, for example, has a suitable cation exchange resin.
  • the foreign metal ions can advantageously be exchanged for other cations without the addition of anions in the anolyte.
  • the foreign metal ions can preferably be exchanged for protons or zinc ions.
  • the cation-permeable membrane serves to retain a majority of the foreign metal ions contained in the deposition electrolyte, such as ions of the group consisting of nickel, cobalt, manganese or iron, although the membrane is essentially for these ions is also permeable.
  • the Applicant assumes that the voltage gradient of about 1 volt across the membrane is a barrier which is difficult to overcome for the foreign metal ions contained in the deposition electrolyte.
  • the foreign metal ions which nevertheless migrate into the anolyte are intercepted via the device to be provided according to the invention for exchanging the foreign metal ions and are preferably exchanged for zinc ions and / or protons.
  • the device serves not only to catch any foreign metal ions which may be present in the anolyte, but also to maintain a certain zinc ion level in the anolyte.
  • the anolyte has, in addition to zinc ions, an acid and / or alkali metal ions.
  • Suitable acids in the anolyte may be, for example, boric acid, acetic acid, citric acid, tartaric acid, aminoacetic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid and the like.
  • Suitable sources of zinc ions in the anolyte may be soluble zinc compounds such as zinc chloride, zinc sulfate or organic zinc compounds such as zinc methanesulfonate.
  • Suitable sources of alkali ions may be, for example, alkali salts such as sodium fluoride, sodium chloride, sodium bromide, lithium chloride, lithium fluoride, potassium chloride, potassium fluoride, potassium bromide and the like.
  • Suitable membranes for separating the cell spaces are according to the invention cation exchange membranes which are permeable to 2-valent cations, such as perfluorinated membrane. Furthermore, microporous membranes such as dialysis membranes are suitable for use in the galvanic bath according to the invention.
  • both this second anode and the zinc anode accommodated in the cell space accommodating the anolyte can be electrically connected to the substrate via a single rectifier.
  • the adjustment of the deposition ratio between zinc and the further metal to be deposited is carried out according to the invention by varying the anolyte composition.
  • the variation of the alkali metal concentration is decisive, since this has a significant influence on the conductivity of the anolyte and thus on its electrical resistance.
  • a plurality of separate cell spaces for receiving the anolyte may be provided in the galvanic bath, which are each equipped with a zinc anode.
  • the individual Anolyte dreams are hydraulically connected to each other, so that an exchange of the anolyte between the individual Anolyt society is possible.
  • the anolyte is withdrawn in a first anolyte space, fed to the device for exchanging any foreign metal ions contained in the anolyte, and returned from the latter to the anolyte space removed from the first anolyte space.
  • ion exchange resin for exchanging the foreign metal ions for zinc ions and / or protons.
  • Suitable cation exchangers are, for example, weakly acidic, macroporous resins with chelating lminodiacetic acid groups which selectively bind heavy metal cations.
  • the cation exchange resins are usually conditioned and loaded with zinc ions by means of a zinc ion-containing solution, such as, for example, a zinc chloride solution.
  • the cation exchange device When flowing through the anolyte by the cation exchange device then possibly containing in the anolyte Foreign metal ions are taken up by the cation exchange resin and exchanged for zinc ions.
  • the cation exchange device acts as a kind of zinc ion buffer, whereby the zinc ion level in the anolyte can be maintained at a desired level.
  • Fig. 1 shows an embodiment of a galvanic bath 1 according to the invention, in which a substrate 2 to be coated is arranged, wherein the galvanic bath 1 is divided by means of a cation exchange membrane 3 into a cell space 5 and a cell space 6, wherein the cell space 5 is a neutral or acidic anolyte and the Cell space 6 receives the deposition electrolyte.
  • a dissolving zinc anode 4 is arranged in the cell space 5.
  • a second anode 7 is provided in the cell space 6, which consists of the mitabzuscheidenden metal and is preferably also designed to dissolve.
  • the anode 4, and in the case of the co-deposition of other metals and the anode 7, are electrically connected via rectifier 8 to the substrate 2.
  • metal ions are now deposited on the substrate 2 from the deposition electrolyte.
  • zinc ions dissolve from the zinc electrode 4 and diffuse out of the cell space 5 through the cation exchange membrane 3 into the cell space 6. This results in a constant level of zinc in the cell space 6.
  • At the cation exchange membrane 3 is formed 1 volts, whereby further foreign metal ions contained in the deposition electrolyte, such as nickel, cobalt, manganese or iron ions, are substantially prevented from passing through the cation exchange membrane 3 into the cell space 5.
  • the anolyte contained in the cell space 5 is at least partially removed from the cell space 5 by means of suitable conveying devices such as a pump 11 and passed through a cation exchanger 9 before being returned to the cell space 5 becomes.
  • the cation exchange device 9 is filled with a cation exchange resin 10 which has been charged with zinc ions in an upstream conditioning step. The foreign ions contained in the anolyte are now absorbed in the cation exchange device 9 on the cation exchange resin 10 and exchanged for zinc ions.
  • Fig. 2 shows an embodiment of the galvanic bath 1 according to the invention, in which in addition to the cell space 6, a second cell space 12 is separated by a cation exchange membrane 13 from the cell space 5.
  • Cell space 12 in this case takes on a further anolyte, such as a manganese-containing anolyte and a foreign metal anode 7, which may be formed, for example, recorded in a titanium basket Elektrolytmangan.
  • the anolyte in cell space 12 has a manganese ion source such as manganese (II) sulfate and is by means of suitable acids such. As sulfuric acid, adjusted to a pH ⁇ 2.
  • manganese ions are released through the cation exchange membrane 13 to the deposition electrolyte under current flow.
  • Example 1 Deposition of a zinc-nickel layer
  • a deposition electrolyte is presented which 40-100 g / l zinc chloride,
  • an anolyte containing 120 g / l of zinc chloride, 215 g / l of potassium chloride and 20 g / l of boric acid is charged.
  • the concentration of the anolyte-containing components can be varied in a range between 80 g / l and 500 g / l for zinc chloride, 150 g / l to 300 g / l for potassium chloride and 15 g / l to 25 g / l for boric acid , whereby the deposition ratio between zinc and nickel on the substrate surface can be influenced.
  • a dissolving zinc anode is arranged, whereas in the cell space 6 a dissolving nickel anode is arranged.
  • a substrate to be coated screws are filled in a galvanizing drum, wherein the cathodic contacting takes place via centrally arranged contact pins.
  • a temperature of the deposition electrolyte of 25 ° C to 50 ° C and a pH of pH 5 to pH 6 for the deposition electrolyte is at a cathodic current density of 0.1 to 1.5 A / dm 2, a zinc nickel layer with a Deposition speed deposited to about 0.4 microns per minute on the screws serving as a substrate.
  • Example 2 Deposition of a zinc-nickel layer
  • a deposition electrolyte which 40-100 g / l zinc chloride, 60-130 g / l nickel chloride hexahydrate, 140-220 g / l potassium chloride, 10-30 g / l boric acid, 25 g / l sodium acetate trihydrate, 30 g / l aminoacetic acid, 2-12 g / l sodium saccharin, 0.025-0.20 g / l benzalacetone, 0.006-0.01 g / l orthochlorobenzaldehyde, 0.8-1.2 g / l octanol ethoxylate and 2.5-3.2 g / l potassium salt of the sulfopropylated polyalkoxylated naphthol.
  • the pH of the electrolyte composition described herein is between 5 and 6.
  • an anolyte containing 120 g / l of zinc chloride, 215 g / l of potassium chloride and 20 g / l of boric acid is charged.
  • the concentration of the anolyte-containing components can be varied in a range between 80 g / l and 500 g / l for zinc chloride, 150 g / l to 300 g / l for potassium chloride and 15 g / l to 25 g / l for boric acid , whereby the deposition ratio between zinc and nickel on the substrate surface can be influenced.
  • dissolving zinc pellets are arranged in an anode basket made of titanium, whereas in the cell space 6 a dissolving nickel anode is arranged.
  • the substrate to be coated castings are attached to largely insulated racks, wherein the cathodic contacting takes place via the metallic tips of the frame.
  • a temperature of the deposition electrolyte of 25 ° C to 50 ° C and a pH of pH 5 to pH 6 for the deposition electrolyte is at a cathodic current density of 0.1 to 4 A / dm 2, a zinc nickel layer with a deposition rate to deposited at 1 micron per minute on the casting used as a substrate.
  • Example 3 Deposition of a zinc-cobalt layer
  • a deposition electrolyte which 60-70 g / l zinc chloride, 100 - 130 g / l cobalt chloride hexahydrate, 190 - 220 g / l potassium chloride, 15 - 20 g / l boric acid, 25 g / l sodium acetate trihydrate, 30 g / l aminoacetic acid, 2-12 g / l sodium saccharin, 0.025-0.20 g / l benzalacetone, 0.006-0.01 g / l orthochlorobenzaldehyde and 2.5-3.2 g / l potassium salt of the sulfopropylated polyalkoxylated Naphtols contains.
  • the pH of the electrolyte composition described herein is between 5 and 6.
  • anolyte which consists of 250 g / l zinc chloride.
  • concentration of the zinc chloride contained in the anolyte can vary in a range between 80 g / l and 500 g / l zinc chloride.
  • dissolving zinc pellets are arranged in a titanium anode basket, whereas in the cell space 6 a dissolving cobalt anode is arranged.
  • a substrate to be coated screws are filled in a galvanizing drum, wherein the cathodic contact via contact pins.
  • a temperature of the deposition electrolyte of 25 ° C to 50 ° C and a pH of pH 5.3 to pH 5.6 for the deposition electrolyte is at a cathodic current density of 0.2 to 4 A / dm 2, a zinc Cobalt layer deposited with a deposition rate of up to about 1 micron per minute on the serving as a substrate screws.
  • Example 4 Deposition of a bright zinc coating
  • a deposition electrolyte is presented, which 40-90 g / l zinc chloride, 180 - 230 g / l potassium chloride, 20 - 30 g / l boric acid, 0.025 - 0.20 g / l benzalacetone, 0 , 8-1.2 g / l octanol ethoxylate and 2.5-3.2 g / l potassium salt of the sulfopropylated polyalkoxylated naphtol.
  • the pH of the electrolyte composition described herein is between 5 and 6.
  • anolyte which consists of 250 g / l zinc chloride and 220 g / l potassium chloride.
  • concentration of the zinc chloride contained in the anolyte can vary in a range between 80 g / l and 500 g / l zinc chloride.
  • Potassium chloride can be used in a concentration of 10 to 300 g / l.
  • dissolving zinc pellets are arranged in a titanium anode basket.
  • As a substrate to be coated screws are filled in a galvanizing drum, wherein the cathodic contact via contact pins.
  • a temperature of the deposition electrolyte of 25 ° C to 50 ° C and a pH of pH 5.3 to pH 5.6 for the deposition electrolyte is at a cathodic current density of 0.1 to 2 A / dm 2, a zinc layer deposited at a deposition rate of up to about 0.5 microns per minute on the serving as a substrate screws.
  • Example 5 Deposition of a zinc-manganese layer
  • a deposition electrolyte is presented, which 40-62 g / l divalent zinc, 80-110 g / l of divalent manganese, 190-220 g / l of a conductive salt, 30 -100 g / l of a Buffer, 10 -15 g / l of a wetting agent, 0.1-0.6 g / l of a defoamer, 0-10 g / l of an antioxidant and 0-1 g / l of a brightener.
  • anolyte which consists of 250 g / l zinc chloride and 220 g / l potassium chloride.
  • concentration of the zinc chloride contained in the anolyte can vary in a range between 80 g / l and 500 g / l zinc chloride.
  • Potassium chloride can be used in a concentration of 10 to 300 g / l.
  • a dissolving zinc plate is arranged in the cell space 5.
  • an anolyte containing 150 g / l of manganese (II) sulfate and 30 g / l of sulfuric acid is contained in the third cell space 12, which has no connection to the cation exchange device 12 and which is separated from the cell space 6 by a cation exchange membrane 13, an anolyte containing 150 g / l of manganese (II) sulfate and 30 g / l of sulfuric acid is contained ,
  • concentration of the manganese (II) sulfate contained in this anolyte can vary within a range between 50 g / l to 250 g / l manganese (II) sulfate.
  • the initially used amount of sulfuric acid of 30 g / l is supplemented during operation so that the pH remains below pH 2.
  • broken electrolyte manganese is used in a titanium anode basket.
  • a substrate to be coated screws are filled in a galvanizing drum, wherein the cathodic contact via contact pins.
  • a temperature of the deposition electrolyte of 25 ° C to 50 ° C and a pH of pH 5 to pH 6 for the deposition electrolyte at a cathodic current density of 0.2 to 2 A / dm 2 a zinc layer with a deposition rate to About 0.5 microns per minute deposited on serving as a substrate screws.

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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)
  • Electrolytic Production Of Metals (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
EP09014111A 2008-11-11 2009-11-11 Bain galvanique et procédé pour la déposition de couches contenant du zinc Active EP2184384B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09014111T PL2184384T3 (pl) 2008-11-11 2009-11-11 Wanna galwaniczna i sposób osadzania warstw zawierających cynk

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102008056776A DE102008056776A1 (de) 2008-11-11 2008-11-11 Galvanisches Bad und Verfahren zur Abscheidung von zinkhaltigen Schichten

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EP2184384A1 true EP2184384A1 (fr) 2010-05-12
EP2184384B1 EP2184384B1 (fr) 2012-06-06

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EP (1) EP2184384B1 (fr)
DE (1) DE102008056776A1 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3358045A1 (fr) * 2017-02-07 2018-08-08 Dr.Ing. Max Schlötter GmbH & Co. KG Procédé de dépôt par placage de revêtements en zinc et en alliage de zinc à partir d'un bain de revêtement alcalin à élimination réduite des additifs de bain organiques
CN110684997A (zh) * 2019-10-10 2020-01-14 广州三孚新材料科技股份有限公司 镀锌电镀液及其制备方法

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Publication number Priority date Publication date Assignee Title
US9899695B2 (en) 2015-05-22 2018-02-20 General Electric Company Zinc-based electrolyte compositions, and related electrochemical processes and articles
PL3461933T3 (pl) * 2017-09-28 2020-03-31 Atotech Deutschland Gmbh Sposób elektrolitycznego osadzania warstwy stopu cynkowo-niklowego co najmniej na podłożu przeznaczonym do obróbki
JP6750186B1 (ja) * 2019-11-28 2020-09-02 ユケン工業株式会社 めっき液の亜鉛濃度の上昇を抑制する方法および亜鉛系めっき部材の製造方法

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EP1717353A1 (fr) 2005-04-26 2006-11-02 ATOTECH Deutschland GmbH Bain galvanique contenant une membrane de filtration
EP1726683A1 (fr) 2005-05-25 2006-11-29 Enthone Inc. Procédé et appareil pour ajuster la concentration d'ions d'un électrolyte

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DE19538419A1 (de) 1994-10-25 1996-05-02 Enthone Omi Inc Alkalische Zink- und Zinklegierungs-Galvanisierbäder und Verfahren
DE10146559A1 (de) 2001-09-21 2003-04-10 Enthone Omi Deutschland Gmbh Verfahren zur Abscheidung einer Zink-Nickel-Legierung aus einem Elektrolyten
DE10306823A1 (de) 2003-02-19 2004-09-02 Enthone Inc., West Haven Verfahren zur Hochgeschwindigkeitsabscheidung von Zink-Mangan-Legierungen
DE10322120A1 (de) 2003-05-12 2004-12-09 Blasberg Werra Chemie Gmbh Verfahren und Vorrichtungen zur Verlängerung der Nutzungsdauer einer Prozesslösung für die chemisch-reduktive Metallbeschichtung
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EP1717353A1 (fr) 2005-04-26 2006-11-02 ATOTECH Deutschland GmbH Bain galvanique contenant une membrane de filtration
EP1726683A1 (fr) 2005-05-25 2006-11-29 Enthone Inc. Procédé et appareil pour ajuster la concentration d'ions d'un électrolyte

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3358045A1 (fr) * 2017-02-07 2018-08-08 Dr.Ing. Max Schlötter GmbH & Co. KG Procédé de dépôt par placage de revêtements en zinc et en alliage de zinc à partir d'un bain de revêtement alcalin à élimination réduite des additifs de bain organiques
WO2018146041A1 (fr) * 2017-02-07 2018-08-16 Dr.-Ing. Max Schlötter Gmbh & Co. Kg Procédé pour le dépôt électrolytique de revêtements de zinc et d'alliage de zinc à partir d'un bain de revêtement alcalin, avec dégradation réduite des additifs organiques du bain
CN110325669A (zh) * 2017-02-07 2019-10-11 马克斯·施洛特尔股份有限两合公司 由有机浴添加剂的降解减少的碱性镀浴电沉积锌和锌合金涂层的方法
JP2019530800A (ja) * 2017-02-07 2019-10-24 デーエル．−イーエヌゲー． エムアーイクス シュロッター ゲーエムベーハー ウント コー． カーゲー 有機浴添加物の分解が低減されたアルカリ性コーティング浴から亜鉛及び亜鉛合金被膜をガルバニック堆積するための方法
US11339492B2 (en) 2017-02-07 2022-05-24 Dr.-Ing. Max Schlötter Gmbh & Co. Kg Method for electrodepositing zinc and zinc alloy coatings from an alkaline coating bath with reduced depletion of organic bath additives
CN110684997A (zh) * 2019-10-10 2020-01-14 广州三孚新材料科技股份有限公司 镀锌电镀液及其制备方法

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US8282806B2 (en) 2012-10-09
PL2184384T3 (pl) 2012-11-30
DE102008056776A1 (de) 2010-05-12
EP2184384B1 (fr) 2012-06-06
US20100116677A1 (en) 2010-05-13

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