EP2103717A1 - Bain à base de pyrophosphate destiné à la déposition de couches d'alliage d'étain - Google Patents

Bain à base de pyrophosphate destiné à la déposition de couches d'alliage d'étain Download PDF

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Publication number
EP2103717A1
EP2103717A1 EP08003786A EP08003786A EP2103717A1 EP 2103717 A1 EP2103717 A1 EP 2103717A1 EP 08003786 A EP08003786 A EP 08003786A EP 08003786 A EP08003786 A EP 08003786A EP 2103717 A1 EP2103717 A1 EP 2103717A1
Authority
EP
European Patent Office
Prior art keywords
carbamoyl
pyridinium chloride
pyrophosphate
benzyl
aqueous cyanide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08003786A
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German (de)
English (en)
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EP2103717B1 (fr
Inventor
Philip Hartmann
Lars Kohlmann
Heiko Brunner
Klaus Dieter Schulz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to PT08003786T priority Critical patent/PT2103717E/pt
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to PL08003786T priority patent/PL2103717T3/pl
Priority to AT08003786T priority patent/ATE465283T1/de
Priority to EP08003786A priority patent/EP2103717B1/fr
Priority to ES08003786T priority patent/ES2340973T3/es
Priority to DE502008000573T priority patent/DE502008000573D1/de
Priority to JP2010547984A priority patent/JP5688841B2/ja
Priority to KR1020107018440A priority patent/KR101540615B1/ko
Priority to BRPI0907497-0A priority patent/BRPI0907497A2/pt
Priority to CA2716115A priority patent/CA2716115A1/fr
Priority to US12/864,180 priority patent/US8647491B2/en
Priority to CN2009801015016A priority patent/CN101918618B/zh
Priority to PCT/EP2009/000802 priority patent/WO2009109271A2/fr
Priority to TW098104123A priority patent/TWI439580B/zh
Publication of EP2103717A1 publication Critical patent/EP2103717A1/fr
Application granted granted Critical
Publication of EP2103717B1 publication Critical patent/EP2103717B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

Definitions

  • the present invention relates to an aqueous cyanide-free bath and a process for the cyanide-free deposition of tin alloys, in particular tin-copper alloys containing N-methylpyrrolidone as organic brightener.
  • the invention enables the cyanide-free deposition of homogeneous, shiny tin alloy layers, in particular tin-copper alloy layers, the alloy ratio of which can be selectively adjusted depending on the metal salt ratio used within the electrolyte.
  • Tin alloys and especially copper-tin alloys, have come into focus as an alternative to nickel deposits. Electrodeposited nickel layers are commonly used for both decorative and functional applications.
  • nickel layers are problematic due to their sensitizing properties, especially in the case of direct skin contact. For this reason, alternatives are of the highest interest.
  • Cyanide-containing copper-tin alloy baths are industrially established. Due to stricter regulations and the high toxicity and problematic and expensive disposal of these cyanide-containing baths, there is a growing demand for cyanide-free copper-tin electrolytes.
  • JP 10-102278 A a pyrophosphate-based copper-tin alloy bath which contains as an additive a reaction product of an amine and an epihalodrin derivative (molar ratio 1: 1), an aldehyde derivative and, optionally, depending on the application, surfactants.
  • the US 6416571 B1 also describes a pyrophosphate-based bath which also contains as additives a reaction product of an amine and an epihalohydrin derivative (molar ratio 1: 1), a cationic surfactant, optionally further surface-active surfactants and an antioxidant.
  • a disadvantage of the abovementioned baths is that no uniform alloy layers are obtained, especially in the case of drum galvanizations, so that the products do not have a uniform coloring and gloss.
  • a pyrophosphate-containing copper-tin alloy bath containing as an additive a reaction product of an amine derivative, more preferably piperazine, an epihalohydrin derivative, especially epichlorohydrin, and a glycidyl ether.
  • an amine derivative more preferably piperazine
  • an epihalohydrin derivative especially epichlorohydrin
  • a glycidyl ether for the preparation of this reaction product, a mixture consisting of epichlorohydrin and the glycidyl ether is added slowly under precise temperature control to an aqueous solution of piperazine, wherein the temperature from 65 to 80 ° C must be maintained.
  • a disadvantage of this additive is the difficult to control reaction, especially at high temperatures, since such reaction products tend at too high reaction and / or storage temperatures for post-reaction and thus formation of high molecular weight and thus partially water-insoluble and ineffective polymers.
  • a way out of this dilemma can be achieved only by a reaction in very high dilution ( ⁇ 1 wt .-%). It comes with such low concentration additive solutions with repeated replenishment to an adverse solution buildup of the electrolyte. This can lead to fluctuating deposits with longer use of electrolyte.
  • this electrolyte exhibits weaknesses in rack plating applications.
  • the quality of the deposited layers which often show a haze, very much depends on the nature of the movement of goods during the electrolysis.
  • the copper-tin coatings obtained in this way also often have pores, which is problematic especially in decorative coatings.
  • the invention is therefore based on the object to develop a galvanic bath for tin alloys, which allows the production of optically attractive tin alloy layers.
  • a more homogeneous tin-alloy metal distribution and an optimal tin-metal ratio should be set.
  • a uniform layer thickness with high gloss and the uniformity of the distribution of the alloy components in the coating should be maintained over a wide current density range.
  • the electrolytic bath according to the invention may further comprise an acid (iii) and / or a pyrophosphate source (iv).
  • the component (iii) of the aqueous cyanide-free electrolyte bath according to the invention is any acid which can be used in known electrolyte baths.
  • they are organic sulfonic acids, orthophosphoric acid, sulfuric acid and boric acid.
  • the aqueous cyanide-free electrolyte bath according to the invention preferably also contains additives which are selected from antioxidants and / or further organic brighteners.
  • Preferred organic brighteners here are morpholine, 2-morpholineethanesulfonic acid, hexamethylenetetramine, 3- (4-morpholino) -1,2-propanediol, 1,4-diazabicyclo [2.2.2] octane, 1-benzyl-3-carbamoyl-pyridinium chloride , 1- (2'-Chloro-benzyl) -3-carbamoyl-pyridinium chloride, 1- (2'-fluoro-benzyl) -3-carbamoyl-pyridinium chloride, 1- (2'-methoxy-benzyl) - 3-carbamoyl-pyridinium chloride, 1- (2'-carboxy-benzyl) -3-carbamoyl-pyridinium chloride, 1- (2'-carbamoyl-benzyl) -3-carbamoyl-pyridinium chloride, 1- (3 'Chloro-benzy
  • the additives according to the invention can be used with N-methylpyrrolidone alone or as a mixture of a plurality of different brightener systems of the abovementioned representatives in a concentration of 0.0001 to 20 g / l and more preferably of 0.001 to 1 g / l.
  • the tin ion source and the source of another alloying element may be pyrophosphates.
  • the tin ion source and the source of another alloying element are also pyrophosphate sources within the meaning of the aforementioned component (iv) of the electrolytic bath according to the invention.
  • the pyrophosphate concentration of the source for another alloying element is 0.5 to 50 g / l, and preferably 1 to 5 g / l.
  • the bath according to the invention may contain copper pyrophosphate in an amount of 0.5 to 50 g / l, preferably 1 to 5 g / l or zinc pyrophosphate in these amounts.
  • the concentration is generally 0.5 to 100 g / l, with concentrations of 10 to 40 g / l being particularly preferred.
  • tin and metal pyrophosphates In addition to the above-mentioned tin and metal pyrophosphates, other water-soluble tin and metal salts, such as tin sulfate, tin methanesulfonate, copper sulfate, copper methanesulfonate, or the corresponding Zinc salts are used, which can be umkomplexiert by the addition of suitable alkali metal pyrophosphates within the electrolyte into the corresponding pyrophosphates.
  • the concentration ratio of pyrophosphate to tin / metal should be 3 to 80, more preferably 5 to 50.
  • Pyrophosphate sources according to component (iv) are particularly preferably the sodium, potassium and ammonium pyrophosphates in concentrations of 50 to 500 g / l, more preferably from 100 to 400 g / l.
  • the aforementioned antioxidants include hydroxylated aromatic compounds, e.g. Catechol, resorcinol, pyrocatechol, hydroquinone, pyrogallol, ⁇ - or ⁇ -naphthol, phloroglucin and sugar-based systems such as e.g. Ascorbic acid, sorbitol in concentrations of 0.1 to 1 g / l.
  • hydroxylated aromatic compounds e.g. Catechol, resorcinol, pyrocatechol, hydroquinone, pyrogallol, ⁇ - or ⁇ -naphthol, phloroglucin
  • sugar-based systems such as e.g. Ascorbic acid, sorbitol in concentrations of 0.1 to 1 g / l.
  • organic sulfonic acids both mono- and polyalkylsulfonic acids, e.g. Methanesulfonic acid, methanedisulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2-propanesulfonic acid, butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid and salts thereof and their hydroxylated derivatives are used. Particularly preferred is the use of methanesulfonic acid in a concentration of 0.01 to 1 g / l.
  • the baths according to the invention have a pH of 3 to 9, more preferably 6 to 8.
  • N-methylpyrrolidone a significant improvement in the deposited layers can be achieved with regard to gloss and freedom from pores, preferably in a concentration of 0.1 to 50 g / l, more preferably 0.1 to 4 g / l.
  • the baths according to the invention can be prepared by conventional methods, for example by adding the specific amounts of the above-described components to water.
  • the amount of bases, acids and acids Buffer components such as sodium pyrophosphate, methanesulfonic acid and / or boric acid should preferably be chosen so that the bath reaches the pH range of at least 6 to 8.
  • the baths according to the invention deposit a bright, even and ductile copper-tin alloy layer at any customary temperature of about 15 to 50 ° C, preferably 20 ° C to 40 ° C, more preferably 25 ° C to 30 ° C from. At these temperatures, the baths according to the invention are stable and effective over a wide current density range of 0.01 to 2 A / dm 2 , more preferably 0.25 to 0.75 A / dm 2 .
  • the baths of the invention may be operated in a continuous or intermittent manner, and from time to time the components of the bath will have to be supplemented.
  • the components of the bath may be added singly or in combination. Furthermore, they can be varied over a wide range, depending on the consumption and present concentration of the individual components.
  • An advantage of the baths according to the invention compared to the electrolyte of WO 2004/005528 is the good reproducibility and long-term stability of the formulations according to the invention in comparison to the reaction products of piperazine with epichlorohydrin and glycidyl ether.
  • the aqueous baths according to the invention can generally be used for all types of substrates on which tin alloys can be deposited.
  • substrates on which tin alloys can be deposited.
  • useful substrates include copper-zinc alloys, chemically copper or chemically nickel-coated ABS plastic surfaces, mild steel, stainless steel, spring steel, chrome steel, chromium-molybdenum steel, copper and tin.
  • Another object is therefore a process for the electrodeposition of copper-tin alloys on conventional substrates, wherein the inventive Bath is used.
  • the substrate to be coated is introduced into the electrolyte bath.
  • the deposition of the coatings at a current density of 0.25 to 0.75 A / dm 2 and at a temperature of 15 to 50 ° C, preferably 25 to 30 ° C.
  • the method according to the invention can be carried out in the application for mass parts, for example as a drum electroplating method and for depositing on larger workpieces as a rack electroplating method.
  • anodes are used which may be soluble, such as copper anodes, tin anodes or suitable copper-tin alloy anodes, which simultaneously serve as copper and / or tin ion source, so that the deposited on the cathode copper and / or tin by dissolution is substituted by copper and / or tin at the anode.
  • insoluble anodes e.g., platinized titanium mixed oxide anodes
  • the copper and tin ions withdrawn from the electrolyte must be re-added in some other way, e.g. by addition of the corresponding soluble metal salts.
  • galvanic deposition it is also possible to operate the process according to the invention under nitrogen or argon injection, with goods movement or without movement, without resulting in any disadvantages for the coatings obtained.
  • the tin (II) ions can be used with the separation of the electrode spaces or with the use of membrane anodes, whereby a significant stabilization of the electrolyte can be achieved.
  • the current source used are commercial DC converters or pulse rectifiers.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.1 g / l 1- (pentafluorobenzyl) -3-carbamoyl pyridinium chloride
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 20 ml / l N-methylpyrrolidone 0.06 g / l 1-benzyl-3-acetyl-pyridinium chloride
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high glossy, light veil deposit in the low current density range was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.03 g / l 1- (4-methoxy-benzyl) -3-carbamoyl pyridinium chloride
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A brilliant deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.03 g / l 1,1 '- (xylenyl) -3', 3-bis-carbamoyl-bis-pyridinium dichloride
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1 A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.12 g / l 1- (4'-Carboxy-benzyl) -3-carbamoyl pyridinium chloride
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 3 ml / l 1- (Benzyl) -3-carbamoylpyridinium chloride 35% solution
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 3 g / l morpholine
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 5 g / l 2-morpholino-ethane sulfonic acid
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 3 g / l 3- (4-morpholino) -1,2-propanediol
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.

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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)
  • Chemically Coating (AREA)
  • Physical Vapour Deposition (AREA)
  • Coating With Molten Metal (AREA)
EP08003786A 2008-02-29 2008-02-29 Bain à base de pyrophosphate destiné à la déposition de couches d'alliage d'étain Not-in-force EP2103717B1 (fr)

Priority Applications (14)

Application Number Priority Date Filing Date Title
PL08003786T PL2103717T3 (pl) 2008-02-29 2008-02-29 Kąpiel oparta na pirofosforanach do nakładania warstw stopów cyny
AT08003786T ATE465283T1 (de) 2008-02-29 2008-02-29 Pyrophosphat-basiertes bad zur abscheidung von zinn-legierungsschichten
EP08003786A EP2103717B1 (fr) 2008-02-29 2008-02-29 Bain à base de pyrophosphate destiné à la déposition de couches d'alliage d'étain
ES08003786T ES2340973T3 (es) 2008-02-29 2008-02-29 Baño basado en pirofosfato para la deposicion de capas de aleaciones de estaño.
DE502008000573T DE502008000573D1 (de) 2008-02-29 2008-02-29 Pyrophosphat-basiertes Bad zur Abscheidung von Zinn-Legierungsschichten
PT08003786T PT2103717E (pt) 2008-02-29 2008-02-29 Banho com base em pirofosfato para deposição de camadas de ligas de estanho
KR1020107018440A KR101540615B1 (ko) 2008-02-29 2009-02-05 주석 합금층의 도금을 위한 피로인산염계 전해조
BRPI0907497-0A BRPI0907497A2 (pt) 2008-02-29 2009-02-05 Banho baseado em pirofosfatos para revestimento de camadas de ligas de estanho
JP2010547984A JP5688841B2 (ja) 2008-02-29 2009-02-05 スズ合金層のメッキのためのピロリン酸系浴
CA2716115A CA2716115A1 (fr) 2008-02-29 2009-02-05 Bain a base de pyrophosphate pour le plaquage de couches d'alliage d'etain
US12/864,180 US8647491B2 (en) 2008-02-29 2009-02-05 Pyrophosphate-based bath for plating of tin alloy layers
CN2009801015016A CN101918618B (zh) 2008-02-29 2009-02-05 用于电镀锡合金层的焦磷酸盐基镀液
PCT/EP2009/000802 WO2009109271A2 (fr) 2008-02-29 2009-02-05 Bain à base de pyrophosphate pour le plaquage de couches d’alliage d’étain
TW098104123A TWI439580B (zh) 2008-02-29 2009-02-10 用於電鍍錫合金層之焦磷酸鹽基浴

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP08003786A EP2103717B1 (fr) 2008-02-29 2008-02-29 Bain à base de pyrophosphate destiné à la déposition de couches d'alliage d'étain

Publications (2)

Publication Number Publication Date
EP2103717A1 true EP2103717A1 (fr) 2009-09-23
EP2103717B1 EP2103717B1 (fr) 2010-04-21

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP08003786A Not-in-force EP2103717B1 (fr) 2008-02-29 2008-02-29 Bain à base de pyrophosphate destiné à la déposition de couches d'alliage d'étain

Country Status (14)

Country Link
US (1) US8647491B2 (fr)
EP (1) EP2103717B1 (fr)
JP (1) JP5688841B2 (fr)
KR (1) KR101540615B1 (fr)
CN (1) CN101918618B (fr)
AT (1) ATE465283T1 (fr)
BR (1) BRPI0907497A2 (fr)
CA (1) CA2716115A1 (fr)
DE (1) DE502008000573D1 (fr)
ES (1) ES2340973T3 (fr)
PL (1) PL2103717T3 (fr)
PT (1) PT2103717E (fr)
TW (1) TWI439580B (fr)
WO (1) WO2009109271A2 (fr)

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DE102011121799B4 (de) 2011-12-21 2013-08-29 Umicore Galvanotechnik Gmbh Elektrolyt und Verfahren zur elektrolytischen Abscheidung von Cu-Zn-Sn-Legierungsschichten und Verfahren zur Herstellung einer Dünnschichtsolarzelle
DE102011121798B4 (de) 2011-12-21 2013-08-29 Umicore Galvanotechnik Gmbh Elektrolyt und Verfahren zur elektrolytischen Abscheidung von Cu-Zn-Sn-Legierungsschichten und Verfahren zur Herstellung einer Dünnschichtsolarzelle
CN103849912A (zh) * 2012-11-29 2014-06-11 沈阳工业大学 一种电镀光亮锡锌镍合金工艺
CN103132113B (zh) * 2013-03-08 2015-08-12 大连理工大学 一种弱碱性锡基无铅钎料复合镀液及其应用
EP2801640A1 (fr) * 2013-05-08 2014-11-12 ATOTECH Deutschland GmbH Bain électrolytique de nickel galvanique ou d'alliage de nickel pour déposer un alliage de nickel ou de nickel mi-lustré
CN103668402B (zh) * 2013-10-08 2016-06-08 常州大学 一种纳米复合高锡铜合金电镀材料的制备方法
AR100422A1 (es) * 2014-05-15 2016-10-05 Nippon Steel & Sumitomo Metal Corp Solución para deposición para conexión roscada para un caño o tubo y método de producción de la conexión roscada para un caño o tubo
CN104152955A (zh) * 2014-07-17 2014-11-19 广东致卓精密金属科技有限公司 碱性溶液电镀光亮白铜锡电镀液及工艺
JP6621169B2 (ja) * 2015-04-28 2019-12-18 オーエム産業株式会社 めっき品の製造方法
WO2017199835A1 (fr) * 2016-05-18 2017-11-23 日本高純度化学株式会社 Solution de placage électrolytique de nickel (d'alliage)
CN114351232A (zh) * 2022-01-14 2022-04-15 张家港扬子江冷轧板有限公司 一种电镀锡预电镀漂洗水循环系统及循环方法

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KR101540615B1 (ko) 2015-07-30
EP2103717B1 (fr) 2010-04-21
BRPI0907497A2 (pt) 2015-07-14
JP2011513585A (ja) 2011-04-28
PL2103717T3 (pl) 2010-07-30
US20100300890A1 (en) 2010-12-02
ATE465283T1 (de) 2010-05-15
US8647491B2 (en) 2014-02-11
KR20100120160A (ko) 2010-11-12
JP5688841B2 (ja) 2015-03-25
CN101918618B (zh) 2012-02-22
TW200949021A (en) 2009-12-01
DE502008000573D1 (de) 2010-06-02
CN101918618A (zh) 2010-12-15
ES2340973T3 (es) 2010-06-11
CA2716115A1 (fr) 2009-09-11
PT2103717E (pt) 2010-06-14
WO2009109271A2 (fr) 2009-09-11
TWI439580B (zh) 2014-06-01
WO2009109271A3 (fr) 2010-02-25

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