EP1831435B1 - Verfahren für den kontinuierlichen betrieb von sauren oder alkalischen zink- oder zinklegierungsbädern - Google Patents
Verfahren für den kontinuierlichen betrieb von sauren oder alkalischen zink- oder zinklegierungsbädern Download PDFInfo
- Publication number
- EP1831435B1 EP1831435B1 EP05808579A EP05808579A EP1831435B1 EP 1831435 B1 EP1831435 B1 EP 1831435B1 EP 05808579 A EP05808579 A EP 05808579A EP 05808579 A EP05808579 A EP 05808579A EP 1831435 B1 EP1831435 B1 EP 1831435B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- phase
- bath
- separation
- zinc alloy
- 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.)
- Revoked
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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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
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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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
-
- 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
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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
-
- 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 invention relates to a method for the deposition of functional layers of acidic or alkaline zinc or zinc alloy baths, the organic additives selected from brighteners, wetting agents and complexing agents, a soluble zinc salt and optionally other metal salts selected from Fe, Ni, Co, Sn salts in which the bath can be continuously cleaned so that the process can be operated without interruption.
- a weakly acidic zinc bath therefore contains about 10-20 g / l of organic compounds, corresponding to a content of organically bound carbon (total organic carbon, TOC) of approx. 5-10 g / l.
- Losses of organic active substances occurring during production due to degradation processes and removal are to be compensated for by continuous replenishment.
- a charge throughput of 10 kAh 0.5 to 1.5 kg of organic compounds are metered in.
- the degree of determination of the organic impurities is the determination of the cloud point. Desired is a cloud point at the highest possible temperature, since above the temperature of the cloud point no satisfactory coating more.
- Bath dilution reduces the concentration of impurities in proportion to the degree of dilution.
- a dilution is easy to carry out, but has the disadvantage that the amount of electrolyte removed from the bath has to be supplied to cost-intensive disposal.
- a complete new approach of the bath can be considered in this context as a special case of Badver Mednung.
- Activated carbon treatment by stirring 0.5-2 g / l of activated carbon into the bath followed by filtration reduces the concentration of impurities by adsorption on the coal. Disadvantage of this method is that it is laborious is, causes only a relatively small reduction and removed a large part of the gloss-forming bath additives with.
- Alkaline Zn baths contain a factor of 5 to 10 lower proportion of organic additives as acidic baths. Accordingly, contamination by decomposition products is generally less critical. In the case of alkaline alloy baths, however, the addition of significant amounts of organic complexing agents is required to complex the alloying additive (Fe, Co, Ni, Sn). These are oxidatively degraded at the anode and the accumulated decomposition products have a negative effect on the production process.
- the EP 1 369 505 A2 discloses a method for purifying a zinc-nickel electrolyte in a galvanic process in which a portion of the process bath used in the process is evaporated until phase separation into a lower phase, at least one middle phase and an upper phase occurs, and the lower one and the upper phase are separated. This process requires several stages and is disadvantageous in terms of its energy requirements from a cost point of view.
- the DE 198 34 353 describes a galvanic bath for applying zinc-nickel coatings. To avoid the undesirable decomposition of additives at the anode, it is proposed to separate the anode from the alkaline electrolyte through an ion exchange membrane. However, the invention has the disadvantage that the use of such membranes is cost-intensive and maintenance-prone.
- the invention has for its object to provide a method and an apparatus for performing this method, with or with the time and effort of the bathroom cleaning with permanent guarantee of constant good bath quality and minimal use of chemicals can be reduced.
- the invention further relates to an apparatus for carrying out this method, comprising a container (1) for receiving a zinc or zinc alloy bath, an associated mixing device (2) with a further metering device (7) for receiving an acidic or alkaline Solution or an alkaline solid is connected, at least one separator (3) and (3 ') for receiving the removed part of the zinc or zinc alloy bath, optionally means (6) for receiving the aqueous phase from the at least one separating device (3) and (3'), a container (8) for receiving the organic phase from the separating device (3), optionally a container (8 ') for receiving the solid phase from the separating device (3'), and for the recording required lines and optionally valves, the separation of the organic or enable solid phase.
- the at least one separating device (3) and (3 ') can have devices for stirring (4) and for temperature control (5).
- the order in which the organic and the solid phase are separated can be freely selected. Preferably, first the organic and then the solid phase is separated off.
- the mixing device (2) and the separating device (3) need not be spatially separated. It is possible first to mix the solution of the zinc and zinc alloy bath (1) and the solution from the metering device for receiving an acidic or alkaline solution or the basic solid (7) and then to separate the phases in the same container ,
- the separation of the organic phase in the device (3) and the inorganic phase in the device (3 ') can be carried out in one unit.
- the means for temperature control (5) must be heated to separate the organic phase and cooled to separate the solid phase.
- both the organic phase and the solid phase can be separated off first.
- a further separation unit 3 ' may expediently be used.
- the solid phase is separated. This is preferably done by cooling the solution, whereby the solubility of the ingredients is reduced so far that they crystallize and can be separated.
- Typical compounds which can be separated in this way from alkaline zinc and zinc alloy baths include carbonates, oxalates, sulfates and cyanides.
- the separation of toxic cyanides, which form by the anodic decomposition of nitrogen-containing compounds, for example from the complexing agents, is a desired positive effect of the method according to the invention.
- a preferred embodiment of the invention comprises a container (1) for receiving a zinc or zinc alloy bath, a mixing device (2) connected thereto via a pump (9) and having a metering device (7) for receiving an acidic or alkaline solution or an alkaline solid via a pump or chute (9), at least one separating device (3) and (3 ') for receiving the removed part of the zinc or zinc alloy bath, optionally a device (6) for receiving the aqueous phase the separating device (3) or (3 '), a container (8) for receiving the organic phase from the separating device (3), optionally a container (8') for receiving the solid phase from the separating device (3 ') and for the recording required lines and valves (11).
- the at least one separating device (3) and (3 ') and the mixing device (2) can have devices for stirring (4) and for temperature control (5).
- the separation of the organic and the solid phase can be carried out in the separation device (3) and (3 ') either simultaneously or in two steps one after the other.
- the solid phase can be separated by means of a crystallizer.
- a crystallizer Such systems for the separation of crystalline impurities from electroplating baths are known from the prior art and, for example, in US 5,376,256 described. Commercially, such a system is available from USFilter under the name CARBOLUX.
- the separation of organic and aqueous phase takes place by means of gravity.
- the device comprises a container (1) for receiving a zinc or zinc alloy bath, a mixing device (2) connected thereto via a pump (9), a separating device (3) connected to the mixing device (2) for receiving the removed one Part of the zinc or zinc alloy bath having a lower portion for separating the aqueous phase (3a) and a narrower upper portion for separating the organic phase (3b) and having an upper effluent for the organic phase (3c) and a lower effluent for the purified aqueous Phase (3d) is provided, optionally a further separation device (3 ') for separating the solid phase and a metering device (7) for receiving an acidic or alkaline solution or an alkaline solid, via a pump or chute (9) the mixing device (2) is connected, optionally a device (6) for receiving the aqueous phase from the separating device (3) or (3 ') and at least one
- the at least one separating device (3) and (3 ') and the mixing device (2) can have devices for stirring (4) and for temperature control (5).
- the separator (3) has means for temperature control (5), which preferably consists of a jacket which surrounds the separator (3a) and (3b) and contains as heat carrier, for example water or oil and the uniform heat distribution in the system and the preheating of removed portion of the zinc or Zinkleg réellesbad allows.
- the temperature is adjusted so that the density of the organic phase is smaller than the density of the aqueous phase.
- the densities of the phases are plotted as a function of the temperature. Shown are two intersecting curves, where the temperature to the right of the intersection represents the preferred temperature range.
- the temperature is selected so that the density difference between the two phases is at least 1 - 1.5%.
- the course of the two phases takes place by means of gravity.
- the level difference of the process (3d-3c) is set to greater than 5 mm, preferably 0.8 to 1.5 cm at a total height of the device (3a) / (3b) of 1.50 - 2.50 m.
- the solid constituents crystallize at the bottom of the separation vessel to receive the withdrawn portion of the zinc or zinc alloy bath (3) and can be separated there by suitable means as already described above.
- the method according to the invention makes use of the fact that a phase separation occurs by lowering the pH or increasing the hydroxide ion concentration. If, for example, the pH of the bath is lowered to a pH ⁇ 1 by the addition of concentrated hydrochloric acid, the anionic surfactants contained in the bath are protonated so that they lose their emulsifying action. This leads to phase separation, i. in a separation of the zinc or zinc alloy bath in an aqueous phase and an organic phase, which is also referred to as oil phase hereinafter.
- the organic or oil phase contains a majority of Badverungraphyen.
- the oil phase may comprise up to 10% of the bath volume.
- phase separation is achieved by addition of preferably solid sodium hydroxide, with a concentration greater than 200 g / l of sodium hydroxide being advantageous.
- the oil phase floats either on the aqueous phase and can be transferred from there from the separator (3) in the container (8), or it forms on the bottom of the separator (3) and then from there into the Pumped container (8).
- the aqueous phase is added to the bath to adjust the pH of the bath to the set point, bath additives lost with the oil phase are replenished, and it can be produced again with good quality.
- the aqueous phase can be stored in a container (6) and added to the bath as needed.
- the acidified bath is preferably adjusted to a temperature of 20-70 ° C, more preferably 20-50 ° C for accelerating the phase separation, said temperature range being merely preferred and not critical, i. the process can also be carried out at a temperature in the range of 5 to 90 ° C.
- phase separation can also be effected by increasing the hydroxide ion concentration of the bath.
- phase separation occurs, for example, when the sodium hydroxide content is raised to a level> 200 g / l.
- sodium hydroxide in an amount of 1-10 kg / 10 kAh in the container (7) presented.
- Solid sodium hydroxide can then be dissolved from the container (7) in the mixing device (2) in parts of the bath and pumped into the separation means (3) or (3 ') - there occurs a phase separation, wherein in the Usually a lower solid, mostly crystalline phase and a partially crystalline upper phase occur. The upper phase is then separated and transferred to the container (8).
- the bath may be cooled to a temperature in the range of -5 to 30 ° C, and preferably 0-8 ° C to remove unwanted inorganic components by crystallization. This is preferably done in the second separation device (3 '), but both devices can also be realized in a single unit.
- This crystalline precipitate can in turn be separated off in a container (8 ') and the remaining aqueous electrolyte phase can be supplied to the bath, optionally with heating.
- the aqueous phase is transferred into the container (6).
- the aqueous phase can be stored in a container (6) and added to the bath as needed.
- the oil phase formed in the separator (3) is discharged via appropriate lines and collected in a separate container (8) and disposed of.
- the crystalline phase formed in the separation device (3 ') is discharged via corresponding lines and collected and disposed of in a separate container (8').
- the lines are provided at the separation devices (3) and (3 ') so that both a settling at the bottom of the separation vessel as well as a floating phase on the aqueous phase can be separated. Expediently, devices for physical phase differentiation are provided.
- the method according to the invention can be automated by means of a controller with the aid of pH sensors, temperature sensors, fill level meters and the said devices for physical phase differentiation.
- the controller registers the level in the separating devices (3) and (3 ') and automatically actuates a pump as soon as it falls below a predetermined minimum value.
- the pump then transfers as long as a proportionate solution from the zinc or zinc alloy bath (1) until a predetermined maximum level is reached in the separation devices.
- the controller controls the optionally provided in the separators means for stirring (4) and the temperature control (5) of the removed part of the bath.
- the controller also ensures the metered addition of an acidic or alkaline solution or an alkaline solid from the metering device (7).
- the control unit switches off the stirring and temperature control devices, so that a phase separation is made possible.
- the regenerated phase is transferred to a device (6) which, for example (ie with a total bath volume of 20,000 l), can take up a solution amount of 200 l.
- the device may also be provided with level gauges and level control devices and is connected to the bath (1).
- bath solution (1) which has been regenerated from the device (6) is introduced into the bath (1) to correct the pH or the hydroxide ion concentration is transferred. While the process of the present invention has been described above essentially with reference to the use of an acid for phase separation, it may also be carried out using bases such as, preferably, alkali or alkaline earth hydroxides, and especially sodium hydroxide, as mentioned.
- a significant advantage of the method according to the invention is that the production process does not have to be interrupted for cleaning or replacement of the bath. Impurities can be removed continuously or discontinuously and any required bath components can be added.
- phase separation is achieved by the addition of an acid or base, which would have to be added to the zinc or zinc alloy bath anyway due to process control.
- a bath sample of a weakly acid zinc bath with a TOC content of 30.2 g / l and 2.6 ml / l brightener and 35.8 ml / l additional solution was lowered to pH ⁇ 1 with 20 ml / l hydrochloric acid (37%).
- a device according to FIG. 2 with a separation unit (3) and a container (6) for receiving the aqueous phase from the separation tank (3) used. A slow separation of two phases was observed. Within 24 h, 25 ml / l of a dark brown, viscous phase settled on the bottom of the vessel.
- the clear supernatant solution contained, after analysis, 21.5 g / l TOC, 1.5 ml / l brightener, and 26.4 ml / l adjuvant.
- Testing by Hull cell after adjusting the pH to the working range (pH 5) showed a predominantly shiny sheet, but with burns in the high current density range.
- the cloud point of the bath before treatment was 50 ° C, after treatment and adjustment at 75 ° C.
- a bath sample with a TOC content of 30.2 g / l and 2.6 ml / l brightener and 35.8 ml / l additional solution was lowered to pH ⁇ 1 with 20 ml / l hydrochloric acid (37%).
- a device according to FIG. 3 with a separation unit (3) and a container (6) for receiving the aqueous phase from the separation tank (3) used.
- the level difference (3c) - (3d) was 15 mm, the total height of the device (3a) + (3b) 2 m.
- the sample was heated to 50 ° C. Within 2 h separated 55 ml / l of a dark brown oil phase above the aqueous phase.
- the clear aqueous phase contained by analysis 13.1 g / l TOC, 0.6 ml / l brightener and 21.8 ml / l additional solution.
- Testing by Hull cell after adjustment of the pH to the working range (pH 5) showed a uniformly shiny sheet with low fogging in the low current density range.
- the cloud point of the bath before treatment was 50 ° C, after treatment and adjustment at 85 ° C.
- the separated oil phase consists of 10-15% of functional bath additives and 85-90% of impurities.
- the separation unit (3 ') comprised a crystallizer from Carbolux.
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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)
- Automation & Control Theory (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004061255A DE102004061255B4 (de) | 2004-12-20 | 2004-12-20 | Verfahren für den kontinuierlichen Betrieb von sauren oder alkalischen Zink- oder Zinklegierungsbädern und Vorrichtung zur Durchführung desselben |
PCT/EP2005/012689 WO2006066689A2 (de) | 2004-12-20 | 2005-11-28 | Verfahren für den kontinuierlichen betrieb von sauren oder alkalischen zink- oder zinklegierungsbädern |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1831435A2 EP1831435A2 (de) | 2007-09-12 |
EP1831435B1 true EP1831435B1 (de) | 2008-11-05 |
Family
ID=36051511
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05808579A Revoked EP1831435B1 (de) | 2004-12-20 | 2005-11-28 | Verfahren für den kontinuierlichen betrieb von sauren oder alkalischen zink- oder zinklegierungsbädern |
Country Status (11)
Country | Link |
---|---|
US (1) | US8475874B2 (pt) |
EP (1) | EP1831435B1 (pt) |
JP (1) | JP4764886B2 (pt) |
KR (1) | KR101237037B1 (pt) |
CN (1) | CN101278077B (pt) |
AT (1) | ATE413479T1 (pt) |
BR (1) | BRPI0519144A2 (pt) |
CA (1) | CA2591932A1 (pt) |
DE (2) | DE102004061255B4 (pt) |
ES (1) | ES2313434T3 (pt) |
WO (1) | WO2006066689A2 (pt) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007040005A1 (de) | 2007-08-23 | 2009-02-26 | Ewh Industrieanlagen Gmbh & Co. Kg | Verfahren zum Abscheiden funktioneller Schichten aus einem Galvanikbad |
DE102008058086B4 (de) * | 2008-11-18 | 2013-05-23 | Atotech Deutschland Gmbh | Verfahren und Vorrichtung zur Reinigung von galvanischen Bädern zur Abscheidung von Metallen |
CN102234795B (zh) * | 2011-06-02 | 2016-09-07 | 杭州震达五金机械有限公司 | 用于双金属复合线材加工的锌基多元合金沉积液 |
CN102324276B (zh) * | 2011-06-02 | 2017-02-22 | 杭州震达五金机械有限公司 | 铜包铝镁双金属导线生产工艺 |
US9120111B2 (en) | 2012-02-24 | 2015-09-01 | Rain Bird Corporation | Arc adjustable rotary sprinkler having full-circle operation and automatic matched precipitation |
US9156043B2 (en) | 2012-07-13 | 2015-10-13 | Rain Bird Corporation | Arc adjustable rotary sprinkler with automatic matched precipitation |
CN103668192A (zh) * | 2012-09-01 | 2014-03-26 | 无锡新大中薄板有限公司 | 一种铝合金板用四元浸锌锡镍铁工艺 |
CN104911683A (zh) * | 2015-05-05 | 2015-09-16 | 武汉科技大学 | 一种侧线脱除硫酸锌电镀液中铁离子的方法 |
Family Cites Families (23)
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US2434191A (en) * | 1942-02-02 | 1948-01-06 | Du Pont | Removing organic impurities from copper-cyanide electroplating baths |
US2861927A (en) * | 1956-04-25 | 1958-11-25 | Westinghouse Electric Corp | Process for adjusting the components in aqueous alkali cyanide electrolytes |
US3821095A (en) * | 1972-09-26 | 1974-06-28 | M & T Chemicals Inc | Zinc electroplating process and electrolyte therefor |
US3887445A (en) * | 1974-04-26 | 1975-06-03 | R O Hull & Company Inc | Method for the reduction of zinc ion concentration and removal of organic impurities in a neutral or acidic, aqueous zinc plating bath |
JPS5262136A (en) * | 1975-11-18 | 1977-05-23 | Kosaku Kk | Regeneration method of inferion plating bath |
DE3138792C2 (de) | 1981-09-30 | 1986-08-21 | Basf Ag, 6700 Ludwigshafen | Verwendung von Benzalaceton in roher Form als Spitzenglanzbildner in sauren galvanischen Zinkbädern |
JPS6096781A (ja) | 1983-11-01 | 1985-05-30 | Ube Ind Ltd | 水酸化カリウム電解液の再生方法 |
JPH0726239B2 (ja) * | 1989-07-04 | 1995-03-22 | 三菱電機株式会社 | メッキ液の回収方法 |
US5246591A (en) * | 1990-07-13 | 1993-09-21 | Pact, Incorporated | Separation of metal ions on an anion exchange resin by chromatographic elution |
DE4200774C2 (de) * | 1992-01-15 | 1993-11-25 | Rene Leutwyler | Verfahren zum Entfernen von Carbonaten aus galvanischen Bädern |
DE4410347A1 (de) | 1994-03-25 | 1995-09-28 | Rene Leutwyler | Verfahren zum Entfernen von anorganischen Metallverbindungen aus Lösungen |
DE19525509C2 (de) | 1994-07-22 | 1997-10-02 | Lpw Anlagen Gmbh | Anwendung der UV/H¶2¶O¶2¶-Oxidationsbehandlung zur betriebsmäßigen Wiederverwendungs- oder Weiterverwendungsaufbereitung eines Bades für die galvanotechnische Beschichtung von Gegenständen mit metallischen Überzügen |
DE19506297A1 (de) * | 1995-02-23 | 1996-08-29 | Schloemann Siemag Ag | Verfahren und Anlage zum Regenerieren von Sulfatelektrolyt bei der Stahlband-Verzinkung |
DE19810859A1 (de) | 1998-03-13 | 1999-09-16 | A C K Aqua Concept Gmbh Wasser | Kombinationsverfahren zur Behandlung eines schäumend eingestellten galvanischen Bads |
DE19834353C2 (de) | 1998-07-30 | 2000-08-17 | Hillebrand Walter Gmbh & Co Kg | Alkalisches Zink-Nickelbad |
US6391209B1 (en) | 1999-08-04 | 2002-05-21 | Mykrolis Corporation | Regeneration of plating baths |
DE19956666B4 (de) | 1999-11-25 | 2009-10-29 | Enthone Gmbh | Verfahren zur kontinuierlichen Abscheidung blendfreier Metallüberzüge auf einer metallischen Oberfläche |
US6602395B1 (en) * | 2000-04-11 | 2003-08-05 | Innovative Technology Licensing, Llc | Patterning of polymer light emitting devices using electrochemical polymerization |
JP2001316894A (ja) * | 2000-05-08 | 2001-11-16 | Tokyo Electron Ltd | 液処理装置、液処理システム、及び液処理方法 |
JP3568460B2 (ja) * | 2000-07-03 | 2004-09-22 | 大日本スクリーン製造株式会社 | メッキ液再生装置及び基板メッキ装置並びにメッキシステム |
JP2002253899A (ja) | 2001-02-27 | 2002-09-10 | Emiko Watanabe | 衣類干し補助具 |
JP2002322599A (ja) * | 2001-04-23 | 2002-11-08 | Shigeo Hoshino | 3価クロムめっき方法 |
DE10225203A1 (de) * | 2002-06-06 | 2003-12-18 | Goema Ag | Verfahren und Vorrichtung zur Spülwasserrückführung und Reinigung eines Prozessbades |
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2004
- 2004-12-20 DE DE102004061255A patent/DE102004061255B4/de not_active Revoked
-
2005
- 2005-11-28 WO PCT/EP2005/012689 patent/WO2006066689A2/de active Application Filing
- 2005-11-28 EP EP05808579A patent/EP1831435B1/de not_active Revoked
- 2005-11-28 CN CN2005800425142A patent/CN101278077B/zh not_active Expired - Fee Related
- 2005-11-28 JP JP2007545870A patent/JP4764886B2/ja not_active Expired - Fee Related
- 2005-11-28 KR KR1020077014826A patent/KR101237037B1/ko active IP Right Grant
- 2005-11-28 ES ES05808579T patent/ES2313434T3/es active Active
- 2005-11-28 US US11/722,137 patent/US8475874B2/en not_active Expired - Fee Related
- 2005-11-28 AT AT05808579T patent/ATE413479T1/de not_active IP Right Cessation
- 2005-11-28 DE DE502005005921T patent/DE502005005921D1/de active Active
- 2005-11-28 CA CA002591932A patent/CA2591932A1/en not_active Abandoned
- 2005-11-28 BR BRPI0519144-0A patent/BRPI0519144A2/pt not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
EP1831435A2 (de) | 2007-09-12 |
BRPI0519144A2 (pt) | 2008-12-30 |
CA2591932A1 (en) | 2006-06-29 |
KR20070086772A (ko) | 2007-08-27 |
JP4764886B2 (ja) | 2011-09-07 |
WO2006066689A3 (de) | 2007-11-08 |
KR101237037B1 (ko) | 2013-02-25 |
US8475874B2 (en) | 2013-07-02 |
DE102004061255A1 (de) | 2006-06-29 |
DE102004061255B4 (de) | 2007-10-31 |
ATE413479T1 (de) | 2008-11-15 |
WO2006066689A2 (de) | 2006-06-29 |
CN101278077A (zh) | 2008-10-01 |
JP2008524436A (ja) | 2008-07-10 |
CN101278077B (zh) | 2013-01-09 |
US20090130315A1 (en) | 2009-05-21 |
ES2313434T3 (es) | 2009-03-01 |
DE502005005921D1 (de) | 2008-12-18 |
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