US20110210006A1 - Process and device for cleaning galvanic baths to plate metals - Google Patents

Process and device for cleaning galvanic baths to plate metals Download PDF

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US20110210006A1
US20110210006A1 US13/123,934 US200913123934A US2011210006A1 US 20110210006 A1 US20110210006 A1 US 20110210006A1 US 200913123934 A US200913123934 A US 200913123934A US 2011210006 A1 US2011210006 A1 US 2011210006A1
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zinc
process according
ion exchanger
electrolyte
cyanide
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Serdar Turan Karagöl
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Atotech Deutschland GmbH and Co KG
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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
    • 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 invention concerns a process and a device for cleaning galvanic baths to plate metals, in particular alkaline zinc-nickel alloy baths, using ion exchangers in order to prolong the lifetime of electrolytes and remove any undesirable decomposition products.
  • Zinc-nickel coatings are used in all applications that require high quality surface protection when subject to corrosion.
  • the conventional field of application is the automobile manufacture for components that are used in the engine bay, on braking systems and in the landing gear bay.
  • alkaline zinc-nickel electrolytes have been used more recently as published in U.S. Pat. No. 4,889,602, which for example have the following electrolyte composition:
  • the amines in the electrolyte act as complexing agents for the nickel ions.
  • Complexing agents are constituents of numerous galvanic and chemical processes which are used in the separation of metals.
  • the zinc-nickel electrolyte is usually driven by insoluble nickel anodes.
  • the zinc content is kept constant by adding a suitable zinc ion source and the nickel content is kept constant by adding a source of nickel ions.
  • the colour of the zinc-nickel electrolyte however changes from blue-purple to brown after a certain time of operation.
  • nitriles (so-called organically bonded cyanide which can contain nitriles as well as isonitriles) and cyanide ions are formed in the zinc-nickel electrolytes through anodic oxidation from the amine-containing complexing agents.
  • the problem of cyanide pollution requires the continuous replacement of the electrolytes and a special waste water treatment which in turn significantly affects the operating costs of the electrolyte.
  • the top phase is dark brown. This phase causes considerable problems when the work pieces are coated, for instance the uneven distribution of the coating thickness or blistering.
  • the continuous removal or skimming of this second brown phase is therefore absolutely essential.
  • the activated carbon cleaning process is a common process that is used in electroplating to remove organic impurities in nickel electrolytes.
  • the quantities of activated carbon used are determined in preliminary tests. The quantities most frequently used for activated carbon cleaning are 2-5 g/l.
  • the activated carbon is added at a temperature of between 50-60° C. Once added, the electrolyte is stirred intensively. After approximately half an hour, the absorbable substances are absorbed by the activated carbon and are filtered out.
  • the disadvantage of this process is that all organic constituents are thereby removed from the electrolytes. For zinc-nickel electrolytes this would mean that not only the decomposition products, but also all other organic constituents such as for example brighteners and complexing agents, are removed.
  • the publication EP 1 344 850 A1 features a device to reduce the build-up of cyanide by separating the anode from the alkaline electrolyte using an ion exchanger membrane. This separation prevents a reaction of the amines on the nickel anodes and therefore also any undesirable side-reactions. The occurring side-reactions, problems of disposal, formation of a second phase and the adverse impact on the quality of the plated zinc-nickel layer, are thereby also avoided. It is therefore no longer necessary to replace the bath and spend lots of time and money on skimming the second phase which has formed.
  • the zinc-nickel electrolyte acts as a catholyte.
  • the medium in the anode compartment which is separated using the aforementioned ion exchanger membrane is known as the anolyte whereby in this case either sulphuric acid or phosphoric acid can be used.
  • the disadvantage of this process is the use of a costly and high-maintenance ion exchanger membrane, which can also not be used for all common metallization baths.
  • FIG. 1 Ion exchanger regeneration unit
  • FIG. 2 Hull cell set-up
  • FIG. 3 Procedure and regeneration effect using a combination of an ion exchanger and the freezing out of sodium carbonate
  • FIG. 4 Comparison of the layer thickness distribution of different zinc-nickel electrolytes
  • the aim of this invention is to selectively remove the cyanide and nitriles that have formed during the metallization process, from the electrolytes.
  • ion exchange resins which are able to bind cyanide ions, it was possible to remove not only the cyanide ions but also the nitriles from the bath.
  • the use of ion exchange resins for this specific purpose is unknown in prior art.
  • a nitrile compound is formed during the operation.
  • the disadvantage of the decomposition product is that as the lifetime of the electrolyte is extended or as the decomposition product increases, an oily and waxy second phase is formed.
  • the formation of the decomposition product is responsible for the loss of expensive complexing agents and the formation of highly toxic cyanide.
  • nitriles R—CN, this always includes isonitriles, R—NC) are formed, initially in the oxidative reaction at the anode, which then react further to form cyanide ions (CN ⁇ ).
  • the efficiency is the percentage part of the total current introduced to plate a defined amount of metal.
  • the current density is usually increased, which however in turn accelerates the decomposition rate of the complexing agent to the nitrile (R—CN) and cyanide.
  • Tests have shown that the second phase contains large quantities of cyanide, metal and sodium carbonate (Na 2 CO 3 ). It can therefore be assumed that these decomposition products are influenced by the nitrile or that they exist together as the concentration continues to increase and form a second phase. From a procedural point of view, it is difficult to separate the second phase since the liquid in the bath is constantly moving.
  • the cyanide and organically bonded cyanide is to be removed using an ion exchange resin.
  • Ion exchange resins are used to remove toxic substances or interfering anions or cations from waste water.
  • the advantage of this process is that it does not require a precipitation or chemical destruction since the interfering substances can be removed from the waste water without being changed.
  • Ion exchange resins are high-molecular organic substances.
  • the rigid and insoluble frame has easily interchangeable counterions on it. These are easily movable and interchangeable counterions, usually hydrogen ions or hydroxyl ions.
  • the regeneration of galvanic process baths is therefore a suitable process to extend the lifetime of electrolytes by removing interfering cations or anions.
  • the batch operation is a process for the ion exchange.
  • the ion exchanger resins come into contact with the electrolyte solution in a receptacle.
  • the process is finished as soon as there is an exchange equilibrium between the counterions from the exchanger and similarly charged ions from the electrolyte solution. If additional ions have to be removed from the electrolyte using the ion exchanger resins, then new resins have to be added. The resins are filtered out once the equilibrium is established.
  • the column process is the process most commonly used in the laboratory.
  • the ion exchanger resin is packed into a column. All necessary operations are then performed in the pack which has been created.
  • Two different work techniques are distinguished, namely working with a decreasing and increasing liquid layer. With the decreasing liquid layer, the electrolyte flows through the column from the top down and with the increasing liquid layer from the bottom up. Filling the column is a straightforward operation.
  • the resin in its current form is first of all transferred to a beaker containing distilled water to swell the resins. This operation is necessary to prevent the column from shattering and to avoid the column from being to densely packed as the resins swell. Two hours is usually sufficient for the resins to swell.
  • washing between operations is necessary to remove any residues of reagents in the ion exchanger column.
  • the exchanger pack is transformed to its original state (non-loaded state). If the ion that was exchanged during the ion exchange is to be recovered again, it is removed by the ion exchanger by eluting with a suitable liquid.
  • the process solution flows through the ion exchanger resins, whereby the cyanides are taken up on the anchor groups through interactions and the hydroxide anions are released on the electrolytes.
  • nitrile compounds can also be removed in this way.
  • Each ion exchanger resin that is capable of binding cyanide ions can be used within the framework of the present invention.
  • Suitable ion exchange resins to bind cyanide ions are for example described in Ludwig Hartinger: Handbuch der Abwasser- and Recyclingtechnik, 2 nd ed. 1991 on pages 352-361, which is incorporated herein by reference.
  • According to paragraph 5.2.3.3.4 and Table 5-1 anions like cyanide can be exchanged utilizing strongly alkaline anion exchange resins.
  • Such resins comprise resins made from polyacrylamide possessing quaternary ammonium groups.
  • Such resin material is commercially available and for example described in Table 13 (page 89) of: Robert Kunin, Ion Exchange Resins, reprint 1985, which is herein incorporated by reference.
  • Quaternary strong base resins suitable comprise Amberlite IRA-400 (Rohm & Haas Co.), Amberlite IRA-401 (Rohm & Haas Co.), Amberlite IRA-410 (Rohm & Haas Co.), Dowex 1 (Nalcite SBR) (Dow Chemical Co.), Dowex 2 (Nalcite SAR) (Dow Chemical Co.).
  • All such resins are also capable of binding nitriles.
  • FIG. 1 shows the column process with an increased liquid layer according to one embodiment of the present invention.
  • a glass, ceramic or plastic frit, or a spray register or spray pole or sieve ( 6 ) through which the process solution can flow evenly through the ion exchanger resin ( 5 ).
  • the ion exchanger resin ( 5 ) is embedded in the column.
  • the contaminated process solution which is conveyed through the column using a hose pump ( 2 ). Once the process solution has passed through the column, it is collected in a receptacle ( 7 ) which can be identical to receptacle ( 1 ).
  • the device used for the metallization process comprises, as shown in FIGS.
  • a receptacle ( 1 ) to take a zinc or zinc alloy bath a connected pump system ( 2 ), which is connected to the ion exchanger device ( 4 ) to take the zinc or zinc alloy bath, which contains ion exchanger resin ( 5 ) and a collection device ( 7 ) for the zinc or zinc alloy bath passing through the ion exchanger resin ( 5 ), which can be identical to receptacle ( 1 ).
  • the ion exchanger resin ( 5 ) in the ion exchanger device ( 4 ) can be on a spray register, spray pole or sieve.
  • the receptacle ( 1 ) is generally equivalent to the galvanic zinc or zinc alloy bath and consists of at least an anode, a cathode (the substrate to be coated) and a voltage source.
  • the freezing device ( 8 ) includes a cooling unit ( 9 ) to cool the solution to a temperature that is preferably below 10° C., more preferably between 2-5° C. and an outlet ( 10 ) to separate the crystallised sodium carbonate.
  • the regeneration solution with sodium chloride was moved into the very alkaline range (pH value >10) with a 0.5% by weight sodium hydroxide, since cyanides can quickly decompose below this pH value and form toxic hydrogen cyanide.
  • the regeneration tests were examined using three different concentrations of sodium chloride (6, 12 and 18% by weight, Tables 2-7). The regeneration operation was realised at a linear speed of 5 m/h.
  • One litre of sodium chloride solution was used for the regeneration and conveyed through the ion exchanger pack. Four portions of sample fractions having a volume of 250 ml each were taken and the content of different electrolyte parameters was analysed, compared and assessed.
  • the aged electrolyte which is to be regenerated should if possible be as close as possible to the original state (new batch).
  • New batches of alkaline zinc-nickel electrolytes usually have an efficiency of 70% for a current density of 1 A/dm 2 .
  • the Hull cell test in order to assess the regeneration effect, the Hull cell test can be used and there is the option to determine the efficiency of the electrolyte using Faraday's law. Based on the layer thickness distribution of the electrolyte, it is possible to assess how good the regeneration effect is using an ion exchange resin.
  • the Hull cell is used to determine the effects of the bath parameters (eg. temperature, pH value, electrolyte composition, lack of or surplus of additives, cleanliness, impurities from foreign metals) on the property of the plated layer depending on the current density.
  • bath parameters eg. temperature, pH value, electrolyte composition, lack of or surplus of additives, cleanliness, impurities from foreign metals
  • the cathode Since in a Hull cell the cathode is diagonal to the anode (see FIG. 2 ), there is a distribution of current densities on the cathode. This makes it possible to examine the effect of the current density in a single experiment. Understandably the current density is higher at the edge nearest the anode than at the edge away from the anode ( FIG. 2 ).
  • the quality of coated surfaces ie. the composition, thickness, evenness and other properties, therefore primarily depend on the composition of the electrolyte and the plating conditions.
  • the key quality factors are the composition of the electrolyte and the current parameters which must be monitored to assure a high quality coating.
  • the composition of the electrolyte plays a significant role in this instance.
  • Each individual additive in the electrolyte influences the properties of the electrolyte and the plated layer.
  • concentration of the electrolyte constituents must be within certain limits.
  • the majority of electrolytes contain, in addition to the inorganic constituents, additional organic-type additives. These organic constituents are designed to influence the properties of the layer that is to be plated. This includes for instance brightening, levelling, hardness, ductility and throwing power ability.
  • the Hull cell test was carried out to examine the appearance of the plated layer and the zinc-nickel composition. Tests were carried out with the Hull cell on a new, on an aged and on an electrolyte that had been regenerated using ion exchange resins.
  • This test is designed to give an indication as to how effective it is to come close to the original state (new batch).
  • the Hull cell can be used to establish how losses during the ion exchange process affect the plating rate.
  • the additives however only work effectively if they are used in a certain concentration and composition.
  • the reduction in the TOC (Total Organic Carbon) content is due to the reduction of the nitrile concentration and that of the amine-containing complexing agents.
  • the ion exchange process can preferably be carried out in conjunction with the freezing out of sodium carbonate to further increase the efficiency of the process and match the plating performance of a non-aged electrolyte.
  • the electrolyte solution can be conveyed through a cooling device either before or after treatment in the ion exchange resin column (see FIG. 3 ). During cooling, a sodium carbonate phase which can be separated, is formed.
  • the old electrolyte is preferably treated in the freezer unit first and then in the ion exchange resin unit.
  • the volume flow rate is 1000 ml/h. This represents a rate of 1.51 m/h and is within the value range specified by the manufacturer.
  • a reference sample was taken from the zinc-nickel electrolyte which was to be regenerated (Sample 0 in the tables corresponds to an aged electrolyte).
  • sample 0 in the tables corresponds to an aged electrolyte.
  • sample 1-4 in Tables 8 and 9 the volume flow rate
  • the content of the different constituents was then examined in the sample fractions and compared with one another.
  • the metal content, sodium hydroxide content, sodium carbonate content, sodium sulphate content, content of the complexing agents, TOC content and the total cyanide content of the samples was examined.
  • the test shows that the resin Lewatit MonoPlus M600 retains the interfering cyanide from the process solution.
  • the test also shows that the resin's absorption capacity has by no means been reached and that the cyanide content dropped even after 60 minutes.
  • the cyanide concentration is initially accompanied by a reduction in the concentration of zinc, sodium hydroxide, sodium carbonate, sodium sulphate and the complexing agent in the first fraction (Sample 1).
  • the nickel concentration remains virtually constant throughout the whole test period.
  • the Hull cell tests were carried out to examine the appearance of the plated layer and the zinc-nickel composition. Tests were carried out with the Hull cell on a new, on an aged and on an electrolyte that had been regenerated using ion exchangers.
  • the Hull cell can be used to establish how losses during the ion exchange process effect the plating rate.
  • the Hull cell was filled with 250 ml of electrolyte as per Table 1. A nickel anode was used as the anode. Once the Hull cell plate had been cleaned, a 1-ampere current was applied. The coating time was fifteen minutes.
  • the low current density range shows an even and bright plating result.
  • the high and low current density ranges shown in FIG. 2 act as measuring points for determining a layer thickness and the alloy composition of the zinc-nickel layer.
  • the layer thicknesses were measured using an X-ray fluorescence measurement device at the two measuring points A (high current density range) and B (low current density range). Five measurements were taken at each measuring point.
  • the X-ray fluorescence analysis is a standard method used for a quick and non-destructive determination of layer thicknesses. By using this measurement method, it was possible to ascertain the layer thickness and the amount of nickel and zinc. Based on the layer thickness distribution, it was then possible to draw a conclusion concerning the effect of the ion exchange process on the electrolyte parameters.
  • the base or reference value which is to be obtained using the regeneration process is the layer thickness distribution of the newly included electrolyte [Table 10].
  • a comparison of the layer thickness distribution for a new and an aged electrolyte [Table 11] also shows how quickly the efficiency level and thereby also the separation rate of the electrolyte drops as the lifetime increases.
  • the initial concentration (Sample 0) is needed for this.
  • the Hull cell test shows that the plated layer thickness at measuring points A and B is considerably higher and is closer to the non aged electrolyte, in comparison to the aged electrolyte [Table 11]. The result also shows that the nickel and zinc composition has not changed in the layer. It can therefore be said that removing the cyanide and organically bonded cyanide accelerates the separation rate of the alkaline zinc-nickel electrolyte and that the bath quality is significantly increased in comparison to the aged plating bath by using an ion exchanger system.
  • the efficiency of the electrolyte can be increased further by freezing out the sodium carbonate.
  • An examination of the efficiency of the electrolyte once the sodium carbonate had been frozen out revealed a 7% increase in the efficiency of the electrolyte.
  • a regeneration of the zinc-nickel electrolyte by freezing out the sodium carbonate and removing the cyanide and nitrile using the ion exchanger is particularly advantageous.

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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)
  • Treatment Of Water By Ion Exchange (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
US13/123,934 2008-11-18 2009-11-17 Process and device for cleaning galvanic baths to plate metals Abandoned US20110210006A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102008058086A DE102008058086B4 (de) 2008-11-18 2008-11-18 Verfahren und Vorrichtung zur Reinigung von galvanischen Bädern zur Abscheidung von Metallen
DE102008058086.4 2008-11-18
PCT/EP2009/008408 WO2010057675A2 (en) 2008-11-18 2009-11-17 Process and device for cleaning galvanic baths to plate metals

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US (1) US20110210006A1 (de)
EP (1) EP2358927B2 (de)
JP (1) JP5730210B2 (de)
KR (1) KR20110090934A (de)
CN (1) CN102216498B (de)
BR (1) BRPI0921037B1 (de)
CA (1) CA2740644C (de)
DE (1) DE102008058086B4 (de)
ES (1) ES2402338T5 (de)
WO (1) WO2010057675A2 (de)

Cited By (1)

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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

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ES2404844T3 (es) * 2010-05-07 2013-05-29 Dr.Ing. Max Schlötter Gmbh & Co. Kg Regeneración de electrolitos de cinc-níquel alcalinos mediante la eliminación de iones cianuro
PL2431500T3 (pl) * 2010-09-21 2013-08-30 Dr Ing Max Schloetter Gmbh & Co Kg Regeneracja zasadowych elektrolitów cynkowo-niklowych przez usuwanie jonów cyjankowych za pomocą rozpuszczalnych czwartorzędowych związków amoniowych
DE102014223169A1 (de) * 2014-11-13 2016-05-19 Henkel Ag & Co. Kgaa Verfahren zur selektiven Entfernung von Zink-Ionen aus alkalischen Badlösungen in der Oberflächenbehandlung von metallischen Bauteilen in Serie
DE102016008333A1 (de) * 2015-11-12 2017-05-18 Liebherr-Aerospace Lindenberg Gmbh Verfahren zur wasserstoffarmen Zink-Nickel Beschichtung eines hochfesten Vergütungsstahls
CN107367438A (zh) * 2017-07-14 2017-11-21 东莞市同欣表面处理科技有限公司 一种利用方形霍尔槽测试电镀电流效率的方法
CN110373706B (zh) * 2019-08-22 2021-05-14 电子科技大学 一种酸性光亮镀铜电镀液的在线维护方法

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ES2402338T5 (es) 2017-07-25
CA2740644C (en) 2016-07-26
DE102008058086A1 (de) 2010-05-27
CN102216498B (zh) 2014-08-06
JP5730210B2 (ja) 2015-06-03
EP2358927A2 (de) 2011-08-24
ES2402338T3 (es) 2013-04-30
KR20110090934A (ko) 2011-08-10
EP2358927B2 (de) 2017-03-01
BRPI0921037A2 (pt) 2015-12-29
DE102008058086B4 (de) 2013-05-23
WO2010057675A2 (en) 2010-05-27
CN102216498A (zh) 2011-10-12
JP2012509401A (ja) 2012-04-19
CA2740644A1 (en) 2010-05-27
BRPI0921037B1 (pt) 2020-01-07
WO2010057675A3 (en) 2010-08-05

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