EP2039810A2 - Procédé et dispositifs pour prolonger la durée d'utilisation d'une solution de procédé utilisée dans un processus de revêtement métallique par réduction chimique - Google Patents

Procédé et dispositifs pour prolonger la durée d'utilisation d'une solution de procédé utilisée dans un processus de revêtement métallique par réduction chimique Download PDF

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Publication number
EP2039810A2
EP2039810A2 EP08022592A EP08022592A EP2039810A2 EP 2039810 A2 EP2039810 A2 EP 2039810A2 EP 08022592 A EP08022592 A EP 08022592A EP 08022592 A EP08022592 A EP 08022592A EP 2039810 A2 EP2039810 A2 EP 2039810A2
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EP
European Patent Office
Prior art keywords
process solution
cation exchanger
acidic cation
weakly acidic
solution
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EP08022592A
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German (de)
English (en)
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EP2039810A3 (fr
EP2039810A8 (fr
Inventor
Alexander Schiffer
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Blasberg Werra Chemie GmbH
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Blasberg Werra Chemie GmbH
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Publication of EP2039810A2 publication Critical patent/EP2039810A2/fr
Publication of EP2039810A3 publication Critical patent/EP2039810A3/fr
Publication of EP2039810A8 publication Critical patent/EP2039810A8/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1617—Purification and regeneration of coating baths
    • 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
    • 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

Definitions

  • the invention relates to a method and apparatus for extending the useful life of a process solution used in chemical-reductive metal deposition.
  • the chemical-reductive metal deposition is used to coat workpieces with a metal coating (Cu, Ni, Ag or Au).
  • reaction equation can be set up by way of example for nickel deposition: 3NaH 2 PO 2 + 3H 2 O + NiSO 4 ⁇ 3 NaH 2 PO 3 + H 2 SO 4 + Ni + 2H 2 (Equation 1)
  • reducing agents here NaH 2 PO 2
  • metal ions of the coating metal here Ni 2+
  • the oxidized reducing agent here NaH 2 PO 3
  • protons are formed as reaction products equivalent to the amount of metal deposited.
  • the redosing of the reducing agent and of the metal ions of the coating metal takes place by adding the appropriate salts and adjusting the pH by adding alkalis to the process solution.
  • pH adjustment replenishment of the consumed components and removal of base material, foreign substances accumulate in the process solution, disrupting the process of metal deposition and adversely affecting the quality of the layers produced.
  • To remove the foreign substances is usually a Molversch the process solution, with their sewage treatment is problematic because of the complex composition.
  • MTO metal throughput
  • the compressive stress in the nickel-phosphorus layer disadvantageously already after 2 to 4.5 MTO in a tensile stress and therefore the useful life of the process solution is usually limited to 5 MTO.
  • the post-dosing of the metal ions is carried out by adding nickel salts, wherein US 2,726,969
  • basic nickel salts such as nickel hydroxide or nickel carbonate
  • a pH adjustment without the use of other alkalis to be achieved.
  • these sparingly soluble compounds has the disadvantage that it contaminates the process solution with solids, which can be incorporated into the deposited metal layers and thus adversely affect their properties.
  • DD 36,889 discloses a process for the continuous regeneration of acid solutions for chemical nickel plating in which the solution is passed through a combination of a nickel-loaded weakly acidic cation exchanger and a hypophosphite-loaded, (weak to) moderately basic anion exchanger.
  • the weakly acidic cation exchanger is to be used for adjusting the pH and for subsequent addition of nickel ions, while the weak to medium basic anion exchanger is to be used for the subsequent addition of hypophosphite and the separation of orthophosphite.
  • the weakly acidic cation exchanger and the (weak to medium) basic anion exchanger are connected in series with a matched capacity.
  • the monitoring of the functionality of the cation exchanger is intended in DD 36,889 via the coloring of the weakly acidic cation exchange resin. As soon as it has changed from green (nickel loading) to a yellowish white (unloaded exchanger), the exchangers should be regenerated. This color change of the weakly acidic cation exchange resin is very poorly usable for the control of the functionality of the ion exchanger, since a process solution for the chemical-reductive nickel deposition itself is intensely colored green.
  • the object of the invention is to provide methods and devices with which the useful life of a process solution for the chemical-reductive metal coating can be extended.
  • the object is achieved by a method for extending the service life of a process solution for chemical-reductive metal deposition, in which the metal ions of the coating metal consumed in the metal deposition are metered in and the pH value in the process solution is adjusted.
  • the replenishment of the metal ions and the pH adjustment is carried out with the aid of at least one weakly acidic cation exchanger, which is loaded with ions of the coating metal.
  • the pH value in the process solution is monitored and, when the pH of the process solution falls, part of the process solution, optionally after dilution, is passed through the weakly acidic cation exchanger 14 .
  • the solution prepared by the weakly acidic cation exchanger 14 is returned to the process solution directly.
  • the functionality of the weakly acidic cation exchanger is monitored by controlling the pH in the effluent of the weakly acidic cation exchanger 14 , the cation exchanger exchanging the pH value in the effluent of the weakly acidic cation exchanger for the pH of the process solution for reuse with ions of the Coating metal is loaded.
  • the salt entry into the process solution is considerably reduced by the process according to the invention with the weakly acidic cation exchanger.
  • the useful life of the process solution can be significantly extended.
  • the solution is enriched with ions of the coating metal by the weakly acidic cation exchanger.
  • the risk of undesirable metal deposition from such enriched solutions is great, especially if a sufficient amount of reducing agent is present.
  • the pH of the process solution is adjusted to a nominal value of pH 3 to pH 6.
  • the phosphorus content of the deposited metal layer increases with the H + ion concentration in the process solution.
  • the monitoring of the functionality of the weakly acidic cation exchanger is carried out by controlling the pH in the feed (or in the solution to be abandoned) and in the course of the weakly acidic cation exchanger.
  • the capacity of the weakly acidic cation exchanger is exhausted as soon as the pH in the outlet of the exchanger has almost equaled that of the feed (difference ⁇ 0.2 pH units).
  • d. H When the capacity of the ion exchange column is exhausted, the ion exchange material can be exchanged or the flow of the process solution can be diverted to another cation exchanger.
  • the end of the period of use of the weakly acidic cation exchanger can be determined according to the invention, before the pH value and the content of ions of the coating metal in the process solution exceed the tolerance range of the process leaves.
  • the method according to the invention therefore makes it possible to keep the content of ions of the coating metal and the pH of the process solution almost constant.
  • ion exchanger is understood in the context of the present invention in each case a device which z. B. in the form of a column, column or filter chamber is either partially or completely filled with an ion exchange material.
  • organic or inorganic ion exchange materials which have functional groups that are capable of ion exchange.
  • the ion exchange materials may be solid or liquid.
  • the ion exchanger can be further characterized, e.g. as strongly acidic or weakly acidic cation exchanger or as weakly basic or strongly basic anion exchanger.
  • the substances bound by the ion exchanger can be removed again by regeneration of the functional groups, the regeneration in cocurrent or countercurrent is possible.
  • a dilute process solution is understood below to mean a process solution which is diluted (for example by mixing with the rinse solution) to a content of 5% to 90% of the concentration of the process solution, preferably 10 to 50%.
  • ingredients of the process solution are extracted into the rinse solution.
  • foreign substances such as the oxidized reducing agent, the counterions of the reducing agent, usually Na + , and other interfering ions in the rinse solution.
  • the rinse solution thus also represents a dilute process solution from which the foreign substances can be removed.
  • the term dilute process solution therefore includes the rinse solution.
  • the replenishment of the metal ions of the coating metal consumed in the metal deposition is carried out by applying the process solution or a dilute process solution to a weakly acidic cation exchanger which is loaded with the cations of the coating metal. This releases metal ions into the process solution.
  • no disturbing counterions are introduced into the process solution.
  • the process solution can be contacted directly with ion exchange materials without resulting in significant metal deposition on the materials. This can be achieved by cooling the process solution to temperatures ⁇ 60 ° C prior to application to the ion exchanger. Alternatively, metal deposition on the ion exchange materials can be avoided by adding a dilute process solution to the ion exchange materials.
  • the process solution (if appropriate after dilution) is preferably added to the one or more ion exchangers at a flow rate of less than 20 m / h, more preferably less than 10 m / h.
  • V ⁇ P c F . z c F . z - c F . R ⁇ m ⁇ F c F . z - c F . R ⁇ m ⁇ F c F . 9 - V EA ⁇ ⁇ 1 - ⁇ R
  • Its value is determined by the introduction of foreign substances into the process solution ( ⁇ F ), the foreign substance concentrations in the feed (c F, z ) and in the effluent (c F, R ) of the cleaning device and by the degree of return of the withdrawn components ( ⁇ R ).
  • the mass flow of the foreign substance input can be determined by the stoichiometry of the deposited amount of nickel.
  • the degree of recycling depends on what proportion of the rinse solution is transferred to the coating vessel to compensate for the evaporation losses, and may be between 0 and 1.
  • the above-described replenishment of the ions of the coating metal is combined with a process in which interfering cations that accumulate in the process solution during metal deposition are separated by means of at least one strongly acidic cation exchanger which has been previously loaded with protons ,
  • this separation of the interfering cations is temporarily performed as needed in a special cleaning process.
  • This essentially serves to remove cations which are introduced from the base material into the process solution during metal deposition.
  • the process solution is brought into contact with a strongly acidic cation exchanger, which was previously loaded with protons.
  • ions of the metal to be deposited are removed and entered protons in the process solution.
  • the cations of the coating metal must then be subsequently metered in and the protons introduced during the purification of the process solution must be removed again.
  • the eluate obtained in the regeneration of the strongly acidic cation exchanger is used after a pH adjustment for the loading of the weakly acidic cation exchanger with the cations of the coating metal.
  • the ions of the coating metal are replenished by a weakly acidic cation exchanger, which is loaded with the corresponding cations of the coating metal. At the same time, it binds the protons that have been introduced into the process solution through the cleaning process.
  • Another possible use of the invention is a method for extending the service life of a process solution for the chemical-reductive metal deposition, in which the consumed in the metal deposition reducing agent and the metal ions of the coating metal is post-dosed and the pH in the process solution can be adjusted, with interfering cations and Anions that accumulate in the process solution during metal deposition are removed from the process solution or a dilute process solution using ion exchange processes.
  • interfering cations at least one strongly acidic cation exchanger is used for this, which was previously loaded with protons, while the weakly basic anion exchanger is converted by protons into the protonated form for the removal of the interfering anions.
  • the protons released by the strongly acidic cation exchanger as described above, when it binds interfering cations.
  • the reducing agent in the form of a water-soluble salt preferably sodium hypophosphite (NaH 2 PO 2), or a corresponding solution, is preferably added directly into the process solution or into a dilute process solution.
  • the separation of the interfering anions via the weakly basic anion exchanger and the interfering cations via the strongly acidic cation exchanger preferably takes place from a dilute process solution.
  • the interfering cations are separated by the strongly acidic cation exchanger and the interfering anions are separated from the flushing system by the weakly basic anion exchanger.
  • the strongly acidic cation exchanger After the cations of the coating metal are removed by the strongly acidic cation exchanger in addition to the cationic impurities from the base material but also the towed into the rinse solution, the strongly acidic cation exchanger must be regenerated more frequently than if it were part of a separate auxiliary circuit of a membrane electrolysis cell. The rinsing solution thus purified is returned to the process solution to compensate for the evaporation losses occurring in the metal deposition.
  • the supply of the metal ions of the coating metal in the previously purified solution by means of a weakly acidic cation exchanger, which has been previously loaded with the metal ions of the coating metal.
  • a weakly acidic cation exchanger which has been previously loaded with the metal ions of the coating metal.
  • the eluate of the strongly acidic cation exchanger can be used after a pH adjustment for the loading of the weakly acidic cation exchanger with the metal ions of the coating metal.
  • the invention relates to a device for extending the service life of a process solution for the chemical-reductive metal deposition, consisting of at least one weakly acidic cation exchanger for use for the pH adjustment and the post-dosing of ions of the coating metal in a plant for the chemical-reductive metal deposition.
  • the device has elements which serve to connect the inlet and outlet of the weakly acidic cation exchanger 14 with at least one container containing the process solution, dilute process solution, cooled process solution or pretreated process solution.
  • the device includes associated peripherals, such. As pumps, valves, measuring devices for pH, conductivity, temperatures.
  • the weakly acidic cation exchanger 14 is connected with its feed to at least one container containing process solution, dilute process solution or cooled process solution or pretreated process solution.
  • the effluent of the weakly acidic cation exchanger 14 is directly connected to at least one container containing process solution.
  • the device contains measuring devices for monitoring the pH of the process solution and the pH in the effluent of the weakly acidic cation exchanger 14.
  • the solution is enriched with ions of the coating metal by the weakly acidic cation exchanger.
  • the risk of undesirable metal deposition from such enriched solutions is great, especially if a sufficient amount of reducing agent is present.
  • the direct introduction according to the invention of the effluent of the weakly acidic cation exchanger into the process solution minimizes undesirable metal deposition between the cation exchanger and the process bath.
  • the measuring device for monitoring the pH in the course of the weakly acidic cation exchanger 14 makes it possible to continuously monitor the functionality of the weakly acidic cation exchanger, since the weakly acidic cation exchanger, as long as it is loaded with ions of the coating metal, raises the pH of the ( acidic) solution takes place. As soon as the ion exchanger is discharged, the pH value of the effluent corresponds to that of the discontinued solution.
  • the exhaustion of the weakly acidic cation exchanger can thus be determined according to the invention before the pH value and the content of the process solution to ions of the coating metal leaves the tolerance range of the process.
  • the device therefore makes it possible to keep the content of ions of the coating metal and the pH of the process solution almost constant.
  • the measuring device for monitoring the pH value is also suitable for connection to a computer and thus makes an automatic change to a second cation exchanger and the automatic control of the regeneration process possible.
  • the weakly acidic cation exchanger is loaded with the cations of the coating metal.
  • this is done in two steps: First, the weakly acidic cation exchanger for conditioning, with an alkali, preferably with sodium hydroxide, converted into the salt form.
  • an alkali preferably with sodium hydroxide
  • it is then brought into contact with a water-soluble salt of the coating metal in dissolved form.
  • a water-soluble salt of the coating metal in dissolved form.
  • an aqueous solution of nickel sulfate or nickel chloride is chosen for the loading of metal ions.
  • the loading of metal ions is preferably carried out in two stages with different concentrations of metal salt solutions, wherein in the second stage - preferably carried out by a circulation - a complete loading with metal ions of the coating metal.
  • This step-by-step procedure ensures complete transfer of the weakly acidic resin into the charge of ions of the coating metal and, at the same time, good material utilization of the ions of the coating metal used.
  • the ion exchanger is washed with demineralized water to remove the corresponding sodium salts from the ion exchanger, so that they are not entered into the process solution as foreign substances.
  • the weakly acidic cation exchanger is charged with process solution and releases metal ions into it. At the same time he binds protons.
  • the maximum proton uptake capacity of the weakly acidic cation exchanger is achieved upon complete conversion to the salt form. The capacity is controlled by the pH in its course.
  • the efficiency of the pH correction decreases when the complete discharge of the weakly acidic cation exchanger has been achieved and the pH value in the effluent of the weakly acidic cation exchanger approaches the pH value of the feed of the weakly acidic cation exchanger.
  • the weakly acidic cation exchanger When fully discharged, the weakly acidic cation exchanger is in the H form.
  • the weakly acidic cation exchanger must be converted back into the salt form with an alkali and then loaded with ions of the coating metal.
  • the weakly acidic cation exchanger regenerated in this way can be used again for the pH adjustment as well as for the subsequent addition of metal ions.
  • the weakly acidic cation exchanger has a high selectivity for protons, so that the protons formed in the chemical-reductive metal deposition are bound by this cation exchanger. In return, the metal ions previously bound to the cation exchanger are released into the process solution.
  • the divalent cations used for metal deposition are more strongly bound by the weakly acidic cation exchanger than monovalent cations.
  • the exchanger can therefore be easily converted into the salt form with sodium hydroxide solution and then loaded with the divalent cations of the coating metal.
  • the column capacity of the weakly acidic cation exchanger is selected according to the desired service life and the amount of metal to be deposited.
  • the cation exchanger contains a weakly acid cation exchange material having carboxylic acid groups as functional groups.
  • the weakly acidic cation exchanger brought into direct contact with the process solution and not only replenished the ions of the coating metal, but also the pH of the process solution can be adjusted. This is achieved by the fact that the weakly acidic cation exchanger, when it comes into contact with the process solution, binds the H + ions formed in the metal deposition.
  • the weakly acidic cation exchanger loaded with the cations of the coating metal it is advantageously not necessary to add alkalis and metal salts to the process solution according to the prior art in order to bind the H + ions and to replenish the spent metal ions.
  • the addition of the ions of the coating metal without interfering counterions and the pH adjustment without addition of alkali is considerably reduced by the weakly acidic cation exchanger according to the invention in comparison with the prior art. If a conventional system for chemical-reductive metal deposition is supplemented solely with the weakly acidic cation exchanger according to the invention, the useful life of the process solution can be significantly increased.
  • Another object of the invention is a device for extending the service life of a process solution for the chemical-reductive metal deposition, consisting of at least one loaded with H + ions strongly acidic cation exchanger for use for the removal of interfering cations in a plant for the chemical-reductive metal deposition.
  • the device has elements for recycling the process solution or cooled or pretreated process solution via the strongly acidic cation exchanger 15.
  • the strongly acidic cation exchanger 15 is connected with its inlet and its outlet directly to at least one container containing process solution, dilute process solution or cooled process solution or pretreated process solution.
  • the device contains associated peripherals, such. As pumps, valves, measuring devices for pH, conductivity, temperatures.
  • the invention also relates to the combination of the weakly acidic cation exchanger described above with the strongly acidic cation exchanger described above in a device for use in a chemical-reductive metal deposition plant in order to extend the useful life of a process solution for chemical-reductive metal deposition.
  • the device contains at least one strongly acidic cation exchanger for the removal of interfering cations, which is connected in series or in parallel with at least one weakly acidic cation exchanger for use for the pH adjustment and subsequent addition of ions of the coating metal.
  • the apparatus also includes elements which cool the compound of the weakly acidic cation exchanger and the strongly acidic cation exchanger with at least one container, the process solution, dilute process solution Process solution or pretreated process solution contains serve.
  • the device contains associated peripherals, such. As pumps, valves, measuring devices for pH, conductivity, temperatures.
  • the invention relates to the combination of the strongly acidic H + ions-loaded strong acid cation exchanger 15 described above with the weakly acidic cation exchanger 14 loaded with ions of the coating metal.
  • the strongly acidic cation exchanger is preceded by the weakly acidic cation exchanger.
  • the z. B. originate from the material to be coated.
  • ions of the coating metal are bound by the strongly acidic cation exchanger and the pH value in the applied solution is lowered.
  • the pH of the solution is raised again and enriched with ions of the coating metal.
  • the abovementioned ion exchangers are column exchangers which are filled with a solid, water-insoluble, ion exchange material.
  • the organic or inorganic ion exchange material contains functional groups capable of ion exchange.
  • the above-mentioned ion exchange materials are each part of a filter or membrane apparatus.
  • liquid ion exchange materials are used in at least one of the ion exchange materials used.
  • the one or more ion exchangers in this embodiment each consist of a container which contains a liquid immiscible with the process solution, in which an ion exchange material is distributed or dissolved.
  • the ion exchange material consists of a reagent containing the functional groups required for the ion exchange action, e.g. be used in the reactive extraction.
  • the system contains connecting cables between the individual components as well as the associated peripherals, such as pumps, valves, measuring devices for pH, conductivity, temperatures etc.
  • the coating container contains the process solution in which the workpiece to be coated is immersed.
  • the plant according to the invention consists of a coating container, a rinsing system and a device with a weakly acidic cation exchanger for pH adjustment as described above and subsequent metering of the metal to be deposited, which is connected to inlet and outlet with the coating container.
  • the process solution is cooled before being contacted with the sensitive components of the devices, particularly the ion exchange materials and the membranes.
  • the process solution prepared by the device must be returned to the process temperature before being returned to the coating vessel.
  • the inlet and the outlet of the weakly acidic or strongly acidic cation exchanger are therefore connected to the coating vessel via a heat exchanger.
  • the heat exchanger uses the energy of the cooling process for the warm-up process of purified process solution.
  • the weakly acidic cation exchanger loaded with ions of the coating metal is preferably used as the last step in the work-up. Its process is initiated directly into the process solution.
  • the invention advantageously achieves virtually constant process conditions in the case of the chemical-reductive metal coating and thus a particularly uniform deposition of the metal on the workpiece to be coated. Due to the low impurity content of the process solution, which is achieved in the system according to the invention, nickel-phosphorus layers can be deposited, which are in the compressive stress range, which in particular causes the quality of the coating of the deposition.
  • Fig. 1 shows a scheme of a plant for chemical-reductive metal coating, in which by means of a coated with ions of the coating metal low-acid cation exchanger 14, the required ions of the coating metal are replenished without interfering anions and at the same time the pH of the process solution is adjusted and thus prolongs the useful life of the process solution can be.
  • the plant after Fig. 1 consists of a coating container 1, a multi-stage flushing system 3 in cascade connection and a weakly acidic cation exchanger 14 , as well as connecting pipes and associated peripherals, such as pumps, valves, measuring devices for pH, conductivity, temperatures, etc. The latter have not been included for reasons of clarity Fig. 1 located.
  • the coating container 1 contains process solution in which a workpiece 2 to be coated is immersed.
  • the workpiece 2 to be coated has a steel surface.
  • the multi-stage flushing system 3 consists of three cascaded containers containing an aqueous rinse solution. Between the left and right rinse tanks 3 , as indicated by the broken line in FIG Fig. 1 indicated, but not shown, another rinsing bin queued. The left washing container 3 contains a feed for fresh water. The right rinse tank 3 is connected to the coating tank 1.
  • the weakly acidic cation exchanger 14 is connected with its inlet and outlet to the coating container 1 , so that a certain volume flow of the process solution can be passed over him.
  • the weakly acidic cation exchanger consists of an ion exchange column 14 which is filled with the weakly acidic cation exchange polymer Lewatit CNP 80 from Lanxess AG, Leverkusen, Germany.
  • Lewatit CNP 80 from Lanxess AG, Leverkusen, Germany.
  • comparable weakly acidic cation exchanger polymers from other manufacturers, e.g. C 104 of Fa. Purolite, Ratingen, Germany.
  • This weakly acidic cation exchange polymer is loaded with ions of the coating metal prior to use.
  • the ion exchanger is first converted into the salt form with sodium hydroxide solution and then loaded with ions of the coating metal by the application of a metal salt solution.
  • the weakly acidic cation exchange polymer is loaded with nickel ions, for which purpose a NiSO 4 solution is passed over the ion exchange column. This loading is carried out in two steps with nickel salt solutions of different concentrations, the first Loading step, a deficiency of nickel ions is applied to the ion exchanger.
  • the weakly acidic cation exchanger is washed with demineralized water in order to remove interfering ions from the polymer bulk layer. By this rinsing process, the excess of nickel ions is removed again from the polymer bulk layer.
  • the course of the second fraction of the loading process is intermediately stacked together with the first fraction of the rinse water and used in the subsequent loading of the weakly acidic cation exchanger as the first loading fraction.
  • the process solution is composed in a known manner.
  • the ions of the coating metal in the form of nickel sulfate (6.0 g Ni 2+ / l) are added.
  • the reducing agent is added in the form of sodium hypophosphite (17.0 g H 2 PO 2 - / l).
  • the solution is buffered in the range of pH 4 to pH 5.
  • the temperature of the process solution surrounding the workpiece 2 to be coated is adjusted to 85 ° C.
  • Metal ions deposit on the steel surface of the workpiece 2 to be coated.
  • elemental phosphorus which is formed by side reactions of the reducing agent, alloyed into the resulting metal layer, whereby a nickel-phosphorus alloy is formed.
  • the Reducing agent sodium hypophosphite oxidized to sodium orthophosphite. This consumption of reducing agent is compensated for by adding sodium hypophosphite to the process solution.
  • the pH value and the nickel content in the process solution also decrease. Therefore, the pH in the process solution is monitored. If the pH of the process solution falls below a specified value, e.g. from pH 4.5 to pH 4.2, then a partial stream of the process solution is passed through the weakly acidic cation exchanger 14 at a flow rate ⁇ 5 m / h. This results in the course of the weakly acidic cation exchanger 14, an increase in the nickel content of 5 g / l to 8 g / l and an increase in the pH of 4.2 to pH> 5.
  • a specified value e.g. from pH 4.5 to pH 4.2
  • the functionality of the weakly acidic cation exchanger is monitored. With increasing metal release, the weakly acidic cation exchanger is converted into the H + form, which is why the pH falls in the course of the cation exchanger.
  • the pH in the effluent of the weakly acidic cation exchanger approaches the pH of the process solution (in this case pH 4.5), the cation exchanger is re-used for re-use, as described above, into the nickel charge.
  • the salt content in the process solution rises to high values already after a metal throughput of 5.5 MTO due to the introduced or formed foreign substances (in particular Na +, SO 42 -, H 2 PO 3 -). so that at this time, the deposition rate at 90 ° C to values ⁇ 5 microns / h drops and the properties of the deposited layers no longer meet the requirements.
  • the SO 42 content of the process solution does not increase with increasing metal throughput, since the nickel ions are introduced into the process solution without interfering SO 42 .
  • the Na + content increases considerably slower here, since the adjustment of the pH without addition of NaOH in the process solution ..
  • the process solution by the slower increase in the impurity content up to a Metal throughput of about 8 MTO can be used. The useful life of the process solution is thus almost doubled by the use according to the invention of the weakly acidic cation exchanger 14.
  • Fig. 2 shows a scheme of a system for chemical-reductive metal coating with a weakly acidic cation exchanger 14, which via a heat exchanger 4 with the coating container 1 is connected.
  • this system is designed according to the system Fig. 1 built up.
  • this plant contains a storage tank 5 and a stack container 13, which are each connected via the heat exchanger 4 with the coating container 1.
  • the weakly acidic cation exchanger 14 corresponds in its construction to that Fig. 1 , In contrast to Fig. 1 However, he is not directly connected to the coating container 1 in this system, but with its inlet to the feed tank 5 and with its outlet to the stack container 13th
  • the weakly acidic cation exchanger 14 is loaded here with cooled process solution.
  • a volume flow of the process solution is passed through the heat exchanger 4 and cooled in this from the treatment temperature of 85 ° C to temperatures ⁇ 50 ° C.
  • This cooled solution is collected in the storage tank 5, and passed from this over the weakly acidic cation exchanger 14.
  • the weakly acidic cation exchanger 14 takes place in analogy to Fig. 1 , an enrichment of the treated solution with nickel ions and an increase in the pH.
  • the treated solution is collected in the stack container 13 and returned to the coating container 1 via the heat exchanger 4.
  • the weakly acidic cation exchanger 14 is subjected to a cooled process solution, which significantly reduces the risk of a chemical-reductive metal deposition on the cation exchange polymer.

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  • Chemical Treatment Of Metals (AREA)
EP08022592A 2003-05-12 2004-05-12 Procédé et dispositifs pour prolonger la durée d'utilisation d'une solution de procédé utilisée dans un processus de revêtement métallique par réduction chimique Withdrawn EP2039810A3 (fr)

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DE2003122120 DE10322120A1 (de) 2003-05-12 2003-05-12 Verfahren und Vorrichtungen zur Verlängerung der Nutzungsdauer einer Prozesslösung für die chemisch-reduktive Metallbeschichtung
EP04738516A EP1623058A2 (fr) 2003-05-12 2004-05-12 Procede et dispositifs pour prolonger la duree d'utilisation d'une solution de procede utilisee dans un processus de revetement metallique par reduction chimique

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EP04738516.6 Division 2004-05-12

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EP04738516A Withdrawn EP1623058A2 (fr) 2003-05-12 2004-05-12 Procede et dispositifs pour prolonger la duree d'utilisation d'une solution de procede utilisee dans un processus de revetement metallique par reduction chimique

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DE102004038693B4 (de) * 2004-08-10 2010-02-25 Blasberg Werra Chemie Gmbh Vorrichtung und Verfahren zur Entfernung von Fremdstoffen aus Prozesslösungen und Verfahren zur Regenerierung eines Kationenaustauschers
EP1803837B2 (fr) 2005-11-25 2024-10-23 MacDermid Enthone Inc. Procédé pour le nettoyage de solutions de traitement
DE102008056776A1 (de) 2008-11-11 2010-05-12 Enthone Inc., West Haven Galvanisches Bad und Verfahren zur Abscheidung von zinkhaltigen Schichten
DE102018008312A1 (de) * 2018-10-22 2020-04-23 RIAG Oberflächentechnik AG Verfahren zur Beschichtung von Substratoberflächen, Vorrichtung mit Beschichtungsbad, Dichtemesseinrichtung, Entnahmeeinrichtung, Zugabeeinrichtungen und Steuerung
CN110880449B (zh) * 2019-09-30 2022-07-19 王偲偲 一种硅片清洗方法

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US2726969A (en) 1953-12-03 1955-12-13 Gen Motors Corp Chemical reduction plating process
US2726968A (en) 1953-12-03 1955-12-13 Gen Motors Corp Electroless nickel solution control

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US4863612B1 (en) * 1987-08-10 1994-11-01 Kineticon Inc Apparatus and method for recovering materials from process baths
US5112392A (en) * 1991-06-21 1992-05-12 Martin Marietta Energy Systems, Inc. Recovery process for electroless plating baths
DE4310366C1 (de) * 1993-03-30 1994-10-13 Fraunhofer Ges Forschung Verfahren zum Regenerieren von wässrigen, außenstromlos arbeitenden Beschichtungsbädern
DE19851180C1 (de) * 1998-11-06 2000-04-20 Guv Ges Fuer Umweltvertraeglic Verfahren zum Regenerieren einer Prozeßlösung

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US2726969A (en) 1953-12-03 1955-12-13 Gen Motors Corp Chemical reduction plating process
US2726968A (en) 1953-12-03 1955-12-13 Gen Motors Corp Electroless nickel solution control

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EP2039810A3 (fr) 2011-11-02
WO2004101866A3 (fr) 2005-07-21
EP1623058A2 (fr) 2006-02-08
DE10322120A1 (de) 2004-12-09
WO2004101866A2 (fr) 2004-11-25
EP2039810A8 (fr) 2011-12-14

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