EP1979511A2 - Procédé et dispositif pour revêtir les surfaces d'un substrat - Google Patents

Procédé et dispositif pour revêtir les surfaces d'un substrat

Info

Publication number
EP1979511A2
EP1979511A2 EP07703047A EP07703047A EP1979511A2 EP 1979511 A2 EP1979511 A2 EP 1979511A2 EP 07703047 A EP07703047 A EP 07703047A EP 07703047 A EP07703047 A EP 07703047A EP 1979511 A2 EP1979511 A2 EP 1979511A2
Authority
EP
European Patent Office
Prior art keywords
electrolyte
density
coating
bath
density value
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP07703047A
Other languages
German (de)
English (en)
Other versions
EP1979511B1 (fr
Inventor
Helmut Horsthemke
Franz-Josef Stark
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MacDermid Enthone Inc
Original Assignee
Enthone Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Enthone Inc filed Critical Enthone Inc
Priority to PL07703047T priority Critical patent/PL1979511T3/pl
Priority to EP07703047.6A priority patent/EP1979511B1/fr
Publication of EP1979511A2 publication Critical patent/EP1979511A2/fr
Application granted granted Critical
Publication of EP1979511B1 publication Critical patent/EP1979511B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C23C18/1633—Process of electroless plating
    • C23C18/1675—Process conditions
    • C23C18/1683—Control of electrolyte composition, e.g. measurement, adjustment
    • 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
    • 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
    • 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
    • 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
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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

Definitions

  • the present invention relates to a method and a device for coating substrate surfaces with a metallic or oxidic layer in a coating bath.
  • a substrate surface is to be provided with a metallic coating
  • the substrate to be coated is brought into contact with a treatment solution which contains the metal to be deposited in the form of its cations.
  • the cations in solution can be deposited as a metallic layer on the substrate surface.
  • the reduction can take place with the aid of a voltage applied between the substrate and a counterelectrode or else by means of reducing agents present in the solution. Accordingly, these are galvanic (electrochemical) or autocatalytic (electroless) brushing methods.
  • the treatment solutions which are generally referred to as electrolytes, comprise further additives which, in particular, have the properties of the deposited layers, such as, for example, B. influence the compressive residual stress or hardness.
  • the said method has in common that the electrolytes used change their composition during the treatment process.
  • the electrolyte is depleted by the ions of the metal to be deposited.
  • corresponding metal ion releasing components must be added to the electrolyte.
  • a measure of the performance of an electrolyte is the number of so-called metal turn-overs (MTO).
  • MTO metal turn-overs
  • This object is achieved with regard to the method by a method for coating substrate surfaces with a metallic or oxidic layer in a coating bath, wherein the bath has at least one component whose concentration changes in the course of the coating process and which consequently leads to the preservation of the coating Bath quality added or removed, characterized in that the addition and / or removal of the electrolyte component takes place in dependence on the density of the bath composition.
  • the basic idea of the present invention to maintain the density of the electrolyte composition in the equilibrium state, that is, in a state in which optimum coating results are obtained, by suitable means, so that the density does not further increase in the further course of the process.
  • this is achieved by determining the density of the electrolyte, comparing the determined density value with a stored nominal density value for an optimum electrolyte composition, ie an electrolyte composition in the equilibrium state, and at least one component of the electrolyte as a function of the deviation of the determined density value from the nominal density value removed and / or supplemented.
  • this can be done by continuously withdrawing from the coating bath a tunable amount of the electrolyte composition from the electrolyte, thereby artificially depriving electrolyte.
  • the method according to the invention deposits layers while the electrolyte composition remains the same, resulting in consistent coating results and layer properties, such as consistently high compressive residual stress, over the entire period of use of the electrolyte.
  • the determination of the density of the electrolyte composition may be continuous or discontinuous during the coating process.
  • the determined density value of the coating bath is compared according to the invention with a setpoint density value and the supplementation and / or removal takes place as a function of the deviation of the determined density value from the setpoint density value.
  • the setpoint density value can be stored in a data storage unit.
  • the setpoint density value can then be compared by means of a computer unit with the determined density value of the coating bath.
  • the computer unit determines the deviation of the current density value of the coating bath from the setpoint density value and determines the amount of electrolyte composition to be taken and / or supplemented or at least one component thereof.
  • the computer unit controls an electronically controllable removal and / or supplemental device for removing or supplementing the electrolyte composition or at least one component of the electrolyte composition, with the proviso to adjust the density of the coating bath to the stored nominal density value.
  • the withdrawn amount of electrolyte or electrolyte component can be collected and fed to a central reprocessing.
  • electrolytes can be used in the equilibrium state, which can be held in this by means of the method according to the invention.
  • the user immediately has an electrolyte available, which immediately, ie without start-up phase, delivers consistent coating results.
  • the inventive method can be used both for the galvanic and for the autocatalytic deposition of metal or metal alloy layers on surfaces of a substrate.
  • the method according to the invention can also be used in treatment solutions for forming an oxide layer on the surface of a metallic substrate.
  • These treatment solutions can also be optimized by controlling the density of the treatment solution. For example, the anodizing of aluminum surfaces is mentioned here.
  • a device for the continuous removal and / or addition of at least one electrolyte component of an electrolyte for coating substrate surfaces with a metallic or oxidic layer which comprises a device for removing and / or adding at least one electrolyte component Device for determining the density of the electrolyte and a computer unit, wherein the means for removing and / or adding the at least one electrolyte component is controlled by the computer unit, wherein the computer unit determined by the means for determining the density of the electrolyte density value with a stored desired density value compares with the proviso that the density of the Electrolytes the predetermined and stored in the data storage device setpoint density is adjusted by adding and / or removing at least one component of the electrolyte.
  • the means for adding and / or removing may advantageously be a pump or a valve.
  • the device for determining the density may be a pycnometer, a spindle, a density balance, a bending vibrator or any other suitable device for density determination.
  • the density can be determined indirectly via the calculation index by means of a refractometer.
  • the device according to the invention can comprise further devices for determining bathing properties such as temperature, conductivity, pH, specific extinction or absorption, turbidity, wherein the values determined by means of this device can also be fed to the computer unit and compared with desired values stored in the storage device can be, with the computer unit can further control the determined bathing properties influencing facilities such as heating and cooling systems, filter systems or regeneration systems, with the proviso to adjust the bathing properties to the stored setpoints.
  • bathing properties such as temperature, conductivity, pH, specific extinction or absorption, turbidity
  • the device according to the invention can be integrated into existing coating systems.
  • the amount of electrolyte removed by means of the device or at least one component of the electrolyte can be in. suitable facilities are collected and fed to a central reprocessing.
  • suitable devices may be, for example, reusable containers, tank systems and the like.
  • the method according to the invention and the device according to the invention can be combined with further methods or devices for improving the duration of use of electrolyte compositions.
  • the process according to the invention can be combined with the process for electroless deposition of metals known from European patent application EP 1 413 646 A2, in which metal-base salts are used whose anions are volatile.
  • the increase in density occurring during the lifetime of an electrolyte is reduced by the escape of the anions from the electrolyte composition, which can be further optimized in combination with the method according to the invention and the device according to the invention.
  • Such an electrolyte for the electroless deposition of metal layers contains a metal-base salt, a reducing agent, a complexing agent, an accelerator and a stabilizer, wherein the electrolyte comprises, as metal-base salt, a metal salt whose anions are volatile, preferably in a concentration of 0.01 to 0.3 mol / l.
  • This metal salt whose anions are volatile is preferably at least one salt selected from the group consisting of metal acetate, metal formate, metal nitrate, metal oxalate, metal propionate, metal citrate and metal ascorbate, preferably metal acetate.
  • the life of the electrolyte can be extended at high deposition rates and uniformly deposited layers with constant layer properties. At the same time, layers with compressive residual stress are deposited.
  • Such an electrolyte is basically composed of one or more metal base salts, preferably metal acetate and a reducing agent, preferably sodium hypophosphite. Furthermore, the electrolyte Various additives, such as complexing agents, accelerators and stabilizers, which are advantageously used in acidic electrolytes for the electroless deposition of nickel added. Since the deposition rate is significantly higher in an acidic medium, an acid is preferably added to the electrolyte as a complexing agent.
  • carboxylic acids and / or polycarboxylic acids turns out to be particularly advantageous since, on the one hand, it determines the advantageous solubility of the metal salts and the controlled control of the free metal ions and, on the other hand, prescribes the adjustment of the pH required for the process due to their acid strength . facilitated.
  • the pH of the electrolyte is advantageously in the range of 4.0 to 5.2.
  • the dissolved metal is particularly advantageously complexed by the use of carboxylic acids and / or polycarboxylic acids whose salts and / or derivatives, preferably hydroxy (poly) carboxylic acids, particularly preferably 2-hydroxypropanoic acid and / or propanedioic acid. At the same time, these compounds serve as activators and as pH buffers and contribute significantly to the stability of the bath by their advantageous properties.
  • a sulfur-containing heterocycle is added to the electrolyte as accelerator.
  • the sulfur-containing heterocycle used is preferably saccharin, its salts and / or derivatives, particularly preferably sodium saccharin.
  • the addition of saccharinate, even in higher concentrations, does not adversely affect the corrosion resistance of the deposited metal layers.
  • a stabilizer is added to the electrolyte in order to counteract a spontaneous decomposition of the metallizing bath.
  • a stabilizer may be, for example, metals, halogen compounds and / or sulfur compounds, such as thioureas.
  • metals such as thioureas.
  • the use of metals as stabilizers has proved to be particularly advantageous.
  • These salts are preferably one or more of the salts from the group consisting of acetates, formates, nitrates, oxalates, propionates, citrates and ascorbinates, more preferably acetates.
  • the metal layers should have, besides phosphorus further components, such as, for example, additional metals, preferably cobalt, and / or finely dispersed particles are incorporated into the layer.
  • additional components such as salts, preferably potassium iodide.
  • the quality of the metallization bath is improved and the life is considerably extended, up to an unlimited lifetime of the metallization bath.
  • This has the advantage that not only high deposition rates are achieved by the use of the method according to the invention, but also that the deposited by the process layers are uniform and high quality, have a very good adhesion and are consistently free of pores and cracks.
  • the metallization of the surface is improved, especially by more complex substrates.
  • the method proposed by the invention .. is in a preferred embodiment by the composition of the electrolyte in combination with the addition and / or removal of at least one bath component depending on the density. In this embodiment, therefore, it is advantageously economical and more environmentally friendly than the conventional methods known from the prior art.
  • An electrolyte as described above for the preferred implementation of the method according to the invention, may, for example in the case of nickel plating, have essentially the following composition:
  • metal salts whose anions are volatile are advantageously used as metal receivers.
  • Preferred metal salts whose anions are volatile are one or more salts from the group consisting of metal acetates, metal formates, metal nitrates, metal oxalates, metal propionates, metal citrates and metal ascorbinates, more preferably exclusively metal acetate.
  • the electrolyte according to the invention thus operates in a pH range of 4.0 to 5.2 throughout the deposition process, preferably 4.3 to 4.8, without having to be additionally added larger amounts of alkaline media. Due to the extremely advantageous pH self-regulation can be dispensed with during the process on a continuous pH control and alkaline additives.
  • the concentration of the metal base salts is based on nickel at 0.04 to 0.16 mol / l, preferably 0.048 to 0.105 mol / l, wherein the content of metal between 0.068 to 0.102 mol / l, preferably 0.085 mol / l.
  • the reducing agent used is preferably sodium hypophosphite having a concentration of from 25 to 65 g / l.
  • the complexing agents used are carboxylic acids and / or polycarboxylic acids, their salts and / or derivatives, preferably hydroxy (poly) carboxylic acids, particularly preferably 2-hydroxypropanoic acid and / or propanedioic acid.
  • the dissolved nickel is particularly advantageously complexed, so that the deposition rate can be maintained in a corresponding interval of 7 to 14 .mu.m / h, preferably 9 to 12 .mu.m / h with continuous addition of such complexing agents.
  • the concentration of complexing agents in the base electrolyte is between 25 and 70 g / l, preferably 30 to 65 g / l.
  • the concentration of the accelerator preferably using a sulfur-containing heterocycle, more preferably saccharin, its salts and / or derivatives, most preferably sodium saccharin, is from 1 to 25 g / l, preferably from 2.5 to 22 g / l.
  • Stabilizers which may be used are halogen compound and / or sulfur compound, preferably thiourea. Particularly advantageous, however, is the use of metals, preferably lead, bismuth, zinc and / or tin, particularly preferably in the form of salts whose anions are volatile. These salts are preferably selected from the group consisting of acetates, formates, nitrates, oxalates, propionates, citrates and ascorbinates.
  • the nitrates of the metals used as stabilizers are advantageously from 0.1 to 2 mg / l, preferably from 0.3 to 1 mg / l.
  • further constituents for example potassium iodide, in a concentration of 0 to 3 g / l may also be added to the base electrolyte.
  • this basic electrolyte a variety of substrates are introduced and galvanized. To support the lifetime and the stability of the electrolyte, it can be regenerated during the deposition process by means of electrodialysis and / or ion exchange resins. Likewise, supplemental solutions (as exemplified below) may be added to the electrolyte during the deposition process. These replenisher solutions are specially designed to control the individual contents of the basic components and added to the electrolyte in different amounts.
  • a first replenisher solution includes, for example, the following composition:
  • the same substances as in the base electrolyte are advantageously used. This results in another very important advantage of the method according to the invention. Since the same substances are used continuously and there are almost no impurities and precipitations, even the compounds from the sink can be returned to the electrolyte.
  • the process of the invention thus has a decided material cycle, which makes the process thus more economical and environmentally conscious.
  • the complexing agent content and the content of alkaline buffer are chosen so that the total content of the complexing agents in the electrolyte is 70 to 90 g / l.
  • the content of the accelerator in the electrolyte is controlled so that, for example, in the case of a nickel electrolyte in the use of Sodium saccharinate as accelerator per gram of deposited nickel between 0.100 and 0.200 g, preferably 0.150 g are added.
  • the following composition can be used:
  • the complexing agent of the second replenisher solution may be the same as in the first replenisher or, if necessary, another.
  • a hydroxycarboxylic acid for example 2-hydroxypropanoic acid of 60 g / l
  • propanedioic acid with a content of 0.5 g / l
  • the content of propanedioic acid is then increased by 0.005 to 0.015 g / g of deposited nickel.
  • metal sulfate in addition to the metal base salts described so far, a deposition of adherent metal layers with compressive residual stresses at a throughput of at least 14 MTO guaranteed.
  • metal-base salts whose anion has at least one carbon atom and which preferably originate from the group of acetates, formates, oxalates, propionates, citrates and ascorbinates, the lifetime of the electrolyte continues to increase.
  • the already mentioned compressive residual stress is an extremely important and very desirable layer property. It positively influences the bending cycle stress and increases the ductility. So z.
  • metal layers with a ductility of> 0.5% are deposited.
  • the residual compressive stresses have a positive effect on the corrosion resistance of the metal-phosphorus layers.
  • other components such as additional metals, preferably copper, and / or finely disperse particles, such as finely dispersed fluorine-containing thermoset or thermosetting plastic, may be added to the electrolyte as well as the replenisher, which in the deposited layers additional hardness, dry lubricating effects and / or achieve other properties.
  • Such an electrolyte has a self-regulating pH range of 4.3 to 4.8 and allows deposition rates of 8 to 12 ⁇ m / hr.
  • the internal stress of the deposited layers is -10 to - 40 N / mm 2 .
  • the method and apparatus of the present invention can also be advantageously combined with electrodialysis methods and apparatus or other means of regenerating coating compositions.
  • the electrolyte according to the invention can be regenerated, for example, by means of electrodialytic processes.
  • metal salts whose anions are volatile the separation effect of the electrodialysis plant is significantly increased.
  • the number of electrolysis cells for the separation of orthophosphite ions can be reduced with the same separation efficiency.
  • the withdrawn and collected amounts of electrolyte in the case of a hypophosphite as the reducing agent having electrolyte in a central recycling of a phosphate recovery are supplied.
  • the coating bath has at least one component whose concentration changes in the course of the coating process and which must be supplemented or removed in order to maintain the bath quality, wherein the supplementation and / or removal the component is a function of the density of the bath composition and the bath composition comprises a metal base salt, a reducing agent, a complexing agent, an accelerator and a stabilizer, wherein the bath composition comprises as metal base salt a metal salt whose anions are volatile and in an initial concentration of 0.01 to 0.30 mol / 1 is present.
  • Fig. 1 shows the density profile of an electrolyte as a function of the operating time.
  • Fig. 3 shows the loss of material in electrolytes at constant operating mode.
  • FIG. 4 shows a process diagram of a device according to the invention.
  • Fig. 1 the profile of the density of different electrolyte compositions depending on the operating time of the electrolyte and the removed Amount of electrolyte reflected.
  • Curve No. 1 shows the density profile of an electrolyte known from the prior art for the deposition of nickel layers.
  • Curve No. 2 shows the density profile of an electrolyte known from the prior art for depositing a nickel layer at a set removal quantity of electrolyte of 3.3%.
  • Curve No. 3 shows the density profile of an electrolyte, as known from the European patent application EP 1 413 646, in which the metal base salt of the electrolyte composition used is metal salts whose anions are volatile.
  • Curve No. 4 shows the electrolyte described in Curve No. 3 at a 3.3% electrolyte removal set.
  • Curve No. 5 shows the electrolyte described for Curve No. 3 at a set removal amount of electrolyte of 10%.
  • Fig. 3 shows the relative loss of material in the electrolyte per MTO compared to the electrolyte age in the equilibrium state.
  • the left borderline represents a conventional electrolyte system.
  • the right border corresponds to an electrolyte system according to EP 1 413 646 A2.
  • FIG. 4 shows a process diagram of a device according to the invention.
  • the individual components required for the production of the electrolyte are transferred into the electrolyte bath 2 by means of suitable conveying media, such as pumps.
  • the electrolyte composition in the electrolyte bath 2 is analyzed either directly in the electrolyte bath or in an external control module 3 supplied with a partial flow from the electrolyte bath, with regard to its chemophysical properties such as density, pH, temperature, conductivity or metal content.
  • Both the component container 1 A to 1 F and the electrolyte bath and the receptacle for withdrawn electrolyte advantageously have level sensors that register exceeding or falling below filling limits and output appropriate messages and / or initiate appropriate process steps to maintain the trouble-free coating operation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Automation & Control Theory (AREA)
  • Chemically Coating (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

La présente invention concerne un procédé pour revêtir les surfaces d'un substrat d'une couche métallique ou oxydique dans un bain de revêtement qui comprend au moins une composante dont la concentration varie au cours du processus de revêtement et dont on doit pour cette raison assurer le complément ou le prélèvement afin de conserver la qualité du bain. Le procédé de l'invention se caractérise en ce que le complément et/ou le prélèvement de la composante s'effectue en fonction de la masse volumique de la composition du bain.
EP07703047.6A 2006-02-02 2007-01-26 Procédé pour revêtir les surfaces d'un substrat Active EP1979511B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL07703047T PL1979511T3 (pl) 2006-02-02 2007-01-26 Sposób powlekania powierzchni substratu
EP07703047.6A EP1979511B1 (fr) 2006-02-02 2007-01-26 Procédé pour revêtir les surfaces d'un substrat

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06002099A EP1816237A1 (fr) 2006-02-02 2006-02-02 Procédé et appareil pour le placage de surfaces d'un substrat
EP07703047.6A EP1979511B1 (fr) 2006-02-02 2007-01-26 Procédé pour revêtir les surfaces d'un substrat
PCT/EP2007/000658 WO2007088008A2 (fr) 2006-02-02 2007-01-26 Procédé et dispositif pour revêtir les surfaces d'un substrat

Publications (2)

Publication Number Publication Date
EP1979511A2 true EP1979511A2 (fr) 2008-10-15
EP1979511B1 EP1979511B1 (fr) 2018-10-31

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP06002099A Withdrawn EP1816237A1 (fr) 2006-02-02 2006-02-02 Procédé et appareil pour le placage de surfaces d'un substrat
EP07703047.6A Active EP1979511B1 (fr) 2006-02-02 2007-01-26 Procédé pour revêtir les surfaces d'un substrat

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP06002099A Withdrawn EP1816237A1 (fr) 2006-02-02 2006-02-02 Procédé et appareil pour le placage de surfaces d'un substrat

Country Status (8)

Country Link
US (1) US20090324804A1 (fr)
EP (2) EP1816237A1 (fr)
JP (1) JP5695295B2 (fr)
KR (1) KR101466995B1 (fr)
CN (1) CN101437986B (fr)
ES (1) ES2706874T3 (fr)
PL (1) PL1979511T3 (fr)
WO (1) WO2007088008A2 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US20090324804A1 (en) 2009-12-31
WO2007088008A3 (fr) 2008-04-17
JP2009525404A (ja) 2009-07-09
EP1816237A1 (fr) 2007-08-08
KR20080093451A (ko) 2008-10-21
WO2007088008A2 (fr) 2007-08-09
EP1979511B1 (fr) 2018-10-31
KR101466995B1 (ko) 2014-12-01
CN101437986A (zh) 2009-05-20
CN101437986B (zh) 2013-12-11
PL1979511T3 (pl) 2019-05-31
ES2706874T3 (es) 2019-04-01
JP5695295B2 (ja) 2015-04-01

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