EP3000918A1 - Procédé et dispositif d'application galvanique d'un revêtement de surface - Google Patents

Procédé et dispositif d'application galvanique d'un revêtement de surface Download PDF

Info

Publication number
EP3000918A1
EP3000918A1 EP14186089.0A EP14186089A EP3000918A1 EP 3000918 A1 EP3000918 A1 EP 3000918A1 EP 14186089 A EP14186089 A EP 14186089A EP 3000918 A1 EP3000918 A1 EP 3000918A1
Authority
EP
European Patent Office
Prior art keywords
reactor
electrolyte solution
temperature
electrolyte
surface coating
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
EP14186089.0A
Other languages
German (de)
English (en)
Other versions
EP3000918B1 (fr
Inventor
Karl Müll
Thomas Bolch
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.)
Topocrom Systems AG
Original Assignee
Topocrom Systems AG
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 Topocrom Systems AG filed Critical Topocrom Systems AG
Priority to EP14186089.0A priority Critical patent/EP3000918B1/fr
Publication of EP3000918A1 publication Critical patent/EP3000918A1/fr
Application granted granted Critical
Publication of EP3000918B1 publication Critical patent/EP3000918B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/04—Electroplating with moving electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/02—Tanks; Installations therefor
    • 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
    • C25D21/02—Heating or cooling
    • 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
    • C25D21/04—Removal of gases or vapours ; Gas or pressure control
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • 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
    • 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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium

Definitions

  • the present invention relates to a method and a device for electroplating a surface coating, in particular a chromium coating.
  • machine components For various technical applications, it is desirable or even necessary to use machine components with special surface properties. Examples include filament-leading components in the textile and carbon fiber area, rollers and rollers in the printing area, rollers in feed machines in the sheet metal industry, as well as temper rolling for texturing of sheets for example, the automotive industry called.
  • a suitable method for providing such surface coatings is a chrome plating of a corresponding component.
  • the TOPOCROM ® process is carried out in a galvanic bath containing a chromium electrolyte, such as a sulphate of chromium electrolyte.
  • a chromium electrolyte such as a sulphate of chromium electrolyte.
  • the component to be coated forms the Cathode.
  • an anode for example made of platinum-plated titanium
  • a chromium layer is deposited on the component acting as a cathode.
  • the present invention relates to a method for electroplating a surface coating, in particular a chromium coating, on a body, for example a machine component, wherein a layer of a compound which can be oxidized by an inserted electrolyte solution is applied to the body before the surface coating is applied by electroplating, preferably a polyhydroxy compound having a viscosity of at least 1000 mPas at 25 ° C is applied.
  • Electroplating a surface coating is well known. Basically, this is an electrochemical process in which electrodes are placed in an electrolyte bath. If direct current is applied to the electrodes, a redox reaction (electrolysis) occurs and an associated generation of chemical elements or compounds at the electrodes occurs.
  • a redox reaction electrolysis
  • a chromic acid-containing solution In the case of a chrome plating a surface is used as the electrolyte, a chromic acid-containing solution. Chromic acid (H 2 CrO 4 ) forms in dilute aqueous solutions of CrO 3 . The reduction of the Cr (VI) ions from the electrolyte to the element Cr succeeds in the presence of a catalyst.
  • sulfuric acid (H 2 SO 4 ) is used alone or together with hydrofluoric acid, complex fluorides or an aliphatic sulfonic acid having one to three carbon atoms (preferably methanesulfonic acid).
  • Common electrolyte solutions contain, for example, 250 g CrO 3 and 2.5 g sulfuric acid in 1 l water, or 200-300 g CrO 3 , 1.9-3.3 g H 2 SO 4 and 1.5-12 g methanesulfonic acid in 1 l Water.
  • anode of lead or preferably of platinized titanium can be used as the anode.
  • the body to be coated with chromium is used as the cathode.
  • any body can be used as the cathode, which can be coated with chromium.
  • the body to be coated is preferably a machine component, for example conveyor rollers for the textile and carbon fiber sector, for rolls and rolls in the printing field, rolls in feed machines in the sheet metal industry, as well as temper rolling for texturing of sheets for, for example, the automotive industry.
  • Such bodies are usually made of iron or steel, but may also consist of other materials.
  • the body to be coated is preferably a rotationally symmetrical body which can be rotated during the galvanic process to achieve a uniform surface coating.
  • the chrome plating is usually carried out with a direct current of 10 to 200 A / dm 2 , preferably 25 to 150 A / dm 2 and more preferably 30 to 100 A / dm 2 .
  • a current guide as used in the EP-0 565 070 B1 and the EP-0 722 515 B1 is described, ie by means of a DC application method, wherein by means of at least one initial pulse of the electrical voltage and / or the electric current on the surface to be coated nucleations of the deposition material are achieved and that subsequently by means of at least one subsequent pulse growth of Abscheidematerialkeime by addition of further deposition material is brought about, wherein during the nucleation phase, the increase of the electrical voltage and / or the electric current takes place in several stages, the time between the increases between 0.1 and 30 seconds, whereby current density changes in steps of 1 to 6 mA / cm 2 ,
  • the body functioning as a cathode usually undergoes several pretreatment stages prior to use in the described electrodeposition process.
  • the chrome plating of surfaces is difficult and runs with low current yields in the range of only about 15-20%.
  • a high current density (overvoltage) is required, whereby the reduction to elemental chromium at the cathode in competition with the formation of hydrogen (from the H 3 O + ions of the acidic aqueous electrolyte solution) as well as the formation of Cr 3+ ions from the chromic acid stands.
  • the current density required for the chromium deposition depends, inter alia, on the cathode material and the nature of the surface of the cathode material.
  • cathode materials are usually mechanically pretreated, for example by grinding or sandblasting, in order to obtain the smoothest possible surface. Additional chemical and / or electrochemical pretreatment stages usually follow. The entire pre-treatment of the body to be coated requires several separate pretreatment baths, it waste water and it must be taken costly measures for protection at work.
  • the surface of the body to be coated is provided with a layer of a compound oxidizable by an inserted electrolyte solution, preferably a polyhydroxy compound, with a viscosity of at least 1000 mPas at 25 ° C.
  • each compound can be used for the pretreatment, which is oxidizable on the one hand by an inserted electrolyte solution, but on the other hand is sufficiently viscous that it dwells sufficiently long on the surface of the body to be coated and does not flow off the surface too quickly, ie forms a surface film
  • Cr (VI) compounds are known to be strong oxidants and can, for example, oxidize alcohols. It has been found according to the invention that polyhydroxy compounds, ie chemical compounds having at least two hydroxyl groups, are very suitable for the pretreatment according to the invention, provided they have a sufficient viscosity.
  • the polyhydroxy compound is preferably selected from the group consisting of glycerol, carbohydrates, such as glucose, fructose or sucrose, preferably glucose, and certain polyalkylene oxides, such as polyethylene glycol.
  • carbohydrates such as glucose, fructose or sucrose, preferably glucose
  • certain polyalkylene oxides such as polyethylene glycol.
  • polyalkylene oxides which are liquid at room temperature or solutions of polyalkylene oxides such as, for example, polyethylene glycol 1500 (from Merck) can be used.
  • Glycerol or polyethylene glycol 1500 is preferred according to the invention.
  • the compound to be used for the pretreatment must be sufficiently viscous that it lingers sufficiently long on the surface of the body to be coated and does not flow off the surface too quickly.
  • the compound to be used should have a viscosity of at least 1000 mPas at 25 ° C. According to the invention, this is a dynamic viscosity which is measured using a conventional rotary viscometer (Searle system) according to DIN 53 019-1; 2008-09 at 25 ° C is determined.
  • a compound to be used for the pretreatment preferably has a viscosity of from 1000 mPas to 6000 mPas, preferably from 1200 to 4500 mPas, at 25 ° C.
  • the compound to be used for the pretreatment can be used manually or advantageously with a cleaning cloth impregnated with the substance be applied by machine to the surface of the body to be coated.
  • the application is preferably carried out with the aid of an orbital sander, which is provided with the compound to be used for the pretreatment and moved uniformly over the surface of the body to be coated.
  • the pretreatment step according to the invention leads to various unexpected advantages.
  • the body to be coated can be subjected to the galvanic coating process after any mechanical pretreatment such as grinding or sandblasting without additional complex chemical and / or electrochemical pretreatment.
  • the body to be coated is preferably cleaned with an alcohol, preferably ethanol, before the pretreatment process according to the invention.
  • an alcohol preferably ethanol
  • wipes impregnated with alcohol may be provided and passed over the surface of the body to be coated manually or by means of a suitable machine. As a result, any residues on the surface due to mechanical pretreatment such as grinding or sandblasting are removed.
  • This layer obviously supports the subsequent deposition of chromium during the galvanic process, which can be concluded from the fact that due to the pretreatment according to the invention, an otherwise usual polarity reversal of the electrodes for activating the surface of the body to be coated is no longer necessary.
  • This represents a considerable advantage since iron ions (in the case of a body to be coated made of iron) or other foreign ions are formed during a conventional polarity reversal of the electrodes and pass into the electrolyte. This leads to increasing contamination of the electrolyte and requires its relatively early replacement.
  • this reversal step is eliminated, which lengthens the life of the electrolyte extraordinarily. Especially with regard to the expected regulatory tightening when dealing with Cr (VI) -containing compositions, this is of considerable importance.
  • a chromium plating process such as the TOPOCROM ® process
  • several layers of metal preferably chromium layers deposited one above the other.
  • a base layer is first applied in one embodiment of the TOPOCROM ® process which is little cracking and has a thickness of preferably 25 to 40 .mu.m, in particular 30 microns.
  • a so-called structural layer can be applied to this base layer.
  • the structured chromium layer formed therein comprises hemispherical dome.
  • a cover layer for protecting the structure layer can subsequently also be applied to the structure layer, which preferably has a thickness of preferably 2 to 20 ⁇ m, more preferably 3 to 15 ⁇ m and in particular 4 to 10 ⁇ m.
  • the preparation of such a three-layer structure of chromium is for example in the EP-0 565 070 B1 and the EP-0 722 515 B1 described.
  • the present invention furthermore relates to a process for the electroplating of a surface coating, in particular a chromium coating, onto a body, for example a machine component, wherein the surface coating is carried out in a preferably closed reactor in an at least two-stage, preferably three-stage process, characterized in that an electrolyte solution containing in the reactor with a temperature T1 for the implementation of a subsequent process stage is replaced by an electrolyte solution with a temperature T2 ⁇ T1.
  • a multilayer structure here means the production of at least two, preferably three, but optionally also more layers one above the other on the surface of a body to be coated.
  • an error-free multilayer coating is realized on the surface of a body to be coated, without the body being removed from the reactor must be removed.
  • the process can be operated in compliance with the currently expected tightening of regulatory requirements without waste water and emissions (ie without pollution at the workplace, the exhaust air from the reactor is discharged through a closed system, cleaned and then easily discharged).
  • the process is very gentle with respect to the electrolytes used.
  • the electrolytes used have a very long lifetime, which is of considerable importance, in particular with regard to the expected regulatory tightening when handling Cr (VI) -containing compositions.
  • the individual process stages are not realized by heating or cooling a single electrolyte contained in the reactor. Rather, according to the invention, an electrolyte solution having a temperature T1 for the next process stage is replaced by an electrolyte solution having a temperature T2 ⁇ T1, i. There is an exchange of electrolyte solutions instead.
  • the replacement is preferably carried out by replacing the electrolyte solution with a temperature T1 by an electrolyte solution having a temperature T2 ⁇ T1 by introducing the electrolyte solution having a temperature T2 ⁇ T1 into the reactor and causing the electrolyte solution to extrude at a temperature T1 ,
  • an electrolyte solution having a temperature T2 ⁇ T1 in the bottom area of the reactor or in the lower area, preferably in the lower third, particularly preferably in the lower quarter of the reactor for carrying out the galvanic process.
  • the inlet is preferably equipped with a locking device, for example a valve or a door.
  • at least one outlet opening is arranged in the upper region, preferably in the upper third and particularly preferably in the upper fourth of the reactor.
  • the inlet is opened into the reactor and electrolyte solution with a temperature T2 ⁇ T1 introduced into the reactor, this electrolyte displaces the existing electrolyte in the reactor with a temperature T1, wherein the electrolyte is led out with the temperature T1 through the outlet from the reactor.
  • the outlet may be equipped with a locking device, such as a valve or a door.
  • the outlet can also be designed as an overflow system, ie at normal electrolyte level in the reactor, the outlet is above the electrolyte. Only by supplying electrolyte solution with a temperature T2 ⁇ T1 in the reactor, the electrolyte level in the reactor is raised so that it reaches the outlet and can flow through it from the reactor.
  • the various electrolyte solutions are preferably stored in separate containers and adjusted to the desired temperature outside the reactor for carrying out the galvanic process. It may be in the containers and conventional liquid tanks, which are resistant to the electrolyte used.
  • the adjustment of the temperature of the electrolyte can be carried out in a known manner, for example by heating elements.
  • the electrolyte containers are connected via connecting lines, preferably pipes, to the reactor for carrying out the galvanic process.
  • the from the different electrolyte containers coming pipes can be fed via separate inlets into the reactor.
  • blocking devices should be provided, for example a valve or a door, to allow selective introduction of a given electrolyte solution into the reactor.
  • the outlet or the outlets from the reactor are connected via connecting lines, preferably tubes, to the respective electrolyte containers.
  • the tubes leading into the various electrolyte containers can be connected to the interior of the reactor via separate outlets in the upper region of the reactor.
  • locking means such as a valve or door, are provided in the individual tubes prior to the point of fusion of the tubes, to allow selective transfer of a particular electrolyte solution from the reactor to the container intended for that electrolyte solution.
  • the electrolyte solution contained in the reactor during a process stage is circulated continuously by discharging out of the reactor and replacing it with the same electrolyte solution.
  • This can be done, for example, in that for this electrolyte solution, an inlet into the reactor and an outlet from the reactor can be flowed through (preferably by opening corresponding blocking devices) and this electrolyte solution, for example is continuously circulated by operating a circulation pump. This ensures a constant quality of the electrolyte solution in the reactor.
  • the present invention thus further relates to a device for electroplating a surface coating, in particular a chromium coating, in particular for carrying out a method described above, comprising a reactor for receiving a body to be coated, for example a machine component, an anode and at least two, preferably two, electrolyte containers. characterized in that the electrolyte containers (are connected via connecting lines through separate inlets and outlets to the interior of the reactor.
  • the inventive method is particularly preferably designed such that the surface coating is carried out in a three-stage process, wherein the first process stage is performed in the reactor with an electrolyte solution having a temperature T1, then the second process stage with an electrolyte solution having a temperature T2 ⁇ T1 is performed , and the third process stage is performed with an electrolyte solution having a temperature T3 ⁇ T2.
  • T3 is equal to the temperature T1.
  • T2 ⁇ T1, and most preferably T2 ⁇ T1 and T1 T3.
  • This embodiment of the method according to the invention can be used to successively apply a base chrome layer, a structural chrome layer and a top layer in a chromium coating in three successive process steps.
  • the current flow in these process stages can be as in the EP-0 565 070 B1 and EP-0 722 515 B1 described carried out become.
  • an electrolyte is introduced into the reactor having a temperature in the range of 40 to 60 ° C, preferably 45 to 55 ° C.
  • this electrolyte is replaced by a second electrolyte having a lower temperature in the range of 25 to 39 ° C, preferably 30 to 38 ° C.
  • this second electrolyte With the aid of this second electrolyte, the deposition of the structural chromium layer is carried out.
  • this electrolyte is replaced by a third electrolyte again having a higher temperature in the range of 40 to 60 ° C, preferably 45 to 55 ° C.
  • the deposition of the top layer of chromium is carried out. If the same temperature is to be set for the first and third electrolytes, the same electrolyte can also be used for the first and third process stages.
  • the reactor for carrying out the galvanic process can have any desired shape.
  • a cylindrical shape is preferred.
  • the height and base area of the reactor can be varied depending on the body to be coated.
  • the top surface of the reactor can be opened, i.
  • the reactor is provided with one or more inlets and one or more outlets for the electrolyte solutions, which are connected via respective connecting lines to the containers for the electrolyte solutions.
  • the reactor is connected via power lines to a rectifier, from which the reactor is supplied with the power required for the galvanic process.
  • Rectifiers are known and need not be explained here.
  • it is not necessary to use reversible rectifiers, since polarity reversal is not required for the method according to the invention.
  • Advantageously according to the invention therefore cheaper, non-reversible rectifier can be used.
  • an anode is fixed.
  • an anode of platinized titanium is preferably used in the process according to the invention.
  • Lead electrodes can indeed be used in many cases, but have some disadvantages.
  • the body functioning as the cathode to be coated is arranged in the reactor such that its surface is at a distance from the anode in the range from 5 to 80 cm, preferably 30 to 60 cm.
  • any body can be used as the cathode, which can be coated with the process according to the invention, preferably can be coated with chromium.
  • the body to be coated is preferably a component of a machine, for example conveyor rollers for the textile and carbon fiber area, rollers and rollers in the printing area, rollers in drawing machines in the sheet metal industry, as well as temper rolling for texturing of metal sheets for example the automotive industry.
  • Such bodies are usually made of iron or steel, but may also consist of other materials.
  • the body to be coated is preferably a rotationally symmetrical body which can be rotated during the galvanic process to achieve a uniform surface coating.
  • the reactor is preferably equipped with a motor for rotating the body.
  • the motor is preferably arranged on the top surface of the reactor and can be connected in a simple manner, for example by means of a plug connection, to the body to be coated.
  • the galvanic process is preferably carried out while rotating the rotationally symmetrical body to be coated.
  • both measures described here are combined with one another, ie. the galvanic process is carried out in an at least two-stage, preferably three-stage process, wherein an electrolyte solution containing in the reactor with a temperature T1 for the implementation of a subsequent process stage is replaced by an electrolyte solution having a temperature T2 ⁇ T1, and wherein the body before the galvanic Applying the surface coating, a layer of a compound oxidizable by an inserted electrolyte solution, preferably a polyhydroxy compound, having a viscosity of at least 1000 mPas at 25 ° C is applied.
  • the polyhydroxy compound according to the invention is preferably selected from the group consisting of Glycerin, carbohydrates, and certain polyalkylene oxides such as polyethylene glycol, for example, polyethylene glycol 1500 (ex Merck).
  • polyalkylene oxides which are liquid at room temperature or solutions of polyalkylene oxides can be used.
  • Glycerol or polyethylene glycol 1500 is preferred according to the invention.
  • the pretreatment can be carried out as described above.
  • the reactor is furthermore preferred according to the invention for the reactor to be operated during the surface coating by means of a ventilation system for removing emerging gases.
  • a ventilation system for removing emerging gases.
  • hydrogen is formed at the cathode and oxygen at the anode.
  • the gaseous atmosphere in the reactor is preferably removed, for example by means of a suction pump, continuously or at certain times.
  • the entire inventive method can be carried out in a completely closed system. All process parameters and process steps, such as the current regulation, the supply and removal of the various electrolyte solutions, if appropriate, the suction of the reactor atmosphere, can be monitored and carried out with the aid of an electronic control unit.
  • the entire electrolyte solution is removed from the reactor and the coated body preferably with water or an aqueous Cleaning solution cleaned. Only then is the reactor opened to remove the coated body. There is no emission burden throughout the process.
  • the electrolyte used is stored in sealed containers and has a very long shelf life.
  • the present invention is by way of non-limiting
  • Fig. 1 is a schematic representation of an inventive device for carrying out the inventive method.
  • the device 1 comprises a reactor 2 for carrying out the galvanic process.
  • the reactor 2 is closed by a removable cover 3.
  • a body to be coated 4 preferably a rotationally symmetrical body, introduced as a cathode. Furthermore, an anode 5 is arranged in the reactor 2, which preferably consists of platinum-plated titanium.
  • the body 4 to be coated is connected to the lid 3 via a rotatable rod 6.
  • Electrolyte solution can be introduced into the reactor 2 from the electrolyte containers 7, 8 via connection lines 7a, 8a.
  • connection lines 7a, 8a In the Fig. 1 are only two containers 7, 8 with respective connecting lines 7a, 8a shown; however, additional containers and connecting lines may be provided as needed.
  • the connecting lines 7a, 8a can be opened and closed by means of blocking devices 7b, 8b, which are preferably valves, so that only a specific electrolyte selectively reaches the reactor 2.
  • connection lines 7 a, 8 a terminate in inlets arranged in the bottom surface of the reactor 2. In the upper third of the reactor 2 outlets are arranged, via which drain electrolyte and can flow back via connecting lines 7c, 8c in the electrolyte container 7,8.
  • the connection lines 7c, 8c can be opened and closed by means of blocking devices 7d, 8d, which are preferably valves, so that only a specific electrolyte from the reactor 2 reaches the intended electrolyte container 7, 8 in a targeted manner.
  • pumps (not shown) are provided.
  • a rectifier 9 operated with alternating voltage supplies the cathode 4 and anode 5 with the direct current required for the process via power lines 9a, 9b.
  • the device 1 is controlled by means of an electronic processing unit (not shown).
  • the rotationally symmetrical body is preferably pretreated before it is introduced into the reactor 2.
  • a mechanical surface treatment for example by grinding or sandblasting
  • the surface of the body 4 is first cleaned with a soaked in ethanol cleaning cloth.
  • a film of polyethylene glycol 1500 from Merck is applied to the surface of the body 4.
  • the thus pretreated body 4 for example a steel cylinder, is brought into the reactor 2, and the reactor 2 is closed with the lid 3.
  • a mixture of 250 g of CrO 3 and 2.5 g of sulfuric acid in 1 l of water is pumped from the container 7 as an electrolyte into the reactor 2.
  • the electrolyte is previously heated to 50 ° C.
  • the body 4 is rotated, current is applied, and a first chromium layer is formed.
  • the blocking devices 7b and 7d are opened and the blocking devices 8b, 8d are closed, and the electrolyte from the container 7 is continuously circulated.
  • the locking device 7b is closed and for the locking device 8b opened.
  • the locking device 7d remains open while the locking device 8d is closed.
  • a mixture of 250 g of CrO 3 and 2.5 g of sulfuric acid in 1 l of water is pumped from the container 8 as an electrolyte into the reactor 2.
  • the electrolyte is previously heated to 37 ° C.
  • the electrolyte from the container 8 forces the warmer electrolyte originating from the container 7 back into the container 7 via the line 7c.
  • the blocking device 7d is closed and the blocking device 8d is opened.
  • the body 4 is rotated, it is applied current, and it forms a second chromium layer (structure layer).
  • the blocking devices 8b and 8d are opened and the electrolyte from the container 8 is continuously circulated.
  • the locking device 8b is closed and for the locking device 7b opened.
  • the locking device 8d remains open while the locking device 7d is closed.
  • a mixture of 250 g of CrO 3 and 2.5 g of sulfuric acid in 1 l of water is pumped from the container 7 as an electrolyte into the reactor 2.
  • the electrolyte is previously heated to 50 ° C.
  • the electrolyte from the container 7 forces the warmer electrolyte originating from the container 8 back into the container 8 via the line 8c.
  • the blocking device 8d is closed and the blocking device 7d is opened.
  • the body 4 is rotated, it is applied current, and it forms a third chromium layer (cover layer).
  • the blocking devices 7b and 7d are opened, and the electrolyte from the container 7 is continuously circulated.
  • the gas atmosphere in the reactor 2 can be sucked off by means of a pump (not shown) in order to prevent the formation of a blast gas mixture.
  • the locking device 7b is closed while the locking device 7d remains open.
  • the entire electrolyte is removed from the reactor 2.
  • the coated body 4 is cleaned with water or an aqueous solution which is introduced from a line (not shown) into the reactor 2.
  • the cleaning water is then discharged from the reactor 2 and cleaned.
  • the reactor 2 is now opened and the coated body 4 is removed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
EP14186089.0A 2014-09-24 2014-09-24 Procédé et dispositif d'application galvanique d'un revêtement de surface Active EP3000918B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14186089.0A EP3000918B1 (fr) 2014-09-24 2014-09-24 Procédé et dispositif d'application galvanique d'un revêtement de surface

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP14186089.0A EP3000918B1 (fr) 2014-09-24 2014-09-24 Procédé et dispositif d'application galvanique d'un revêtement de surface

Publications (2)

Publication Number Publication Date
EP3000918A1 true EP3000918A1 (fr) 2016-03-30
EP3000918B1 EP3000918B1 (fr) 2018-10-24

Family

ID=51609993

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14186089.0A Active EP3000918B1 (fr) 2014-09-24 2014-09-24 Procédé et dispositif d'application galvanique d'un revêtement de surface

Country Status (1)

Country Link
EP (1) EP3000918B1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017076456A1 (fr) * 2015-11-05 2017-05-11 Topocrom Systems Ag Procédé et dispositif d'application d'un revêtement de surface par galvanisation
EP3650586A1 (fr) * 2018-11-09 2020-05-13 FRAUNHOFER-GESELLSCHAFT zur Förderung der angewandten Forschung e.V. Procédé de fabrication de composants revêtus galvaniquement et composant revêtus galvaniquement
CN112708910A (zh) * 2019-10-25 2021-04-27 联芯集成电路制造(厦门)有限公司 电化学电镀方法
EP4012074A1 (fr) 2020-12-14 2022-06-15 topocrom systems AG Revêtement de surface et son procédé de fabrication

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB335161A (en) * 1929-06-13 1930-09-15 Eugene Victor Hayes Gratze Improvements in or relating to electro deposition of chromium
US3406105A (en) * 1963-09-03 1968-10-15 Chromium Corp Of America Method of treating surfaces
GB1312723A (en) * 1969-08-26 1973-04-04 Nippon Kokan Kk Method of electroplating readily oxidizable metlas
WO1995009938A1 (fr) * 1993-10-07 1995-04-13 Heidelberger Druckmaschinen Aktiengesellschaft Procede d'application d'un revetement superficiel par galvanisation
JPH08218193A (ja) * 1995-02-14 1996-08-27 Sumitomo Metal Ind Ltd 有機複合被覆鋼板
EP0565070B1 (fr) 1992-04-09 1997-07-30 Heidelberger Druckmaschinen Aktiengesellschaft Procédé d'électrodéposition
US20040206622A1 (en) * 2001-07-25 2004-10-21 Katsuji Kawakami Apparatus for plating treatment
US20110027940A1 (en) * 2009-07-30 2011-02-03 Oladeji Isaiah O Method for fabricating copper-containing ternary and quaternary chalcogenide thin films
US20140083843A1 (en) * 2012-09-25 2014-03-27 Southern Taiwan University Of Science And Technology Preparation apparatus for porous alumina template

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB335161A (en) * 1929-06-13 1930-09-15 Eugene Victor Hayes Gratze Improvements in or relating to electro deposition of chromium
US3406105A (en) * 1963-09-03 1968-10-15 Chromium Corp Of America Method of treating surfaces
GB1312723A (en) * 1969-08-26 1973-04-04 Nippon Kokan Kk Method of electroplating readily oxidizable metlas
EP0565070B1 (fr) 1992-04-09 1997-07-30 Heidelberger Druckmaschinen Aktiengesellschaft Procédé d'électrodéposition
WO1995009938A1 (fr) * 1993-10-07 1995-04-13 Heidelberger Druckmaschinen Aktiengesellschaft Procede d'application d'un revetement superficiel par galvanisation
EP0722515B1 (fr) 1993-10-07 1998-01-28 Heidelberger Druckmaschinen Aktiengesellschaft Procede d'application d'un revetement superficiel par galvanisation
JPH08218193A (ja) * 1995-02-14 1996-08-27 Sumitomo Metal Ind Ltd 有機複合被覆鋼板
US20040206622A1 (en) * 2001-07-25 2004-10-21 Katsuji Kawakami Apparatus for plating treatment
US20110027940A1 (en) * 2009-07-30 2011-02-03 Oladeji Isaiah O Method for fabricating copper-containing ternary and quaternary chalcogenide thin films
US20140083843A1 (en) * 2012-09-25 2014-03-27 Southern Taiwan University Of Science And Technology Preparation apparatus for porous alumina template

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 199644, 27 August 1996 Derwent World Patents Index; AN 1996-439918, XP002737695 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017076456A1 (fr) * 2015-11-05 2017-05-11 Topocrom Systems Ag Procédé et dispositif d'application d'un revêtement de surface par galvanisation
US11136685B2 (en) 2015-11-05 2021-10-05 Topocrom Systems Ag Method and device for the galvanic application of a surface coating
US11732373B2 (en) 2015-11-05 2023-08-22 Topocrom Systems Ag Method and device for the galvanic application of a surface coating
EP3650586A1 (fr) * 2018-11-09 2020-05-13 FRAUNHOFER-GESELLSCHAFT zur Förderung der angewandten Forschung e.V. Procédé de fabrication de composants revêtus galvaniquement et composant revêtus galvaniquement
CN112708910A (zh) * 2019-10-25 2021-04-27 联芯集成电路制造(厦门)有限公司 电化学电镀方法
CN112708910B (zh) * 2019-10-25 2021-11-23 联芯集成电路制造(厦门)有限公司 电化学电镀方法
EP4012074A1 (fr) 2020-12-14 2022-06-15 topocrom systems AG Revêtement de surface et son procédé de fabrication

Also Published As

Publication number Publication date
EP3000918B1 (fr) 2018-10-24

Similar Documents

Publication Publication Date Title
EP3666931B1 (fr) Procédé de fabrication d'une bande métallique ayant un revêtement de chrome et d'oxyde de chrome avec un électrolyte à base de chromium trivalent
EP3000918B1 (fr) Procédé et dispositif d'application galvanique d'un revêtement de surface
DE102008063187A1 (de) Anodisierungsvorrichtung
CH688282A5 (de) Galvanische Metallabscheidungsvorrichtung.
DE102010044551A1 (de) Anode sowie deren Verwendung in einem alkalischen Galvanikbad
EP2386378A2 (fr) Procédé de fabrication de prothèses vasculaires médicales
WO2017076456A1 (fr) Procédé et dispositif d'application d'un revêtement de surface par galvanisation
EP3666928B1 (fr) Procédé de fabrication d'une bande métallique ayant un revêtement de chrome et d'oxyde de chrome avec un électrolyte à base de chromium trivalent
DE202015103646U1 (de) Filmbildende Struktur auf einem Erzeugnis
EP3250733B1 (fr) Réalisation de couches de chrome sur des cylindres gravés
EP2047012B1 (fr) Procédé de traitement de la surface d'une piece
EP3088115B1 (fr) Procede de fabrication d'une pieces usinee
WO2009152915A2 (fr) Procédé de galvanisation au cuivre et dispositif pour mettre en oeuvre ce procédé
EP0829558A1 (fr) Procédé et dispositif pour le dépÔt électrolytique d'une couche de chrome sur une cylindre d'impression
DE10132349B4 (de) Verfahren und Anlage zur kataphoretischen Tauchlackierung von Gegenständen
WO1998006884A1 (fr) Procede et installation de traitement electrochimique d'objets longilignes
DE102004038693B4 (de) Vorrichtung und Verfahren zur Entfernung von Fremdstoffen aus Prozesslösungen und Verfahren zur Regenerierung eines Kationenaustauschers
DE19722983C2 (de) Verfahren zur elektrochemischen Behandlung von stabförmigem Behandlungsgut und Vorrichtung zur Durchführung des Verfahrens
EP3733932A1 (fr) Procédé de fabrication d'une bande métallique revêtue d'un revêtement de chrome et d'oxyde de chrome à base d'une solution électrolytique avec un composé à base de chrome trivalent et système d'électrolyse permettant la mise en oeuvre dudit procédé
DE10235117B3 (de) Anlage zur kataphoretischen Tauchlackierung von Gegenständen
EP4012074A1 (fr) Revêtement de surface et son procédé de fabrication
EP0975826B1 (fr) Procede de revetement electrolytique de produits continus metalliques ou non metalliques et dispositif pour la mise en oeuvre de ce procede
DE112014003650T5 (de) Filmabscheidevorrichtung für Metallfilm und Metallfilmabscheideverfahren
EP2910669B1 (fr) Installation de revêtement galvanique et son procédé de fonctionnement
DE1962249B2 (de) Verfahren zum Kühlen von Behandlungsbädern

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

17P Request for examination filed

Effective date: 20160916

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170512

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C25D 5/04 20060101AFI20180615BHEP

Ipc: C25D 3/06 20060101ALN20180615BHEP

Ipc: C25D 5/14 20060101ALI20180615BHEP

Ipc: C25D 17/02 20060101ALI20180615BHEP

Ipc: C25D 21/12 20060101ALN20180615BHEP

Ipc: C25D 21/04 20060101ALI20180615BHEP

Ipc: C25D 21/02 20060101ALI20180615BHEP

Ipc: C25D 5/36 20060101ALI20180615BHEP

Ipc: C25D 7/00 20060101ALI20180615BHEP

INTG Intention to grant announced

Effective date: 20180719

RIC1 Information provided on ipc code assigned before grant

Ipc: C25D 3/06 20060101ALN20180706BHEP

Ipc: C25D 21/12 20060101ALN20180706BHEP

Ipc: C25D 5/04 20060101AFI20180706BHEP

Ipc: C25D 21/02 20060101ALI20180706BHEP

Ipc: C25D 5/36 20060101ALI20180706BHEP

Ipc: C25D 17/02 20060101ALI20180706BHEP

Ipc: C25D 5/14 20060101ALI20180706BHEP

Ipc: C25D 7/00 20060101ALI20180706BHEP

Ipc: C25D 21/04 20060101ALI20180706BHEP

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1056771

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502014009849

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: HEPP WENGER RYFFEL AG, CH

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20181024

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190124

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190224

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190124

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190224

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190125

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502014009849

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190725

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190924

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190924

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190930

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1056771

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190924

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190924

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20140924

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20230920

Year of fee payment: 10

Ref country code: GB

Payment date: 20230831

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20230906

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20231130

Year of fee payment: 10