EP2730683B1 - Objekt mit Oberflächendeckschicht, die hergestellt ist durch elektrolytische Ablagerung, verwendete Elektrolytlösung für die Ablagerung und Verfahren zur Herstellung dieses Gegenstandes - Google Patents
Objekt mit Oberflächendeckschicht, die hergestellt ist durch elektrolytische Ablagerung, verwendete Elektrolytlösung für die Ablagerung und Verfahren zur Herstellung dieses Gegenstandes Download PDFInfo
- Publication number
- EP2730683B1 EP2730683B1 EP13005253.3A EP13005253A EP2730683B1 EP 2730683 B1 EP2730683 B1 EP 2730683B1 EP 13005253 A EP13005253 A EP 13005253A EP 2730683 B1 EP2730683 B1 EP 2730683B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolytic solution
- deposition
- surface covering
- covering layer
- electrolytic
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims description 43
- 239000008151 electrolyte solution Substances 0.000 title claims description 34
- 230000008021 deposition Effects 0.000 title claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 238000005234 chemical deposition Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 229910020462 K2SnO3 Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 45
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000011282 treatment Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002344 surface layer Substances 0.000 description 7
- 229910001369 Brass Inorganic materials 0.000 description 6
- 239000010951 brass Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000007769 metal material Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 229910000906 Bronze Inorganic materials 0.000 description 3
- 239000010974 bronze Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000005068 transpiration Effects 0.000 description 3
- 229910020464 K2SnO3.3H2O Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 2
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- LLCOQBODWBFTDD-UHFFFAOYSA-N 1h-triazol-1-ium-4-thiolate Chemical class SC1=CNN=N1 LLCOQBODWBFTDD-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910000743 fusible alloy Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CNQCVBJFEGMYDW-UHFFFAOYSA-N lawrencium atom Chemical compound [Lr] CNQCVBJFEGMYDW-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- 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
-
- 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
- C25D17/005—Contacting devices
-
- 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
Definitions
- the present invention concerns the technical field of production of objects with a surface covering.
- the present invention concerns the production of objects with a surface covering obtained through electrolytic deposition.
- the present invention concerns also the method for making said objects and the electrolytic solution used in said method.
- metal objects comprising, for example, accessories for bags, shoes, belts (such as buckles, rings, spring catches, chains, fasteners etc.), parts of glasses (such as sides, bridges, inserts etc.), zip fasteners, buttons, components of watches (such as casings, buckles, bracelet meshes etc.), trinkets (such as bracelets, rings, earrings, pendants etc.), handles (for pieces of furniture, doors, refrigerators etc.), valves, gift items (such as trays, vases and pots, cups, tea pots, milk pots etc.), technical items (such as bushings).
- accessories for bags such as shoes, belts (such as buckles, rings, spring catches, chains, fasteners etc.), parts of glasses (such as sides, bridges, inserts etc.), zip fasteners, buttons, components of watches (such as casings, buckles, bracelet meshes etc.), trinkets (such as bracelets, rings, earrings, pendants etc.), handles (for pieces of furniture, doors, refrigerators
- the objects indicated above are typically produced using brass as base material.
- the brass that is commonly used and ensures good workability contains a certain percentage of lead.
- the presence of lead may cause problems related to its toxicity and its release into the environment.
- the surface layer is obtained by means of a galvanic finishing treatment by means of which a layer of an appropriate alloy suited to cover the underlying part in zama alloy is deposited thereon.
- the deposited layer is typically made with alloys containing copper, tin and zinc or copper and zinc, a few microns thick.
- the same covering technique with a galvanic treatment is used also in sectors where base materials of a different type are used, like for example plastic, resins, low-melting alloys etc.
- the surface layer is typically made with alloys containing copper, tin and zinc or copper and zinc, a few microns thick.
- a first drawback of the objects obtained through the above mentioned covering techniques is represented by the appearance of defects as a result of corrosion phenomena, in particular between the surface covering layer and the underlying material, due to transpiration through the surface layer, which can give rise to dangerous electrochemical processes.
- Another drawback posed by the objects obtained using the techniques of the known type is due to the wearing action to which the external surface of the object is subjected, which causes a deterioration of the aesthetic characteristics of the object and/or the need to restore the ideal conditions with a new covering treatment.
- the main object of the present invention is to at least partially overcome the drawbacks described above.
- Patent document US 1,970,548 describes a composite article comprising a base material made of ferrous metal and having surface irregularities therein, an electroplated coating composed of 10 - 25 % tin and balance copper bonded to said metal and having a smooth buffed surface free from corresponding surface irregularities, and an overcoating of another metal, preferably chromium.
- Patent document EP 0 163 419 A2 describes a coin comprising a coin-shaped core of mintable metallic material and an electroplated coating completely encasing the core, wherein the electroplated coating has a thickness of 10 to 150 ⁇ m, preferably 30 to 50 ⁇ m, and contains from 8 to 16 %, preferably 11 to 14 wt.% tin and the balance copper.
- Patent document US 2006/0068219 A1 is described a coin comprising a metallic core and an electroplated layer of white bronze adhered to the external surfaces of the core and encasing the core.
- the present invention is based on the general consideration that it is desirable to make an object having a surface covering layer constituted by an alloy comprising copper and tin whose thickness exceeds 30 micrometres.
- the subject of the same is, therefore, an object of the type comprising a main body and a surface covering layer suited to at least partially cover said main body, wherein said surface covering layer is constituted by an alloy comprising copper in a percentage varying in weight from 90 to 95 %, tin in a percentage varying in weight from 10 to 5% and impurities in a percentage varying in weight from 0 to 1%, and wherein the thickness of said surface covering layer exceeds 30 micrometres.
- the main body comprises a conductive material.
- Said main body properly comprises a zama alloy.
- the surface covering layer is obtained through electrolytic deposition.
- the alloy of the deposited layer does not comprise zinc.
- the subject of the invention is an object being a fashion accessory or a trinket, and belonging to the group comprising: accessories for bags, for shoes, for belts, for example buckles, rings, spring catches, chains, fasteners; parts of glasses, for example sides, bridges, inserts; components of watches, for example casings, buckles, bracelet meshes; trinkets, for example bracelets, rings, earrings, pendants.
- the subject of the invention is a fashion accessory, like for example said accessories for bags, shoes, belts, for example buckles, rings, spring catches, chains, fasteners etc., or it is a trinket like for example said bracelets, rings, earrings, pendants, etc..
- the subject of the same is an aqueous electrolytic solution used in an electrolytic deposition process for making an object, wherein the solution comprises:
- the electrolytic solution does not comprise zinc.
- Said electrolytic solution is preferably used to make an object belonging to the group comprising: accessories for bags, for shoes, for belts, for example buckles, rings, spring catches, chains, fasteners; parts of glasses, for example sides, bridges, inserts; components of watches, for example casings, buckles, bracelet meshes; trinkets, for example bracelets, rings, earrings, pendants.
- said electrolytic solution is used for making a fashion accessory, like for example said accessories for bags, shoes, belts, for example buckles, rings, spring catches, chains, fasteners etc., or a trinket, like for example said bracelets, rings, earrings, pendants, etc..
- the subject of the same is a method for making an object of the type comprising a main body and a surface covering layer suited to cover said main body at least partially, said method comprising a stage during which said surface covering layer is obtained through electrolytic deposition in an aqueous electrolytic solution, wherein said electrolytic solution is of the type described above.
- the pH value of the electrolytic solution is maintained between 12 and 12.5.
- the temperature of the electrolytic solution is maintained between 58 and 62 °C.
- the process current is maintained between 0.3 and 2.5 A/dm2.
- Said method is used to make an object belonging to the group comprising: accessories for bags, for shoes, for belts, for example buckles, rings, spring catches, chains, fasteners; parts of glasses, for example sides, bridges, inserts; components of watches, for example casings, buckles, bracelet meshes; trinkets, for example bracelets, rings, earrings, pendants.
- said method is used for making a fashion accessory, like for example said accessories for bags, for shoes, for belts, for example buckles, rings, spring catches, chains, fasteners etc., or a trinket, like for example said bracelets, rings, earrings, pendants, etc..
- the present invention has proved particularly useful when applied to objects comprising a base material constituted by a metallic material, in particular a zama alloy, as is explained in greater detail below. It should however be noted that the present invention is not limited to the production of said objects. On the contrary, the present invention can be conveniently applied in all those cases requiring the production of objects comprising a base material having an external layer made of a non-precious metal, for example objects comprising a base material such as plastic or resin.
- the base material furthermore, can be solid or hollow, without distinction.
- the invention can be applied to the production of other objects, in particular metal objects like, for example, accessories for bags, for shoes, for belts (such as buckles, rings, spring catches, chains, fasteners etc.), parts of glasses (such as sides, bridges, inserts etc.), zip fasteners, buttons, components of watches (such as casings, buckles, bracelet meshes etc.), trinkets (such as bracelets, rings, earrings, pendants etc.), handles (for pieces of furniture, doors, refrigerators etc.), valves, gift items (such as trays, vases and pots, cups, tea pots, milk pots etc.), technical items (such as bushings).
- accessories for bags for shoes, for belts (such as buckles, rings, spring catches, chains, fasteners etc.), parts of glasses (such as sides, bridges, inserts etc.), zip fasteners, buttons, components of watches (such as casings, buckles, bracelet meshes etc.), trinkets (such as bracelets, rings, earrings, pendant
- the invention is applied to the production of a fashion accessory, like for example said accessories for bags, for shoes, for belts, for example buckles, rings, spring catches, chains, fasteners etc., or of a trinket, like for example said bracelets, rings, earrings, pendants etc..
- a fashion accessory like for example said accessories for bags, for shoes, for belts, for example buckles, rings, spring catches, chains, fasteners etc.
- a trinket like for example said bracelets, rings, earrings, pendants etc.
- the object of the invention meaning the buckle 1, comprises a base material or core 2 and a surface covering layer 3, as shown in the sectioned detail illustrated in Figure 2 .
- the base material 2 comprises a metallic material, preferably a zama alloy.
- a known process for the production of said objects uses electrolytic deposition technology.
- the apparatus 101 is substantially constituted by an apparatus for electrolytic deposition.
- the apparatus 101 substantially comprises a tank 102 suited to contain an electrolytic solution, or electrolytic bath, in which the elements to be deposited and intended to make up the surface covering layer 3 of the object 1 of the invention are dissolved, as will be described in greater detail below.
- the tank 102 containing the electrolytic solution is preferably arranged inside a suitable external tank 121.
- the apparatus 101 furthermore comprises a supporting system 103 for the objects 1 to be made. Typically, a plurality of said objects 1 are made at the same time in the apparatus 101.
- buckles 1 there are six buckles 1. It is evident that in variant embodiments of the invention a different number of objects having any shape can be made, for example rings, earrings, etc., as already explained.
- the supporting system 103 preferably comprises a centre rotary shaft 104 provided with arms 105 on which the objects 1 to be made are properly arranged.
- the rotary shaft 4 is properly piloted by power means that are not represented herein.
- a centre control unit of the apparatus 101 is advantageously connected to said power means.
- the centre control unit can be constituted, for example, by a PLC unit installed on a control cabinet.
- the apparatus 101 is also provided with a suitable power supply system suited to create an electric electrodeposition circuit through which a given current I flows.
- the power supply system comprises a power supply unit electrically connected with a first one of its poles, for example the negative one (cathode), to the supporting system 103 and connected with its second pole, for example the positive one (anode), to annular electrodes 112 arranged inside the tank 121.
- a power supply unit electrically connected with a first one of its poles, for example the negative one (cathode), to the supporting system 103 and connected with its second pole, for example the positive one (anode), to annular electrodes 112 arranged inside the tank 121.
- the power supply unit is preferably piloted by the control unit, in such a way as to define the voltage and/or current values that are appropriate for the electric electrodeposition circuit.
- the apparatus 101 will also be provided with further elements, not illustrated herein, suited to allow and guarantee the correct operation of the apparatus 101 itself.
- the apparatus 101 will be preferably provided with an electrolytic solution feeding system and a top-up system suited to compensate for the variations in the components of the electrolytic solution during operation.
- the apparatus 101 will be preferably provided also with a stirring system suited to mix the electrolytic solution in order to maintain its conditions of homogeneity inside the tank 102 during operation.
- the apparatus 101 will be preferably provided also with a heating system suited to bring the electrolytic solution to a desired operating temperature T and to maintain it at that temperature.
- the apparatus 101 will be provided with suitable sensors for measuring operating parameters like, for example, sensors for detecting the level and the temperature of the electrolytic solution.
- the apparatus 101 is preferably provided with a filtering system suited to filter any impurities present in the electrolytic solution.
- a core made of a conductive material in a suitable shape is prepared, for example, in the case illustrated herein, in the shape of a buckle.
- the core 2 is positioned on the supporting system 103 and immersed in the electrolytic solution previously prepared.
- the electrolytic solution is constituted by an aqueous solution comprising:
- the electrolytic solution comprises the four elements indicated above, in the corresponding quantities, properly dissolved in water.
- the values of the parameters that will determine the successive deposition stage are then defined.
- the values are defined within which a series of process parameters should be maintained, including:
- the pH value is preferably maintained within the range 12 ⁇ 12.5.
- the temperature T of the electrolytic solution is preferably maintained within the range 58 ⁇ 62 °C.
- the process current I is preferably maintained within the range 0.3 ⁇ 2.5 A/dm2.
- the expected duration t1 of the deposition stage will depend on the desired thickness of the surface covering layer 3, taking into account the deposition speed that derives from the previously set parameter values.
- the process will make it possible to deposit a layer with a thickness of 1 micrometre in a time t1 equal to 100 seconds, with a process current I equal to 2.0 A/dm2, or it will allow the deposit of a layer with a thickness of 1 micrometre in 400 seconds, with a process current I equal to 0.5 A/dm2.
- a surface covering layer 3 is deposited on the core 2.
- the electrolytic solution is advantageously kept moving by means of the specific stirrers, not represented herein, while, advantageously, the objects 1 and the supporting element 103 are set rotating through the power means.
- a surface covering layer 3 will be obtained on the core 2, said layer being constituted by an alloy comprising copper in a percentage varying in weight from 90 to 95 %, tin in a percentage varying in weight from 10 to 5% and impurities in a percentage varying in weight from 0 to 1 %, wherein the thickness of said alloy layer will exceed 30 micrometres.
- the object 1 obtained as described above is ready for its final use. In variant embodiments of the invention, however, further external finishing operations can be carried out.
- Usable finishing operations may preferably include mechanical polishing treatments, like for example a vibratory finishing treatment, a tumbling treatment, a rumbling treatment, a lapping treatment, or further galvanic finishing treatments intended to deposit layers a few micrometres thick, using, for example, white bronze, silver, palladium, ruthenium, gold, alloys of these elements, etc.
- mechanical polishing treatments like for example a vibratory finishing treatment, a tumbling treatment, a rumbling treatment, a lapping treatment, or further galvanic finishing treatments intended to deposit layers a few micrometres thick, using, for example, white bronze, silver, palladium, ruthenium, gold, alloys of these elements, etc.
- the possibility to obtain a thickness of 30 micrometres or more for the surface covering layer 3 makes it possible to obtain a substantially tight covering for the underlying layer 2, actually eliminating the phenomenon of transpiration through the surface layer itself, which instead is present in the known art. Consequently, there is a tendency to avoid creating situations that trigger electrochemical processes that would deteriorate the object 1.
- the possibility to obtain thicknesses of 30 micrometres or more derives from the fact that there is no zinc, in any form, in the electrolytic solution.
- the surface covering layer may comprise, in addition to copper or tin, low percentages of other elements, or impurities, with values below 1%.
- a thicker layer in addition to further guaranteeing the tightness provided by the surface covering layer 3, makes it possible to carry out welding operations at the level of the surface covering layer 3.
- Such a thickness value considerably higher than the values of a few microns obtainable with the known technique, allows the welded object to maintain the desired mechanical resistance characteristics.
- the object 51 described differs from the previously described object due to the fact that the core 52 comprises a layer of non-metallic material 54, for example represented in Figure 6 . It is known, in fact, that in order to deposit a material on an object through electrolysis, said object must have electric conductivity properties.
- the metallization stage makes it possible to create the layer of conductive material 55 on top of the layer of non-metallic material 54 so as to obtain the core 52 to be immersed in the electrolytic solution.
- the metallization process is preferably carried out by depositing a conductive layer through spraying, as schematically shown exactly in Figure 6 , preferably a layer of a material containing microparticles in silver or copper or brass.
- the core 52 obtained in this way that is, the core 52 provided with the conductive layer 55, is then subjected to the successive deposition stages, according to the description provided above, through the use of the apparatus 101.
- the object 51 obtained in this way will therefore have the same characteristics and offer the same advantages described above with reference to the first embodiment.
- further intermediate layers can be present between the underlying core and the surface covering layer.
- a layer of alkaline copper or acid copper in particular when the core is constituted by a zinc alloy.
- Said intermediate layers make it possible to improve the mechanical and/or ornamental characteristics of the object as a whole.
- the present invention allows the set objects to be achieved.
- it makes it possible to produce an object provided with a surface covering layer having reduced defects compared to the objects belonging to the known art.
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)
Claims (8)
- Ein Modeaccessoire oder Modeschmuck (1, 51) des Typs, der ein Grundmaterial (2) und eine durch elektrolytische Ablagerung gebildete Oberflächendeckschicht (3) umfasst, welche dazu geeignet ist, das besagte Grundmaterial (2) wenigstens teilweise zu bedecken, dadurch gekennzeichnet, dass das besagte Grundmaterial (2) eine Zamak-Legierung umfasst, und die besagte Oberflächendeckschicht (3) aus einer Legierung besteht, die einen zwischen 90 und 95 % variierenden Gewichtsanteil Kupfer, einen zwischen 10 bis 5 % variierenden Gewichtsanteil Zinn, und einen zwischen 0 bis 1 % variierenden Gewichtsanteil Verunreinigungen enthält, und dadurch, dass die Dicke der besagten Oberflächendeckschicht (3) mehr als 30 Mikrometer beträgt.
- Modeaccessoire oder Modeschmuck (1, 51) gemäß eines jeden der vorstehenden Patentansprüche, dadurch gekennzeichnet, dass die besagte Legierung kein Zink enthält.
- Modeaccessoire oder Modeschmuck (1, 51) gemäß eines jeden der vorstehenden Patentansprüche, dadurch gekennzeichnet, dass es ein Objekt (1; 51) ist, welches zu der Gruppe gehört, die Folgendes umfasst: Accessoires für Taschen, für Schuhe, für Gürtel, zum Beispiel Schnallen, Ringe, Karabinerhaken, Ketten, Verschlüsse; Teile von Brillen wie zum Beispiel Bügel, Stege, Einsätze; Komponenten von Armbanduhren wie zum Beispiel Gehäuse, Schnallen, Armbandmaschen; Modeschmuck wie zum Beispiel Armreifen, Ringe, Ohrringe, Anhänger.
- Verfahren zur Herstellung eines Modeaccessoires oder Modeschmucks (1, 51) gemäß eines der Patentansprüche von 1 bis 3, wobei das besagte Verfahren eine Phase der Ausführung der besagten Oberflächendeckschicht (3) durch elektrolytische Ablagerung in wässriger Elektrolytlösung umfasst, dadurch gekennzeichnet, dass die besagte Elektrolytlösung Folgendes umfasst:- Kupfercyanid (CuCN) mit Werten zwischen 15 und 30 g/l, besonders bevorzugt zwischen 24 und 28 g/l, noch bevorzugter gleich 26 g/l;- Kaliumstannat (K2Sn03 · 3H20) mit Werten zwischen 10 und 25 g/l, besonders bevorzugt zwischen 18 und 22 g/l, noch bevorzugter gleich 20 g/l;- Kaliumcyanid (KCN) mit Werten zwischen 40 und 50 g/l, besonders bevorzugt zwischen 43 und 47 g/l, noch bevorzugter gleich 45 g/l;- freies Kaliumhydroxid (KOH) mit Werten zwischen 5 und 20 g/l, besonders bevorzugt zwischen 8 und 14 g/l, noch bevorzugter gleich 11 g/l.
- Verfahren gemäß Patentanspruch 4, dadurch gekennzeichnet, dass die besagte Elektrolytlösung kein Zink enthält.
- Verfahren gemäß Patentanspruch 5, dadurch gekennzeichnet, dass während der besagten chemischen Ablagerung der pH-Wert der besagten Elektrolytlösung bei 12 bis 12,5 gehalten wird.
- Verfahren gemäß Patentanspruch 5 oder 6, dadurch gekennzeichnet, dass während der besagten chemischen Ablagerung die Temperatur der besagten Elektrolytlösung bei 58° bis 62°C gehalten wird.
- Verfahren gemäß eines jeden der Patentansprüche von 5 bis 7, dadurch gekennzeichnet, dass während der besagten chemischen Ablagerung der Verfahrensstrom zwischen 0,3 und 2,5 A/dm2 gehalten wird.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT000300A ITVI20120300A1 (it) | 2012-11-08 | 2012-11-08 | Oggetto con strato superficiale di copertura ottenuto per deposizione elettrolitica, soluzione elettrolitica impiegata in tale deposizione e metodo di realizzazione di tale oggetto. |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2730683A1 EP2730683A1 (de) | 2014-05-14 |
EP2730683B1 true EP2730683B1 (de) | 2017-12-20 |
Family
ID=47471962
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13005253.3A Active EP2730683B1 (de) | 2012-11-08 | 2013-11-07 | Objekt mit Oberflächendeckschicht, die hergestellt ist durch elektrolytische Ablagerung, verwendete Elektrolytlösung für die Ablagerung und Verfahren zur Herstellung dieses Gegenstandes |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2730683B1 (de) |
ES (1) | ES2661493T3 (de) |
IT (1) | ITVI20120300A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT202100008084A1 (it) | 2021-03-31 | 2022-10-01 | Bluclad S P A | Soluzione elettrolitica per l’elettrodeposizione su substrato metallico di uno strato preparatore a base di rame e stagno |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE688155C (de) * | 1938-12-08 | 1940-02-14 | Degussa | Baeder fuer die elektrolytische Abscheidung von Messing |
FR2097527A5 (de) * | 1970-07-09 | 1972-03-03 | Meyer Marie Therese | |
US6054037A (en) * | 1998-11-11 | 2000-04-25 | Enthone-Omi, Inc. | Halogen additives for alkaline copper use for plating zinc die castings |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR743797A (de) * | 1931-10-19 | 1933-04-06 | ||
US1970549A (en) * | 1932-10-18 | 1934-08-21 | City Auto Stamping Co | Process of electroplating bronze |
CA1219708A (en) * | 1984-05-01 | 1987-03-31 | Michael J.H. Ruscoe | Aureate coins, medallions and tokens |
US7296370B2 (en) * | 2004-09-24 | 2007-11-20 | Jarden Zinc Products, Inc. | Electroplated metals with silvery-white appearance and method of making |
US7780839B2 (en) * | 2007-12-12 | 2010-08-24 | Rohm And Haas Electronic Materials Llc | Electroplating bronze |
-
2012
- 2012-11-08 IT IT000300A patent/ITVI20120300A1/it unknown
-
2013
- 2013-11-07 EP EP13005253.3A patent/EP2730683B1/de active Active
- 2013-11-07 ES ES13005253.3T patent/ES2661493T3/es active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE688155C (de) * | 1938-12-08 | 1940-02-14 | Degussa | Baeder fuer die elektrolytische Abscheidung von Messing |
FR2097527A5 (de) * | 1970-07-09 | 1972-03-03 | Meyer Marie Therese | |
US6054037A (en) * | 1998-11-11 | 2000-04-25 | Enthone-Omi, Inc. | Halogen additives for alkaline copper use for plating zinc die castings |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT202100008084A1 (it) | 2021-03-31 | 2022-10-01 | Bluclad S P A | Soluzione elettrolitica per l’elettrodeposizione su substrato metallico di uno strato preparatore a base di rame e stagno |
Also Published As
Publication number | Publication date |
---|---|
ITVI20120300A1 (it) | 2014-05-09 |
EP2730683A1 (de) | 2014-05-14 |
ES2661493T3 (es) | 2018-04-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10662542B2 (en) | Material and process for electrochemical deposition of nanolaminated brass alloys | |
CN106795641B (zh) | 具有高硬度的镍-铬纳米层压涂层或包层 | |
Di Bari | Nickel plating | |
CN102224280B (zh) | 用于装饰制品的含贵金属的序列层 | |
WO2010102516A1 (en) | Method of manufacturing hard gold jewellery | |
AT514818A1 (de) | Abscheidung von Cu, Sn, Zn-Beschichtungen auf metallischen Substraten | |
CN108138346A (zh) | 用于电化学沉积Cu-Sn-Zn-Pd合金的电镀浴、所述合金的电化学沉积方法、包含所述合金的基材和基材的用途 | |
CN110699713A (zh) | 一种无氰金合金电铸液及其使用方法 | |
EP2730683B1 (de) | Objekt mit Oberflächendeckschicht, die hergestellt ist durch elektrolytische Ablagerung, verwendete Elektrolytlösung für die Ablagerung und Verfahren zur Herstellung dieses Gegenstandes | |
CN103484901A (zh) | 一种五金件的镀镍工艺 | |
KR20090123928A (ko) | 블랙 루테늄의 장식층 및 기술층을 전착시키기 위한 전해액 및 방법 | |
KR101551420B1 (ko) | 장신구 제조방법 | |
US5792565A (en) | Multiple layered article having a bright copper layer | |
CN102899695B (zh) | 无镍合金镀层的电镀方法 | |
CN111826686A (zh) | 一种制备硬金陀飞轮支架的方法 | |
CA2235408A1 (en) | Electroplating processes compositions and deposits | |
EP2554716B1 (de) | Verfahren zur Herstellung metallischer Objekte | |
WO2015017913A1 (en) | Single solution for electro-electroless deposition of metals | |
WO2016020812A1 (en) | Electrolytic bath, electrolytic deposition method and item obtained with said method | |
Plating et al. | Nickel Electroplating | |
CN116157557A (zh) | 钌合金层及其层组合 | |
GB2306508A (en) | Gold-iron alloy electroplating processes compositions and deposits | |
Lou | Pretreatment of aluminum alloy plating. | |
WO2015097917A1 (ja) | 2重金めっき方法及び電子部品 | |
Hitchin | White precious metals |
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 |
|
17P | Request for examination filed |
Effective date: 20131107 |
|
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 |
|
R17P | Request for examination filed (corrected) |
Effective date: 20150212 |
|
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 |
|
17Q | First examination report despatched |
Effective date: 20160415 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C25D 3/58 20060101AFI20170125BHEP Ipc: C25D 7/00 20060101ALI20170125BHEP |
|
INTG | Intention to grant announced |
Effective date: 20170302 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
GRAL | Information related to payment of fee for publishing/printing deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR3 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTC | Intention to grant announced (deleted) | ||
INTG | Intention to grant announced |
Effective date: 20170726 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
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: GB Ref legal event code: FG4D |
|
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 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 956473 Country of ref document: AT Kind code of ref document: T Effective date: 20180115 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602013030959 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: SEDIN SA, CH |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2661493 Country of ref document: ES Kind code of ref document: T3 Effective date: 20180402 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20171220 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20180320 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: 20171220 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: 20171220 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: 20171220 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 956473 Country of ref document: AT Kind code of ref document: T Effective date: 20171220 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20171220 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: 20171220 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: 20171220 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: 20180321 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: 20180320 |
|
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: 20171220 |
|
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: 20171220 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: 20171220 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: 20171220 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: 20171220 |
|
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: 20171220 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: 20180420 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: 20171220 Ref country code: AT 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: 20171220 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: 20171220 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602013030959 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 6 |
|
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: 20180921 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20171220 |
|
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: 20171220 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20181107 |
|
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: 20171220 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181107 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20181130 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
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: 20181107 |
|
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: 20181130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181107 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20181107 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20171220 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20171220 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: 20131107 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20171220 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20231207 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20231027 Year of fee payment: 11 Ref country code: IT Payment date: 20231016 Year of fee payment: 11 Ref country code: FR Payment date: 20231024 Year of fee payment: 11 Ref country code: DE Payment date: 20231024 Year of fee payment: 11 Ref country code: CH Payment date: 20231202 Year of fee payment: 11 |