EP3067444A2 - Separation of decorative palladium iron alloy coatings on metallic substances - Google Patents
Separation of decorative palladium iron alloy coatings on metallic substances Download PDFInfo
- Publication number
- EP3067444A2 EP3067444A2 EP16156476.0A EP16156476A EP3067444A2 EP 3067444 A2 EP3067444 A2 EP 3067444A2 EP 16156476 A EP16156476 A EP 16156476A EP 3067444 A2 EP3067444 A2 EP 3067444A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- palladium
- iron
- objects
- alloy
- 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
Links
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
-
- 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
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
-
- 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
- C25D3/20—Electroplating: Baths therefor from solutions of iron
-
- 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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- 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
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth 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
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- 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
- C25D7/005—Jewels; Clockworks; Coins
-
- 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
Definitions
- the present invention is directed to an electrolytic bath composition for depositing white, high-gloss, crack-free, abrasion and corrosion-resistant palladium-iron alloys from alkaline aqueous baths, objects and articles coated with these alloys, and a process for producing the coated objects Items.
- the electrolytes are out JP, 2001-192885 A, are also based on ammonium salts and contain additional brighteners and possibly different alloying metals such as iron or tellurium.
- JP, 2001-181887 A describes palladium-iron alloy baths which are also based on ammonium salts and additionally contain EDTA.
- strong chelating agents are generally undesirable in electrolytes since they introduce difficulties in wastewater treatment.
- JP, 10-046384 A describes palladium alloy baths for the electronics industry. Iron as alloying metal is mentioned, the electrolytes are based on ammonium salts. The examples, however, relate only to palladium-cobalt alloys. Alloys of palladium-iron, palladium-nickel, palladium-rhodium and palladium-ruthenium should be produced in the same way.
- DE2657925 describes ammonia-free, semi-glossy to bright palladium and palladium alloy baths for electrical engineering, but iron is not mentioned as alloying metal.
- the object of the present invention to develop baths from which high gloss, binary palladium-iron alloys can be deposited without any addition of other metals and.
- the alloy baths during operation should not present an odor nuisance or health hazard through the release of irritating gases or vapors, and moreover contain no strong complexing agents such as EDTA or NTA, which would cause problems in wastewater treatment.
- the production is to be cheapened by the use of such alloy baths, and resources of the expensive palladium are spared.
- Such alloys are therefore particularly well suited for any metallic white decorative coating, e.g. of costume jewelery, but also for industrial applications, especially in the electronics industry.
- the baths contain 0.5-15 g / l of palladium, 0.2-2 g / l of iron, conductive salts, brighteners and wetting agents. It is possible to deposit layer thicknesses> 5 ⁇ high-gloss, crack-free. The corrosion resistance is comparable to pure palladium, the abrasion resistance is better than pure palladium.
- the invention relates to a novel electrolyte bath for the cathodic deposition of binary alloys and / or layer sequences to form white, corrosion-resistant, crack-free and high-gloss coatings on at least on their surface metallic or electrically conductive or conductive coated objects, which bath as electrolyte at least one complex Palladium compound and at least one iron salt, and characterized in that it - for the deposition of a PdFe alloy containing 5-15 wt .-% Fe - as aqueous, alkaline solution is present and in addition to containing as metal compounds, as a further essential component at least one wetting agent from the group of amphoteric surfactants and additionally at least one of the additives contained in galvanic palladium in the usual manner brightener and conductive salts, pH stabilizers and stress reducer.
- the pH of the new alloy bath should be maintained in the range of 7.5 - 9, since at lower pH values (approximately between 7 and 7.5) the incorporation rates of iron decrease. At higher pH values (approximately between 9 and 10), burns occur in the high current density range.
- the pH is advantageously adjusted by means of sodium or potassium hydroxide.
- the iron content of the deposited alloy at 5-15 wt .-% Fe, since at incorporation rates> 15 wt .- Fe Fe the layers are cracked, and at incorporation rates ⁇ 5% by weight, the deposition receives a milky appearance.
- palladium in divalent form e.g. as palladium chloride, sulfate, nitrate, and iron
- the ferric salt e.g. be present as sulfate, chloride, nitrate or citrate in the electrolyte bath.
- an electrolyte bath is advantageously provided for the deposition of a coating, which is characterized in that it has a content of palladium of 0.5 to 15 g / l, preferably from 2 to 8 g / l, and particularly preferably from 4 to 6 g / l, and iron of 0.2 to 2 g / l, preferably from 0.5 to 1.5 g / l.
- the wetting agents essential to the extraordinary properties of the novel alloy coatings in particular from the group of amphoteric surfactants, e.g. Betaine and sulfobetaines are advantageously added to the electrolyte in amounts of 0.5-2 g / l.
- the new electrolyte bath As for other components of the new electrolyte bath than the essential metal compounds and wetting agents, it has proven to be advantageous if it contains brighteners. Such brighteners for palladium baths are known and come for example from the group of substituted aromatic N-heterocycles. It has also proved to be advantageous if the electrolyte contains stress reducers such as saccharin or organic sulfonates.
- conductive salts and pH stabilizers such as sodium or potassium sulfate, nitrate, chloride, citrate, tartrate or malonate, and possibly further surface-active or wetting agents, for example alkyl ether sulfonates, alkyl ether phosphates or fatty alcohol alkoxylates.
- All conductive salts or pH stabilizers used in the invention are sodium or potassium salts.
- ammonia or ammonium salts When using ammonia or ammonium salts at elevated temperatures of about 50 ° C, ammonia is constantly expelled. As a result, the pH of the bath constantly adjusted and continuous work is much more difficult. In addition, there is a constant odor nuisance and health hazard for the operator of the electrolyte.
- no organic acids or salts are used which, when the bath is heated at elevated temperature, release vapors which can lead to an odor nuisance and / or health hazard to the operators of the electrolyte, e.g. Propionic acid / propionates, acetic acid / acetates.
- Another very important object of the invention are objects or articles, in particular jewelery or decorative articles, and further electro-technical or electronic components and components of a preferably physiologically acceptable metal, in particular brass, zinc, tin, iron or steel, or from alloys thereof or else from a conductive plastic with a coating of a binary alloy of palladium and iron deposited from an abovementioned electrolyte bath, in which the iron content is from 5 to 12% by weight, to which in particular reference is made to claim 7 becomes.
- a preferably physiologically acceptable metal in particular brass, zinc, tin, iron or steel, or from alloys thereof or else from a conductive plastic with a coating of a binary alloy of palladium and iron deposited from an abovementioned electrolyte bath, in which the iron content is from 5 to 12% by weight, to which in particular reference is made to claim 7 becomes.
- the total thickness of the binary palladium-iron coating to be achieved in the context of the invention is 0.1 to 5 ⁇ m, in particular about 0.5 to 3 ⁇ m, depending on the field of use.
- the intermediate layer of adhesive gold has a thickness of 0.05 to 0.3 microns.
- the new objects or articles will have a final layer of one with rhodium and ruthenium, preferably in the weight% ratio of (70 to 90) to (30 to 10), especially about 80 to 20 , formed alloy.
- the working temperature of the electrolyte baths according to the invention is between 35 and 75 ° C.
- the current density can be set to between 0.01 and 10 amps / dm 2 , depending on the type of coating system.
- insoluble anodes those made of a material selected from the group consisting of platinized titanium and iridium-transition metal mixed oxide or combinations of these materials are preferably used. Particular preference is given to using platinized titanium anodes.
- This palladium-iron alloy can be either final or final layer, or further coated by methods known per se. Further z. B. intermediate or final coatings may, as mentioned above, gold-containing or other noble metal-containing layers, such as those of rhodium, platinum, ruthenium or their alloys.
- the base material is first copper-plated, then coated with palladium and finally receives the desired finish by coating with gold, rhodium or other precious metals or their alloys.
- a thickness of the palladium layer of about 0.5-5 microns is recommended. Usually a layer thickness of about 1 ⁇ m is considered sufficient.
- rhodium-ruthenium alloy instead of a rhodium final layer. If, for example, an alloy in the ratio by weight of rhodium to ruthenium of 80:20 is deposited as the final layer, in addition to the savings in the intermediate layers mentioned above, 20% of the very expensive rhodium would be saved.
- the invention further relates to a per se conventional method for cathodic deposition of the binary alloys according to the invention with an Fe content of 5-15% by weight on at least on their surface metallic or electrically conductive or conductive coated objects or articles using the electrolyte according to the invention according to claim 15.
- the invention further relates to the use of the electrolyte bath according to the invention for the cathodic deposition of binary alloys on at least on their surface metallic or electrically conductive or conductive coated objects or articles according to claim 16.
- the jewelry blank is rinsed in deionized water, dekapiert in 5% sulfuric acid solution for 30 s and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company. Ing. Garhöfer GesmbH), 20 ⁇ m copper are deposited in a shiny, shiny finish at 4 A / dm 2 and 25 ° C. The blank is rinsed again.
- the corrosion resistance of the palladium-iron alloy in comparison with a coating of a pure palladium electrolyte (Gapal TS, product of Garhöfer GesmbH), produced on the same base material in the SO 2 test is equally good.
- a brass disc in the palladium-iron electrolyte of example 1 and a brass disc in a pure palladium electrolyte (Gapal TS, product of Garhöfer GesmbH) were coated with 2 .mu.m. Ansch manend both discs were abraded. The pure palladium was rubbed much earlier than the palladium-iron alloy.
- a jewelery blank made of die-cast zinc is electrolytically degreased in a weakly alkaline cyanide-free cleaner (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 seconds at 10 A / dm 2 .
- a weakly alkaline cyanide-free cleaner degreasing 1018, product of the company Ing. W. Garhöfer GesmbH
- the jewelry blank is rinsed in deionized water and in an alkaline cyanide Vorkupferbad with 22 g / l Cu and 34 g / l KCN ("Cuproga", product of the company Ing. W. Garhöfer GesmbH) were 5 microns of copper at 1 A / dm 2 and 50 ° C deposited.
- the pre-coppered jewelry blank is then dekapiert in 5% sulfuric acid solution for 30 s and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company Ing. W. Garhöfer GesmbH) 15 ⁇ m copper leveling and high gloss deposited at 4 A / dm 2 and 25 ° C.
- the thus coppered part is rinsed and pre-immersed in a 10% KCN solution.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Die Erfindung betrifft ein Elektrolytbad für das kathodische Abscheiden von binären Legierungen und/oder Schichtfolgen unter Bildung von weißen, korrosionsbeständigen, rissfreien und (hoch)glänzenden Überzügen auf zumindest an ihrer Oberfläche metallischen bzw. elektrisch leitfähigen oder leitfähig beschichteten Objekten, welches Bad als Legierungsmetalle aus zumindest einer Palladiumverbindung, insbesondere einem Palladiumsalz, als Primärmetall und zumindest einer Eisenverbindung, insbesondere einem Eisensalz als Sekundärmetall besteht. Die Erfindung ist dadurch gekennzeichnet, dass es - zur Abscheidung einer Pd/Fe-Legierung mit einem Gehalt von 5-15 Gew-% Fe - als wässerige, alkalisch reagierende Lösung, insbesondere mit einem pH-Wert von 7,5 bis 9, vorliegt und außer den Metall-Verbindungen, als wesentliche weitere Komponente zumindest ein Netzmittel, insbesondere aus der Gruppe der amphoteren Tenside, und zusätzlich mindestens einen der in galvanischen Palladiumbädern in üblicher Weise enthaltenen Glanzzusatz sowie Leitsalze, insbesondere pH-Stabilisatoren und insbesondere Spannungsverminderer enthält, wobei das Elektrolytbad frei von Ammoniak und Ammoniumverbindungen ist.The invention relates to an electrolytic bath for the cathodic deposition of binary alloys and / or layer sequences with the formation of white, corrosion-resistant, crack-free and (high) glossy coatings on at least metallic or electrically conductive or conductively coated objects on their surface, which bath is composed of alloying metals at least one palladium compound, in particular a palladium salt, as a primary metal and at least one iron compound, in particular an iron salt as a secondary metal. The invention is characterized in that it is - for the deposition of a Pd / Fe alloy containing 5-15% by weight of Fe - as an aqueous, alkaline solution, in particular having a pH of 7.5 to 9, is present and in addition to the metal compounds, as an essential further component at least one wetting agent, in particular from the group of amphoteric surfactants, and additionally at least one of the additives contained in galvanic palladium in the usual way brightener and conductive salts, in particular pH stabilizers and in particular stress reducer contains, wherein the Electrolyte bath is free of ammonia and ammonium compounds.
Description
Die vorliegende Erfindung ist auf eine Elektrolytbadzusammensetzung zur Abscheidung weißer, hochglänzender, rissfreier, abriebs- und korrosionsbeständiger Palladium-Eisenlegierungen aus alkalischen wässrigen Bädern gerichtet, weiters auf Objekte und Artikel, welche mit diesen Legierungen beschichtet sind sowie auf ein Verfahren zur Herstellung der beschichteten Objekte und Artikel.The present invention is directed to an electrolytic bath composition for depositing white, high-gloss, crack-free, abrasion and corrosion-resistant palladium-iron alloys from alkaline aqueous baths, objects and articles coated with these alloys, and a process for producing the coated objects Items.
Methoden zur Abscheidung von Palladium-Eisenlegierungen aus wässrig alkalischen Elektrolyten sind aus dem AiF Forschungsvorhaben Nr. 10302 N des Forschungsinstitutes für Edelmetalle und Metallchemie Schwäbisch Gmünd, "Galvanische Abscheidung von Palladium-Eisen-Legierungsüberzügen für funktionelle Anwendungen und deren Charakterisierung" bekannt. Jedoch konnten mit einem dort beschriebenen Elektrolyten unter den dort beschriebenen Bedingungen keine hochglänzenden Legierungen abgeschieden werden. Außerdem basiert der beschriebene Elektrolyt auf Ammoniumsalzen, der pH-Wert wird mit Ammoniak eingestellt. Bei Elektrolyttemperaturen von 55 °C muss daher ständig Ammoniak nachgeliefert werden, um den pH-Wert konstant zu halten, außerdem entstehen dadurch enorme Geruchs- und Gesundheitsbelästigungen für die Betreiber solcher Bäder.Methods for the deposition of palladium-iron alloys from aqueous alkaline electrolytes are known from the AiF research project No. 10302 N of the Research Institute for Precious Metals and Metal Chemistry Schwäbisch Gmünd, "Galvanic deposition of palladium-iron alloy coatings for functional applications and their characterization". However, with the electrolyte described there, no high-gloss alloys could be deposited under the conditions described there. In addition, the electrolyte described is based on ammonium salts, the pH is adjusted with ammonia. At electrolyte temperatures of 55 ° C, therefore, ammonia must be constantly replenished in order to keep the pH constant, and in addition there are enormous odor and health nuisances for the operators of such baths.
Die Elektrolyte die aus
Es ist Ziel der gegenwärtigen Erfindung, Bäder zu entwickeln, aus denen hochglänzende, binäre Palladium-Eisen-Legierungen ohne jeglichen Zusatz von weiteren Metallen und abgeschieden werden können. Insbesondere sollen die Legierungsbäder beim Betrieb keine Geruchsbelästigung oder Gesundheitsgefahr durch die Freisetzung von reizenden Gasen oder Dämpfen darstellen und darüber hinaus keine starken Komplexbildner wie EDTA oder NTA enthalten, die Probleme bei der Abwasserbehandlung hervorrufen würden.
Zusätzlich soll die Produktion durch den Einsatz derartiger Legierungsbäder verbilligt werden, und Ressourcen des teuren Palladiums geschont werden.
Eine Kostenersparnis von etwa 15% beim Einsatz derartiger Legierungsbäder im Vergleich zu Reinpalladiumbädern ergibt sich zum einen aus der geringeren Dichte der abgeschiedenen Palladium-Eisen-Legierung, zum anderen aus geringeren Ausschleppungsverlusten von Edelmetall, da Reinpalladiumbäder meist etwa mit einer Palladiumkonzentration von 10 g/l Palladium arbeiten, das Palladium-Eisen-Legierungsbad vorliegender Erfindung jedoch mit etwa der halben Konzentration auskommen kann.It is the object of the present invention to develop baths from which high gloss, binary palladium-iron alloys can be deposited without any addition of other metals and. In particular, the alloy baths during operation should not present an odor nuisance or health hazard through the release of irritating gases or vapors, and moreover contain no strong complexing agents such as EDTA or NTA, which would cause problems in wastewater treatment.
In addition, the production is to be cheapened by the use of such alloy baths, and resources of the expensive palladium are spared.
A cost saving of about 15% when using such alloy baths in comparison to pure palladium baths results on the one hand from the lower density of the deposited palladium-iron alloy, on the other hand from lower Ausleppungsverlusten of precious metal, since pure palladium baths usually about with a palladium concentration of 10 g / l Palladium work, but the palladium-iron alloy bath of the present invention can get by with about half the concentration.
Derartige Legierungen eignen sich daher besonders gut für jegliche metallisch weiße, dekorative Beschichtung, z.B. von Modeschmuck, aber durchaus auch für industrielle Anwendungen, wie insbesondere in der Elektronikindustrie.Such alloys are therefore particularly well suited for any metallic white decorative coating, e.g. of costume jewelery, but also for industrial applications, especially in the electronics industry.
Gemäß vorliegender Erfindung enthalten die Bäder 0,5-15 g/l Palladium, 0,2-2 g/l Eisen, Leitsalze, Glanzzusätze und Netzmittel. Es können Schichtdicken >5 µ hochglänzend, rissfrei abgeschieden werden. Die Korrosionsbeständigkeit ist vergleichbar mit Reinpalladium, die Abriebbeständigkeit ist besser als Reinpalladium.In the present invention, the baths contain 0.5-15 g / l of palladium, 0.2-2 g / l of iron, conductive salts, brighteners and wetting agents. It is possible to deposit layer thicknesses> 5 μ high-gloss, crack-free. The corrosion resistance is comparable to pure palladium, the abrasion resistance is better than pure palladium.
Die Erfindung betrifft ein neues Elektrolytbad für das kathodische Abscheiden von binären Legierungen und/oder Schichtfolgen unter Bildung von weißen, korrosionsbeständigen, rissfreien und hochglänzenden Überzügen auf zumindest an ihrer Oberfläche metallischen bzw. elektrisch leitfähigen oder leitfähig beschichteten Objekten, welches Bad als Elektrolyt zumindest eine komplexe Palladiumverbindung und zumindest ein Eisensalz enthält, und dadurch gekennzeichnet ist, dass es - zur Abscheidung einer PdFe-Legierung mit einem Gehalt von 5-15 Gew.-% Fe - als wässerige, alkalisch reagierende Lösung vorliegt und außer den als Metall-Verbindungen, als wesentliche weitere Komponente zumindest ein Netzmittel aus der Gruppe der amphoteren Tenside und zusätzlich mindestens einen der in galvanischen Palladiumbädern in üblicher Weise enthaltenen Glanzzusatz sowie Leitsalze, pH-Stabilisatoren und Spannungsverminderer enthält.The invention relates to a novel electrolyte bath for the cathodic deposition of binary alloys and / or layer sequences to form white, corrosion-resistant, crack-free and high-gloss coatings on at least on their surface metallic or electrically conductive or conductive coated objects, which bath as electrolyte at least one complex Palladium compound and at least one iron salt, and characterized in that it - for the deposition of a PdFe alloy containing 5-15 wt .-% Fe - as aqueous, alkaline solution is present and in addition to containing as metal compounds, as a further essential component at least one wetting agent from the group of amphoteric surfactants and additionally at least one of the additives contained in galvanic palladium in the usual manner brightener and conductive salts, pH stabilizers and stress reducer.
Der pH-Wert des neuen Legierungsbades soll im Bereich 7,5 - 9 gehalten werden, da bei niedrigeren pH-Werten (etwa zwischen 7 und 7,5) die Einbauraten an Eisen sinken. Bei höheren pH-Werten (etwa zwischen 9 und 10) kommt es zu Anbrennungen im hohen Stromdichtebereich. Der pH-Wert wird vorteilhafterweise mittels Natrium- oder Kaliumhydroxid eingestellt.The pH of the new alloy bath should be maintained in the range of 7.5 - 9, since at lower pH values (approximately between 7 and 7.5) the incorporation rates of iron decrease. At higher pH values (approximately between 9 and 10), burns occur in the high current density range. The pH is advantageously adjusted by means of sodium or potassium hydroxide.
Gemäß vorliegender Erfindung liegt der Eisengehalt der abgeschiedenen Legierung bei 5-15 Gew.-% Fe, da bei Einbauraten >15 Gew.-% Fe die Schichten rissig werden, und bei Einbauraten <5 Gew-% die Abscheidung ein milchiges Aussehen erhält.According to the present invention, the iron content of the deposited alloy at 5-15 wt .-% Fe, since at incorporation rates> 15 wt .- Fe Fe the layers are cracked, and at incorporation rates <5% by weight, the deposition receives a milky appearance.
Im Rahmen der vorliegenden Erfindung hat es sich als vorteilhaft erwiesen, wenn Palladium in zweiwertiger Form, z.B. als Palladiumchlorid, -Sulfat, -Nitrat, und Eisen als Eisen-III-Salz, z.B. als Sulfat, Chlorid, Nitrat oder Citrat im Elektrolytbad vorliegen.For the purposes of the present invention, it has proven advantageous to use palladium in divalent form, e.g. as palladium chloride, sulfate, nitrate, and iron as the ferric salt, e.g. be present as sulfate, chloride, nitrate or citrate in the electrolyte bath.
Demgemäß ist für die Abscheidung eines Überzugs ein Elektrolytbad vorteilhafterweise vorgesehen, das sich dadurch auszeichnet, dass es einen Gehalt Palladium von 0,5 bis 15 g/l, bevorzugt von 2 bis 8 g/l, und besonders bevorzugt von 4 bis 6 g/l, und an Eisen von 0,2 bis 2 g/l, bevorzugt von 0,5 bis 1,5 g/l enthält.Accordingly, an electrolyte bath is advantageously provided for the deposition of a coating, which is characterized in that it has a content of palladium of 0.5 to 15 g / l, preferably from 2 to 8 g / l, and particularly preferably from 4 to 6 g / l, and iron of 0.2 to 2 g / l, preferably from 0.5 to 1.5 g / l.
Die für die außerordentlichen Eigenschaften der neuen Legierungs-Überzüge wesentlichen Netzmittel insbesondere aus der Gruppe der amphoteren Tenside z.B. Betaine und Sulfobetaine werden vorteilhafterweise in Mengen von 0,5-2 g/l dem Elektrolyten zugesetzt.The wetting agents essential to the extraordinary properties of the novel alloy coatings, in particular from the group of amphoteric surfactants, e.g. Betaine and sulfobetaines are advantageously added to the electrolyte in amounts of 0.5-2 g / l.
Was andere Komponenten des neuen Elektrolytbads als die wesentlichen Metallverbindungen und Netzmittel betrifft, so hat es sich als vorteilhaft erwiesen, wenn es Glanzmittel enthält. Derartige Glanzmittel für Palladiumbäder sind bekannt und kommen zum Beispiel aus der Gruppe der substituierten aromatischen N-Heterocyclen. Es hat sich außerdem als vorteilhat erwiesen, wenn der Elektrolyt Spannungsverminderer enthält wie Saccharin oder organische Sulfonate.As for other components of the new electrolyte bath than the essential metal compounds and wetting agents, it has proven to be advantageous if it contains brighteners. Such brighteners for palladium baths are known and come for example from the group of substituted aromatic N-heterocycles. It has also proved to be advantageous if the electrolyte contains stress reducers such as saccharin or organic sulfonates.
Weiters enthalten sind Leitsalze sowie pH-Stabilisatoren wie Natrium- oder Kaliumsulfat, - Nitrat, -Chlorid, -Citrat, -Tartrat, oder -Malonat, und eventuell weitere oberflächenaktive bzw. Netzmittel, beispielsweise Alkylethersufonate, Alkyletherphosphate oder Fettalkoholalkoxylate.Also included are conductive salts and pH stabilizers such as sodium or potassium sulfate, nitrate, chloride, citrate, tartrate or malonate, and possibly further surface-active or wetting agents, for example alkyl ether sulfonates, alkyl ether phosphates or fatty alcohol alkoxylates.
Alle in der Erfindung verwendeten Leitsalze bzw. pH-Stabilisatoren sind Natrium- oder Kaliumsalze. Beim Einsatz von Ammoniak bzw. Ammoniumsalzen bei erhöhten Temperaturen von etwa 50°C wird ständig Ammoniak ausgetrieben. Dadurch verstellt sich der pH-Wert des Bades ständig und ein kontinuierliches Arbeit ist deutlich erschwert. Außerdem kommt es zu einer ständigen Geruchsbelästigung und Gesundheitsgefahr für die Bediener des Elektrolyten.All conductive salts or pH stabilizers used in the invention are sodium or potassium salts. When using ammonia or ammonium salts at elevated temperatures of about 50 ° C, ammonia is constantly expelled. As a result, the pH of the bath constantly adjusted and continuous work is much more difficult. In addition, there is a constant odor nuisance and health hazard for the operator of the electrolyte.
Weiters werden im Elektrolyten der vorliegenden Erfindung keine organischen Säuren oder Salze verwendet, die beim Betrieb des Bades mit erhöhter Temperatur Dämpfe freisetzen, die zu einer Geruchsbelästigung und/oder Gesundheitsgefahr für die Bediener des Elektrolyten führen können, z.B. Propionsäure/Propionate, Essigsäure/Acetate.Furthermore, in the electrolyte of the present invention, no organic acids or salts are used which, when the bath is heated at elevated temperature, release vapors which can lead to an odor nuisance and / or health hazard to the operators of the electrolyte, e.g. Propionic acid / propionates, acetic acid / acetates.
Die verschiedenen vorteilhaften erfindungsgemäßen bzw. erfindungsgemäß eingesetzten Elektrolytbäder sind im Einzelnen in den Ansprüchen 2 bis 5 beschrieben.The various advantageous electrolyte baths according to the invention or used according to the invention are described in detail in claims 2 to 5.
Ein weiterer, ganz wesentlicher Gegenstand der Erfindung sind Objekte bzw. Artikel, insbesondere Schmuck- bzw. Dekorartikel, sowie weiters elektrotechnische bzw. elektronische Komponenten und Bauteile aus einem bevorzugterweise physiologisch verträglichen Metall, insbesondere aus Messing, Zink, Zinn, Eisen oder Stahl, oder aus Legierungen derselben oder aber aus einem leitfähig ausgerüsteten Kunststoff mit einem aus einem wie oben genannten Elektrolytbad abgeschiedenen Überzug aus einer binären Legierung aus Palladium und Eisen, in welcher das Eisen Gehalt von 5 bis 12 Gew-% vorliegt, wozu insbesondere auf den Anspruch 7 verwiesen wird.Another very important object of the invention are objects or articles, in particular jewelery or decorative articles, and further electro-technical or electronic components and components of a preferably physiologically acceptable metal, in particular brass, zinc, tin, iron or steel, or from alloys thereof or else from a conductive plastic with a coating of a binary alloy of palladium and iron deposited from an abovementioned electrolyte bath, in which the iron content is from 5 to 12% by weight, to which in particular reference is made to claim 7 becomes.
Was die im Rahmen der Erfindung üblicherweise zu erreichende Gesamtdicke der binären Palladium-Eisen-Beschichtung betrifft, so beträgt dieselbe -jeweils abhängig vom Einsatzgebiet - 0,1 bis 5 µm, insbesondere etwa 0,5 bis 3 µm.As far as the total thickness of the binary palladium-iron coating to be achieved in the context of the invention is concerned, it is 0.1 to 5 μm, in particular about 0.5 to 3 μm, depending on the field of use.
Es kann - siehe insbesondere Ansprüche 6 bis 14 - weiters vorgesehen sein, dass auf der Palladium-Eisen-Beschichtung außen eine auf derselben festhaftende weitere, elektrolytisch abgeschiedene Finalschicht aus Gold und/oder aus einem anderem Edelmetall, wie insbesondere aus Rhodium, Platin, Ruthenium oder aus einer Legierung aus denselben, angeordnet ist, durch welche die an sich schon hohe Gebrauchsfähigkeit und der Glanz des Überzugs noch gesteigert wird.It can - see in particular claims 6 to 14 - further be provided that on the outside of the palladium-iron coating on the same adherent another, electrodeposited final layer of gold and / or other precious metal, such as in particular rhodium, platinum, ruthenium or of an alloy from the same, is arranged, by which the already high usability and gloss of the coating is still increased.
Für weitere Verbesserungen der neuen Überzüge der neuen Objekte bzw. Artikel kann des Weiteren vorgesehen sein, dass auf dem Palladium-Eisen-Überzug eine auf demselben festhaftende, elektrolytisch abgeschiedenen Zwischenschicht aus Haftgold angeordnet ist, und auf dieser eine elektrolytisch abgeschiedene, haftfeste Finalschicht aus Gold und/oder aus einem anderem Edelmetall, wie insbesondere Rhodium, Platin, Ruthenium oder aus einer Legierung aus denselben, angeordnet ist.For further improvements of the new coatings of the new objects or articles may further be provided that on the palladium-iron coating on the same adherent, electrodeposited intermediate layer of adhesive gold is disposed, and on this an electrodeposited, adherent final layer of gold and / or of another noble metal, in particular rhodium, platinum, ruthenium or an alloy of the same.
Üblicherweise wird dafür Sorge getragen, dass die Zwischenschicht aus Haftgold eine Dicke von 0,05 bis 0,3 µm aufweist.Usually it is ensured that the intermediate layer of adhesive gold has a thickness of 0.05 to 0.3 microns.
Schließlich besteht letztlich die Möglichkeit darin, dass die neuen Objekte bzw. Artikel eine Finalschicht aus einer mit Rhodium und Ruthenium, vorzugsweise im Gew.-%-Verhältnis von (70 bis 90) zu (30 bis 10), insbesondere von etwa 80 zu 20, gebildeten Legierung aufweisen.Finally, the ultimate possibility is that the new objects or articles will have a final layer of one with rhodium and ruthenium, preferably in the weight% ratio of (70 to 90) to (30 to 10), especially about 80 to 20 , formed alloy.
Es ist das Ziel der vorliegenden Erfindung die Konzentration der Metallsalze, Netzmittel, Glanzzusätze und der zusätzlichen Inhaltsstoffe in der Form einzustellen und im Rahmen der erfindungsgemäßen Gewichts-Verhältnisse so zu variieren, dass die Elektroytlösung klar ist und bleibt, dass also keine Metallsalze ausfallen, und dass eben die erfindungsgemäß angestrebten, glänzenden, festhaftenden, rissfreien, abriebs- und korrosionsbeständigen Schichten bzw. Überzüge abgeschieden werden.It is the object of the present invention to adjust the concentration of the metal salts, wetting agents, brighteners and the additional ingredients in the mold and to vary within the weight ratios according to the invention so that the electrolyte solution is clear and remains, so that no metal salts precipitate, and that just according to the invention desired, shiny, adherent, crack-free, abrasion and corrosion resistant layers or coatings are deposited.
Im Zuge des Verfahrens zur elektrolytischen Aufbringung der neuen binären Palladium-Eisen-Legierungen auf die jeweiligen Grundmaterialien werden die zu beschichtenden Gegenstände, Objekte oder Artikel in das jeweilige, erfindungsgemäße Elektrolytbad getaucht und dort als Kathode geschaltet.In the course of the process for electrolytic application of the new binary palladium-iron alloys to the respective base materials to be coated objects, objects or articles are immersed in the respective inventive electrolyte bath and switched there as a cathode.
Die Arbeitstemperatur der erfindungsgemäßen Elektrolytbäder liegt zwischen 35 und 75 °C. Die Stromdichte kann auf zwischen 0,01 und 10 Ampere/dm2 eingestellt werden, jeweils abhängig von der Art der Beschichtungsanlage.The working temperature of the electrolyte baths according to the invention is between 35 and 75 ° C. The current density can be set to between 0.01 and 10 amps / dm 2 , depending on the type of coating system.
So werden in Trommelbeschichtungsverfahren Stromdichten zwischen 0,05 und 0,50 A/dm2 besonders bevorzugt. In Gestellbeschichtungsverfahren wählt man bevorzugt Stromdichten zwischen 0,2 und 10 A/dm2, besonders bevorzugt 0,2 bis 5 A/dm2.Thus, in drum coating processes, current densities between 0.05 and 0.50 A / dm 2 are particularly preferred. In rack coating processes, preference is given to choosing current densities between 0.2 and 10 A / dm 2 , particularly preferably 0.2 to 5 A / dm 2 .
Beim Einsatz der erfindungsgemäßen Elektrolytbäder können verschiedene unlösliche Anoden eingesetzt werden.When using the electrolyte baths according to the invention, various insoluble anodes can be used.
Als derartig unlösliche Anoden werden bevorzugt solche aus einem Material, ausgewählt aus der Gruppe bestehend aus platiniertem Titan und Iridium-Übergangsmetall-Mischoxid oder Kombinationen dieser Materialien eingesetzt. Besonders bevorzugt finden platinierte Titananoden Einsatz.As such insoluble anodes, those made of a material selected from the group consisting of platinized titanium and iridium-transition metal mixed oxide or combinations of these materials are preferably used. Particular preference is given to using platinized titanium anodes.
Die Herstellung der erfindungsgemäß beschichteten Objekte bzw. Artikel erfolgt üblicherweise folgendermaßen:
- Auf einem jeweiligen Grundmaterial, beispielsweise bestehend aus Messing, Zink, Eisen, Stahl bzw. deren Legierungen oder auch anderen zumindest auf ihrer Oberfläche leitfähig gemachten Materialien wird entweder direkt oder auf eine dort vorher aufgebrachte Kupfer- Unterschicht, abgeschieden aus cyanidischen oder nicht cyanidischen alkalischen und/oder aus sauren Kupferbädern, wird entweder direkt oder auf dort aufgebrachte Cu/Sn/Zn-Legierung aus cyanidischen Brozebädern die neue binäre Palladium-Eisen-Legierung abgeschieden.
- On a respective base material, for example made of brass, zinc, iron, steel or their alloys or other materials made conductive at least on its surface is either directly or on a previously applied there copper undercoat, deposited from cyanide or non-cyanide alkaline and or from acidic copper baths, the new binary palladium-iron alloy is deposited either directly or on Cu / Sn / Zn alloy of cyanidic broze baths applied there.
Diese Palladium-Eisen-Legierung kann entweder End- bzw. Finalschicht sein, oder aber nach an sich bekannten Verfahren weiter beschichtet werden. Weitere z. B. Zwischen- oder Final-Beschichtungen können, wie schon oben erwähnt, goldhaltige oder andere edelmetallhaltige Schichten, wie solche aus Rhodium, Platin, Ruthenium oder deren Legierungen sein.This palladium-iron alloy can be either final or final layer, or further coated by methods known per se. Further z. B. intermediate or final coatings may, as mentioned above, gold-containing or other noble metal-containing layers, such as those of rhodium, platinum, ruthenium or their alloys.
Aus dem Stand der Technik ist - ergänzend zu den schon eingangs genannten Dokumenten - an sich bekannt, dass Palladium als Nickelersatz, als Diffusionssperre und als Korrosionsschutz eingesetzt wird. Bei diesen Produkten wird das Grundmaterial zuerst verkupfert, anschließend mit Palladium beschichtet und erhält zuletzt das gewünschte Finish durch Beschichtung mit Gold, Rhodium oder anderen Edelmetallen oder deren Legierungen.
Um einen ausreichenden Korrosionsschutz zu schaffen, wird eine Dicke der Palladiumschicht von etwa 0,5-5 µm empfohlen. Meist wird eine Schichtdicke von etwa 1µm als ausreichend betrachtet.From the prior art is - in addition to the documents already mentioned - known per se that palladium is used as a nickel substitute, as a diffusion barrier and as corrosion protection. In these products, the base material is first copper-plated, then coated with palladium and finally receives the desired finish by coating with gold, rhodium or other precious metals or their alloys.
In order to provide sufficient corrosion protection, a thickness of the palladium layer of about 0.5-5 microns is recommended. Usually a layer thickness of about 1 μm is considered sufficient.
Gemäß vorliegender Erfindung wurde gefunden, dass das Aufbringen einer gleich dicken Palladium-Legierungsschichte zu gleich guten Korrosionsergebnissen führt, wie sie bei rein-palladiumbeschichteten Grundmaterialien erzielt werden, die Abriebsbeständigkeit jedoch besser ist. Die Kostenersparnis beträgt allein aufgrund der geringeren Dichte ca. 15%.According to the present invention, it has been found that the application of an equally thick palladium alloy layer leads to equally good corrosion results as are achieved in pure palladium-coated base materials, but the abrasion resistance is better. The cost savings alone is about 15% due to the lower density.
Will man die Produkte besonders effizient herstellen, kann man statt einer Rhodium-Finalschicht eine Rhodium-Ruthenium-Legierung abscheiden. Scheidet man als Finalschicht beispielsweise eine Legierung im Gew.-Verhältnis Rhodium zu Ruthenium von 80:20 ab, würde man zusätzlich zu der Ersparnis bei den wie oben genannten Zwischenschichten noch 20 % des an sich sehr teuren Rhodiums einsparen.If one wants to produce the products particularly efficiently, one can deposit a rhodium-ruthenium alloy instead of a rhodium final layer. If, for example, an alloy in the ratio by weight of rhodium to ruthenium of 80:20 is deposited as the final layer, in addition to the savings in the intermediate layers mentioned above, 20% of the very expensive rhodium would be saved.
Im einzelnen ist hierzu insbesondere auf die Ansprüche 6 bis 14 zu verweisen.In detail, reference is made in particular to claims 6 to 14.
Die Erfindung betrifft weiters ein an sich übliches Verfahren zum kathodischen Abscheiden der erfindungsgemäßen binären Legierungen mit einem Fe-Gehalt von 5-15 Gew-% auf zumindest an ihrer Oberfläche metallischen bzw. elektrisch leitfähigen oder leitfähig beschichteten Objekten bzw. Artikeln unter Einsatz des erfindungsgemäßen Elektrolytbads gemäß Anspruch 15.The invention further relates to a per se conventional method for cathodic deposition of the binary alloys according to the invention with an Fe content of 5-15% by weight on at least on their surface metallic or electrically conductive or conductive coated objects or articles using the electrolyte according to the invention according to claim 15.
Die Erfindung betrifft des Weiteren die Verwendung des erfindungsgemäßen Elektrolytbads zum kathodischen Abscheiden von binären Legierungen auf zumindest an ihrer Oberfläche metallischen bzw. elektrisch leitfähigen oder leitfähig beschichteten Objekten bzw. Artikeln gemäß Anspruch 16.The invention further relates to the use of the electrolyte bath according to the invention for the cathodic deposition of binary alloys on at least on their surface metallic or electrically conductive or conductive coated objects or articles according to claim 16.
Anhand der folgenden, nicht einschränkend zu verstehenden Beispiele wird die Erfindung näher erläutert:Reference to the following, non-limiting examples, the invention is explained in more detail:
Elektrolytbad:
- 4 g/l Pd aus Pd-II-chlorid
- 0,6 g/l Fe aus Fe-III-sulfat
- 80 g/l Kaliumsulfat
- 40 g/l Zitronensäure
- 1 g/l Netzmittel PF (Betain, Produkt der Fa. Ing. W. Garhöfer GesmbH) 0,1 g/l Fettalkoholethoxylat
- 2 g/l Saccharin
- 2 ml/l Glanzmittel: "Brightener PF" (Gemisch substituierter aromatischer N-Heterocyclen, ,
- Produkt der Fa. Ing. W. Garhöfer GesmbH)
- pH-Wert: 8,0 eingestellt mittels KOH
- 4 g / l Pd of Pd-II chloride
- 0.6 g / l Fe of Fe-III sulfate
- 80 g / l potassium sulfate
- 40 g / l citric acid
- 1 g / l wetting agent PF (betaine, product of the company Ing. W. Garhöfer GesmbH) 0.1 g / l fatty alcohol ethoxylate
- 2 g / l saccharin
- 2 ml / l brightener: Brightener PF (mixture of substituted aromatic N-heterocycles,
- Product of the company Ing. W. Garhöfer GesmbH)
- pH value: 8.0 adjusted by means of KOH
Schichtfolge und deren Herstellung:
- Ein Schmuckrohling aus Messing wird in einem schwach alkalischen cyanidfreien Reiniger, "Entfettung 1018", Produkt der Fa. Ing. W. Garhöfer GesmbH) bei 25 °C 30 s lang bei 10 A/dm2 elektrolytisch entfettet.
- A brass jewelry blank is electrolytically degreased in a weakly alkaline cyanide-free cleaner, "degreasing 1018", product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 seconds at 10 A / dm 2 .
Anschließend wird der Schmuckrohling in deionisiertem Wasser gespült, in 5%iger Schwefelsäurelösung 30 s lang dekapiert und in einem sauren Kupferbad mit 50 g/l Cu und 60 g/l Schwefelsäure ("IWG Cu 550", Produkt der Fa. Ing. W. Garhöfer GesmbH) werden 20 µm Kupfer einebnend und hochglänzend bei 4 A/dm2 und 25 °C abgeschieden. Der Rohling wird wiederum gespült.Subsequently, the jewelry blank is rinsed in deionized water, dekapiert in 5% sulfuric acid solution for 30 s and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company. Ing. Garhöfer GesmbH), 20 μm copper are deposited in a shiny, shiny finish at 4 A / dm 2 and 25 ° C. The blank is rinsed again.
Hierauf werden aus einem Palladium-Eisen-Elektroytbad gemäß vorliegender Erfindung 2µm Palladium-Eisen der Zusammensetzung Palladium: 90,3 %, Eisen: 9,7 %, bei 50 °C, und 1 A/dm2 innerhalb von 10 min aus dem Elektrolytbad abgeschieden.Then from a palladium-iron-Elektroytbad according to the present invention 2μm palladium-iron of the composition palladium: 90.3%, iron: 9.7%, at 50 ° C, and 1 A / dm 2 within 10 minutes from the electrolyte bath deposited.
Abschließend wurde der galvanisierte Schmuckteil in deionisiertem Wasser gespült und getrocknet.Finally, the galvanized jewelry was rinsed in deionized water and dried.
Optische Beurteilung:
- Der auf diese Weise erhaltene, galvanisierte Schmuckteil bzw. dessen Oberfläche war weiß und hochglänzend.
- Die Weissheit gemessen nach CIELAB betrug L* = 85. (Reinpalladiumschichten haben eine Weissheit von L* = 87)
- The obtained in this way, galvanized jewelry part or its surface was white and high gloss.
- The whiteness measured according to CIELAB was L * = 85 (pure palladium layers have a whiteness of L * = 87)
Korrosionsbeständigkeit nach DIN 50018:
- Die Korrosionsbeständigkeit des galvanisierten Schmuckteiles wurde nach DIN 50018, Prüfung im Kondenswasser-Wechselklima mit schwefeldioxidhaltiger Atmosphäre, Juni 1997, geprüft.
- The corrosion resistance of the galvanized decorative part was tested in accordance with DIN 50018, Testing in a condensed water climate with sulfur dioxide-containing atmosphere, June 1997.
Die Korrosionsbeständigkeit der Palladium-Eisen-Legierung im Vergleich mit einem Überzug aus einem Reinpalladium-Elektrolyten (Gapal TS, Produkt der Fa. Garhöfer GesmbH), produziert auf jeweils gleichem Grundmaterial im SO2-Test ist gleich gut.The corrosion resistance of the palladium-iron alloy in comparison with a coating of a pure palladium electrolyte (Gapal TS, product of Garhöfer GesmbH), produced on the same base material in the SO 2 test is equally good.
Es wurden jeweils eine Messingscheibe in dem Palladium-Eisen-Elektrolyt aus Bespiel 1 und eine Messingscheibe in einem Reinpalladium-Elektrolyten (Gapal TS, Produkt der Fa. Garhöfer GesmbH) mit 2µm beschichtet. Anschießend wurden beide Scheiben abgerieben. Das Reinpalladium war deutlich früher durchgerieben als die Palladium-Eisen-Legierung.In each case, a brass disc in the palladium-iron electrolyte of example 1 and a brass disc in a pure palladium electrolyte (Gapal TS, product of Garhöfer GesmbH) were coated with 2 .mu.m. Anschießend both discs were abraded. The pure palladium was rubbed much earlier than the palladium-iron alloy.
Elektrolyt:
- 4 g/l Pd aus Pd-II-chlorid
- 0,6 g/l Fe aus Fe-III-sulfat
- 80 g/l Kaliumsulfat
- 40 g/l Zitronensäure
- 1 g/l Netzmittel PF (Betain, Produkt der Fa. Ing. W. Garhöfer GesmbH)
- 0,1 g/l Fettalkoholethoxylat
- 2 g/l Saccharin
- 2 ml/l Glanzmittel: "Brightener PF" (Gemisch substituierter aromatischer N-Heterocyclen, ,
- Produkt der Fa. Ing. W. Garhöfer GesmbH)
- pH-Wert: 8,0 eingestellt mittels KOH
- 4 g / l Pd of Pd-II chloride
- 0.6 g / l Fe of Fe-III sulfate
- 80 g / l potassium sulfate
- 40 g / l citric acid
- 1 g / l wetting agent PF (betaine, product of the company Ing. W. Garhöfer GesmbH)
- 0.1 g / l fatty alcohol ethoxylate
- 2 g / l saccharin
- 2 ml / l brightener: Brightener PF (mixture of substituted aromatic N-heterocycles,
- Product of the company Ing. W. Garhöfer GesmbH)
- pH value: 8.0 adjusted by means of KOH
Ein Schmuckrohling aus Zinkdruckguß wird in einem schwach alkalischen cyanidfreien Reiniger, (Entfettung 1018, Produkt der Fa. Ing. W. Garhöfer GesmbH) bei 25 °C 30s lang bei 10 A/dm2 elektrolytisch entfettet.A jewelery blank made of die-cast zinc is electrolytically degreased in a weakly alkaline cyanide-free cleaner (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 seconds at 10 A / dm 2 .
Anschließend wird der Schmuckrohling in deionisiertem Wasser gespült und in einem alkalisch cyanidischen Vorkupferbad mit 22 g/l Cu und 34 g/l KCN ("Cuproga", Produkt der Fa. Ing. W. Garhöfer GesmbH) wurden 5µm Kupfer bei 1 A/dm2 und 50 °C abgeschieden.Subsequently, the jewelry blank is rinsed in deionized water and in an alkaline cyanide Vorkupferbad with 22 g / l Cu and 34 g / l KCN ("Cuproga", product of the company Ing. W. Garhöfer GesmbH) were 5 microns of copper at 1 A / dm 2 and 50 ° C deposited.
Der vorverkupferte Schmuckrohling wird dann in 5%iger Schwefelsäurelösung 30 s lang dekapiert und in einem sauren Kupferbad mit 50 g/l Cu und 60 g/l Schwefelsäure ("IWG Cu 550", Produkt der Fa. Ing. W. Garhöfer GesmbH) werden 15µm Kupfer einebnend und hochglänzend bei 4 A/dm2 und 25 °C abgeschieden. Der so verkupferte Teil wird gespült und in einer 10% KCN-Lösung vorgetaucht.The pre-coppered jewelry blank is then dekapiert in 5% sulfuric acid solution for 30 s and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company Ing. W. Garhöfer GesmbH) 15μm copper leveling and high gloss deposited at 4 A / dm 2 and 25 ° C. The thus coppered part is rinsed and pre-immersed in a 10% KCN solution.
Hierauf werden aus einem Bronzeelektroytbad ("Weissbronze CT 15 LF, Produkt der Fa. Ing. W. Garhöfer GesmbH) 2µm Bronzelegierung bei 60 °C und 1 A/dm2 innerhalb von 10 min aus dem Elektrolyten abgeschieden. Danach wird in deionisierem Wasser gespült und in 5%iger Schwefelsäurelösung dekapiert. 2 μm of bronze alloy are then removed from the electrolyte within a period of 10 minutes from a bronze electrolytic bath (Weissbronze CT 15 LF, product of the company Ing. W. Garhöfer GesmbH) and then rinsed in deionized water and decanted in 5% sulfuric acid solution.
Hierauf werden aus einem Palladium-Eisen-Elektroytbad gemäß vorliegender Erfindung 2µm Palladium-Eisen der Zusammensetzung Palladium: 90,3 %, Eisen: 9,7 %, bei 50 °C, und 1 A/dm2 innerhalb von 10 min aus dem Elektrolytbad abgeschieden.Then from a palladium-iron-Elektroytbad according to the present invention 2μm palladium-iron of the composition palladium: 90.3%, iron: 9.7%, at 50 ° C, and 1 A / dm 2 within 10 minutes from the electrolyte bath deposited.
Der so erhaltene Schmuckteil wird nach erneutem Spülen und Säuretauchen mit 0,1 µm Haftgold aus einem schwach sauren Elektrolyten mit 2,5 g/l Au ("MC 218", Produkt der Fa. Ing. W. Garhöfer GesmbH) bei 1,5 A/dm2 und 35 °C versehen. Dann wird sorgfältig in demineralisiertem Wasser gespült, in 5%iger Schwefelsäurelösung dekapiert und mit 0,2µm Rhodium aus einem Elektrolyten mit 2 g/l Rh und 50 g/l Schwefelsäure ("Rhodium C2", Produkt der Fa. Ing. W. Garhöfer GesmbH) bei 3V und 35 °C rhodiniert.After renewed rinsing and acid immersion with 0.1 μm adhesive gold from a weakly acidic electrolyte with 2.5 g / l Au ("MC 218", product of the company Ing. W. Garhöfer GesmbH), the jewelery thus obtained is 1.5 A / dm 2 and 35 ° C provided. Then rinsed thoroughly in demineralized water, dekapiert in 5% sulfuric acid solution and 0.2 .mu.m rhodium from an electrolyte with 2 g / l Rh and 50 g / l sulfuric acid ("rhodium C2", product of the company Ing. W. Garhöfer GesmbH) rhodinated at 3V and 35 ° C.
Abschließend wurde der galvanisierte Teil in deionisiertem Wasser gespült und getrocknet.Finally, the galvanized part was rinsed in deionized water and dried.
Optische Beurteilung:
- Der auf diese Weise erhaltene, galvanisierte Schmuckteil bzw. dessen Oberfläche war rein weiß und hochglänzend.
- The obtained in this way, galvanized jewelry or its surface was pure white and high gloss.
Korrosionsbeständigkeit nach DIN 50018:
- Der galvanisierte Schmuckteil schnitt in den Korrosionstests gleich gut ab wie ein nach dem gleichen Verfahren, aber mit Reinpalladium beschichteter Schmuckteil.
- The galvanized part of the jewelry performed just as well in the corrosion tests as a jewelery part coated with pure palladium using the same process.
Claims (16)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ATA50188/2015A AT516876B1 (en) | 2015-03-09 | 2015-03-09 | Deposition of decorative palladium-iron alloy coatings on metallic substances |
Publications (3)
Publication Number | Publication Date |
---|---|
EP3067444A2 true EP3067444A2 (en) | 2016-09-14 |
EP3067444A3 EP3067444A3 (en) | 2016-12-07 |
EP3067444B1 EP3067444B1 (en) | 2019-03-27 |
Family
ID=60153001
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16156476.0A Active EP3067444B1 (en) | 2015-03-09 | 2016-02-19 | Deposition of decorative palladium iron alloy coatings on metallic substances |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP3067444B1 (en) |
AT (1) | AT516876B1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10612149B1 (en) | 2019-09-05 | 2020-04-07 | Chow Sang Sang Jewellery Company Limited | Platinum electrodeposition bath and uses thereof |
EP3733930A1 (en) * | 2019-05-03 | 2020-11-04 | IWG Ing. W. Garhöfer Gesellschaft m. b. H. | Coating system for deposition by means of electrodeposition on a blank |
AT523922A4 (en) * | 2020-09-08 | 2022-01-15 | Iwg Ing W Garhoefer Ges M B H | Electrolyte bath for palladium-ruthenium coatings |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2657925A1 (en) | 1976-12-21 | 1978-06-22 | Siemens Ag | AMMONIA-FREE, AQUATIC BATH FOR GALVANIC DEPOSITION OF PALLADIUM OR. PALLADIUM ALLOYS |
JPH1046384A (en) | 1996-05-10 | 1998-02-17 | Lucent Technol Inc | Palladium alloy plating bath |
JP2001181887A (en) | 1999-12-24 | 2001-07-03 | Bikutoria:Kk | Palladium/iron alloy plating solution and palladium alloy plated base material |
JP2001192885A (en) | 1999-10-27 | 2001-07-17 | Kojima Kagaku Yakuhin Kk | Palladium plating solution |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2364980A1 (en) * | 1976-09-17 | 1978-04-14 | Parker Ste Continentale | Electrodeposition of palladium alloys for jewellery - or protective coatings, using bath contg. organic cpds. and brighteners |
DE2906783A1 (en) * | 1979-02-22 | 1980-10-16 | Degussa | Pretreatment of light metals before electroplating in aq. solns. - where substrates are first coated with palladium alloy contg. cobalt and/or iron, to ensure adhesion of plating |
DE19512888A1 (en) * | 1995-04-06 | 1996-10-10 | Vacuumschmelze Gmbh | Process for the electrolytic coating of rare earth permanent magnets with minimal surface damage |
US6251249B1 (en) * | 1996-09-20 | 2001-06-26 | Atofina Chemicals, Inc. | Precious metal deposition composition and process |
GB2382353B (en) * | 1999-10-27 | 2004-10-27 | Kojima Chemicals Co Ltd | Palladium Plating Solution |
CN101400830B (en) * | 2006-01-06 | 2012-07-04 | 恩索恩公司 | Electrolyte and process for depositing a matt metal layer |
KR101502804B1 (en) * | 2008-05-07 | 2015-03-16 | 유미코아 갈바노테히닉 게엠베하 | Pd and Pd-Ni electrolyte baths |
ES2355283T3 (en) * | 2008-11-21 | 2011-03-24 | Umicore Galvanotechnik Gmbh | SEQUENCE OF LAYERS WITH CONTENT IN PRECIOUS METALS FOR DECORATIVE ITEMS. |
DE102009055828A1 (en) * | 2008-12-19 | 2010-07-01 | Merck Patent Gmbh | Preparing metal coated particles, useful e.g. in lacquers, colors, inks, pigment mixtures, comprises electrochemical metal deposition of metals on the particle substrate, whose surface is electrically conductive or semi-conductive |
-
2015
- 2015-03-09 AT ATA50188/2015A patent/AT516876B1/en active
-
2016
- 2016-02-19 EP EP16156476.0A patent/EP3067444B1/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2657925A1 (en) | 1976-12-21 | 1978-06-22 | Siemens Ag | AMMONIA-FREE, AQUATIC BATH FOR GALVANIC DEPOSITION OF PALLADIUM OR. PALLADIUM ALLOYS |
JPH1046384A (en) | 1996-05-10 | 1998-02-17 | Lucent Technol Inc | Palladium alloy plating bath |
JP2001192885A (en) | 1999-10-27 | 2001-07-17 | Kojima Kagaku Yakuhin Kk | Palladium plating solution |
JP2001181887A (en) | 1999-12-24 | 2001-07-03 | Bikutoria:Kk | Palladium/iron alloy plating solution and palladium alloy plated base material |
Non-Patent Citations (7)
Title |
---|
"Legor group responds to environmental challenges", TECHNICAL NEWS PROGRAM, no. 1, 2013, XP055401487, Retrieved from the Internet <URL:http://www.unionfiliere.it/uploaded/Generale/News/JTF2014Program.pdf> |
"Palladium plating by Legor", JNA, 28 September 2014 (2014-09-28), pages 1 - 2, XP055402236, Retrieved from the Internet <URL:http://uat.jewellerynewsasia.com/en/search/search_result/11160/Palladium-plating-by-Legor.html> |
LEGOR GROUP: "Legor group responds to environmental challenges", TECHNICAL NEWS, no. 1, 2013, pages 2 - 6, XP055402239 |
LEGOR GROUP: "Palladium Iron Electrolyte", TECHNICAL BULLETIN, 5 June 2014 (2014-06-05), pages 1 - 4, XP055402243 |
MAURO GAJO: "Nickel-free palladium thickness", SUR/FIN 2014, June 2014 (2014-06-01), pages 833 - 845, XP055402244 |
MAURO GAJO: "Thick nickel-free palladium alloys", 10TH JEWELRY TECHNOLOGY FORUM, 19 January 2014 (2014-01-19), XP055401490 |
MSDS: "PD4-FE, palladium iron plating solution, 4g/l", SAFETY DATA SHEET, 29 October 2013 (2013-10-29), XP055401497, Retrieved from the Internet <URL:http://products.legor.com/EN/item/36#sheets> |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3733930A1 (en) * | 2019-05-03 | 2020-11-04 | IWG Ing. W. Garhöfer Gesellschaft m. b. H. | Coating system for deposition by means of electrodeposition on a blank |
US10612149B1 (en) | 2019-09-05 | 2020-04-07 | Chow Sang Sang Jewellery Company Limited | Platinum electrodeposition bath and uses thereof |
AT523922A4 (en) * | 2020-09-08 | 2022-01-15 | Iwg Ing W Garhoefer Ges M B H | Electrolyte bath for palladium-ruthenium coatings |
AT523922B1 (en) * | 2020-09-08 | 2022-01-15 | Iwg Ing W Garhoefer Ges M B H | Electrolyte bath for palladium-ruthenium coatings |
EP3964610A1 (en) * | 2020-09-08 | 2022-03-09 | IWG Ing. W. Garhöfer Gesellschaft m. b. H. | Electroplating bath for palladium ruthenium coatings |
Also Published As
Publication number | Publication date |
---|---|
EP3067444A3 (en) | 2016-12-07 |
AT516876B1 (en) | 2016-11-15 |
EP3067444B1 (en) | 2019-03-27 |
AT516876A1 (en) | 2016-09-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AT514818B1 (en) | Deposition of Cu, Sn, Zn coatings on metallic substrates | |
EP2116634B1 (en) | Modified copper-tin electrolyte and method of depositing bronze layers | |
EP2283170B1 (en) | Pd and pd-ni electrolyte baths | |
EP2192210B1 (en) | Multilayer of precious metals for decorative items | |
DE102005059367B4 (en) | Electrolytic composition and method of depositing crack-free, corrosion-resistant and hard chromium and chromium alloy layers | |
DE102008050135A1 (en) | Process for depositing platinum rhodium layers with improved brightness | |
DE670403C (en) | Process for the electrolytic production of coatings consisting essentially of tin | |
EP3067444B1 (en) | Deposition of decorative palladium iron alloy coatings on metallic substances | |
DE60202378T2 (en) | ELECTROLYTIC BATH FOR THE ELECTROCHEMICAL SEPARATION OF GOLD AND GOLD ALLOYS | |
DE1222348B (en) | Galvanic gold or gold alloy bath | |
AT514427B1 (en) | Electrolyte bath and thus available objects or articles | |
DE860300C (en) | Electrolyte containing copper and tin salts for the production of copper-tin alloy coatings and a method for producing these coatings | |
DE2114119A1 (en) | Process for the electrolytic deposition of ruthenium and electrolysis bath to carry out this process | |
DE756279C (en) | Process for the electrolytic production of highly ductile zinc coatings | |
DE2226699A1 (en) | Electroplating bath for the deposition of rhodium-platinum alloys | |
AT523922B1 (en) | Electrolyte bath for palladium-ruthenium coatings | |
DE3244092A1 (en) | AQUEOUS BATH FOR GALVANIC DEPOSITION OF GOLD AND METHOD FOR GALVANIC DEPOSIT OF HARD GOLD USING ITS USE | |
EP4259856A1 (en) | Silver-bismuth electrolyte for separating hard silver layers | |
DE804278C (en) | Electrolyte for the galvanic production of coatings from nickel and nickel alloys on metal and non-conductors | |
DE2439656C2 (en) | Aqueous acid bath for the electrodeposition of a tin-nickel alloy | |
DE102014019753A1 (en) | Borsaur-free nickel bath | |
EP0163944A2 (en) | Aqueous acid electrolytes containing nickel and cobalt ions for the galvanic deposition of hardly discolouring lustrous white alloy coatings | |
DE102020131371A1 (en) | Ruthenium alloy layer and their layer combinations | |
DE102014118614A1 (en) | Boric acid-free nickel bath | |
DE963389C (en) | Bath for the production of galvanic nickel deposits |
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: A2 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 |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 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 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C25D 5/34 20060101ALN20161102BHEP Ipc: C25D 7/00 20060101AFI20161102BHEP Ipc: C25D 3/56 20060101ALI20161102BHEP Ipc: C25D 5/10 20060101ALI20161102BHEP |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20170601 |
|
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 |
|
TPAC | Observations filed by third parties |
Free format text: ORIGINAL CODE: EPIDOSNTIPA |
|
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: 20170824 |
|
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 7/00 20060101AFI20181129BHEP Ipc: C25D 5/34 20060101ALN20181129BHEP Ipc: C25D 5/10 20060101ALI20181129BHEP Ipc: C25D 3/56 20060101ALI20181129BHEP |
|
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 7/00 20060101AFI20181211BHEP Ipc: C25D 3/56 20060101ALI20181211BHEP Ipc: C25D 5/34 20060101ALN20181211BHEP Ipc: C25D 5/10 20060101ALI20181211BHEP |
|
INTG | Intention to grant announced |
Effective date: 20190103 |
|
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: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1113201 Country of ref document: AT Kind code of ref document: T Effective date: 20190415 |
|
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: DE Ref legal event code: R096 Ref document number: 502016003871 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20190327 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: 20190327 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: 20190327 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: 20190627 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20190327 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20190327 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: 20190327 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: 20190327 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: 20190628 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: 20190327 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: 20190627 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20190327 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: 20190327 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: 20190327 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: 20190327 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: 20190327 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: 20190727 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: 20190327 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: 20190327 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20190327 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: 20190327 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20190727 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502016003871 Country of ref document: DE |
|
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: 20190327 |
|
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 |
|
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: 20190327 |
|
26N | No opposition filed |
Effective date: 20200103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR 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: 20190327 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502016003871 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20200219 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20200229 |
|
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: 20190327 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200219 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200229 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200229 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200901 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200219 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200219 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200229 |
|
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: 20200229 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 1113201 Country of ref document: AT Kind code of ref document: T Effective date: 20210219 |
|
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: 20210219 |
|
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: 20190327 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: 20190327 |
|
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: 20190327 |