EP1366219A2 - Bain electrolytique pour deposer de l'or et des alliages en or, et son utilisation - Google Patents

Bain electrolytique pour deposer de l'or et des alliages en or, et son utilisation

Info

Publication number
EP1366219A2
EP1366219A2 EP02744906A EP02744906A EP1366219A2 EP 1366219 A2 EP1366219 A2 EP 1366219A2 EP 02744906 A EP02744906 A EP 02744906A EP 02744906 A EP02744906 A EP 02744906A EP 1366219 A2 EP1366219 A2 EP 1366219A2
Authority
EP
European Patent Office
Prior art keywords
bath
gold
compound
bismuth
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02744906A
Other languages
German (de)
English (en)
Other versions
EP1366219B1 (fr
Inventor
Susanne Rübel
Manfred Stümke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ivoclar Vivadent AG
Original Assignee
Wieland Dental and Technik GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2001110743 external-priority patent/DE10110743A1/de
Application filed by Wieland Dental and Technik GmbH and Co KG filed Critical Wieland Dental and Technik GmbH and Co KG
Priority to EP02744906.5A priority Critical patent/EP1366219B1/fr
Publication of EP1366219A2 publication Critical patent/EP1366219A2/fr
Application granted granted Critical
Publication of EP1366219B1 publication Critical patent/EP1366219B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • 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
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold

Definitions

  • the invention relates primarily to a bath for the electrodeposition of gold and gold alloys and the use thereof.
  • the gold is in the form of a gold sulfite complex.
  • a homogeneous layer structure ie a homogeneous structure, is as Uniform layer thickness and a reproducible composition of the deposited layer is a prerequisite for subsequently being able to apply a ceramic or plastic veneer to the molded part. This applies in particular to ceramic veneers, where the molded part has to be fired at higher temperatures after the ceramic material has been applied.
  • the metallic framework must also have the necessary fire stability. Minimum requirements must also be met with regard to other properties such as wear resistance, porosity, corrosion resistance and others.
  • the deposited layers must meet special aesthetic requirements, particularly in the dental field, for example in terms of color, gloss or surface quality.
  • certain additional requirements may be placed on the composition of the deposited layers, for example with regard to biocompatibility.
  • a biocompatibility of the materials can be particularly important, especially in the dental field, since gold or gold alloy layers with the highest possible purity are required for allergy sufferers, for example.
  • gold and gold alloy baths contain certain additives in order to at least partially meet the requirements imposed on the galvanic precipitation.
  • additives are also referred to as fine grain additives or gloss additives.
  • These can be organic additives, such as polyamines, polyimines and mixtures thereof, or semimetal compounds, for example arsenic, antimony or thallium. All of the additives mentioned can be more or less built into the deposited gold layer. With organic additives, this is problematic in the dental field because the layer properties (e.g. ductility and firing stability) can be negatively influenced by this incorporation.
  • antimony compounds are added to baths based on gold sulfite complexes
  • the antimony is mostly used as Sb (III), for example as potassium antimony tartrate.
  • Sb (III) for example as potassium antimony tartrate.
  • the latter reacts in the bath to form gelatin-like antimony oxide hydrate gel, which is probably the mode of action of this additive.
  • the antimony oxide hydrate gel is not stable under the usual bath conditions and reacts to crystalline antimony oxide, which no longer has the desired effect. This is the reason that the additive can only be added to the bath before use and that the additive loses its effectiveness after some time. It is therefore not possible to produce a gold or gold alloy bath that is functional over a long period of time with all the necessary components.
  • the additives not only have to be added subsequently, but also that the correct dosage, ie the necessary amount of additive, depends on the other bath and process parameters.
  • the influencing factors here are, for example, the proportions of the other constituents in the bath, the concentration of the electroactive ions, the geometry of the separation container (cell geometry), the temperature and the current density.
  • one tries to solve these problems by using a so-called dosage table from the manufacturer of the bath due to the lack of chemical-technical expertise and measuring the amount of additive according to the number of objects to be electroplated.
  • EP-B1-0 126 921 describes an aqueous bath for the electrodeposition of gold-copper-bismuth alloys that contains the gold in the form of a gold cyanide complex. Ternary alloys with high bismuth contents are deposited. The bathroom described there is particularly suitable for the deposition of rose to violet-colored coatings on decorative objects such as jewelry, watches and glasses. The technical significance is said to be that the bismuth can be incorporated in the alloys with extremely high contents up to 30% by weight and higher. This is intended to create new areas of application, such as. B. the finishing e- electronic components such as plug connections, because the corresponding precipitation is particularly hard and has good electrical conductivity and abrasion resistance.
  • the baths mentioned in EP-B1-0 126 921 are not suitable for the dental field, inter alia because of their high toxicity and also because the bismuth with high contents is to be incorporated into the alloy.
  • DE-C2-2 723 910 (corresponds to FR-A-2353656) claims a large number of additional mixtures for baths for the electrolytic deposition of gold or gold alloys. These additional mixtures are said to improve the properties of the deposited precipitates.
  • Essential components of these additional mixtures are at least one organic water-soluble nitro compound with a certain general formula and at least one water-soluble metal compound of an element from the group arsenic, antimony, bismuth, thallium and selenium.
  • Additional mixtures which contain a water-soluble bismuth compound in addition to the nitro compound are also restricted here to use in cyanide baths.
  • an additive for a bath based on a gold sulfite complex is known from US Pat. No. 5,277,790, which likewise contains both an organic polyamine or a mixture of polyamines and an aromatic organic nitro compound.
  • DE-A1-3 400 670 describes a bath based on gold sulfite complex, which is an additive from water-soluble thallium salt and a carboxylic acid which is free of hydroxyl and amino groups.
  • the object of the invention is to provide a bath for the galvanic deposition of gold and gold alloys which at least partially avoids the disadvantages described above.
  • the galvanic production of prosthetic dental molded parts is to be made even more reliable and safe, and the handling of the baths used for this purpose is to be further simplified.
  • the possibility is to be created to provide the user with a bath that is already provided with all the necessary components and additives and is therefore functional.
  • the corresponding baths should be able to be operated largely with biocompatible, that is to say physiologically harmless, compounds without the quality of the deposited layers being impaired.
  • the bath according to the invention for the electrodeposition of gold and gold alloys based on a gold sulfite complex is characterized in that it contains at least one bismuth compound in addition to any other metal compounds and other customary additives / additives for such gold sulfite baths.
  • This bismuth compound is preferably a water-soluble bismuth compound, which results in the bath itself also preferably being an aqueous bath.
  • all suitable inorganic or organic bismuth compounds can be used as the bismuth compound.
  • the bismuth compound is preferably a complex compound, preferably a so-called chelate compound.
  • Such compounds are known to be cyclic compounds in which a ligand (complexing agent) occupies several coordination sites of a central atom (metal), so that these are generally particularly stable complex compounds. It is further preferred according to the invention if the bismuth compound contains an organic complexing agent, preferably an organic chelating agent.
  • the complexing agents or chelating agents here are in particular NTA (nitrilotriacetic acid), HEDTA (N- (2-hydroxyethyl) ethylenediamine triacetic acid), TEPA (tetraethylene pentamine), DTPA (diethylenetriamine pentaacetic acid), EDNTA (ethylene dinitrilotetraacetic acid) and / as a preferred complexing agent To name EDTA (ethylenediaminetetraacetic acid).
  • Bismuth compounds which can be used according to the invention are, for example, water-soluble bismuth salts (e.g. sulfates, nitrates, sulfamates, phosphates, pyrophosphates, acetates, citrates, phosphonates, carbonates, oxides, hydroxides, etc.).
  • water-soluble bismuth salts e.g. sulfates, nitrates, sulfamates, phosphates, pyrophosphates, acetates, citrates, phosphonates, carbonates, oxides, hydroxides, etc.
  • preferred complexing agents such as NTA and the like.
  • organic complexing agents organic phosphonic acids, carboxylic acids, dicarboxylic acids, polyoxicarboxylic acids, hydroxycarboxylic acids, diketones, diphenols, salicylaldehydes, polyamines, polyamino carboxylates, diols, polyols, di-polyamines, amino alcohols, aminocarboxylic acids, aminoparboxylic acids, amino carbonic acids ,
  • the bismuth compound (or possibly several such compounds) is (are) present in the bath in a concentration between 0.05 mg / l and the saturation concentration of these bismuth compound (s).
  • concentrations in the bath between 0.05 mg / 1 and 1 g / l are preferred.
  • concentrations are preferred, with concentrations between 0.1 mg / l and 10 mg / l to be emphasized within the last-mentioned range.
  • the bath according to the invention is essentially free of physiologically questionable (harmful) additives / additives, the bath preferably being free of arsenic, antimony and thallium compounds.
  • physiologically questionable additives / additives the bath preferably being free of arsenic, antimony and thallium compounds.
  • the addition of bismuth compounds according to the invention is also able to reduce or even prevent the incorporation of physiologically questionable additives / additives into the prosthetic molded part.
  • conventional gold sulfite baths contain at least one antimony compound as an additive.
  • the antimony is incorporated into the prosthetic molded part in a concentration of normally 0.2 per thousand.
  • an antimony compound such as potassium-antimony tartrate
  • a bismuth compound such as bismuth-EDTA
  • both antimony and bismuth are present in the deposited molded part in amounts of less than 30 ppm and 40 ppm (these are Detection limits for the analysis method used for these elements).
  • the concentration of gold in the bath according to the invention is in principle not critical.
  • the gold in the bath is preferably present in a concentration between 5 and 150 g / l.
  • gold concentrations NEN in the bath between 10 and 100 g / l, preferably between 10 and 50 g / l.
  • a particular advantage of the invention is shown in the fact that gold concentrations in the bath can be chosen between 30 and 48 g / l.
  • prosthetic molded parts with layer thicknesses of approximately 200 ⁇ m can be obtained in less than 14 hours, preferably in less than 12 hours. It is even possible, with a suitable procedure, to deposit molded parts with such layer thicknesses in less than 6 hours.
  • the particular advantages of the invention are also evident in the case of deposits which are carried out in less than two hours, preferably within one to two hours. In this context, reference is also made to the examples.
  • At least one further metal is contained in the bath.
  • This metal can be built into the deposited layer and is referred to as alloy metal in these cases. In other cases, however, it can only serve to (better) deposit the gold or gold alloy layer.
  • This metal can in particular be copper and / or iron and / or at least one noble metal.
  • noble metals those from the so-called platinum group are to be mentioned with preference, these being, in particular, palladium or platinum.
  • Precious metals, especially those of the platinum group are particularly suitable in the field of prosthetic dental molded parts due to their high biocompatibility.
  • the concentration of the other metal in the bath is also dependent, for example, on the alloy to be deposited. can be varied within wide limits.
  • the metals can be added in the form of their preferably water-soluble compounds, in particular salts, or in the form of preferably water-soluble complex compounds.
  • the complexing agents and chelating agents already mentioned above for bismuth can also be used in this context.
  • the concentrations of the metal compounds can preferably be selected between 0.1 mg / l and 200 g / l. Within this range, the concentration can be between 0.1 and 500 mg / l and in particular between 1 and 20 mg / l. Low concentrations are preferred here too. Within the latter range, concentrations between 2 mg / l and 10 mg / l are further preferred.
  • the gold sulfite complex in the bath according to the invention can in principle be all known complexes as are known from the prior art. It is preferably a so-called ammonium-gold sulfite complex, in which the gold ion is complexed by the sulfite ions and at least one ammonium ion is present as the “counter ion”.
  • the baths according to the invention preferably have a pH of at least 7, i.e. they are either neutral or alkaline.
  • the baths are (weakly) alkaline, with pH values of 7 to 9 being preferred.
  • the preferred ammonium gold sulfite complex has a number of advantages over other gold sulfite complexes. For example, compared to sodium / potassium gold sulfite complexes, a significantly increased stability of the complex in the gold bath is responsible for a number of advantageous properties. These are, for example, a longer shelf life, a lower sensitivity to contamination and a lower sensitivity to light. Baths with ammonium gold sulfite complexes can also be used can be operated at a significantly lower pH of around 7-9. This makes handling such baths easier and safer for users with a lack of chemical expertise than Na / Ka gold sulfite complex baths with pH values of around 10.
  • the bath according to the invention which is based on the preferred ammonium-gold sulfite complex and contains at least one bismuth compound, has shown a particularly advantageous relationship between the chemical composition of the gold bath and the chemical composition of the galvanic deposit. This is further improved by the presence of the other metals in the gold bath, in particular copper and / or at least one noble metal and / or iron.
  • an expanded range of applications could be determined, since in addition to plaster, a whole range of dental modeling and framework materials can be used in the gold bath.
  • the bismuth compound By using the bismuth compound, it has been possible to control the composition of the galvanized gold layer and its functional properties precisely and predictably in a surprisingly simple way. So far, this has not been possible or only possible to a limited extent in the known gold baths used in dental technology, so that the composition of the deposition there mostly depends on technical factors such as e.g. Electrode geometry and the other technical factors are determined.
  • the requirements for a gold bath and the electrodeposited layers in the field of dental technology are of a special nature, so that here, in addition to the requirements mentioned at the beginning, the biocompatibility and the desired gold or gold alloy layers with the highest possible Purity should be pointed out. For this reason, it is particularly the importance of specifically controlling the composition of the galvanic precipitates and reproducibly adjusting them.
  • the ratio of bismuth: copper (based on the metals) is ⁇ 1, in particular between 0.3 and 05. If alloys are to be deposited using copper, this ratio is> 1.
  • iron as a further metal in the gold bath, there have surprisingly been further advantages of the bath according to the invention. Iron is safe to handle and is considered essential
  • the iron complexes Fe-DTPA, Fe-EDTA, Fe-EDNTA with bismuth-iron ratios of about 1.5 to about 2 gold layers were particularly advantageous.
  • an advantageous bismuth: iron ratio is about 0.18 to about 0.3.
  • both metals can also be used together in a multitude of ratios of bismuth in the bath according to the invention.
  • the large number of possible combinations for the bismuth-copper-iron ratios thus opens up a broad spectrum of new control options for the properties, the composition and the function of gold and gold alloy layers from baths according to the invention.
  • the proportions of bismuth: copper are preferably> 0.4 and of bismuth: iron> 0.3.
  • the bath according to the invention can thus selectively prevent the incorporation of, for example, antimony even in the presence of various metals such as copper and / or iron.
  • the bath according to the invention can contain further customary additives which are usually contained in such baths based on a gold sulfite complex.
  • additives are known to the person skilled in the art and can be varied within the usual ranges within his specialist knowledge.
  • conductive electrolytes with their conductive salts, buffer systems / buffer mixtures, so-called stabilizers and wetting agents.
  • stabilizers and wetting agents Possibly.
  • the brightener and / or fine-grain additives known from the prior art can also be present in the bath according to the invention.
  • the invention further comprises the use of the described bath according to the invention for the production of prosthetic molded parts for the dental field by means of electrodeposition.
  • Such use is particularly for the manufacture of so-called dental frameworks such as crowns, bridges, superstructures and the like. intended.
  • the prosthetic molded parts are galvanically deposited on a substrate.
  • the self-supporting, stable molded part is separated from the substrate and processed further.
  • the substrate can be, for example, a model molded from a tooth stump or an implant component (prefabricated or individually prepared).
  • the invention comprises the use of at least one bismuth compound, preferably at least one water-soluble bismuth compound, for the production of prosthetic molded parts for the dental field by means of electrodeposition.
  • the bismuth compound is used as part of a bath according to the invention, as described above.
  • Bismuth compounds which can preferably be used have already been explained in detail above, so that reference can be made to the corresponding places in the description.
  • a particularly important feature of the invention is to be emphasized that the bismuth compound used according to the invention and possibly also the compounds of other metals can be added to the bath directly during its manufacture. This means that the user is provided with a functional bath with regard to all components and additives. In contrast to the known baths of the prior art, the user does not have to add any additive / additive before carrying out the electroplating process, which would be associated with the disadvantages already explained above.
  • the bismuth compound used according to the invention can also be metered into the bath before or during the electrodeposition, if this is desired.
  • Such a variant can also be provided, for example, when an aqueous bath is used, to which a completely or partially water-insoluble bismuth compound, for example bismuth oxide, has been added during manufacture.
  • This water-insoluble compound can then be converted into a water-soluble bismuth compound by adding an appropriate complexing agent immediately before or even during the electrodeposition, which then has the desired effect in the bath.
  • a further preferred variant of the invention is the case that the bismuth compound is added to the bath to supplement it after electrodeposition.
  • the use according to the invention is intended for the production of prosthetic molded parts which have sufficient stability in the galvanoforming process. Accordingly, layer thicknesses of the molded part of more than 10 ⁇ m are usually provided.
  • the layer thicknesses of the molded part are preferably between 100 and 300 ⁇ m, with layer thicknesses of approximately 200 ⁇ m in particular being deposited.
  • the invention is not only suitable for the production of crowns, but also of bridges and other superstructures.
  • the invention encompasses a method for producing prosthetic molded parts for the dental field from gold and gold alloys by means of electrodeposition.
  • this method is used to manufacture dental frameworks such as crowns, bridges, superstructures and the like. intended.
  • a gold or gold alloy layer is deposited from a bath according to the invention on a corresponding substrate and the layer obtained is separated (demolded) from the substrate.
  • the substrate may e.g. be a model molded from a tooth stump or an industrially prefabricated or individually machined implant component.
  • the substrate is preferably constructed from an electrically non-conductive material, in particular gypsum or plastic. This affects normal For example, the cases in which a model was molded from the tooth stump.
  • the surface of the non-conductive substrate is then made conductive before the galvanic deposition, in particular with the aid of conductive silver.
  • the substrate is constructed from at least one metal that is itself already conductive.
  • the substrates here are, for example, internal telescopes (usually made from a cast and milled dental alloy) or implant components, such as implant abutments and the like. to call. Such parts are often made of titanium or titanium alloys.
  • the method according to the invention and also the uses according to the invention are preferably characterized in that the deposition takes place at high current densities, which usually results in short electroplating times.
  • Current densities up to 10 A / dm 2 are preferred, in particular current densities up to 8 A / dm 2 . Even with such high current densities, the bath according to the invention can still be used very well.
  • the use according to the invention or the method according to the invention can preferably be carried out in such a way that the deposition takes place in the so-called pulse-plating process.
  • This type of galvanic metal deposition also works with direct current.
  • this direct current is applied as a pulse current, ie in the form of current pulses which are interrupted by pauses.
  • the application of the pulse plating method in dental technology is shown in DE-A1 -198 45 506 by the applicant, the content of which is made by reference to the content of this description.
  • the ing method in the present invention has the advantage that the precipitates can be deposited in the desired thickness, for example of approximately 200 ⁇ m, within comparatively short times.
  • the use according to the invention and the method according to the invention are further preferably characterized in that the deposited prosthetic molded part is veneered with ceramic and / or plastic during its further processing.
  • the desired dentures are produced.
  • a molded part veneered with ceramic is fired in a conventional manner after the ceramic has been applied, for example at temperatures up to about 950 ° C.
  • a molded part veneered with plastic is irradiated with light, in particular with visible light, after the plastic has been applied to harden it, after the surface of the molded part has been conditioned beforehand using suitable processes known to the person skilled in the art.
  • the invention has a number of advantages.
  • the bath according to the invention is thus outstandingly suitable for the production of prosthetic molded parts (dental prosthetic parts).
  • the properties of the precipitates are at least as good as those which were deposited in precipitates from gold sulfite baths which, for example, work with the addition of antimony compounds.
  • the quality of the precipitation in the bath according to the invention corresponds even better to the specific requirements in dental technology.
  • the pure gold layers obtained with the bath according to the invention are golden yellow and highly glossy, so that they have particularly high aesthetic meet requirements. Of course, matt and / or rough surfaces can also be created.
  • the burning stability of these layers, which is essential for their ceramic veneering, is reproducible with certainty, despite the fact that an antimony compound is not used in a gold bath. To the best of the knowledge of the applicant, this has so far not been the case for any bath that can work without an antimony compound.
  • Another advantage of the bath according to the invention is that it is obviously insensitive to plastics introduced into the bath, which are provided, for example, as tooth stump materials or for covering metallic parts which are not to be galvanically coated.
  • plastics molded plastic models
  • lacquers covering lacquers
  • release components during the deposition in the gold bath which have a negative effect on the effect of the fine-grain or gloss additives of the gold bath.
  • This negative effect usually becomes clearer the higher the current density chosen during the deposition.
  • the workability of the bath according to the invention with the same requirement profile for the deposited electroplating layers is absolutely comparable with conventional baths based on gold sulfite complexes, which work, for example, with antimony or arsenic additives. It is even possible to increase the workability if the bismuth additive is chosen accordingly compared to known baths. The possibility of dispensing with potentially harmful compounds, for example arsenic, thallium and possibly also antimony, in the bath according to the invention by using the bismuth additives has already been emphasized above.
  • a further advantage of the bath according to the invention is surprisingly shown in the fact that such a bath with added bismuth works without problems and with above-average results in various devices (also from different manufacturers) used commercially in the dental field for galvanic deposition.
  • the composition of the gold or gold alloy bath had to be precisely matched to the device used, or such a device, in particular in terms of its process parameters, had to be precisely matched to a specific bath.
  • each manufacturer normally offered a specific gold bath for a very specific device that was matched to this gold bath in its process parameters.
  • an AGC Micro device from the applicant which usually reaches a layer thickness of 200 ⁇ m in 12 hours, can be operated with the bath according to the invention as well as an AGC MicroPI us device which already achieves the same layer thickness in 5 hours.
  • the bath according to the invention is also suitable for use in devices which work with the pulse-plating method, for example the AGC speed device from the applicant. In such devices, layer thicknesses of 200 ⁇ m are achieved in 1 to 2 hours, depending on the size of the part to be electroplated.
  • the bath according to the invention can thus advantageously be adapted to the user's existing galvano devices.
  • An electrolytic cell that can be used according to the examples consists of a vessel for holding the bath.
  • This vessel is usually provided with a cover.
  • an anode which can possibly consist of several parts, and at least one cathode are provided.
  • the gold or the gold alloy is electrodeposited on this cathode, which is formed, for example, by the substrate such as a plaster stump or abutment.
  • the anode is made of platinum-plated titanium, for example.
  • a suitable current / voltage source is provided for the deposition itself.
  • a magnetic stirrer with heating is usually provided, which at the same time ensures a constant (usually increased) deposition temperature in the bath and the drive of a magnetic stirring rod present in the electrolysis cell. Accordingly, a temperature sensor is also inserted in the electrolytic cell.
  • the baths used contain customary additives for gold sulfite baths.
  • additives are known to the person skilled in the art.
  • conductive salts sulfites, sulfates and phosphates
  • wetting agents such as nitro acids.
  • the bath according to the invention differs from the known baths in particular by the addition of the bismuth compound, it being possible for additions / additives which are present in conventional baths, such as, for example, antimony compounds or nitro compounds, to be omitted (but not necessarily) on account of this addition.

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  • 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)
  • Dental Preparations (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un bain électrolytique pour déposer de l'or et des alliages en or, et son utilisation pour la fabrication de corps moulés dentaires. L'or de ce bain se présente sous forme de complexe d'aurosulfite. L'invention est caractérisée en ce que le bain contient, outre d'autres métaux éventuels et les additifs usuels pour de tels bains d'aurosulfite, au moins un composé bismuth. Ce composé bismuth est de préférence un composé complexe contenant en particulier les agents complexants NTA, HEDTA, TEPA, DTPA, EDNTA ou EDTA. Cette invention présente toute une série d'avantages, parmi lesquels il est à noter que le bismuth peut être ajouté au bain dès sa réalisation, ce qui permet à l'utilisateur de disposer d'un bain fonctionnel pendant une durée prolongée, bain auquel il n'est pas obligatoire d'ajouter d'autres additifs avant la galvanisation.
EP02744906.5A 2001-02-28 2002-02-28 Bain electrolytique pour deposer des alliages en or et son utilisation Expired - Lifetime EP1366219B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02744906.5A EP1366219B1 (fr) 2001-02-28 2002-02-28 Bain electrolytique pour deposer des alliages en or et son utilisation

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE2001110743 DE10110743A1 (de) 2001-02-28 2001-02-28 Bad zur galvanischen Abscheidung von Gold und Goldlegierungen sowie dessen Verwendung
EP10110743 2001-02-28
EP01108448 2001-04-04
EP01108448A EP1236814A1 (fr) 2001-02-28 2001-04-04 Bain pour le dépôt galvanique d'or et d'alliages d'or et son application
PCT/EP2002/002128 WO2002068728A1 (fr) 2001-02-28 2002-02-28 Bain electrolytique pour deposer de l'or et des alliages en or, et son utilisation
EP02744906.5A EP1366219B1 (fr) 2001-02-28 2002-02-28 Bain electrolytique pour deposer des alliages en or et son utilisation

Publications (2)

Publication Number Publication Date
EP1366219A2 true EP1366219A2 (fr) 2003-12-03
EP1366219B1 EP1366219B1 (fr) 2014-09-03

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EP02744906.5A Expired - Lifetime EP1366219B1 (fr) 2001-02-28 2002-02-28 Bain electrolytique pour deposer des alliages en or et son utilisation

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US (1) US20040065225A1 (fr)
EP (1) EP1366219B1 (fr)
JP (1) JP4183240B2 (fr)
CN (1) CN100392155C (fr)
AU (1) AU2002308221A1 (fr)
BR (1) BR0207724A (fr)
CA (1) CA2438207A1 (fr)
WO (1) WO2002068728A1 (fr)

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EP1366219B1 (fr) 2014-09-03
AU2002308221A1 (en) 2002-09-12
JP2004527653A (ja) 2004-09-09
WO2002068728A1 (fr) 2002-09-06
WO2002068728A8 (fr) 2003-09-18
JP4183240B2 (ja) 2008-11-19
CN100392155C (zh) 2008-06-04
US20040065225A1 (en) 2004-04-08
CN1494606A (zh) 2004-05-05
BR0207724A (pt) 2004-03-23

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