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EP1366219B1 - Bain electrolytique pour deposer des alliages en or et son utilisation - Google Patents

Bain electrolytique pour deposer des alliages en or et son utilisation Download PDF

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Publication number
EP1366219B1
EP1366219B1 EP02744906.5A EP02744906A EP1366219B1 EP 1366219 B1 EP1366219 B1 EP 1366219B1 EP 02744906 A EP02744906 A EP 02744906A EP 1366219 B1 EP1366219 B1 EP 1366219B1
Authority
EP
European Patent Office
Prior art keywords
bath
gold
compounds
bismuth
concentration
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.)
Expired - Lifetime
Application number
EP02744906.5A
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German (de)
English (en)
Other versions
EP1366219A2 (fr
Inventor
Susanne Goehring
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
Ivoclar Vivadent AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2001110743 external-priority patent/DE10110743A1/de
Application filed by Ivoclar Vivadent AG filed Critical Ivoclar Vivadent AG
Priority to EP02744906.5A priority Critical patent/EP1366219B1/fr
Publication of EP1366219A2 publication Critical patent/EP1366219A2/fr
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Publication of EP1366219B1 publication Critical patent/EP1366219B1/fr
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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 its use.
  • the gold is in the form of a gold sulfite complex.
  • the deposited layers must satisfy particular aesthetic requirements, especially in the field of dentistry, for example, in terms of color, gloss or surface texture.
  • certain further requirements can be placed on the composition of the deposited layers, for example with regard to biocompatibility. Biocompatibility of the materials may be particularly important in the dental field, since, for example, allergy patients require gold or gold alloy layers with the highest possible purity.
  • gold and gold alloy baths contain certain additives to at least partially meet the requirements imposed on the electroplating precipitations.
  • additives are also referred to as fine grain additives or gloss additives.
  • These may be organic additives, such as polyamines, polyimines and mixtures thereof or semi-metal compounds, for example arsenic, antimony or thallium. All of these additives can be incorporated more or less strongly in the deposited gold layer. In the case of organic additives, this is problematical in the dental field, since the layer properties (eg ductility and firing stability) can be negatively influenced by this incorporation.
  • the antimony is usually 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 gelatinous antimony oxide hydrate gel, which probably constitutes the mode of action of this additive.
  • the antimony oxide hydrate gel is not stable under the usual bathing conditions and reacts to form crystalline antimony oxide which no longer exhibits the desired effect. This is the reason that the additive can be added to the bath only before use and that the additive loses its effect after some time. Thus production of a long-term functional gold or gold alloy bath with all necessary components is not possible.
  • the additives must not only be added later, but also that the correct dosage, d. H. the necessary amount of additive, depends on the other bath and process parameters. As 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 vessel (cell geometry), the temperature and the current density. In most cases, these problems are attempted to be solved by the user following a so-called dosage table of the manufacturer of the bath due to his lack of chemical-technical expertise and measuring the amount of additive according to the number of objects to be electroplated.
  • the EP-B1-0 126 921 describes an aqueous bath for the electrodeposition of gold-copper-bismuth alloys containing the gold in the form of a gold cyanide complex.
  • This ternary alloys are deposited with high bismuth levels.
  • the bath described there is particularly suitable for the deposition of pink to violet-colored coatings on decorative objects, such as jewelry, watches and glasses.
  • the technical significance of this is that the bismuth can be incorporated into the alloys with extremely high contents up to 30 wt .-% and higher. This should be new applications, such.
  • B. the processing of electronic Components, such as connectors, tap because the corresponding precipitates are particularly hard and have good electrical conductivity and abrasion resistance.
  • For the dental field are in the EP-B1-0 126 921 mentioned baths, among other things, both due to their high toxicity and due to the fact that the bismuth is to be incorporated with high levels in the alloy, not suitable.
  • the DE-C2-2 723 910 (equivalent to FR-A-2353656 ) claims a variety of additive mixtures for baths for the electrodeposition of gold or gold alloys. These additional mixtures should cause an improvement in the properties of the deposited precipitates.
  • Mandatory components of these additional mixtures are at least one organic water-soluble nitro compound having a specific general formula and at least one water-soluble metal compound of an element of 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 limited to use in cyanidic baths.
  • the DE-A1-3 400 670 describes a gold sulfite complex-based bath that has an additive of water soluble thallium salt and a carboxylic acid free of hydroxyl and amino groups.
  • the object of the invention is to provide a bath for the electrodeposition of gold alloys, which at least partially avoids the disadvantages described above.
  • the galvanic production of prosthetic dental moldings should be made even more reliable and safer and the handling of the baths used for this purpose should be further simplified.
  • the possibility should be created to give the user an already provided with all necessary components and additives and thus functional bathroom in the hand.
  • the corresponding baths should be able to be operated largely with biocompatible, ie physiologically harmless compounds, without the quality of the deposited layers is deteriorated.
  • the bath according to the invention for the electrodeposition of 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 conventional additives / additives for such gold sulfite baths.
  • This bismuth compound is preferably a water-soluble bismuth compound, which results in that the bath itself is preferably an aqueous bath.
  • the bismuth compound is preferably a complex compound, preferably a so-called chelate compound.
  • Such compounds are known cyclic compounds in which a ligand (complexing agent) occupies several coordination sites of a central atom (metal), so that these are usually particularly stable complex compounds.
  • the bismuth compound contains an organic complexing agent, preferably an organic chelating agent.
  • NTA nitrilotriacetic acid
  • HEDTA N- (2-hydroxy-ethyl) -ethylenediaminetriacetic acid
  • TEPA tetraethylenepentamine
  • DTPA diethylenetriaminepentaacetic acid
  • EDNTA ethylenedinitrilotetraacetic acid
  • bismuth compounds employable in the present invention are, for example, water-soluble bismuth salts (e.g., sulfates, nitrates, sulfamates, phosphates, pyrophosphates, acetates, citrates, phosphonates, carbonates, oxides, hydroxides, and the like).
  • water-soluble bismuth salts e.g., sulfates, nitrates, sulfamates, phosphates, pyrophosphates, acetates, citrates, phosphonates, carbonates, oxides, hydroxides, and the like.
  • preferred complexing agents such as NTA and the like.
  • organic complexing agents examples include organic phosphonic acids, carboxylic acids, dicarboxylic acids, polyoxycarboxylic acids, hydroxycarboxylic acids, diketones, diphenols, salicylaldehydes, polyamines, polyaminocarboxylates, diols, polyols, di-polyamines, aminoalcohols, aminocarboxylic acids, aminophenols.
  • the bismuth compound (or possibly several such compounds) in the bath in a concentration between 0.05 mg / l and the saturation concentration of bismuth compound (s) in the bath is (are) included.
  • concentrations in the bath between 0.05 mg / l and 1 g / l are preferred.
  • Concentrations are preferred, within the last-mentioned range concentrations between 0.1 mg / l and 10 mg / l are to be emphasized.
  • the bath according to the invention is substantially free of physiologically harmful (harmful) additives / additives, the bath preferably being free of arsenic, antimony and thallium compounds.
  • physiologically harmful additives / additives the bath preferably being free of arsenic, antimony and thallium compounds.
  • the antimony is incorporated into the prosthetic molding 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 molding in amounts of less than 30 ppm and 40 ppm (these are the Detection limits for the analytical method used for these elements). This shows on the one hand that the bismuth itself is not incorporated into the molded part and on the other hand that the bismuth is able to considerably reduce the incorporation of the antimony.
  • the concentration of gold in the bath according to the invention is generally not critical.
  • the gold is contained in the bath in a concentration between 5 and 150 g / l.
  • gold concentrations in the bath selected between 10 and 100 g / l, preferably between 10 and 50 g / l.
  • a particular advantage of the invention is that gold concentrations in the bath between 30 and 48 g / l can be selected.
  • prosthetic moldings with layer thicknesses of about 200 ⁇ m can be obtained in less than 14 hours, preferably in less than 12 hours. It is even possible, with suitable process control, to deposit molded parts with such layer thicknesses in less than 6 hours. The particular advantages of the invention are also evident in deposits made in less than two hours, preferably within one to two hours. In this context reference is also made to the examples.
  • At least one other metal is contained in the bath.
  • This metal can be incorporated into the deposited layer and in these cases be referred to as alloying metal. In other cases, however, it can only serve to (better) deposit the gold or gold alloy layer.
  • This metal may in particular be copper and / or iron and / or at least one noble metal.
  • Precious metals, in particular those of the platinum group are particularly suitable because of their high biocompatibility in the field of prosthetic dental moldings.
  • the concentration of the further metal in the bath is, for example, also within the range of the desired alloy to be deposited wide borders variable.
  • the metals may 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 complex and chelating agents already mentioned above for bismuth can also be used in particular.
  • the concentrations of the metal compounds can be selected between 0.1 mg / l and 200 g / l. Within this range, the concentration may be between 0.1 and 500 mg / l, more preferably between 1 and 20 mg / l. Again, low concentrations are preferred. Within the latter range, concentrations between 2 mg / l and 10 mg / l are more preferred.
  • the gold sulfite complex in the bath according to the invention may in principle be any known complexes known from the prior art.
  • it is a so-called ammonium-gold sulfite complex, in which therefore the gold ion is complexed by the sulfite ions and as a "counterion" at least one ammonium ion is present.
  • the baths of the invention preferably have a pH of at least 7, i. 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 markedly 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 photosensitivity. In addition, baths with ammonium-gold sulfite complexes be operated at significantly lower pH of about 7-9. This makes handling such baths easier and safer for users with a lack of chemical expertise over Na / Ka-gold sulfite complex baths with pH's of about 10.
  • the bath according to the invention which is based on the preferred ammonium-gold sulfite complex and contains at least one bismuth compound, a particularly advantageous relationship between the chemical composition of the gold bath and the chemical composition of the galvanic precipitate has resulted.
  • This is further improved by the presence of the further metals in the gold bath, in particular copper and / or at least one noble metal and / or iron.
  • an extended range of applications has been identified, as apart from gypsum, a whole range of dental modeling and framework materials can also be used in the gold bath.
  • 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 above, again referred to the biocompatibility and the desired gold or gold alloy layers with the highest possible purity shall be. That's why it's special Importance to control the composition of the galvanic precipitation targeted and reproducible set.
  • the ratio of bismuth: copper is ⁇ 1, in particular between 0.3 and 0.5. If copper alloys are used to deposit alloys, this ratio is> 1.
  • Iron is safe to handle and is needed as an essential trace element even by the body. It also allows on the one hand by selecting the bismuth to iron ratio in the gold bath and, on the other hand, by choosing the type of iron compound / iron complex compound, to control even more precisely the composition and properties of the deposited gold layer.
  • iron complexes Fe-DTPA, Fe-EDTA, Fe-EDNTA with bismuth-iron ratios of about 1.5 to about 2 were particularly advantageous gold layers.
  • an advantageous bismuth: iron ratio is about 0.18 to about 0.3.
  • both metals can also be used together in a variety of proportions to bismuth in the bath 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 may contain other conventional additives / additives which are usually contained in such baths based on a gold sulfite complex.
  • additives / additives are known to the person skilled in the art and can be varied within the scope of their specialist knowledge in the customary fields.
  • conductive electrolytes with their conductive salts, buffer systems / buffer mixtures, so-called stabilizers and wetting agents are present.
  • brighteners and / or fine grain additives known from the prior art in the bath according to the invention.
  • the invention further includes the use of the described inventive bath for the production of prosthetic moldings for the dental sector by means of electrodeposition.
  • Such a use is in particular for the production of so-called dental frameworks such as crowns, bridges, superstructures and the like. intended.
  • the prosthetic moldings are thereby electrodeposited on a substrate.
  • the substrate can be, for example, a model molded from a tooth stump or an implant abutment part (prefabricated or individually preprocessed).
  • the invention comprises the use of at least one bismuth compound, preferably at least one water-soluble bismuth compound for producing prosthetic moldings for the dental sector by means of electrodeposition.
  • the bismuth compound is used as part of a bath according to the invention, as described above.
  • Preferred bismuth compounds have already been explained in detail above, so that reference can be made to the corresponding parts of the description and reference can be made.
  • the bismuth compound used according to the invention and optionally also the compounds of further metals can be added to the bath directly during its preparation. This means that the user is provided with a bathroom that is functional 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.
  • a dosing of the bismuth compound used according to the invention to the bath can also take place before or during the electrodeposition, if so desired.
  • a dosing of the bismuth compound used according to the invention to the bath can also take place before or during the electrodeposition, if so desired.
  • Such a variant can also be provided, for example, if an aqueous bath is used to which a completely or partially water-insoluble bismuth compound, eg bismuth oxide, has been added during the preparation.
  • This water-insoluble compound can then be converted into a water-soluble bismuth compound by adding a suitable complexing agent immediately before or during the electrodeposition, which then unfolds the desired effect in the bath.
  • the bismuth compound is added after a galvanic deposition to supplement in the bath. This concerns the cases where the concentration of gold and / or further metal in the bath is sufficient for several, in particular a plurality of deposits. Then the bismuth compound (and possibly also the compounds of the other metals) can be supplemented accordingly for later deposition cycles.
  • the use according to the invention is intended for the production of prosthetic molded parts which have sufficient stability in the electroforming 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 suitable not only for the production of crowns, but also of bridges and other superstructures.
  • the invention comprises a method for the production of prosthetic moldings for the dental sector from gold alloys by electrodeposition.
  • this method is for the production of dental structures such as crowns, bridges, Suprakonstrutationen 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 resulting layer is separated from the substrate (demolded).
  • the substrate may be e.g. a model molded from a tooth stump or an industrially prefabricated or individually machined implant abutment.
  • the substrate is constructed of an electrically non-conductive material, in particular gypsum or plastic. This usually applies the cases in which a model was molded from the tooth stump.
  • the surface of the non-conductive substrate is then made conductive prior to electrodeposition, in particular using conductive silver.
  • the substrate is made up of at least one metal which itself is already conductive.
  • substrates for example, inner telescopes (usually from a cast and milled dental alloy) or implant abutment parts, such as implant abutment posts and the like. to call.
  • implant abutment parts such as implant abutment posts and the like. to call.
  • Such parts are often made of titanium or titanium alloys.
  • the process 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 low electroplating times.
  • current densities up to 10 A / dm 2 , in particular current densities up to 8 A / dm 2 are selected. Even with such high current densities, the bath according to the invention is still very easy to use.
  • 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 method.
  • This type of electrodeposition also uses direct current.
  • this direct current is applied as pulse current, ie in the form of current pulses interrupted by pauses.
  • the state of the art can be referred to the volume " Pulse-Plating "the series Galvanotechnology and surface treatment, Leuze-Verlag, Saulgau, 1990 to get expelled.
  • the application of the pulse-plating method in dental technology shows the DE-A1-198 45 506 the applicant, the content of which is incorporated herein by reference.
  • the application of the pulse-plating method In the present invention has the advantage that within relatively short times, the precipitates in the desired thickness, for example of about 200 microns, can be deposited.
  • the use according to the invention and the method according to the invention are furthermore preferably characterized in that the deposited prosthetic shaped part is veneered with ceramic and / or plastic during its further processing.
  • the desired dentures is made.
  • a ceramic-veneered molding is fired in a conventional manner after application of the ceramic, for example at temperatures up to about 950 ° C.
  • a molded part which is veneered with plastic is irradiated with light, in particular with visible light, after the plastic has been applied to cure it, after the surface of the molded part has been previously conditioned with suitable methods known to the person skilled in the art.
  • the bath according to the invention is outstandingly suitable for the production of prosthetic moldings (dental prosthetic parts).
  • the properties of the precipitation are at least as good as those deposited during precipitation from gold sulfite baths, which work, for example, with an addition of antimony compounds.
  • the quality of the precipitation corresponds to the bath according to the invention even better the specific requirements in dental technology.
  • Another advantage of the bath according to the invention is that it is obviously insensitive to introduced into the bathroom plastics, for example, as Zahnstumpfmaterialien or for covering metallic parts that are not to be electroplated, are provided.
  • plastics molded model plastics
  • lacquers topcoats
  • release components during deposition in the gold bath which have a negative effect on the effect of the fine grain or brightener additives of the gold bath.
  • This negative effect is usually the more pronounced, the higher the current density is chosen during the deposition.
  • This results in the invention in the advantage that due to the insensitivity of the bath against such interference at relatively high current densities (see above up to 8 A / dm 2 or 10 A / dm 2 ) can be used.
  • a further advantage of the bath according to the invention is surprisingly found in the fact that such a bath with bismuth additive works problem-free and with above-average results in various devices commercially used in the dental field (also of different manufacturers) for electrodeposition.
  • the gold or gold alloy bath in its composition had to be precisely matched to the device used, or such a device in particular in its process parameters exactly to a particular bathroom. This has resulted in each manufacturer usually offering a specific gold bath for a specific device, tuned to its process parameters for this gold bath.
  • an Applicant's AGC microdevice which achieves a layer thickness of 200 ⁇ m, usually in 12 hours, can be operated just as well with the bath according to the invention as an AGC MicroPlus 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 use the pulse-plating process, for example the Applicant's AGC Speed device. In such devices, layer thicknesses of 200 microns depending on the size of the part to be plated in 1 to 2 hours can be achieved.
  • the bath according to the invention can be advantageously adapted to existing galvanic devices of the user.
  • the application range from “slow" up to the "fastest” devices, which can also be operated fully automatically, illustrates the particularly good handling of the invention for the user.
  • An electrolysis cell which can be used according to the examples consists of a vessel for receiving the bath.
  • This vessel is usually provided with a cover.
  • an anode which may possibly consist of several parts, as well as at least one cathode is provided.
  • the gold or gold alloy is electrodeposited on this cathode, which is formed, for example, of the substrate such as a plaster stump or mounting post.
  • the anode consists for example of platinized titanium.
  • a suitable current / voltage source is provided.
  • a magnetic stirrer with heating is usually provided, which at the same time ensures a constant (normally elevated) deposition temperature in the bath and for driving a magnetic stirrer bar present in the electrolysis cell. Accordingly, a temperature sensor is introduced into the electrolytic cell.
  • the baths used in addition to the specified ingredients usual additives / additives for gold sulfite baths.
  • additives are known to the person skilled in the art. These are, for example, conductive salts (sulfites, sulfates and phosphates), wetting agents or stabilizers such as nitro acids.
  • the bath according to the invention differs from the known baths in particular by the addition of bismuth compound, due to this addition, additives (if any) present in conventional baths, such as antimony compounds or nitro compounds, may (but need not) be omitted.
  • the separation result of the following table refers to a "defect-free” functionality, this is to mean that the layer obtained during the deposition has no cracks, pores or holes.

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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)

Claims (22)

  1. Bain pour le dépôt galvanique d'alliages d'or, dans lequel l'or se présente sous la forme d'un complexe de sulfite d'or, le bain contenant au moins un composé de bismuth soluble dans l'eau, au moins un composé de cuivre ou un composé de fer et au moins un autre composé métallique et des additifs habituels pour ces bains de sulfite d'or, caractérisé en ce que l'autre composé métallique présente du platine comme métal noble.
  2. Bain selon la revendication 1, caractérisé en ce que le complexe de sulfite d'or est un complexe d'ammonium-sulfite d'or,
  3. Bain selon la revendication 1 ou la revendication 2, caractérisé en ce qu'il possède un pH > 7, de préférence de 7 à 9.
  4. Bain selon l'une des revendications précédentes, caractérisé en ce que les composés de bismuth et les composés des autres métaux sont des composés complexes.
  5. Bain selon la revendication 4, caractérisé en ce que les composés complexes contiennent des agents chélatants organiques.
  6. Bain selon la revendication 5, caractérisé en ce que les agents chélatants sont le NTA, l'HEDTA, le TEPA, le DTPA, l'EDNTA ou en particulier l'EDTA.
  7. Bain selon l'une, des revendications précédentes, caractérisé en ce que les composés de bismuth dans le bain sont contenus en une concentration entre 0,05 mg/l et leur concentration à saturation dans le bain.
  8. Bain selon la revendication 7, caractérisé en ce que les composés de bismuth dans le bain sont contenus en une concentration entre 0,05 mg/l et 1 g/l, en particulier entre 0,1 mg/l et 10 mg/l.
  9. Bain selon l'une des revendications précédentes, caractérisé en ce que les composés des autres métaux dans le bain sont contenus en une concentration entre 0,1 mg/l et 200 mg/l, de préférence entre 0,1 mg/l et 500 mg/l.
  10. Bain selon la revendication 9, caractérisé en ce que les composés des autres métaux dans le bain sont en une concentration entre 1 mg/l et 20 mg/l, de préférence entre 2 mg/l et 10 mg/l.
  11. Bain selon l'une des revendication précédentes, caractérisé en ce qu'il est essentiellement dépourvu d'additifs physiologiquement dangereux, de préférence dépourvu de composés d'arsenic, d'antimoine et de thallium.
  12. Bain selon l'une des revendications précédentes, caractérisé en ce que l'or est contenu dans le bain en une concentration entre 5 et 150 g/l.
  13. Bain selon la revendication 12, caractérisé en ce que l'or dans le bain est contenu en une concentration entre 10 et 100 g/l, de préférence entre 10 et 50 g/l, en particulier entre 30 et 48 g/l.
  14. Utilisation d'un bain selon l'une des revendications précédentes, pour la production de pièces moulées prothétiques pour le domaine dentaire par dépôt galvanique, en particulier pour la production de structures dentaires tels que des couronnes, des bridges, des constructions sur implant, et similaires.
  15. Procédé de production de pièces moulées prothétiques pour le domaine dentaire, en alliages d'or par dépôt galvanique, en particulier pour la production de structures dentaires telles que des couronnes, des bridges, des constructions sur implant et similaires, caractérisé en ce qu'une couche d'or ou d'alliage d'or d'un bain selon l'une des revendications 1 à 3 est déposée sur un substrat correspondant, par exemple sur un modèle formé à partir d'un chicot d'une dent, et ensuite est séparée du substrat.
  16. Procédé selon la revendication 15, caractérisé en ce que le substrat est constitué d'un matériau électriquement non conducteur, en particulier un plâtre ou une matière plastique dont la surface, est rendue conductrice en particulier à l'aide d'argent conducteur.
  17. Procédé selon la revendication 15, caractérisé en ce que le substrat est constitué d'au moins un métal.
  18. Procédé selon l'une des revendications 15 à 17, caractérisé, en ce que le dépôt s'effectue avec une densité de courant élevée, de préférence avec une densité de courant allant jusqu'à 10 A/dm2.
  19. Procédé selon l'une des revendications 15 à 18, caractérisé en ce que le dépôt s'effectue dans le procédé dit de courant pulsé.
  20. Procédé selon l'une des revendications 14 à 19, caractérisé en ce que la pièce moulée prothétique est revêtue de céramique et/ou de matière plastique.
  21. Procédé selon la revendication 20, caractérisé en ce qu'une pièce moulée revêtue de céramique est cuite.
  22. Procédé selon la revendication 20, caractérisé en ce qu'une pièce moulée revêtue de matière plastique est durcie à la lumière, en particulier à la lumière visible.
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 EP1366219A2 (fr) 2003-12-03
EP1366219B1 true 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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1378590A1 (fr) * 2002-07-04 2004-01-07 Metalor Technologies International S.A. Bain pour dépôts electrolytiques d'or
CA2558475A1 (fr) * 2004-02-18 2005-09-01 Marianna Cooley Formulations anti-microbiennes et procedes d'utilisation de celles-ci
CN1308493C (zh) * 2004-07-27 2007-04-04 滕先弟 硫代硫酸金铵络合物及其制备方法
JP5442400B2 (ja) * 2009-11-13 2014-03-12 ルネサスエレクトロニクス株式会社 半導体集積回路装置の製造方法
CN101781758B (zh) * 2010-04-09 2011-12-07 厦门华弘昌科技有限公司 化学镀镍稳定剂、化学镀镍溶液及化学镀镍工艺
US11579344B2 (en) 2012-09-17 2023-02-14 Government Of The United States Of America, As Represented By The Secretary Of Commerce Metallic grating
US10889908B2 (en) * 2012-09-17 2021-01-12 Government Of The United States Of America, As Represented By The Secretary Of Commerce Superconformal filling composition and superconformally filling a recessed feature of an article
ITFI20120208A1 (it) * 2012-10-12 2014-04-13 Bluclad S R L Soluzione per l'elettrodeposizione di una lega di oro e la lega da essa derivante.
ITFI20130057A1 (it) * 2013-03-18 2014-09-19 Bluclad S R L Soluzione per l¿elettrodeposizione di una lega di oro e la lega da essa derivante.
CN103938232B (zh) * 2014-03-04 2015-04-01 深圳市联合蓝海新技术有限公司 一种无氰电镀液及其应用
CN103938231B (zh) * 2014-03-04 2015-04-01 深圳市联合蓝海科技开发有限公司 一种电镀黄金的方法和硬质黄金的制备方法
CN104047037B (zh) * 2014-06-16 2015-06-03 深圳市联合蓝海科技开发有限公司 一种硬化剂
CN104862752B (zh) * 2015-06-12 2016-02-17 深圳市联合蓝海投资控股集团有限公司 改性无氰镀金液及其应用和硬质黄金的制备方法
WO2023041972A1 (fr) * 2021-09-16 2023-03-23 Galvasols P & S Bain d'électroformage/électrodéposition d'or pur à grande vitesse
JP7219847B1 (ja) * 2022-09-26 2023-02-08 Ｅｅｊａ株式会社 金電気めっき液および金電気めっき方法

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BE754151A (fr) * 1969-08-08 1970-12-31 Sel Rex Corp Bain aqueux pour le placage electrolytique d'or ou d'alliage d'or sur un article conducteur, procede de fabrication dudit bain aqueux et utilisation de celui-ci
CH622829A5 (fr) * 1977-08-29 1981-04-30 Systemes Traitements Surfaces
JP2592246B2 (ja) * 1987-04-10 1997-03-19 株式会社ジーシー 歯冠修復用複合冠の内側冠の作製方法及び装置
DE3805627A1 (de) * 1988-02-24 1989-09-07 Wieland Edelmetalle Goldbad
US5277790A (en) * 1992-07-10 1994-01-11 Technic Incorporated Non-cyanide electroplating solution for gold or alloys thereof
DE19629658C2 (de) * 1996-07-23 1999-01-14 Degussa Cyanidfreies galvanisches Bad zur Abscheidung von Gold und Goldlegierungen
DE19845506A1 (de) * 1998-10-02 2000-04-06 Wieland Edelmetalle Verfahren zur Herstellung von prothetischen Formteilen für den Dentalbereich und prothetisches Formteil

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CA2438207A1 (fr) 2002-09-06
BR0207724A (pt) 2004-03-23
US20040065225A1 (en) 2004-04-08
JP4183240B2 (ja) 2008-11-19
CN1494606A (zh) 2004-05-05
WO2002068728A8 (fr) 2003-09-18
EP1366219A2 (fr) 2003-12-03
WO2002068728A1 (fr) 2002-09-06
AU2002308221A1 (en) 2002-09-12
JP2004527653A (ja) 2004-09-09
CN100392155C (zh) 2008-06-04

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