EP0717118A2 - Process for manufacturing gold-titanium alloy castings - Google Patents
Process for manufacturing gold-titanium alloy castings Download PDFInfo
- Publication number
- EP0717118A2 EP0717118A2 EP95117228A EP95117228A EP0717118A2 EP 0717118 A2 EP0717118 A2 EP 0717118A2 EP 95117228 A EP95117228 A EP 95117228A EP 95117228 A EP95117228 A EP 95117228A EP 0717118 A2 EP0717118 A2 EP 0717118A2
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- Prior art keywords
- titanium
- alloy
- gold
- crucible
- alloys
- 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.)
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Classifications
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C27/00—Making jewellery or other personal adornments
- A44C27/001—Materials for manufacturing jewellery
- A44C27/002—Metallic materials
- A44C27/003—Metallic alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D25/00—Special casting characterised by the nature of the product
- B22D25/02—Special casting characterised by the nature of the product by its peculiarity of shape; of works of art
Definitions
- the invention relates to a process for the production of moldings from gold-titanium alloys with 0.1 to 4% by weight of titanium, in particular for dental and jewelry parts, by melting portions of the alloy in air and subsequent casting.
- Gold alloys are the traditional alloy systems used for this purpose. They have been clinically proven for many years. These alloys are still unmatched in terms of corrosion resistance and biocompatibility. The numerous requirements placed on these alloys have so far only been possible with alloy systems that are generally of very complicated construction be fulfilled.
- the high gold alloys are characterized by a gold content from approx. 70% by weight. Palladium and platinum are generally added to increase the high temperature stability during ceramic firing. A number of different base metals are added to increase hardness and mechanical strength. Additional elements are added to ensure the fine-tuning of further data relevant to dental technology, such as thermal expansion coefficient, ceramic adhesion, oxide color or sufficient ductility at high temperature. Other common alloying elements are, for example, silver, copper, indium, zinc, tin and iron.
- dental bonding alloys that only consist of gold and another harmless element and that are as close as possible to pure gold in terms of color and corrosion resistance as well as processability, and at the same time that have mechanical strength required by a Type 4 alloy.
- gold-titanium alloys with 0.1 to 4% by weight of titanium are known, which are used as a material for jewelry or coins. These alloys are harder and therefore more abrasion-resistant than pure gold. They also show a brilliant gold color.
- titanium has a large reactivity in the molten state with the air components and the crucible materials, with the formation of, for example, oxides, nitrides or carbides. This creates disruptive slag layers during melting and pouring, which also change the composition of the alloy and thus its properties.
- EP-A-0 190 648 the alloy and melt of gold and titanium are melted and cast in a vacuum or under a protective gas in the form of argon.
- the melting takes place in a ceramic crucible, the casting in a graphite mold.
- both materials can only be used under vacuum or in an argon atmosphere if slag formation is to be avoided. Slag formation occurs in air, enriching the titanium content of the alloy and rendering the ceramic crucible unusable.
- the crucible should be reusable.
- This object is achieved in that a crucible is used in which the surfaces coming into contact with the alloy melt consist of carbon.
- a graphite crucible is preferably used to melt the gold-titanium alloy.
- the graphite can contain a few percent of another material.
- the melting of gold-titanium alloys with 0.1 to 4% by weight of titanium in crucibles made of carbon in air does not lead to the formation of titanium carbide in disruptive amounts, but instead, after casting, flawless casting pieces with a predetermined titanium content of the gold alloy are obtained.
- the crucible is not noticeably attacked here and can therefore be reused many times.
- a further improvement in the melting of the gold-titanium alloy results if the alloy is introduced into the crucible in as few portion pieces as possible.
- the aim should be the smallest possible ratio of surface to volume of the individual portion pieces. Spheres, cylinder sections or cuboids are therefore preferably used as shaped pieces, the amount of melt being achieved with at most 5 portion pieces.
- the moldings made of gold-titanium alloys with 0.1 to 4% by weight of titanium can be veneered very well with the commercially available dental ceramics.
- the hardness of the mold pieces can also be varied by varying the titanium content.
- the graphite crucible is then reusable.
- the solidified molded body has a casting hardness of 199 HV, which means it contains the specified titanium content. After a simulated ceramic firing, the hardness increases to 219 HV.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Dental Prosthetics (AREA)
- Mold Materials And Core Materials (AREA)
- Adornments (AREA)
- Catalysts (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Gußformstücken aus Gold-Titan-Legierungen mit 0,1 bis 4 Gew.% Titan, insbesondere für Dental- und Schmuckteile, durch Aufschmelzen von Portionsstücken der Legierung an der Luft und anschließendes Vergießen.The invention relates to a process for the production of moldings from gold-titanium alloys with 0.1 to 4% by weight of titanium, in particular for dental and jewelry parts, by melting portions of the alloy in air and subsequent casting.
Festsitzender und herausnehmbarer Zahnersatz wird normalerweise aus korrosionsbeständigen, biokompatiblen Edelmetallegierungen hergestellt, wobei das gegossene Objekt anschließend oft mit Dentalkeramik verblendet wird, um ein dem natürlichen Zahn entsprechendes Aussehen zu erzielen. Die Eignung von Legierungen für diesen Zweck ist an eine Reihe von Eigenschaften geknüpft, die auf die Dentalkeramik abgestimmt sein müssen, wie thermischer Ausdehnungskoeffizient, Schmelzintervall und Haftung zwischen Keramik und Legierung. Grundvorraussetzung ist auch eine gute Korrosionsbeständigkeit und eine ausreichende Festigkeit, um die Belastungen beim Kauvorgang zu ertragen. Nach ihrer mechanischen Belastbarkeit werden Dentallegierungen in verschiedene Klassen von Typ 1 bis Typ 4 eingeteilt. Die höchste Festigkeit und damit die breiteste Indikation besitzen
Typ 4-Legierungen.Fixed and removable dentures are usually made from corrosion-resistant, biocompatible precious metal alloys, with the cast object often being veneered with dental ceramics to achieve a look that matches the natural tooth. The suitability of alloys for this purpose is linked to a number of properties that have to be matched to the dental ceramic, such as thermal expansion coefficient, melting interval and adhesion between ceramic and alloy. A basic requirement is also good corrosion resistance and sufficient strength to withstand the loads during the chewing process. Dental alloys are divided into different classes from type 1 to type 4 according to their mechanical strength. Have the highest strength and thus the broadest indication
Type 4 alloys.
Hochgoldhaltige Edelmetallegierungen sind die traditionellen Legierungssysteme, die für diesen Zweck eingesetzt werden. Sie haben sich seit vielen Jahren klinisch bewährt. In der Korrosionsbeständigkeit und Biokompatibilität sind diese Legierungen nach wie vor unerreicht. Die zahlreichen Anforderungen, die an diese Legierungen gestellt werden, konnten bisher nur mit in aller Regel sehr kompliziert aufgebauten Legierungssystemen erfüllt werden. Die hochgoldhaltigen Aufbrennlegierungen sind charakterisiert durch einen Goldgehalt ab ca. 70 Gew.%. Zur Steigerung der Hochtemperaturstabilität während des Keramikbrandes ist in der Regel Palladium und Platin zulegiert. Zur Erhöhung der Härte und der mechanischen Festigkeit werden eine ganze Reihe verschiedener Nichtedelmetalle zugesetzt. Weitere Elemente werden zulegiert, um die Feinabstimmung weiterer zahntechnisch relevanter Daten, wie thermischer Ausdehnungskoeffizient, Keramikhaftung, Oxidfarbe oder ausreichende Duktilität bei hoher Temperatur zu gewährleisten. Gebräuchliche weitere Legierungselemente sind zum Beispiel Silber, Kupfer, Indium, Zink, Zinn und Eisen. Bekannt ist, daß eine Reihe dieser Elemente auch wieder unerwünschte Eigenschaften haben kann, so daß versucht wird, diese zu vermeiden oder nur in geringer Menge einzusetzen. Beispielsweise kann Silber zu Grünverfärbung bei empfindlichen Keramiken führen und Kupfer kann speziell beim Auftreten von Spaltkorrosionseffekten zu Verfärbungen führen.Gold alloys are the traditional alloy systems used for this purpose. They have been clinically proven for many years. These alloys are still unmatched in terms of corrosion resistance and biocompatibility. The numerous requirements placed on these alloys have so far only been possible with alloy systems that are generally of very complicated construction be fulfilled. The high gold alloys are characterized by a gold content from approx. 70% by weight. Palladium and platinum are generally added to increase the high temperature stability during ceramic firing. A number of different base metals are added to increase hardness and mechanical strength. Additional elements are added to ensure the fine-tuning of further data relevant to dental technology, such as thermal expansion coefficient, ceramic adhesion, oxide color or sufficient ductility at high temperature. Other common alloying elements are, for example, silver, copper, indium, zinc, tin and iron. It is known that a number of these elements can also have undesirable properties, so that attempts are made to avoid them or to use them only in small quantities. For example, silver can cause green discoloration of sensitive ceramics and copper can lead to discoloration, especially when crevice corrosion effects occur.
Im Zuge eines allgemein gestiegenen Gesuchtheitsbewußtseins und einer generell zu beobachtenden höheren Anfälligkeit gegenüber Allergien und Unverträglichkeiten bei den Menschen der modernen Industriestaaten ist auch die Biokompatabilität von Dental- und Schmucklegierungen verstärkt in die Diskussion geraten. Bisherige Untersuchungen zeigen, daß Art und Menge der durch Korrosionsvorgänge in Lösung gehenden Bestandteile einer Legierung für die Biokompatibilität entscheidend sind. Anzustreben ist generell ein möglichst hoher Edelmetallanteil für gute Korrosionsbeständigkeit und eine möglichst geringe Anzahl der Legierungskomponenten, speziell der Nichtedelmetalle, um dadurch die Wahrscheinlichkeit einer allergischen Reaktion auf eine bestimmte Komponente so gering wie möglich zu halten. Selbstverständlich sollten nur Elemente Verwendung finden, die keinerlei toxische Wirkungen besitzen.In the course of a general increase in awareness and a generally observed higher susceptibility to allergies and intolerances among the people of the modern industrialized countries, the biocompatibility of dental and jewelry alloys has also come under increasing discussion. Previous studies have shown that the type and amount of the components of an alloy that dissolve due to corrosion processes are decisive for biocompatibility. In general, the aim should be a high proportion of precious metal for good corrosion resistance and a minimum number of alloy components, especially non-precious metals, in order to keep the probability of an allergic reaction to a certain component as low as possible. Of course, only elements that have no toxic effects should be used.
Aus Gründen der optimalen Biokompatibilität und der Ästhetik wäre es wünschenswert, Dental-Aufbrennlegierungen zur Verfügung zu haben, die lediglich aus Gold und einem weiteren unbedenklichen Element bestehen und die bezüglich der Farbe und der Korrosionsbeständigkeit sowie der Verarbeitbarkeit möglichst nahe am reinen Gold liegen und gleichzeitig die mechanische Festigkeit besitzen, die von einer Typ 4 Legierung gefordert werden.For reasons of optimal biocompatibility and aesthetics, it would be desirable to have dental bonding alloys that only consist of gold and another harmless element and that are as close as possible to pure gold in terms of color and corrosion resistance as well as processability, and at the same time that have mechanical strength required by a Type 4 alloy.
Aus der EP-A-0 190 648 sind Gold-Titan-Legierungen mit 0,1 bis 4 Gew.% Titan bekannt, die als Werkstoff für Schmuckstücke oder Münzen eingesetzt werden. Diese Legierungen sind härter und damit abriebfester als reines Gold. Außerdem zeigen sie eine brillante Goldfarbe.From EP-A-0 190 648, gold-titanium alloys with 0.1 to 4% by weight of titanium are known, which are used as a material for jewelry or coins. These alloys are harder and therefore more abrasion-resistant than pure gold. They also show a brilliant gold color.
Solche Gold-Titanlegierungen sind auch schon für Dentalteile vorgeschlagen worden (Dental Product Report, November 1991).Such gold-titanium alloys have also been proposed for dental parts (Dental Product Report, November 1991).
Generell ist für Dentallegierungen sicherzustellen, daß zur Erzeugung individueller Gußstücke der Feinguß über das Wachsausschmelzverfahren problemlos funktioniert. Dies bedeutet, daß die Legierung durch das Aufschmelzen und Vergießen nicht gravierend in ihren Eigenschaften verändert werden darf und daß der Guß in eine konventionelle zahntechnische Einbettmasse möglich sein sollte. Außerdem sollten solche Güsse an Luft durchgeführt werden können.In general, it must be ensured for dental alloys that the investment casting works smoothly using the lost wax process to produce individual castings. This means that the properties of the alloy must not be changed significantly by melting and casting and that casting in a conventional dental investment material should be possible. Such castings should also be able to be carried out in air.
Titan hat als Legierungsbestandteil im schmelzflüssigen Zustand ein großes Reaktionsvermögen mit den Luftbestandteilen und den Tiegelmaterialien unter Ausbildung von beispielsweise Oxiden, Nitriden oder Carbiden. Dadurch bilden sich während des Aufschmelzens und Vergießens störende Schlackenschichten, die außerdem auch die Zusammensetzung der Legierung und damit deren Eigenschaften verändern.As an alloy component, titanium has a large reactivity in the molten state with the air components and the crucible materials, with the formation of, for example, oxides, nitrides or carbides. This creates disruptive slag layers during melting and pouring, which also change the composition of the alloy and thus its properties.
In der EP-A-0 190 648 erfolgt das Schmelzen und Vergießen der Legierungsschmelze aus Gold und Titan daher im Vakuum oder unter Schutzgas in Form von Argon. Das Schmelzen erfolgt in einem Keramiktiegel, der Guß in eine Graphitform. Beide Materialien sind allerdings nur verwendbar unter Vakuum oder Argonatmosphäre, falls eine Schlackenbildung vermieden werden soll. An Luft erfolgt eine Schlackenbildung unter Anreicherung des Titangehaltes der Legierung und Unbrauchbarwerden des Keramiktiegels.In EP-A-0 190 648 the alloy and melt of gold and titanium are melted and cast in a vacuum or under a protective gas in the form of argon. The melting takes place in a ceramic crucible, the casting in a graphite mold. However, both materials can only be used under vacuum or in an argon atmosphere if slag formation is to be avoided. Slag formation occurs in air, enriching the titanium content of the alloy and rendering the ceramic crucible unusable.
Es war daher Aufgabe der vorliegenden Erfindung, ein Verfahren zur Herstellung von Gußstücken aus Gold-Titan-Legierungen mit 0,1 bis 4 Gew.% Titan, insbesondere für Dental- und Schmuckteile zu entwickeln, durch Aufschmelzen von Portionsstücken der Legierung an der Luft und anschließendes Vergießen, bei dem trotz Anwesenheit von Luft möglichst wenig Schlackenbildung und Anreicherung von Titan erfolgen sollte. Außerdem sollte der Schmelztiegel mehrfach verwendbar sein.It was therefore an object of the present invention to develop a method for producing castings from gold-titanium alloys with 0.1 to 4% by weight of titanium, in particular for dental and jewelry parts, by melting portions of the alloy in air and subsequent casting, in which, despite the presence of air, there should be as little slag formation and enrichment of titanium as possible. In addition, the crucible should be reusable.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß ein Schmelztiegel verwendet wird, bei dem die mit der Legierungsschmelze in Kontakt kommenden Flächen aus Kohlenstoff bestehen.This object is achieved in that a crucible is used in which the surfaces coming into contact with the alloy melt consist of carbon.
Vorzugsweise verwendet man zum Aufschmelzen der Gold-Titan-Legierung einen Graphittiegel. Dabei kann der Graphit einige Prozent eines anderen Materials enthalten.A graphite crucible is preferably used to melt the gold-titanium alloy. The graphite can contain a few percent of another material.
Überraschenderweise führt das Schmelzen von Gold-Titan-Legierungen mit 0,1 bis 4 Gew.% Titan in Tiegeln aus Kohlenstoff an der Luft nicht zur Bildung von Titancarbid in störenden Mengen, sondern man erhält nach dem Angießen einwandfreie Gußformstücke mit vorgegebenem Titangehalt der Goldlegierung. Der Schmelztiegel wird hierbei nicht merklich angegriffen und kann daher vielfach wiederverwendet werden.Surprisingly, the melting of gold-titanium alloys with 0.1 to 4% by weight of titanium in crucibles made of carbon in air does not lead to the formation of titanium carbide in disruptive amounts, but instead, after casting, flawless casting pieces with a predetermined titanium content of the gold alloy are obtained. The crucible is not noticeably attacked here and can therefore be reused many times.
Eine weitere Verbesserung beim Aufschmelzen der Gold-Titan-Legierung ergibt sich, wenn die Legierung in möglichst wenig Portionsstücken in den Schmelztiegel eingebracht wird. Anzustreben ist ein möglichst kleines Verhältnis von Oberfläche zu Volumen der einzelnen Portionsstücke. Man setzt daher vorzugsweise Kugeln, Zylinderabschnitte oder Quader als Formstücke ein, wobei die Schmelzenmenge mit höchstens 5 Portionsstücken erreicht sein sollte.A further improvement in the melting of the gold-titanium alloy results if the alloy is introduced into the crucible in as few portion pieces as possible. The aim should be the smallest possible ratio of surface to volume of the individual portion pieces. Spheres, cylinder sections or cuboids are therefore preferably used as shaped pieces, the amount of melt being achieved with at most 5 portion pieces.
Die Gußformstücke aus Gold-Titan-Legierungen mit 0,1 bis 4 Gew.% Titan lassen sich mit den handelsüblichen Dentalkeramiken sehr gut verblenden. Durch Variation des Titangehaltes lässt sich auch die Härte der Gußformstücke variieren.The moldings made of gold-titanium alloys with 0.1 to 4% by weight of titanium can be veneered very well with the commercially available dental ceramics. The hardness of the mold pieces can also be varied by varying the titanium content.
Folgende Beispiele sollen das erfindungsgemäße Verfahren näher erläutern:
- 1. 80 g einer Gold-Titan-Legierung mit 1,7 Gew.% Titan werden in Form von handelsüblichen Plättchen in einen Keramiktiegel gegeben. Man benötigt hierzu etwa 50 Legierungsplättchen. Nach dem Aufschmelzen bei 1250o C an der Luft wird nach ca. 30 Sekunden in eine Graphitform abgegossen. Im Tiegel verblieb ein Schlackenrest von etwa 5 Gew.%, der den Ausguß verstopfte. Der Tiegel war stark angegriffen und nicht wiederverwendbar war. Der erstarrte Formkörper besitzt eine Gußhärte von 163 HV. Nach einem simulierten Keramikbrand sinkt die Härte weiter auf 144 HV ab, was auf eine nichtreproduzierbare Titanabreicherung schließen lässt.
- 2. 80 g einer Gold-Titan-Legierung mit 1,7 Gew.% Titan werden in Form von zwei Zylinderabschnitten von je ca. 4 cm Länge und je 40 g Gewicht in einen Graphit-Tiegel gegeben und analog Beispiel 1 aufgeschmolzen und abgegossen. Im Tiegel verblieb nur ein Schlackenrest von weniger als 1 %, der sich leicht entfernen lässt.
- 1. 80 g of a gold-titanium alloy with 1.7% by weight of titanium are placed in a ceramic crucible in the form of commercially available platelets. You need about 50 alloy plates. After melting at 1250 o C in air, it is poured into a graphite mold after approx. 30 seconds. A slag residue of about 5% by weight remained in the crucible and blocked the spout. The crucible was badly attacked and was not reusable. The solidified molded body has a casting hardness of 163 HV. After a simulated ceramic firing, the hardness drops further to 144 HV, which suggests a non-reproducible titanium depletion.
- 2. 80 g of a gold-titanium alloy with 1.7% by weight of titanium are placed in a graphite crucible in the form of two cylinder sections, each about 4 cm long and 40 g in weight, and melted and poured off as in Example 1. Only a slag residue of less than 1% remained in the crucible, which can be removed easily.
Der Graphittiegel ist dann wiederverwendbar. Der erstarrte Formkörper besitzt eine Gußhärte von 199 HV, enthält also den vorgegebenen Titangehalt. Nach einem simulierten Keramikbrand steigt die Härte auf 219 HV.The graphite crucible is then reusable. The solidified molded body has a casting hardness of 199 HV, which means it contains the specified titanium content. After a simulated ceramic firing, the hardness increases to 219 HV.
Claims (3)
dadurch gekennzeichnet,
daß ein Schmelztiegel verwendet wird, dessen mit der Legierungsschmelze in Kontakt kommende Flächen aus Kohlenstoff bestehen.Process for the production of moldings from gold-titanium alloys with 0.1 to 4% by weight of titanium, in particular for dental and jewelry parts, by melting portions of the alloy in air and subsequent casting,
characterized by
that a crucible is used, the surfaces of which come into contact with the alloy melt consist of carbon.
dadurch gekennzeichnet,
daß als Schmelztiegel ein Graphit-Tiegel verwendet wird.Method according to claim 1,
characterized by
that a graphite crucible is used as the crucible.
dadurch gekennzeichnet,
daß zum Beschicken des Schmelztiegels Portionsstücke mit einem möglichst kleinen Verhältnis Oberfläche zu Volumen eingesetzt werden und die Zahl der Portionsstücke zum Erreichen der Schmelzenmenge 1 bis 5 beträgt.The method of claim 1 or 2,
characterized by
that portion pieces with as small a surface area to volume ratio as possible are used to feed the crucible and the number of portion pieces to reach the amount of melt is 1 to 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4439793 | 1994-11-08 | ||
| DE4439793A DE4439793C2 (en) | 1994-11-08 | 1994-11-08 | Process for the production of moldings from gold-titanium alloys |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP0717118A2 true EP0717118A2 (en) | 1996-06-19 |
| EP0717118A3 EP0717118A3 (en) | 1997-01-29 |
| EP0717118B1 EP0717118B1 (en) | 2003-08-27 |
| EP0717118B8 EP0717118B8 (en) | 2004-01-02 |
Family
ID=6532729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95117228A Expired - Lifetime EP0717118B8 (en) | 1994-11-08 | 1995-11-02 | Process for manufacturing gold-titanium alloy castings |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0717118B8 (en) |
| AT (1) | ATE248237T1 (en) |
| DE (2) | DE4439793C2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7279054B2 (en) * | 2004-05-14 | 2007-10-09 | The Argen Corporation | Dental prosthesis method and alloys |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0190648A1 (en) | 1985-01-29 | 1986-08-13 | International Gold Corporation Limited | A gold alloy |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2302837C3 (en) * | 1973-01-20 | 1975-09-11 | Dr. Th. Wieland Scheideanstalt, 7530 Pforzheim | Dental gold alloy |
| DE3406711C1 (en) * | 1984-02-24 | 1985-04-25 | Degussa Ag, 6000 Frankfurt | Low gold dental alloys |
| DK0691123T4 (en) * | 1994-07-05 | 2001-12-10 | Cendres & Metaux Sa | Dental alloy with a high content of gold |
-
1994
- 1994-11-08 DE DE4439793A patent/DE4439793C2/en not_active Expired - Fee Related
-
1995
- 1995-11-02 DE DE59510778T patent/DE59510778D1/en not_active Expired - Lifetime
- 1995-11-02 AT AT95117228T patent/ATE248237T1/en active
- 1995-11-02 EP EP95117228A patent/EP0717118B8/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0190648A1 (en) | 1985-01-29 | 1986-08-13 | International Gold Corporation Limited | A gold alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0717118A3 (en) | 1997-01-29 |
| EP0717118B8 (en) | 2004-01-02 |
| DE4439793C1 (en) | 1995-10-26 |
| EP0717118B1 (en) | 2003-08-27 |
| DE4439793C2 (en) | 2001-05-23 |
| DE59510778D1 (en) | 2003-10-02 |
| ATE248237T1 (en) | 2003-09-15 |
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