WO2004101835A1 - Gold alloy and method for manufacturing a dental restoration - Google Patents

Gold alloy and method for manufacturing a dental restoration Download PDF

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Publication number
WO2004101835A1
WO2004101835A1 PCT/NL2004/000344 NL2004000344W WO2004101835A1 WO 2004101835 A1 WO2004101835 A1 WO 2004101835A1 NL 2004000344 W NL2004000344 W NL 2004000344W WO 2004101835 A1 WO2004101835 A1 WO 2004101835A1
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WO
WIPO (PCT)
Prior art keywords
alloy
gold
porcelain
temperature
metal
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Application number
PCT/NL2004/000344
Other languages
French (fr)
Dutch (nl)
Inventor
Joseph Maria Van Der Zel
Theodorus Jacobus Grinwis
Bastiaan Philip Van Dijk
Adrianus Jacobus De Wit
Original Assignee
Elephant Dental B.V.
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
Application filed by Elephant Dental B.V. filed Critical Elephant Dental B.V.
Priority to CA002520131A priority Critical patent/CA2520131A1/en
Priority to JP2007518402A priority patent/JP2007527955A/en
Priority to EP04748587A priority patent/EP1627088A1/en
Priority to BRPI0408748-8A priority patent/BRPI0408748A/en
Publication of WO2004101835A1 publication Critical patent/WO2004101835A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
    • A61K6/844—Noble metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144—Gold (Au) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01014—Silicon [Si]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01046—Palladium [Pd]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0105—Tin [Sn]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01077—Iridium [Ir]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01078—Platinum [Pt]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01079—Gold [Au]

Definitions

  • the invention relates to a gold alloy and more in particular to a gold alloy having a high gold content.
  • the invention further relates to a method for manufacturing a metal-ceramic dental restoration.
  • gold alloys with a high gold content have been used in dental restorations, particularly because of their biological and chemical inertia and their attractive deep yellow color.
  • This pressing procedure comprises the following steps: a supporting structure from a metal alloy is, either provided with a thin coating layer or not, pressed over with a press ceramic by use of the "lost wax method". During the burning out or drying out of the wax, while heating for a long time at a relatively high temperature, with many alloys, a thick oxide layer is formed on the alloy. In many cases, this oxide layer results in a dark edge or contour.
  • steps need to be taken to form as little oxide as possible on the surface of the structure from the metal alloy.
  • an alloy with a high gold content a so-called “high gold alloy” has now been found which remains yellow upon oxidation, which alloy is suitable for use in a metal -ceramic system, in which a gold alloy with an aesthetic yellow color is fired on or pressed on with a dental ceramic or porcelain tailored thereto.
  • the alloy according to the invention has a high degree of biocompatibility.
  • This alloy according to the invention comprises 0.01-0.05 wt.% zinc; 0.01-0.05 wt.% indium; 0.01-0.05 wt.% silver and 0.01-0.05 wt.% manganese in a gold base.
  • the gold base substantially consists of gold, but may contain small amounts of pollutants, as long as they produce no adverse color effects and do not affect the biocompatibility.
  • the alloy according to the invention comprises at least 99 wt.% gold.
  • a very suitable alloy substantially consists of 99.80 wt.% gold; 0.05 wt.% zinc; 0.05 wt.% indium; 0.05 wt.% silver and 0.05 wt.% manganese.
  • the alloy according to the invention provides a stable, very thin, possibly monomolecular oxidation layer which is so light in color than no adverse color effects occur.
  • the oxidation layer is sufficiently strongly bound to the underlying alloy and appears to be capable of a very good metal-press glass or metal-porcelain binding.
  • manganese provides a good bond.
  • Tin and indium ensure a reinforcement of the oxide.
  • the gold alloy according to the invention does not have a very great strength, but this has not been found necessary for the applications for which this alloy is intended.
  • the alloys according to the invention have a solidus temperature of between 1030 and 1100°C; for the preferred alloys, the solidus temperature is between 1045 and 1065°C.
  • the coefficient of thermal expansion (measured from 25 to 500°C) is between 14.5 and 15.5 ⁇ m/m.°C; and for the preferred alloys between 14.8 and 15.3 ⁇ m/m.°C.
  • DE-OS 44 19 408 describes a dental alloy with 95-98 wt.% gold; 1-4 wt.% titanium; and 0.05-1.5 wt.% of one or more elements from the group of Re, Rh, Ru, Ir and Ta.
  • US-A-5,922,276 relates to a dental alloy with an excellent oxide color, which alloy contains at least 99.5 wt.% gold, 0.1-0.25 wt.% zinc, 0.1-0.25 wt.% indium and up to 0.3 wt.% Rt, Pd, Rh, Ir, Re or combinations thereof. It is explicitly stated that elements like copper, manganese and iron should be avoided because they produce dark or colored oxides.
  • the invention relates to a method for manufacturing a metal-ceramic dental restoration, comprising pressing, with heating, a tooth-colored press glass onto a wholly or partly supporting structure from the alloy according to the invention, with the press glass having a coefficient of thermal expansion (CTE) of between 12.5 and 14.5, and preferably between 13.0 and 14.5 km/m.K, measured in the range from 25°C to 500°C or to the glass transformation temperature, depending on which of the two is the lowest, and with the press glass having a pressing temperature which is at least 50°C lower than the solidus temperature of the alloy.
  • CTE coefficient of thermal expansion
  • the press glass is pressed with heating in a mold manufactured by use of the "lost wax" method.
  • Such a method is much more effective and economical than the conventional method in which porcelain was applied layer by layer.
  • fewer bubbles and cracks are formed during pressing compared to applying the porcelain layer by layer.
  • the alloy according to the invention can also be coated with this conventional method.
  • a wax model of one or more teeth and/or molars is made, which model is embedded in a fire-resistant material, for instance Carrara ® Universal Dustless Investment (ex Elephant Dental B.V., Hoorn, The Netherlands). Then, after curing of the die from fire-resistant material, the wax is burnt out. After this, a closed pellet of press glass is brought, on the connecting channels, to the mold, by pressing the glass therein with a fire-resistant cylinder with thermal plasticization.
  • the structure from the high gold alloy according to the invention is present, as stated. This structure may, for instance, be formed by CAD/CAM methodologies.
  • the press glass is available in a tooth color.
  • the coloring of porcelain is known to a skilled person. A suitable method is described in DE-OS- 1999 04 522, which document is understood to be inserted in this specification for the description of the coloring method.
  • a so-called liner may be applied onto the alloy.
  • This liner will, as a rule, have a melting point which is less than 50°C lower than the pressing temperature of the press glass.
  • a suitable liner consists of 58.5 wt.% Si ⁇ , 12.6 wt.% AI2O3, 11.0 wt.% K 2 O, 7.1 wt.% Na 2 O, 10.4 wt.% CeO 2 , 0.4 wt.% LiO 2 .
  • This liner can be applied as a single coating in a thickness of 20-40 ⁇ m and be burnt up at about 900°C.
  • a suitable press glass may have the following (preferred) composition: 7-15 wt.% AI2O3; 13-23 wt.% (K 2 O + Na 2 O), 1-3 wt.% (BaO + CaO), 1-3 wt.% (Sb2 ⁇ 3 + LA2O) and 0.2-1.2 wt.% fluorine, rest Si ⁇ 2 including coloring compositions.
  • the powder formed from these glass compositions preferably has a particle size smaller than 106 ⁇ .
  • This powder is granulated with a binder and uniaxially dry -pressed at room temperature and sintered at a temperature of, for instance, 800-1000°C, preferably 900-960°C, for 1 minute to 1 hour, preferably 1-30 minutes.
  • the invention relates to a method for manufacturing a metal-ceramic dental restoration, comprising firing a dental porcelain onto a supporting structure from the alloy according to any one of claims 1-3, with the porcelain having a coefficient of thermal expansion of between 12.5 and 14.5 ⁇ m/m.K, measured in the range from 25°C to 500°C or to the glass transformation temperature, depending on which of the two is the lowest, and with the porcelain having a firing temperature which is at least 50 °C lower than the solidus temperature of the alloy.
  • a suitable firing ceramic has the following (preferred) composition: 64.1-67.0% Si ⁇ 2, 11.0-12.5% AI2O3, 10.1-11.6% K 2 O, 6.6-8.6% Na 2 O, 0.7-1.1% CaO, 0.4-1.3% BaO, 0-2.1% Sb2 ⁇ 3, 0-0.2% L12O, and 0-0.6% fluorine with pigments.
  • a more preferred firing ceramic has the following composition: 64.1% Si ⁇ 2, 14.2% AI2O3, 11.1% K 2 O, 6.6% Na O, 1.1% CaO, 0.4% BaO, 1.4% Sb 2 O 3 , 0.2% Li 2 O and 0.6% F2 with pigments.
  • Every CTE described in this specification or the claims is measured in the range from 25°C to 500°C or to the glass transformation temperature, depending on which of the two is the lowest. Also, every percentage is a weight percentage related to the weight of the total composition, unless indicated otherwise.
  • the pressing or firing temperature needs to be at least 50°C lower than the solidus temperature of the alloy in order to avoid deformation of the metal structure during pressing.
  • the CTE of the press glass or porcelain needs to be such that the CTE of the alloy is 0.5-2.0 ⁇ m/m.K higher than that of the press glass or porcelain.
  • the alloys were then cast in an electric casting device at 1200 °C into a graphite -containing, phosphate-bound embedding mass die, which had been preheated to 750°C. After oxidation, the alloy has a grey-yellow color.
  • the binding with porcelain is given in Table 3.
  • Example 2 In the same manner as in Example 1, an alloy was produced with the following composition: 98.2 wt.% gold, 1.2 wt.% platinum, 0.1 wt.% zinc,
  • Example 2 In the same manner as in Example 1, an alloy was produced with the following composition: 99.8 wt.% gold, 0.05% zinc, 0.05% indium, 0.05% silver, 0.05% manganese. After oxidation, the alloy has an intensely yellow color.
  • Example 3 In the same manner as in Example 1, an alloy was produced with the following composition: 99.7 wt.% gold, 0.1% zinc, 0.2% indium (see US-A-5,922,276). After oxidation, the alloy has an intensely yellow color, but did not have the good bond of Example 3.
  • a round disk of the alloys was cast with a diameter of 25 mm and a thickness of 1.0 mm. After casting, the casting pieces were ground with coarse and fine aluminum oxide. The metal-ceramic disk was then deformed from the top, with the porcelain downwards, by a stamp with a spherical end. The disk was bent 0.4 mm in the centre to achieve a consistent deformation of the disk and removal of the ceramic with minimal cracks in the metal. After the breaking off of the porcelain, loose particles of porcelain were removed from the surface of fracture with a nylon brush, after which the surface of fracture was placed in an ultrasonic bath for 10 minutes.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Engineering & Computer Science (AREA)
  • Animal Behavior & Ethology (AREA)
  • Metallurgy (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Plastic & Reconstructive Surgery (AREA)
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Abstract

The present invention relates to an alloy with a high gold content. This alloy preferably comprises more than 99 wt.% gold. Further, the invention relates to a method for manufacturing a metal-ceramic dental restoration by pressing on or firing on of a suitable porcelain. The porcelains used here have a certain maximum processing temperature and a coefficient of thermal expansion in a certain range.

Description

Title: Gold alloy and method for manufacturing a dental restoration
The invention relates to a gold alloy and more in particular to a gold alloy having a high gold content. The invention further relates to a method for manufacturing a metal-ceramic dental restoration.
For a number of decennia, gold alloys with a high gold content have been used in dental restorations, particularly because of their biological and chemical inertia and their attractive deep yellow color.
For aesthetical reasons, these alloys are fired on with porcelain. This porcelain was manually built up in layers. In recent years, ceramic is also pressed on. This pressing procedure comprises the following steps: a supporting structure from a metal alloy is, either provided with a thin coating layer or not, pressed over with a press ceramic by use of the "lost wax method". During the burning out or drying out of the wax, while heating for a long time at a relatively high temperature, with many alloys, a thick oxide layer is formed on the alloy. In many cases, this oxide layer results in a dark edge or contour.
From an aesthetic point of view, steps need to be taken to form as little oxide as possible on the surface of the structure from the metal alloy.
However, for a good bond between press ceramic and metal alloy structure, an oxide layer is highly desired. Therefore, there is a need for a high gold alloy with a solidus temperature which is sufficiently high in relation to the application temperature of the ceramic - and is, as a rule, at least 50°C higher than the firing temperature or pressing temperature of the ceramic or porcelain, which alloy forms an oxide layer upon heating in air, which layer is necessary for a good bond with the porcelain to be fired on or pressed on, and which oxide layer is hardly or not visible. According to the invention, an alloy with a high gold content, a so-called "high gold alloy" has now been found which remains yellow upon oxidation, which alloy is suitable for use in a metal -ceramic system, in which a gold alloy with an aesthetic yellow color is fired on or pressed on with a dental ceramic or porcelain tailored thereto. In addition, the alloy according to the invention has a high degree of biocompatibility.
This alloy according to the invention comprises 0.01-0.05 wt.% zinc; 0.01-0.05 wt.% indium; 0.01-0.05 wt.% silver and 0.01-0.05 wt.% manganese in a gold base. The gold base substantially consists of gold, but may contain small amounts of pollutants, as long as they produce no adverse color effects and do not affect the biocompatibility.
In a preferred embodiment, the alloy according to the invention comprises at least 99 wt.% gold. A very suitable alloy substantially consists of 99.80 wt.% gold; 0.05 wt.% zinc; 0.05 wt.% indium; 0.05 wt.% silver and 0.05 wt.% manganese.
With the high gold alloy according to the invention, it has been found possible to fire or press it with ceramic, while the intense gold color is preserved. The alloy according to the invention provides a stable, very thin, possibly monomolecular oxidation layer which is so light in color than no adverse color effects occur. However, the oxidation layer is sufficiently strongly bound to the underlying alloy and appears to be capable of a very good metal-press glass or metal-porcelain binding. Particularly the presence of manganese provides a good bond. Tin and indium ensure a reinforcement of the oxide. Incidentally, the gold alloy according to the invention does not have a very great strength, but this has not been found necessary for the applications for which this alloy is intended. The alloys according to the invention have a solidus temperature of between 1030 and 1100°C; for the preferred alloys, the solidus temperature is between 1045 and 1065°C. For the alloys according to the invention, the coefficient of thermal expansion (measured from 25 to 500°C) is between 14.5 and 15.5 μm/m.°C; and for the preferred alloys between 14.8 and 15.3 μm/m.°C.
High gold alloys were already known in the state of the art. For instance, DE-OS 44 19 408 describes a dental alloy with 95-98 wt.% gold; 1-4 wt.% titanium; and 0.05-1.5 wt.% of one or more elements from the group of Re, Rh, Ru, Ir and Ta.
Further, US-A-5,922,276 relates to a dental alloy with an excellent oxide color, which alloy contains at least 99.5 wt.% gold, 0.1-0.25 wt.% zinc, 0.1-0.25 wt.% indium and up to 0.3 wt.% Rt, Pd, Rh, Ir, Re or combinations thereof. It is explicitly stated that elements like copper, manganese and iron should be avoided because they produce dark or colored oxides.
Further, the invention relates to a method for manufacturing a metal-ceramic dental restoration, comprising pressing, with heating, a tooth-colored press glass onto a wholly or partly supporting structure from the alloy according to the invention, with the press glass having a coefficient of thermal expansion (CTE) of between 12.5 and 14.5, and preferably between 13.0 and 14.5 km/m.K, measured in the range from 25°C to 500°C or to the glass transformation temperature, depending on which of the two is the lowest, and with the press glass having a pressing temperature which is at least 50°C lower than the solidus temperature of the alloy. In this method, the press glass is pressed with heating in a mold manufactured by use of the "lost wax" method. Such a method is much more effective and economical than the conventional method in which porcelain was applied layer by layer. In addition, fewer bubbles and cracks are formed during pressing compared to applying the porcelain layer by layer. Incidentally, the alloy according to the invention can also be coated with this conventional method.
In more detail, in the pressing method according to the invention, a wax model of one or more teeth and/or molars is made, which model is embedded in a fire-resistant material, for instance Carrara ® Universal Dustless Investment (ex Elephant Dental B.V., Hoorn, The Netherlands). Then, after curing of the die from fire-resistant material, the wax is burnt out. After this, a closed pellet of press glass is brought, on the connecting channels, to the mold, by pressing the glass therein with a fire-resistant cylinder with thermal plasticization. In the die, the structure from the high gold alloy according to the invention is present, as stated. This structure may, for instance, be formed by CAD/CAM methodologies.
Preferably, the press glass is available in a tooth color. The coloring of porcelain is known to a skilled person. A suitable method is described in DE-OS- 1999 04 522, which document is understood to be inserted in this specification for the description of the coloring method.
In a preferred embodiment, before the pressing, first, a so-called liner may be applied onto the alloy. This liner will, as a rule, have a melting point which is less than 50°C lower than the pressing temperature of the press glass. A suitable liner consists of 58.5 wt.% Siθ , 12.6 wt.% AI2O3, 11.0 wt.% K2O, 7.1 wt.% Na2O, 10.4 wt.% CeO2, 0.4 wt.% LiO2. This liner can be applied as a single coating in a thickness of 20-40 μm and be burnt up at about 900°C.
A suitable press glass may have the following (preferred) composition: 7-15 wt.% AI2O3; 13-23 wt.% (K2O + Na2O), 1-3 wt.% (BaO + CaO), 1-3 wt.% (Sb2θ3 + LA2O) and 0.2-1.2 wt.% fluorine, rest Siθ2 including coloring compositions. 7-15 wt.% Al2O3; 6-14 wt.% K2O, 5-11 wt.% Na2O, 0.2-2.5 wt.% BaO, 0.1-1.5 wt.% CaO, 1.2-2.5 wt.% Sb2O3, 0.05-0.5 wt.% Li O and 0.5-1.0 wt.% fluorine, rest SiO2 including coloring compositions. The powder formed from these glass compositions preferably has a particle size smaller than 106 μ . This powder is granulated with a binder and uniaxially dry -pressed at room temperature and sintered at a temperature of, for instance, 800-1000°C, preferably 900-960°C, for 1 minute to 1 hour, preferably 1-30 minutes.
In addition, the invention relates to a method for manufacturing a metal-ceramic dental restoration, comprising firing a dental porcelain onto a supporting structure from the alloy according to any one of claims 1-3, with the porcelain having a coefficient of thermal expansion of between 12.5 and 14.5 μm/m.K, measured in the range from 25°C to 500°C or to the glass transformation temperature, depending on which of the two is the lowest, and with the porcelain having a firing temperature which is at least 50 °C lower than the solidus temperature of the alloy. A suitable firing ceramic has the following (preferred) composition: 64.1-67.0% Siθ2, 11.0-12.5% AI2O3, 10.1-11.6% K2O, 6.6-8.6% Na2O, 0.7-1.1% CaO, 0.4-1.3% BaO, 0-2.1% Sb2θ3, 0-0.2% L12O, and 0-0.6% fluorine with pigments. A more preferred firing ceramic has the following composition: 64.1% Siθ2, 14.2% AI2O3, 11.1% K2O, 6.6% Na O, 1.1% CaO, 0.4% BaO, 1.4% Sb2O3, 0.2% Li2O and 0.6% F2 with pigments. Every CTE described in this specification or the claims is measured in the range from 25°C to 500°C or to the glass transformation temperature, depending on which of the two is the lowest. Also, every percentage is a weight percentage related to the weight of the total composition, unless indicated otherwise. The pressing or firing temperature needs to be at least 50°C lower than the solidus temperature of the alloy in order to avoid deformation of the metal structure during pressing. The CTE of the press glass or porcelain needs to be such that the CTE of the alloy is 0.5-2.0 μm/m.K higher than that of the press glass or porcelain. When the difference is greater than 2.0 μm/m.K, cracking in the porcelain may occur; when the difference is smaller than 0.5 μm/m.K, possibly, a structure is obtained in which the bond between press glass or the porcelain and alloy is insufficient. In the range mentioned, the porcelain is subjected to such pressure after cooling that a strong restoration is obtained. The invention will now be illustrated in more detail in and by the following non-hmiting examples.
Example 1 (comparative
Into a crucible of pure alumina, in a vacuum induction furnace, the following metals were weighed and melted under a partial pressure of
400 Torr of argon gas and then cast to a bar in a die which had already been present in the vacuum chamber: 97.625 wt.% gold, 1.5 wt.% platinum, 0.5 wt.% zinc, 0.375 wt.% rhodium. After casting, the die was removed from the vacuum induction furnace and the die was opened. The bar was rolled out to plate with, optionally, glowing between whiles to bring the plate back into a rollable condition. After this, the plate was cut into strips and the alloy was cut into cubes.
The alloys were then cast in an electric casting device at 1200 °C into a graphite -containing, phosphate-bound embedding mass die, which had been preheated to 750°C. After oxidation, the alloy has a grey-yellow color. The binding with porcelain is given in Table 3.
Example 2 (comparative)
In the same manner as in Example 1, an alloy was produced with the following composition: 98.2 wt.% gold, 1.2 wt.% platinum, 0.1 wt.% zinc,
0.3% rhodium and 0.2% indium. After oxidation, the alloy has a gre -yellow color. Example 3
In the same manner as in Example 1, an alloy was produced with the following composition: 99.8 wt.% gold, 0.05% zinc, 0.05% indium, 0.05% silver, 0.05% manganese. After oxidation, the alloy has an intensely yellow color.
Example 4 (comparative')
In the same manner as in Example 1, an alloy was produced with the following composition: 99.7 wt.% gold, 0.1% zinc, 0.2% indium (see US-A-5,922,276). After oxidation, the alloy has an intensely yellow color, but did not have the good bond of Example 3.
Results of Examples 1-4 are shown in the following Table.
Example number (wt.% components)
Metal component 1 2 3 US 5922276
Gold 97.625 98.2 99.8 99.7
Platinum 1.5 1.2 - -
Iridium - - - -
Zinc 0.5 0.1 0.05 0.1
Indium - 0.5 0.05 0.2
Silver - - 0.05 -
Manganese - - 0.05 -
Rhodium 0.375 0.3 - -
Tensile strength, MPa 180 160 133 142
Yield point, MPa 79 63 51 54
Elongation at break, % 23.4 31.9 53 34
Vickers hardness, HV 75 43 37 38
Liquidus, °C 1080 1070 1060 1060
Solidus, °C 1060 1050 1050 1050
Coefficient of thermal expansion
(20-500°C) μm/m.°C 15.3 15.1 15.0 15.1
Oxidation color yellow/ yellow/ yellow yellow grey grey
Binding porcelain, % 75 71 70 61
Binding press ceramic, % 71 73 72 63
A round disk of the alloys was cast with a diameter of 25 mm and a thickness of 1.0 mm. After casting, the casting pieces were ground with coarse and fine aluminum oxide. The metal-ceramic disk was then deformed from the top, with the porcelain downwards, by a stamp with a spherical end. The disk was bent 0.4 mm in the centre to achieve a consistent deformation of the disk and removal of the ceramic with minimal cracks in the metal. After the breaking off of the porcelain, loose particles of porcelain were removed from the surface of fracture with a nylon brush, after which the surface of fracture was placed in an ultrasonic bath for 10 minutes.
After breaking, the samples were tested for the amount of remaining porcelain surface by means of a scanning electron microscope. The percentage of oxidized metal surface which was still coated with ceramic was measured by measuring the amount of silicon on the surface of fracture by means of E.D.A.X. and comparing this to the uncovered part of metal surface and a surface 100% covered with porcelain. The average surface fractions or remaining ceramic were given in the above Table. The values for remaining surface still covered with porcelain show that the majority is still attached to the alloy after the breaking off of the mass of the porcelain. Tests of other alloy systems have shown that a percentage higher than 50% does not cause problems in practice.

Claims

1. An alloy comprising 0.01-0.05 wt.% zinc; 0.01-0.05 wt.% indium; 0.01-0.05 wt.% silver; 0.01-0.05 wt.% manganese; and rest gold basis.
2. An alloy according to claim 1, comprising 99 wt.% gold.
3. An alloy according to claim 1 or 2, substantially consisting of 99.80 wt.% gold; 0.05 wt.% zinc; 0.05 wt.% indium; 0.05 wt.% silver and 0.05 wt.% manganese.
4. A method for manufacturing a metal-ceramic dental restoration, comprising pressing, with heating, a tooth-colored press glass onto a wholly or partly supporting structure from the alloy according to any one of the preceding claims, wherein the press glass has a coefficient of thermal expansion of between 12.5 and 14.5 μm/m.K, measured in the range from 25°C to 500°C or to the glass transformation temperature, depending on which of the two is the lowest, and wherein the press glass has a pressing temperature which is at least 50°C lower than the solidus temperature of the alloy.
5. A method for manufacturing a metal-ceramic dental restoration, comprising the firing a dental porcelain onto a supporting structure from the alloy according to any one of claims 1-3, wherein the porcelain has a coefficient of thermal expansion of between 12.5 and 14.5 μm/m.K, measured in the range from 25°C to 500°C or to the glass transformation temperature, depending on which of the two is the lowest, and wherein the porcelain has a firing temperature which is at least 50 °C lower than the solidus temperature of the alloy.
PCT/NL2004/000344 2003-05-19 2004-05-18 Gold alloy and method for manufacturing a dental restoration WO2004101835A1 (en)

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JP2007518402A JP2007527955A (en) 2003-05-19 2004-05-18 Gold alloy and method for producing dental restoration
EP04748587A EP1627088A1 (en) 2003-05-19 2004-05-18 Gold alloy and method for manufacturing a dental restoration
BRPI0408748-8A BRPI0408748A (en) 2003-05-19 2004-05-18 alloy and method for fabricating a metal-ceramic dental restoration

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EP1595523A1 (en) * 2004-05-14 2005-11-16 The Argen Corporation Dental prosthesis method and alloys

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CN104367383A (en) * 2013-08-16 2015-02-25 刘俐旻 Porcelain tooth structure containing nanogold

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JPH03130332A (en) * 1989-10-16 1991-06-04 Tokuriki Honten Co Ltd White gold alloy for ornament
NL9200564A (en) * 1992-03-26 1993-10-18 Elephant Edelmetaal Bv Dental alloy and dental porcelain for dental purposes.
DE19525361A1 (en) * 1995-02-16 1996-08-22 Herbst Bremer Goldschlaegerei Platinum- and/or palladium-contg. gold@ dental alloy
US5922276A (en) * 1998-02-17 1999-07-13 The Argen Corporation Gold alloy for porcelain/metal dental restorations
EP1193320A1 (en) * 2000-09-29 2002-04-03 Cendres Et Metaux S.A. Fireable dental alloy with a high gold content

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JPH03130332A (en) * 1989-10-16 1991-06-04 Tokuriki Honten Co Ltd White gold alloy for ornament
NL9200564A (en) * 1992-03-26 1993-10-18 Elephant Edelmetaal Bv Dental alloy and dental porcelain for dental purposes.
DE19525361A1 (en) * 1995-02-16 1996-08-22 Herbst Bremer Goldschlaegerei Platinum- and/or palladium-contg. gold@ dental alloy
US5922276A (en) * 1998-02-17 1999-07-13 The Argen Corporation Gold alloy for porcelain/metal dental restorations
EP1193320A1 (en) * 2000-09-29 2002-04-03 Cendres Et Metaux S.A. Fireable dental alloy with a high gold content

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Publication number Priority date Publication date Assignee Title
EP1595523A1 (en) * 2004-05-14 2005-11-16 The Argen Corporation Dental prosthesis method and alloys
US7279054B2 (en) 2004-05-14 2007-10-09 The Argen Corporation Dental prosthesis method and alloys
US7892480B2 (en) 2004-05-14 2011-02-22 The Argen Corporation Dental prosthesis method and alloys

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CN1777688A (en) 2006-05-24
JP2007527955A (en) 2007-10-04
EP1627088A1 (en) 2006-02-22

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