CA1177604A - Metallic prosthesis coated with a vitreous enamel and a method for producing said prosthesis - Google Patents

Metallic prosthesis coated with a vitreous enamel and a method for producing said prosthesis

Info

Publication number
CA1177604A
CA1177604A CA000408600A CA408600A CA1177604A CA 1177604 A CA1177604 A CA 1177604A CA 000408600 A CA000408600 A CA 000408600A CA 408600 A CA408600 A CA 408600A CA 1177604 A CA1177604 A CA 1177604A
Authority
CA
Canada
Prior art keywords
enamel
prosthesis
layer
nickel
alloy
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
Application number
CA000408600A
Other languages
French (fr)
Inventor
Yves Simonpaoli
Paul Hochart
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.)
Boussois SA
Original Assignee
Boussois SA
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 FR8115726A external-priority patent/FR2511361A1/en
Application filed by Boussois SA filed Critical Boussois SA
Application granted granted Critical
Publication of CA1177604A publication Critical patent/CA1177604A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/16—Refractive index
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
    • 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
    • A61K6/804—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising manganese oxide
    • 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
    • A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
    • 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
    • A61K6/824—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising transition metal oxides
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
    • C03C8/12—Frit compositions, i.e. in a powdered or comminuted form containing lead containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels

Abstract

Abstract A metallic dental prosthesis coated with a vitreous enamel is formed of an alloy having a base of nickel and chromium such that the sum of concentrations of nickel and chromium is higher than or equal to 80% by weight and that the ratio of the concentration of nickel to the concentration of chromium is higher than or equal to 2.5. The composition of the vitreous enamel is as follows (expressed in weight percentage)

Description

`- I 177~4 This invention relates to a metallic dental prosthesis provided with a vitreous enamel coating and is also directed to a method for producing a prosthesis of this type.
Up to the present time, enamel-coated metallic prostheses of known types have been made of gold or an alloy composed of gold and other precious metals.
Enamel-coating of dental prostheses is carried out by firing of ceramic material or of an enamel obtained from a composition of borosilicate glass and other oxides, the firing operation being usually carried out within a temperature range of 900-980C.
Gold and alloys of gold with precious metals employed for prostheses of this type are attended by two major drawbacks. In the first place, they have a modulus of elasticity which is incompatible with the fabrication of long-span prostheses or bridges and, secondly, the cost of such metals has risen to a very high level.
For these reasons it has been sought over the past ten years or so to replace gold and gold alloys by stain-less alloys which are less costly and have superior mechanical properties.
In this respect, alloys having a high content of nickel and chromium offer the requisite qualities. However, the dental enamels employed up to the present time for coating prostheses of gold or gold alloy do not adhere to .,, $

:. . '. .

the above-mentioned alloys having a base of nickel and chromium.
It has been found possible to obtain a certain degree of adhesion of the enamel to alloys of this type by providing surface roughness or irregularities such as striae. However, the adhesion obtained by means of such expedients is far from achieving the degree of adhesion obtained when the base metal of the prosthe-sis consists of gold or a gold alloy.
The object of the present invention is to produce a vitreous enamel composition which makes it possible to obtain excellent adhesion to alloys which are relatively inexpensive and have good mechanical properties such as alloys having a high concentration of nickel and chromium.
According to the invention, the metallic prosthesis coated with a vitreous enamel is essentially formed of an alloy having a base of nickel and chromium such that the sum of concentra-tions of nickel and chromium is higher than or equal to 80% by weight and wherein the ratio of the concentration of nickel to the concentration of chromium is higher than or equal to 2.5. The composition of the vitreous enamel is as follows, expressed in weight percentages:
Si02 : 44 to 54 %
B203 16 to 30 %
Na20 : 13 to 20 %
K20 : 0 to 4 %
, Li20 : 0 to 2.5 %
CaO : 0 to 3 %
CaF2 : 0 to 5 %

~., ;
~, . .
.

A123 3 to 9 Zr2 : to 6 ~
N10 : O to 2 %
CoO : O to 1.5 %
MnO2 : O to 1.5 %
Thus, this invention provides a metallic prosthesis coated with a vitreous enamel, wherein said prosthesis is formed of an alloy having a base of nickel and chromium such that the sum of concentrations of nickel and chromium is higher than or equal to 80% by weight and wherein the ratio of the concentration of nickel to the concentration of chromium is higher than or equal to 2.5, said alloy being coated by at least one first enamel layer obtained from an enamel composition containing the following compounds, expressed in weight percentage:
Si~2 : 44 to 54 ~
B203 : 16 to 30 %
I~a20 : 13 to 20 %
K20 : O to 4 %
Li20 : O to 2.5 %
CaO : O to 3 %
CaF2 : O to 5 %
A123 3 to 9 %
Zr2 : to 6 %
NiO : O to 2 %
CoO : O to 1.5%
MnO2 : O to 1.5%
said first layer being coated by a second layer, the composition I 177~04 of said second layer containing the follow~ng compounds, expressed in weight percentage:
SiO2 : 45 to 68 %
B203 : 0 to 8 ~
Na20 : lO to 17 %
K20 : 10 to 20 %
An enamel composition of this type has excellent adhesion to substrates formed of an alloy having a base of nickel and chromium in accordance with the concentrations given in the foregoing.
An explanation for this remarkable degree of adhesion can be found in the fact that the relatively low enamel-firing temperature has the effect of limiting surface oxidation of the alloy and of obtaining a stable chemical bond with this latter by virtue of the lability of the alkali ions contained in the enamel.
The presence of alkali metal oxides (Na20 and K20) makes it possible both to reduce the enamel-firing temperature and to obtain a coefficient of thermal expansion of the enamel within the range of 95 to 110 x lO 7 (CGS units) which is compatible with the NiCr alloy of the prosthesis, thus making it possible to limit stresses which are liable to arise between the enamel layer and the alloy under the action of temperature variations.
In a preferred embodiment of the invention, the alloy of the prosthesis has the following composition, expressed in weight percentages:
Cr : 12 to 40 Ni : 50 to 80%

, C : 0.05 to 0.2 %
; Si : 0.05 to 0.2 %
Mo : O to 0.1 %
Fe : O to 15 %
B : O to 3 %
Ti : O to 5 %
Co : O to 10 %
Zr : O to 5 %
Nb : O to 5 %
An alloy of this type has very good mechanical proper-ties and excellent adhesion to the enamel obtained from the compo-sition according to the invention.
In one of the embodiments of the method according to the invention, there is applied on the alloy having a nickel and chromium base a first layer of enamel which is obtained from a composition according to the invention and to which are added opacifying and/or devitrifying agents such as SnO2 and ZrO2, there being then applied a second enamel layer in which the basic glass can be different according to the teeth to be fabricated.
The g~ass employed is the main constituent of the first enamel layer but contains a smaller quantity of mineral charges ~ in order to ensure that the glass retains a certain degree of t~ans-- lucence. There is added to the glass a small dose of coloring agents such as NiO or TiO2 in order to provide it with the desired coloring.
A glass having a composition which is different from the preceding is employed when it proves~ necessary to fabricate a :

l 1~7604 tooth such as an incisor which has a well-determined shape and translucence. As in the previous instance, a small dose of opacifying and coloring agents is added thereto.
The enamel composition mentioned above is wholly suitable as a first layer by virtue of its excellent degree of adhesion. However, this layer is not sufficiently translucent and has inadequate resistance to chemical agents.
Preferably, said first layer is coated with a second enamel layer containing the following principal compounds, expressed in weight percentages:
SiO2 : 45 to 68 %
B203 : 0 to 8 %
Na20 : 10 to 17 %
K20 : 10 to 20 %
This enamel composition differs from that of the second enamel layer described earlier mainly in the fact that it contains a distinctly higher proportion of K20 (potassium oxide).
Surprisingly, it has been found that this enamel composition made it possible to obtain after firing a perfectly translucent second layer which is strongly adherent to the first enamel layer and has excellent resistance to chemical agents.
The aforesàid composition is not suitable for the formation of the first enamel layer. In fact, tests have shown that a first layer of this type does not adhere to the oxidized surface layer of the nickel-chromium alloy of the prosthesis. This result can be explained by the fact that, in contrast to the sodium atoms and by reason of their lower mobility in comparison with these . . .

.

.

l l776n4 latter, the potassium atoms do not permit a mutual diffusion exchange with the metal oxides of the aforesaid oxidized layer.
On the other hand, the second layer obtained from the composition aforesaid provides exceptional adhesion to the first enamel layer.
Further properties and advantages of the invention will become apparent from the following description which gives a few non-limitative examples of application of the invention.
Example 1 Enameled prosthesis having a base of nickel-chromium alloy.
~ The composition of this alloy is as follows (expressed - in weight percentages):
Cr : 21 %
Ni : 62 ~
C : 0.05 %
Fe : 11 %
B : 3 %
Ti : 3 %
Mn : 1 %
This alloy has mechanical properties which are compatible with the fabrication of long-span dental prostheses or bridges.
In order to enamel this alloy, the starting material consists of a b~rosilicate glass having the following composition (expressed in weight percentages):

, .
.

., 1 1~7604 SiO2 : 52 %
Na20 : 18 %
K20 : 1.5 %
Li20 : 2.5
2 3 4 B203 : 18 %
CaO : 2 %
CaF2 : 2 %
There is applied on the alloy a first layer of enamel having a thickness -smaller than or equal to approximately 0. 5 mm and obtained by firing of the following mixture at about 780C
(expressed in weight percentages):
The glass mentioned above : 70 %
SnO2 : 12 %

Zr2 : 12 %
1203 : 8 %
The stannic oxide (SnO2) which is added to the compo-sition performs the function of opacifier. The zirconium oxide (ZrO2) performs the double function of opacifier and of devitrifi-cation agent.
There is then applied a second and if necessary a third enamel layer obtained by firing the following mixture in a partial vacuum of 10 mbar at 795C (expressed in weight percentages):
The glass mentioned above : 89 %
TiO2 : 1 %
SiO2 : 10 %
NiO O 004 g _ `~:

`` I 17760~

The nickel oxide (NiO) and the titanium oxide (TiO2) which are added to the composition provide the enamel with the desired color.
The enamel applied on the prosthesis has a coefficient of thermal expansion in the vicinity of 100 x 10 7 (CGS units).
This enamel has excellent adhesion. The degree of adhesion is demonstrated by folding at right-angles a strip of alloy having a base of nickel and chromium coated with enamel.
The enamel exhibits crack formation in the fold zone and forms disjointed enamel blocks, the majority of which remain adherent to the base metal.
The test have also shown that the adhesion of the enamel to the base metal was always excellent when the proportions of constituents of the composition varied bet~een the limits indicated below (expressed in weight percentages):
SiO2 : 44 ta 54 %
B203 : 16 to 30 %
Na20 : 13 to 2~ %
K20 : O to 4 %
Li20 : O to 2.5 %
CaO : O to 3 %
CaF2 : O to 5 %
A123 3 to 9 %
Zr2 : to 6 %
NiO : O to 2 %
CoO : O to 1.5 ~

'`~n2 : to 1.5 %

~ -- 10 --The enamel obtained from a composition of this type has a firing temperature below 800C and a coefficient of thermal expansion within the range of 95 to 110 x 10 7 (CGS unit9).
Furthermore, the adhesion of an enamel of this type remains equally excellent when the constituents of the alloy having a nickel and chromium base vary between the following limits (expressed in weight percentages):
Cr : 12 to 40 %
: Ni : 50 to 80 %
C : 0.05 to 0.2 %
Si : 0.05 to 0.5 %
Mo : 0 to 0.1 %
Fe : 0 to 15 %
B : 0 to 3 %
Ti : 0 to 5 %
Co : 0 to 10 %
zr : 0 to 5 %
Nb : 0 to 5 %
Mn : 0 to 1 %
Al : 0 to 3 %
Example 2:
The operation is carried out as in Example 1 by applying on the first enamel layer a second layer formed from the following composition (expressed in weight percentages):
SiO2 : 52.3 %
Na20 : 13.7 %
K20 : 17.5 %

..

I 1 /760~

CaF2 : 2.8 %

BaO : 4.4 %
ZrO2 : 10 . O %
The enamel obtained by firing of the above-mentioned composition at a temperature within the range of 740 to 760C
has a coefficient of thermal expansion within the range of 120 to 125 x 10 7 (CGS units).
The following ingreidents can be added to the aforement-ioned composition prior to firing of this matter (expressed in 10 weight percentages):
TiO2 : 0.8 %
NiO : 0.005 %
SiO2 : 7.2 %
Fe23 0.002 %
These ingredients provide the enamel with a slightly yellowish-grey coloring.
The thickness of this second enamel layer can vary as in the case of the first layer between 0.5 and 3 mm according to the dimension and nature of the teeth.

Claims (3)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A metallic prosthesis coated with a vitreous enamel, wherein said prosthesis is formed of an alloy having a base of nickel and chromium such that the sum of concentrations of nickel and chromium is higher than or equal to 80% by weight and wherein the ratio of the concentration of nickel to the concentration of chromium is higher than or equal to 2.5, said alloy being coated by at least one first enamel layer obtained from an enamel compo-sition containing the following compounds, expressed in weight percentage:
said first layer being coated by a second layer, the composition of said second layer containing the following compounds, expressed in weight percentage:

2. A prosthesis according to claim 1, wherein the alloy has the following composition, expressed in weight percentage:

3. A prosthesis according to one of claims 1 or 2, wherein the composition of said layer contains the following compounds, expressed in weight percentage:

CA000408600A 1981-08-14 1982-08-03 Metallic prosthesis coated with a vitreous enamel and a method for producing said prosthesis Expired CA1177604A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR8115726A FR2511361A1 (en) 1981-08-14 1981-08-14 Vitreous enamel for use on metal dental prostheses - contains borosilicate glass, and is used esp. on prostheses made of nickel-chromium alloy contg. no noble metals
FR8115726 1981-08-14
FR8206818 1982-04-21
FR8206818A FR2525584B2 (en) 1981-08-14 1982-04-21 EMAIL COMPOSITION FOR DENTAL PROSTHESIS, PROSTHESES AND METHOD FOR MAKING SAME

Publications (1)

Publication Number Publication Date
CA1177604A true CA1177604A (en) 1984-11-13

Family

ID=26222511

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000408600A Expired CA1177604A (en) 1981-08-14 1982-08-03 Metallic prosthesis coated with a vitreous enamel and a method for producing said prosthesis

Country Status (4)

Country Link
EP (1) EP0077223A3 (en)
CA (1) CA1177604A (en)
DE (1) DE77223T1 (en)
FR (1) FR2525584B2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5562733A (en) * 1990-07-24 1996-10-08 Dentsply G.M.B.H. Dental ceramic, coated titanium prosthesis
AU706521B2 (en) * 1994-12-05 1999-06-17 Schott Ag Barium-free dental glass having good X-ray absorption

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1229354A (en) * 1984-03-01 1987-11-17 David C. Greenspan Biologically active glass compositions for bonding to alloys
DD278918A3 (en) * 1988-02-15 1990-05-23 Lausitzer Glas Weisswasser Sta CERAMIC MATERIAL WITH CORDIERITE CRYSTAL PHASE AND ITS APPLICATION
US8110035B2 (en) * 2008-05-30 2012-02-07 Dentsply International Inc. Integrated porcelain system for a dental prosthesis

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2340546A1 (en) * 1973-08-10 1975-02-27 Pfaudler Werke Ag METALLIC IMPLANT AND PROCEDURE FOR ITS MANUFACTURING
US3914867A (en) * 1974-05-23 1975-10-28 Dentsply Res & Dev Dental alloy
DE2429943A1 (en) * 1974-06-21 1976-01-08 Pfaelzische Emailschmelze Rolf Decoration on enamelled iron articles - by applying a companion and a dynactive enamel followed by stoving
FR2292679A1 (en) * 1974-11-28 1976-06-25 Aubecq Auxi Enamelling compsn. for iron cooking utensils - has clear appearance and resists acids
JPS5214095A (en) * 1975-07-23 1977-02-02 Sumitomo Chemical Co Implant in bone
JPS535216A (en) * 1976-07-02 1978-01-18 Okuno Chem Ind Co Glass enamel composition
DE3060559D1 (en) * 1979-01-17 1982-08-12 Bayer Ag Coated metal article and method of manufacturing it

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5562733A (en) * 1990-07-24 1996-10-08 Dentsply G.M.B.H. Dental ceramic, coated titanium prosthesis
AU706521B2 (en) * 1994-12-05 1999-06-17 Schott Ag Barium-free dental glass having good X-ray absorption

Also Published As

Publication number Publication date
EP0077223A2 (en) 1983-04-20
EP0077223A3 (en) 1983-06-22
FR2525584A2 (en) 1983-10-28
FR2525584B2 (en) 1986-03-21
DE77223T1 (en) 1983-07-21

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