CA2239861C - Alkali silicate glass - Google Patents
Alkali silicate glass Download PDFInfo
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- CA2239861C CA2239861C CA002239861A CA2239861A CA2239861C CA 2239861 C CA2239861 C CA 2239861C CA 002239861 A CA002239861 A CA 002239861A CA 2239861 A CA2239861 A CA 2239861A CA 2239861 C CA2239861 C CA 2239861C
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- apatite
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- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
- C03C4/0021—Compositions for glass with special properties for biologically-compatible glass for dental use
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/74—Fillers comprising phosphorus-containing compounds
- A61K6/75—Apatite
-
- 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
- A61K6/807—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising magnesium 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
- A61K6/816—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising titanium 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
- A61K6/822—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising rare earth 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
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/833—Glass-ceramic composites
-
- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/16—Halogen containing crystalline phase
-
- 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
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
Abstract
Alkali silicate glasses are described which, in view of their good chemical stability and their optical properties and processing properties, are particularly suitable as a coating or veneering material for ceramic dental frameworks and hence for the production of all-ceramic dental restorations such as crowns or bridges. The alkali silicate glasses each contain the following components:
Component Wt. %
SiO2 55.0 to 71.0 Al2O3 5.0 to 16.0 B2O3 0.2 to 10.0 K2O 4.5 to 10.0 Na2O 3.0 to 14.0 A preferred form of these glasses contain at least one of the following components:
Component Wt.%
CaO 0 to 3.0 F 0 to 3.0 P2O5 0 to 0.6 Li2O 0 to 4.0 BaO 0 to 5.0 ZnO 0 to 4.0 TiO2+Zro2 0.2 to 5.0 CeO2 0 to 2.0
Component Wt. %
SiO2 55.0 to 71.0 Al2O3 5.0 to 16.0 B2O3 0.2 to 10.0 K2O 4.5 to 10.0 Na2O 3.0 to 14.0 A preferred form of these glasses contain at least one of the following components:
Component Wt.%
CaO 0 to 3.0 F 0 to 3.0 P2O5 0 to 0.6 Li2O 0 to 4.0 BaO 0 to 5.0 ZnO 0 to 4.0 TiO2+Zro2 0.2 to 5.0 CeO2 0 to 2.0
Description
Alkali silicate ~lass The invention relates to alkali silicate glass and, in particular, to such a glass which is suitable for adjusting in a desired manner the optical properties and processing properties of coating and veneering material for ceramic dental restorations.
In addition to metallic dental restorations which are veneered with ceramic layers for aesthetic reasons, all-ceramic restorations are increasingly being used in dentistry wherein a ceramic veneering or coating material is applied to a core of ceramic material. Inter alia glass ceramics are suitable for use as both core and coating material.
The optical properties in particular, and the processing properties of glass ceramic coating material are, however, often unsatisfactory. The glass ceramics used exhibit considerable cloudiness due to their high crystal content which is not acceptable, particularly for dental restorations for the incisor region. Moreover, the glass ceramics have a very high expansion coefficient in many cases, for which reason they are unsuitable as a coating material for cores of glass ceramic with a low expansion coefficient, such as lithium disilicate glass ceramic.
As a result of the unsatisfactory adjustment of the expansion coefficients, undesired detachment of the coating material may occur.
It is also known that leucite-containing glass ceramics in particular have very high thermal expansion coefficients. These are attributable to the content of leucite crystals which are formed by controlled crystallisation of an appropriate starting glass.
Alkali silicate glasses are known from EP-A-695 726 which are suitable for veneering primarily metallic dental frameworks and contain no B2O3. During heat treatment at temperatures of 600~C
to lOOO~C and hence under conventional conditions for further dental processing, the glasses, however, form corresponding glass ceramics which, as a result of their crystal content, are very cloudy and are therefore unsuitable for obtaining a high translucence in a glass ceramic coating material.
The crystal content, particularly leucite, also leads to undesirably high 5 expansion coefficients and sintering temperatures, so that they are unsatisfactory for veneering ceramic substrates with low expansion coefficients.
The glass described herein does not crystallise under the conventional 10 conditions of dental processing in the temperature range from 600 ~C to 1000~C, has a low thermal expansion coefficient, a low sintering temperature, good chemical stability and high translucence, and consequently may be added in particular to dental glass ceramic coating material in order to improve the properties thereof.
The alkali silicate glass according to the invention contains the following components:
Component Wt.%
SiO2 55.0 to 71.0 Al2O2 5.0 to 16.0 B2O3 0.2 to 10.0 K2O 4.5 to 10.0 Na2O 3.0 to 14.0 SiO2 is preferably present in an amount of 55.0 to 65.0 wt.%.
The glass according to the invention may additionally contain at least one of the following components:
ComPonent Wt.%
CaO 0 to 3.0 F 0 to 3.0 P2O5 0 to 0.6 Li2O 0 to 4.0 BaO 0 to 5.0 ZnO 0 to 4.0 TiO2 + ZrO2 0.2 to 5.0 -CeO2 0 to 2.0 With the exception of TiO2 and ZrO2, the lower limits for these additional components are usually 0.05 wt.%.
Preferred quantity ranges exist for the individual components of the alkali silicate glass according to the invention. These may be chosen independently of one another and are as follows:
Component Wt. %
SiO2 60.0 to 65.0 Al2O3 6.0 to 10.0 Bz03 0.5 to 8.1 K2O 5.5 to 9.0 NazO 3.5 to 10.0 CaO 0.5 to 3.0 F 0.2 to 2.0 Particularly preferred quantity ranges for the individual components of the glass according to the invention are as follows and these may be chosen independently of one another:
Component Wt. %
SiO 61.0 to 64.0 Al2O3 7.0 to 9.0 s2O30.5 to 4.0 Na2G7.0 to 9.0 CaO 0.5 to 1.5 F 1.0 to 2.0 Li2O 0 to 3.0 BaO 1.5 to 3.5 ZnO 2.0 to 3.5 All the above-mentioned quantities in wt.% relate to the glass.
. .
For the production of the glass according to the invention, it is preferable to proceed in such a way that suitable starting materials, such as carbonates, oxides and fluorides, are melted at temperatures from 1350~C to 1650~C, preferably 1400~C to 1600~C over a period of 30 minutes to 4 hours, preferably one hour to 2.5 hours, with the formation of a homogeneous melt. The molten glass is then usually quenched in water i.e. fritted and, after drying, ground to the desired particle size.
It was possible to ascertain by scanning electron microscope analyses that the glass according to the invention is free from crystals. Additionally, it became apparent that the glass also withstands the conditions prevailing during conventional further dental processing by sintering without the formation of crystals which occurs with known glasses. Crystallisation did not occur even during a heat treatment at temperatures of 600~C to 1000~C
for one minute to 2 hours.
This behaviour is presumably att.ibutable to the special composition of the glass according to the invention.
The glass according to the invention usually has a sintering temperature of 650~C to 1150~C. Glasses having a sintering temperature of 700~C to 1050~C are particularly preferred. Glass which can be sintered at low temperatures of 750~C to 880~C and can thus be processed is quite particularly preferred.
A rate of heating of 3 to 100~C/min and preferably 30 to 80~C/min and a holding time at the sintering temperature of 10 seconds to 1 hour and preferably 30 seconds to 5 minutes is usually chosen for carrying out sintering. It is advantageous to carry out sintering under vacuum so that the sintered body has as few pores as possible.
The thermal expansion coefficient of the glass according to the invention is usually 5.5 to 12.5 x 10 K , preferably 6.0 to 11.0 x 10-6K-l, measured in the temperature interval of 100~C to 400~C.
The glass according to the invention is used by itself or together with other components preferably as dental material.
To this end it is generally used in the form of a powder with an average particle size of less than 90 ~m. Further suitable components are glass ceramics and other glasses, but also dyes, particularly coloured pigments, oxides of the 3d elements or metal colloids, and fluorescent materials, particularly ytterbium silicate doped with d and ~ elements.
Dental material which contains at least one apatite glass ceramic as the further component is particularly advantageous.
A preferred apatite glass ceramic is one containing CaO, P2O5 and F in a molar ratio of CaO : P2O5 : F of 1 : 0.020 to 1.5 : 0.03 to 4.2 and contains apatite crystals as the main crystal phase.
Such apatite glass ceramics are characterised by particularly good chemical stability, which is of great importance especially for use in dental restorations.
Moreover, the use of an apatite glass ceramic which contains at least one of the following components and contains apatite crystals as the main crystal phase is also preferred:
Component Wt. %
SiO2 45.0 to 70.0 Al2O3 5.0 to 22.0 P2O5 0.5 to 6.5 R2O 3.0 to 8.5 Na2O 4.0 to 13.0 CaO 1.5 to 11.0 F 0.1 to 2.5 In particular preference, this apatite glass ceramic additionally contains at least one of the following components: ;
Component Wt.%
B2O3 0 to 8.0 La2O3 ~ to 5.0 Li2O 0 to 5.0 BaO 0 to 5.0 MgO 0 to 5.0 ZnO 0 to 5.0 SrO 0 to 7.0 TiO2 0 to 4.0 ZrO2 0 to 4.0 CeO2 0 to 3.0 The above amounts given in wt.% relate to the apatite glass ceramic.
The apatite glass ceramics described above are produced by melting a starting glass composed of suitable starting materials, such as oxides, carbonates and fluorides, at temperatures of 1200~C to 1650~C, pouring this into water and subjecting the glass granules formed, optionally after further comminution, to a heat treatment at temperatures of more than 900~C and up to 1200~C for a period of 30 minutes to 6 hours.
The apatite glass ceramics obtained are characterised by high translucence, good chemical stability and a low expansion coefficient. These properties are presumably attributabie to their special composition and to the apatite crystals produced during their manufacture, which crystals have in particular a needle-shaped morphology and hence resemble the apatite crystals of natural tooth material.
The dental material according to the invention normally has a thermal expansion coefficient of 5.5 to 12.5 x 106Kl, measured in the temperature range of from 100 to 400~C. The coefficient required in each case can be adjusted by a suitable choice of the type of alkali silicate glass and any other components and the quantities thereof. Favourable dental materials contain 10 to 90 wt.% of alkali silicate glass and 90 to 10 wt.~ of other components, based on the dental material.
The dental material is suitable for coating substrates and in particular for coating or veneering dental restorations. Coating is effected in particular by applying the dental material to the chosen substrate and then sintering it at temperatures of ~50 to 1150~C.
In preference, a powder of the glass according to the invention is mixed with a powder of the other components optionally present and processed to a paste by adding aqueous mixing solutions. This paste is then applied to a substrate and, after the desired shaping, sintering takes place to obtain a firmly adhering coating or veneer.
The dental material according to the invention may be used as a coating or veneering material for substrates such as dental framewor~s, based on ceramic or glass ceramic materials. In view of its low expansion coefficient, it is used preferably with substrate materials with a thermal expansion coefficient of 7.0 to 12.0, particularly 8.0 to 11.0 x 10-6K-l. It is used preferably for coating or veneering ZrO2 ceramics, Al2O3 ceramics, ZrO2/Al2O3 ceramics, ceramic or glass ceramic composite mate~ials and titanium.
It is used particularly advantageously, however, for veneering substrates based on lithium disilicate glass ceramic in order to produce in this way aesthetically very attractive fully ceramic dental products which have very high strength and excellent chemical stability.
, , Lithium disilicate glass ceramics having the following composition which may be obtained e.g. by melting appropriate starting glasses, fritting and heat treatment at 400~C to 1100~C
have proved to be particularly suitable:
ComPonent Wt.%
SiOz57.0 to 80.0 Al2O3 0 to 5.0 La2O30.1 to 6.0 MgO 0 to 5.0 ZnO 0 to 8.0 K2O 0 to 13.5 Li2O11.0 to 19.0 P2O5 0 to 11.0 with the proviso that (a) Al2O3 + La2O3is 0.1 to 7.0 wt.% and (b) MgO + ZnO is 0.1 to 9.0 wt.%.
The amounts given in wt.% are based on the lithium disilicate glass ceramic.
For the production of coatings, dental material according to the invention that has a thermal expansion coefficient that is smaller than that of the substrate to be coated is advantageous.
Dental material whose expansion coefficient is not more than 3.0 x 10-6K-l smaller than t~lat of the substrate is particularly advantageous.
The alkali silicate glass according to the invention and the dental material according to the invention may be processed in the usual way together with the additives optionally present to obtain shaped dental products. Suitable shaped dental products according to the invention cont~i n ing the alkali silicate glass or the dental material are, in particular, dental restorations such as an inlay, an onlay, a bridge, an abutment, a jacket, a veneer, a facet, a filling, or a connector. Particularly preferred dental restorations are bridges, crowns and partial crowns.
The dental products preferably have a core based on ceramic or glass ceramic material, particularly lithium disilicate glass ceramic, onto which the glass according to the in~ention or the dental material according to the invention is applied.
Preferred lithium disilicate glass ceramics have already been described above.
In contrast to conventional glass, crystallisation which would undesirably lower its translucence does not occur with the glass according to the invention under the conditions prevailing during the sintering thereof. It therefore reproduces essentially the colour of the coated substrate which is very desirable, particularly during the production of all-ceramic dental restorations.
The lack of crystal formation and in particular the lack of formation of leucite crystals ascertained in the case of known glasses is a particular advantage since the high expansion coefficient of leucite would confer a high thermal expansion coefficient on the glass. The glass would therefore be unsuitable for coating substrates with low expansion coefficients, such as ZrO~ or lithium disilicate glass ceramic. The lack of adjustment of the expansion coefficients would lead to high stresses which regularly manifest themselves in cracks and chippings. These disadvantages are not exhibited by the glass according to the invention due to its low expansion coefficient, so it is very suitable for coating substrates with low expansion coefficients.
- Moreover, despite its B2O3 content, the glass exhibits excellent chemical stability which is vital for its use as a dental ~ - . .
material, which is permanently flushed by acid fluids in ~he oral cavity.
Finally, the glass may be sintered onto a substrate within a short sintering time even at low temperatures in order to produce a firmly adhering coating or veneer in this way.
A~mi x; ng the glass with apatite glass ceramics in particular leads to dental materials which have increased translucence, a shorter sintering time and lower sintering temperature and a lower thermal expansion coefficient compared with the pure apatite glass ceramic.
The invention will be explained in more detail below on the basis of examples.
Examples Examples 1 to 8 A total of 8 different glasses according to the invention with the chemical compositions given in Table I were produced.
Table 1: Compositions of glasses according to the invention (quantitiès in wt.%) Ex. SjO2 Al2O3 P205 CaO F K:2O Na20 Li20 B203 TiO2 ZrO2 CeO2 BaO ZnO
No.
S-).S 6.7 0.3 3.0 0.9 8.6 6.6 1.4 4.() .. 2.5 1.0 4.7 3.8 - a' 2 61.5 8.7 .. 1.0 1.7 7.0 8.8 .. 2.4 1.5 1.0 0.5 2.9 3.0 1 1-3 60.4 11.9 .. .. 0.3 6.4 7.0 1.8 0.3 1.5 3.5 .. 3.2 3.7 4 61.4 8.5 .. 1.1 1.7 7.8 8.7 0.6 1.9 1.5 1.0 0.5 2.1 3.2 O62.3 R.7 .. 1.3 1.6 7 0 7.0 2.0 1.1 1.4 1.0 0.6 3.0 3.0 6 70.R 8.6 .. 2.1 ().9 6.9 8.3 1.5 0.2 0.7 .. ~ ~- -7 63.4 6.2 0.4 1.7 ~- 6.4 9.6 .. 3.7 1.7 1.1 0.5 2.3 3.0 8 61.9 9.9 .. 1.1 1.5 5.8 3.7 0.2 8.0 1.4 1.1 0.5 2.8 2.1 For the production of said glasses, an appropriate batch of suitable oxides, carbonates and fluorides in each case was melted in a platinum/rhodium crucible at a temperature of 1550~C to 1600~C for a homogenisation period of 1 to 1.5 hours. The glass melt was quenched in water, and the granules of the glass formed were dried and ground to an average particle size of less than 90 ~m.
Selected properties that were determined on specimens composed of the respective glass are given in Table II. The examples illustrate how glasses with different properties may be obtained by altering the chemical composition.
Table II
LS
Ex. Firing Tg [ C] a-value Optical Acid tempe- x 10oK appearance resist2ance rature '100 C- [~g/cm ]
[ C]* ~0~ C) 1 760 500 c.~ translucent 26 2 810 522 9._ very 17.2 translucent 3 880 528 9.5 translucent 17 4 770 494 9.4 very 26.3 translucent 750 468 9.4 very 17.9 translucent 7 840 565 8.9 very 30 translucent 8 880 543 6.6 very <100 translucent * Firing temperature = temperature which was used for production of the specimens by sintering onto quartz (vacuum, 1 minute holding time) Determination of the expansion coefficient a In order to measure the thermal expansion coefficient a, a rod-shaped green compact was prepared from powder of the glass in CA 0223986l l998-06-08 question, and said compact was sintered in a vacuum furnace at a rate of heating of 60~C/min and with a holding time of 1 minute at the respective firing temperature. A glaze bake was then carried out without vacuum at a 20~C higher final temperature and with a holding time of 1 minute. The thermal expansion coefficient was determined on the specimen obtained.
Determination of acid resistance The acid resistance is a measure of the chemical stability of glasses and glass ceramics used in dentistry in particular, since these are permanently exposed to the action of acid substances in the oral cavity.
The acid resistance was determined according to the ISO
specification 6872:1995. To this end, small sample plates 12 mm in diameter and 1 mm thick were prepared initially by sintering together glass granules with an average particle size of 90 ~m.
The granules were kept at the sintering temperature for 1 minute.
The sample plates were then treated for 16 hours in a Soxhlet apparatus with 4 vol.% of aqueous acetic acid and finally the loss of mass occurring was determined as a measure of the acid resistance.
Example 9 This Example describes the use of glasses according to the in~ention according to Example 2 and 4 together with an apatite glass ceramic (A) as a coating material for ceramic frameworks and thus for the production of fully ceramic dental products.
The apatite glass ceramic (A) had the composition SiO2 55.5 wt.%, Al2O. 19.2 wt.%, P2O5 1.2 wt.%, CaO 2.7 wt.%, F 0.6 wt.%, K2O 6.7 wt.%, Na2O 9.7 wt.%, B2O3 0.3 wt.%, TiO2 1.4 wt.%, ZrO2 2.2 wt.%
and CeO~ 0.5 wt.%. For the preparation thereof, a starting glass of the appropriate composition was melted, fritted and ground to a powder. This powder was then heat treated for one hour at 1020~C. The crystals present in the glass ceramic formed could be identified as needle-shaped apatite crystals by X-ray diffractometry.
S
In order to obtain a suitable expansion coefficient and sintering temperature, this apatite glass ceramic (A) was mixed with the alkali silicate glasses 2 and 4 according to the invention in the form of powders with an average particle size of less than 90 ~m and in a weight ratio of 30% apatite glass ceramic (A), 35%
alkali silicate glass according to Example 2 and 35~ alkali silicate glass according to Example 4.
This mixture was sintered at 880~C to a rod-shaped green compact in a vacuum furnace at a rate of heating of 60~C/min and with a holding time of 1 min. A thermal expansion coefficient of 9.5 x 10-6K-l, measured in the temperature range of from lO0 to 400~C, was determined for the sample obtained.
This mixture could thus be used for sintering onto a substrate with a thermal expansion coefficient of 10.6 x 106Kl, such as lithium disilicate glass ceramic, at an advantageous processing temperature of 830~C.
Processing on a tooth substrate can usually take place at temperatures that are 50 to 100~C lower than the sintering temperature on quartz.
E~ample lO
In the same way as Example 9, different glasses according to the invention may be mixed together or with other glass ceramics to obtain desired expansion coefficients and sintering temperatures.
A powder mixture of 25 wt.% of alkali silicate glass according to Example 4 with 50 wt.% of apatite glass ceramic (B) (heat treatment at 1100~C), and 25 wt.% of apatite glass ceramic (A) according to Example 9 (heat treatment 1020~C) was prepared in order to obtain a dental material according to the invention with a low sintering temperature of 830~C and an expansion coefficient of 9.5 x 10-6R-l. Such a material had outstanding optical properties and was highly suitable as a sintering ceramic for an all-ceramic framework structure with a low thermal expansion coefficient.
The apatite glass ceramic (B) used in this case had the composition SiO2 59.2 wt.%, Al2O3 7.9 wt.%, P2O5 3.0 wt.%,,CaO 5.1 wt.%, F 0.6 wt.%, KzO 6.8 wt.%, Na2O 9.6 wt.%, Li2O 0.3 wt.%, B2O3 1.0 wt.%, TiO2 1.5 wt.%, ZrO2 2.5 wt.%, CeO2 0.5 wt.% and ZnO2 2.0 wt.%. For the preparation thereof, a starting glass of the appropriate composition was melted, fritted and ground to a powder. This powder was then heat treated at 1100~C in order to form the glass ceramic.
E~amples 11 to 14 In these Examples, other mixtures of alkali silicate glasses according to the invention with apatite glass ceramics were examined, which are highly suitable as coating or veneering materials that can be sintered onto substrates with low thermal expansion coefficients.
The following apatite glass ceramics were used:
1. Apatite glass ceramic (B) according to Example 10 2. Apatite glass ceramic (C) having the composition:
SiOz 62.8 wt.~, Al2O3 13.1 wt.%, P2O5 1.2 wt.%, CaO 2.7 wt.%, F 0.6 wt.%, K2O 6.3 wt.%, Na2O 5.9 wt.%, ZrO2 1.7 wt.% , CeO2 0.5 wt.%, BaO 1.8 wt.% and ZnO 3.4 wt.%.
3. Apatite glass ceramic (D) having the composition:
SiO2 64.5 wt.%, Al203 8.4 wt.%, P205 1.1 wt.%, CaO 2.8 wt.%, F 0.7 wt.%, K20 6.6 wt.%, Na20 9.6 wt.%, Bz03 2.2 wt.%, TiO2 1.2 wt.%, ZrO2 0.4 wt.%, and ZnO 2.5 wt.%.
The compositions of the individual mixtures and the heat treatment carried out for the production of the apatite glass ceramic used in each case are given in Table III.
The properties determined for these mixtures are also stated in Table III and they show that, by means of a suitable choice of components, it is possible to obtain dental materials with properties adjusted to the application in question.
LS
~a~le III: Properties of mixtures of glasses according to the invention and apatite glass ceramics Ex. Composition llcal Mixing ratio Sintering Tg a~-value Optical Acid _ treatmenl [in wt.~] temp. [~Cl x 10-6Kl appedlance rÇsic~nre [~C/hl [~Cl ( 1 0 0 ~ C - [,ug/cm2l 1 a~
400~C) ,_ 11 Apatite glass ceramic 1050/1 50 850 530 9.3 milky, cloudy, <100 (B) ~- 50 tr:-nclllcen~
Alkali silicate glass 2 ~
12 Apalitc glass ceramic 1020/1 50 870 542 8.0 milky, < 100 ~
(13) .. 50 translucent Alkali silicate glass 8 3 Apalite glass ceramic Illû()/1 40 910 552 8.8 very < 100 (C) .. 60 translucent Alkali silicate glass S
14 Apalite glass ceramic 1050/1 70 850 539 8.7 slightly milky, < 100 (D) ~ 30 slightly opal, Alkali silicate glass 6 Ir,~ r"~
In addition to metallic dental restorations which are veneered with ceramic layers for aesthetic reasons, all-ceramic restorations are increasingly being used in dentistry wherein a ceramic veneering or coating material is applied to a core of ceramic material. Inter alia glass ceramics are suitable for use as both core and coating material.
The optical properties in particular, and the processing properties of glass ceramic coating material are, however, often unsatisfactory. The glass ceramics used exhibit considerable cloudiness due to their high crystal content which is not acceptable, particularly for dental restorations for the incisor region. Moreover, the glass ceramics have a very high expansion coefficient in many cases, for which reason they are unsuitable as a coating material for cores of glass ceramic with a low expansion coefficient, such as lithium disilicate glass ceramic.
As a result of the unsatisfactory adjustment of the expansion coefficients, undesired detachment of the coating material may occur.
It is also known that leucite-containing glass ceramics in particular have very high thermal expansion coefficients. These are attributable to the content of leucite crystals which are formed by controlled crystallisation of an appropriate starting glass.
Alkali silicate glasses are known from EP-A-695 726 which are suitable for veneering primarily metallic dental frameworks and contain no B2O3. During heat treatment at temperatures of 600~C
to lOOO~C and hence under conventional conditions for further dental processing, the glasses, however, form corresponding glass ceramics which, as a result of their crystal content, are very cloudy and are therefore unsuitable for obtaining a high translucence in a glass ceramic coating material.
The crystal content, particularly leucite, also leads to undesirably high 5 expansion coefficients and sintering temperatures, so that they are unsatisfactory for veneering ceramic substrates with low expansion coefficients.
The glass described herein does not crystallise under the conventional 10 conditions of dental processing in the temperature range from 600 ~C to 1000~C, has a low thermal expansion coefficient, a low sintering temperature, good chemical stability and high translucence, and consequently may be added in particular to dental glass ceramic coating material in order to improve the properties thereof.
The alkali silicate glass according to the invention contains the following components:
Component Wt.%
SiO2 55.0 to 71.0 Al2O2 5.0 to 16.0 B2O3 0.2 to 10.0 K2O 4.5 to 10.0 Na2O 3.0 to 14.0 SiO2 is preferably present in an amount of 55.0 to 65.0 wt.%.
The glass according to the invention may additionally contain at least one of the following components:
ComPonent Wt.%
CaO 0 to 3.0 F 0 to 3.0 P2O5 0 to 0.6 Li2O 0 to 4.0 BaO 0 to 5.0 ZnO 0 to 4.0 TiO2 + ZrO2 0.2 to 5.0 -CeO2 0 to 2.0 With the exception of TiO2 and ZrO2, the lower limits for these additional components are usually 0.05 wt.%.
Preferred quantity ranges exist for the individual components of the alkali silicate glass according to the invention. These may be chosen independently of one another and are as follows:
Component Wt. %
SiO2 60.0 to 65.0 Al2O3 6.0 to 10.0 Bz03 0.5 to 8.1 K2O 5.5 to 9.0 NazO 3.5 to 10.0 CaO 0.5 to 3.0 F 0.2 to 2.0 Particularly preferred quantity ranges for the individual components of the glass according to the invention are as follows and these may be chosen independently of one another:
Component Wt. %
SiO 61.0 to 64.0 Al2O3 7.0 to 9.0 s2O30.5 to 4.0 Na2G7.0 to 9.0 CaO 0.5 to 1.5 F 1.0 to 2.0 Li2O 0 to 3.0 BaO 1.5 to 3.5 ZnO 2.0 to 3.5 All the above-mentioned quantities in wt.% relate to the glass.
. .
For the production of the glass according to the invention, it is preferable to proceed in such a way that suitable starting materials, such as carbonates, oxides and fluorides, are melted at temperatures from 1350~C to 1650~C, preferably 1400~C to 1600~C over a period of 30 minutes to 4 hours, preferably one hour to 2.5 hours, with the formation of a homogeneous melt. The molten glass is then usually quenched in water i.e. fritted and, after drying, ground to the desired particle size.
It was possible to ascertain by scanning electron microscope analyses that the glass according to the invention is free from crystals. Additionally, it became apparent that the glass also withstands the conditions prevailing during conventional further dental processing by sintering without the formation of crystals which occurs with known glasses. Crystallisation did not occur even during a heat treatment at temperatures of 600~C to 1000~C
for one minute to 2 hours.
This behaviour is presumably att.ibutable to the special composition of the glass according to the invention.
The glass according to the invention usually has a sintering temperature of 650~C to 1150~C. Glasses having a sintering temperature of 700~C to 1050~C are particularly preferred. Glass which can be sintered at low temperatures of 750~C to 880~C and can thus be processed is quite particularly preferred.
A rate of heating of 3 to 100~C/min and preferably 30 to 80~C/min and a holding time at the sintering temperature of 10 seconds to 1 hour and preferably 30 seconds to 5 minutes is usually chosen for carrying out sintering. It is advantageous to carry out sintering under vacuum so that the sintered body has as few pores as possible.
The thermal expansion coefficient of the glass according to the invention is usually 5.5 to 12.5 x 10 K , preferably 6.0 to 11.0 x 10-6K-l, measured in the temperature interval of 100~C to 400~C.
The glass according to the invention is used by itself or together with other components preferably as dental material.
To this end it is generally used in the form of a powder with an average particle size of less than 90 ~m. Further suitable components are glass ceramics and other glasses, but also dyes, particularly coloured pigments, oxides of the 3d elements or metal colloids, and fluorescent materials, particularly ytterbium silicate doped with d and ~ elements.
Dental material which contains at least one apatite glass ceramic as the further component is particularly advantageous.
A preferred apatite glass ceramic is one containing CaO, P2O5 and F in a molar ratio of CaO : P2O5 : F of 1 : 0.020 to 1.5 : 0.03 to 4.2 and contains apatite crystals as the main crystal phase.
Such apatite glass ceramics are characterised by particularly good chemical stability, which is of great importance especially for use in dental restorations.
Moreover, the use of an apatite glass ceramic which contains at least one of the following components and contains apatite crystals as the main crystal phase is also preferred:
Component Wt. %
SiO2 45.0 to 70.0 Al2O3 5.0 to 22.0 P2O5 0.5 to 6.5 R2O 3.0 to 8.5 Na2O 4.0 to 13.0 CaO 1.5 to 11.0 F 0.1 to 2.5 In particular preference, this apatite glass ceramic additionally contains at least one of the following components: ;
Component Wt.%
B2O3 0 to 8.0 La2O3 ~ to 5.0 Li2O 0 to 5.0 BaO 0 to 5.0 MgO 0 to 5.0 ZnO 0 to 5.0 SrO 0 to 7.0 TiO2 0 to 4.0 ZrO2 0 to 4.0 CeO2 0 to 3.0 The above amounts given in wt.% relate to the apatite glass ceramic.
The apatite glass ceramics described above are produced by melting a starting glass composed of suitable starting materials, such as oxides, carbonates and fluorides, at temperatures of 1200~C to 1650~C, pouring this into water and subjecting the glass granules formed, optionally after further comminution, to a heat treatment at temperatures of more than 900~C and up to 1200~C for a period of 30 minutes to 6 hours.
The apatite glass ceramics obtained are characterised by high translucence, good chemical stability and a low expansion coefficient. These properties are presumably attributabie to their special composition and to the apatite crystals produced during their manufacture, which crystals have in particular a needle-shaped morphology and hence resemble the apatite crystals of natural tooth material.
The dental material according to the invention normally has a thermal expansion coefficient of 5.5 to 12.5 x 106Kl, measured in the temperature range of from 100 to 400~C. The coefficient required in each case can be adjusted by a suitable choice of the type of alkali silicate glass and any other components and the quantities thereof. Favourable dental materials contain 10 to 90 wt.% of alkali silicate glass and 90 to 10 wt.~ of other components, based on the dental material.
The dental material is suitable for coating substrates and in particular for coating or veneering dental restorations. Coating is effected in particular by applying the dental material to the chosen substrate and then sintering it at temperatures of ~50 to 1150~C.
In preference, a powder of the glass according to the invention is mixed with a powder of the other components optionally present and processed to a paste by adding aqueous mixing solutions. This paste is then applied to a substrate and, after the desired shaping, sintering takes place to obtain a firmly adhering coating or veneer.
The dental material according to the invention may be used as a coating or veneering material for substrates such as dental framewor~s, based on ceramic or glass ceramic materials. In view of its low expansion coefficient, it is used preferably with substrate materials with a thermal expansion coefficient of 7.0 to 12.0, particularly 8.0 to 11.0 x 10-6K-l. It is used preferably for coating or veneering ZrO2 ceramics, Al2O3 ceramics, ZrO2/Al2O3 ceramics, ceramic or glass ceramic composite mate~ials and titanium.
It is used particularly advantageously, however, for veneering substrates based on lithium disilicate glass ceramic in order to produce in this way aesthetically very attractive fully ceramic dental products which have very high strength and excellent chemical stability.
, , Lithium disilicate glass ceramics having the following composition which may be obtained e.g. by melting appropriate starting glasses, fritting and heat treatment at 400~C to 1100~C
have proved to be particularly suitable:
ComPonent Wt.%
SiOz57.0 to 80.0 Al2O3 0 to 5.0 La2O30.1 to 6.0 MgO 0 to 5.0 ZnO 0 to 8.0 K2O 0 to 13.5 Li2O11.0 to 19.0 P2O5 0 to 11.0 with the proviso that (a) Al2O3 + La2O3is 0.1 to 7.0 wt.% and (b) MgO + ZnO is 0.1 to 9.0 wt.%.
The amounts given in wt.% are based on the lithium disilicate glass ceramic.
For the production of coatings, dental material according to the invention that has a thermal expansion coefficient that is smaller than that of the substrate to be coated is advantageous.
Dental material whose expansion coefficient is not more than 3.0 x 10-6K-l smaller than t~lat of the substrate is particularly advantageous.
The alkali silicate glass according to the invention and the dental material according to the invention may be processed in the usual way together with the additives optionally present to obtain shaped dental products. Suitable shaped dental products according to the invention cont~i n ing the alkali silicate glass or the dental material are, in particular, dental restorations such as an inlay, an onlay, a bridge, an abutment, a jacket, a veneer, a facet, a filling, or a connector. Particularly preferred dental restorations are bridges, crowns and partial crowns.
The dental products preferably have a core based on ceramic or glass ceramic material, particularly lithium disilicate glass ceramic, onto which the glass according to the in~ention or the dental material according to the invention is applied.
Preferred lithium disilicate glass ceramics have already been described above.
In contrast to conventional glass, crystallisation which would undesirably lower its translucence does not occur with the glass according to the invention under the conditions prevailing during the sintering thereof. It therefore reproduces essentially the colour of the coated substrate which is very desirable, particularly during the production of all-ceramic dental restorations.
The lack of crystal formation and in particular the lack of formation of leucite crystals ascertained in the case of known glasses is a particular advantage since the high expansion coefficient of leucite would confer a high thermal expansion coefficient on the glass. The glass would therefore be unsuitable for coating substrates with low expansion coefficients, such as ZrO~ or lithium disilicate glass ceramic. The lack of adjustment of the expansion coefficients would lead to high stresses which regularly manifest themselves in cracks and chippings. These disadvantages are not exhibited by the glass according to the invention due to its low expansion coefficient, so it is very suitable for coating substrates with low expansion coefficients.
- Moreover, despite its B2O3 content, the glass exhibits excellent chemical stability which is vital for its use as a dental ~ - . .
material, which is permanently flushed by acid fluids in ~he oral cavity.
Finally, the glass may be sintered onto a substrate within a short sintering time even at low temperatures in order to produce a firmly adhering coating or veneer in this way.
A~mi x; ng the glass with apatite glass ceramics in particular leads to dental materials which have increased translucence, a shorter sintering time and lower sintering temperature and a lower thermal expansion coefficient compared with the pure apatite glass ceramic.
The invention will be explained in more detail below on the basis of examples.
Examples Examples 1 to 8 A total of 8 different glasses according to the invention with the chemical compositions given in Table I were produced.
Table 1: Compositions of glasses according to the invention (quantitiès in wt.%) Ex. SjO2 Al2O3 P205 CaO F K:2O Na20 Li20 B203 TiO2 ZrO2 CeO2 BaO ZnO
No.
S-).S 6.7 0.3 3.0 0.9 8.6 6.6 1.4 4.() .. 2.5 1.0 4.7 3.8 - a' 2 61.5 8.7 .. 1.0 1.7 7.0 8.8 .. 2.4 1.5 1.0 0.5 2.9 3.0 1 1-3 60.4 11.9 .. .. 0.3 6.4 7.0 1.8 0.3 1.5 3.5 .. 3.2 3.7 4 61.4 8.5 .. 1.1 1.7 7.8 8.7 0.6 1.9 1.5 1.0 0.5 2.1 3.2 O62.3 R.7 .. 1.3 1.6 7 0 7.0 2.0 1.1 1.4 1.0 0.6 3.0 3.0 6 70.R 8.6 .. 2.1 ().9 6.9 8.3 1.5 0.2 0.7 .. ~ ~- -7 63.4 6.2 0.4 1.7 ~- 6.4 9.6 .. 3.7 1.7 1.1 0.5 2.3 3.0 8 61.9 9.9 .. 1.1 1.5 5.8 3.7 0.2 8.0 1.4 1.1 0.5 2.8 2.1 For the production of said glasses, an appropriate batch of suitable oxides, carbonates and fluorides in each case was melted in a platinum/rhodium crucible at a temperature of 1550~C to 1600~C for a homogenisation period of 1 to 1.5 hours. The glass melt was quenched in water, and the granules of the glass formed were dried and ground to an average particle size of less than 90 ~m.
Selected properties that were determined on specimens composed of the respective glass are given in Table II. The examples illustrate how glasses with different properties may be obtained by altering the chemical composition.
Table II
LS
Ex. Firing Tg [ C] a-value Optical Acid tempe- x 10oK appearance resist2ance rature '100 C- [~g/cm ]
[ C]* ~0~ C) 1 760 500 c.~ translucent 26 2 810 522 9._ very 17.2 translucent 3 880 528 9.5 translucent 17 4 770 494 9.4 very 26.3 translucent 750 468 9.4 very 17.9 translucent 7 840 565 8.9 very 30 translucent 8 880 543 6.6 very <100 translucent * Firing temperature = temperature which was used for production of the specimens by sintering onto quartz (vacuum, 1 minute holding time) Determination of the expansion coefficient a In order to measure the thermal expansion coefficient a, a rod-shaped green compact was prepared from powder of the glass in CA 0223986l l998-06-08 question, and said compact was sintered in a vacuum furnace at a rate of heating of 60~C/min and with a holding time of 1 minute at the respective firing temperature. A glaze bake was then carried out without vacuum at a 20~C higher final temperature and with a holding time of 1 minute. The thermal expansion coefficient was determined on the specimen obtained.
Determination of acid resistance The acid resistance is a measure of the chemical stability of glasses and glass ceramics used in dentistry in particular, since these are permanently exposed to the action of acid substances in the oral cavity.
The acid resistance was determined according to the ISO
specification 6872:1995. To this end, small sample plates 12 mm in diameter and 1 mm thick were prepared initially by sintering together glass granules with an average particle size of 90 ~m.
The granules were kept at the sintering temperature for 1 minute.
The sample plates were then treated for 16 hours in a Soxhlet apparatus with 4 vol.% of aqueous acetic acid and finally the loss of mass occurring was determined as a measure of the acid resistance.
Example 9 This Example describes the use of glasses according to the in~ention according to Example 2 and 4 together with an apatite glass ceramic (A) as a coating material for ceramic frameworks and thus for the production of fully ceramic dental products.
The apatite glass ceramic (A) had the composition SiO2 55.5 wt.%, Al2O. 19.2 wt.%, P2O5 1.2 wt.%, CaO 2.7 wt.%, F 0.6 wt.%, K2O 6.7 wt.%, Na2O 9.7 wt.%, B2O3 0.3 wt.%, TiO2 1.4 wt.%, ZrO2 2.2 wt.%
and CeO~ 0.5 wt.%. For the preparation thereof, a starting glass of the appropriate composition was melted, fritted and ground to a powder. This powder was then heat treated for one hour at 1020~C. The crystals present in the glass ceramic formed could be identified as needle-shaped apatite crystals by X-ray diffractometry.
S
In order to obtain a suitable expansion coefficient and sintering temperature, this apatite glass ceramic (A) was mixed with the alkali silicate glasses 2 and 4 according to the invention in the form of powders with an average particle size of less than 90 ~m and in a weight ratio of 30% apatite glass ceramic (A), 35%
alkali silicate glass according to Example 2 and 35~ alkali silicate glass according to Example 4.
This mixture was sintered at 880~C to a rod-shaped green compact in a vacuum furnace at a rate of heating of 60~C/min and with a holding time of 1 min. A thermal expansion coefficient of 9.5 x 10-6K-l, measured in the temperature range of from lO0 to 400~C, was determined for the sample obtained.
This mixture could thus be used for sintering onto a substrate with a thermal expansion coefficient of 10.6 x 106Kl, such as lithium disilicate glass ceramic, at an advantageous processing temperature of 830~C.
Processing on a tooth substrate can usually take place at temperatures that are 50 to 100~C lower than the sintering temperature on quartz.
E~ample lO
In the same way as Example 9, different glasses according to the invention may be mixed together or with other glass ceramics to obtain desired expansion coefficients and sintering temperatures.
A powder mixture of 25 wt.% of alkali silicate glass according to Example 4 with 50 wt.% of apatite glass ceramic (B) (heat treatment at 1100~C), and 25 wt.% of apatite glass ceramic (A) according to Example 9 (heat treatment 1020~C) was prepared in order to obtain a dental material according to the invention with a low sintering temperature of 830~C and an expansion coefficient of 9.5 x 10-6R-l. Such a material had outstanding optical properties and was highly suitable as a sintering ceramic for an all-ceramic framework structure with a low thermal expansion coefficient.
The apatite glass ceramic (B) used in this case had the composition SiO2 59.2 wt.%, Al2O3 7.9 wt.%, P2O5 3.0 wt.%,,CaO 5.1 wt.%, F 0.6 wt.%, KzO 6.8 wt.%, Na2O 9.6 wt.%, Li2O 0.3 wt.%, B2O3 1.0 wt.%, TiO2 1.5 wt.%, ZrO2 2.5 wt.%, CeO2 0.5 wt.% and ZnO2 2.0 wt.%. For the preparation thereof, a starting glass of the appropriate composition was melted, fritted and ground to a powder. This powder was then heat treated at 1100~C in order to form the glass ceramic.
E~amples 11 to 14 In these Examples, other mixtures of alkali silicate glasses according to the invention with apatite glass ceramics were examined, which are highly suitable as coating or veneering materials that can be sintered onto substrates with low thermal expansion coefficients.
The following apatite glass ceramics were used:
1. Apatite glass ceramic (B) according to Example 10 2. Apatite glass ceramic (C) having the composition:
SiOz 62.8 wt.~, Al2O3 13.1 wt.%, P2O5 1.2 wt.%, CaO 2.7 wt.%, F 0.6 wt.%, K2O 6.3 wt.%, Na2O 5.9 wt.%, ZrO2 1.7 wt.% , CeO2 0.5 wt.%, BaO 1.8 wt.% and ZnO 3.4 wt.%.
3. Apatite glass ceramic (D) having the composition:
SiO2 64.5 wt.%, Al203 8.4 wt.%, P205 1.1 wt.%, CaO 2.8 wt.%, F 0.7 wt.%, K20 6.6 wt.%, Na20 9.6 wt.%, Bz03 2.2 wt.%, TiO2 1.2 wt.%, ZrO2 0.4 wt.%, and ZnO 2.5 wt.%.
The compositions of the individual mixtures and the heat treatment carried out for the production of the apatite glass ceramic used in each case are given in Table III.
The properties determined for these mixtures are also stated in Table III and they show that, by means of a suitable choice of components, it is possible to obtain dental materials with properties adjusted to the application in question.
LS
~a~le III: Properties of mixtures of glasses according to the invention and apatite glass ceramics Ex. Composition llcal Mixing ratio Sintering Tg a~-value Optical Acid _ treatmenl [in wt.~] temp. [~Cl x 10-6Kl appedlance rÇsic~nre [~C/hl [~Cl ( 1 0 0 ~ C - [,ug/cm2l 1 a~
400~C) ,_ 11 Apatite glass ceramic 1050/1 50 850 530 9.3 milky, cloudy, <100 (B) ~- 50 tr:-nclllcen~
Alkali silicate glass 2 ~
12 Apalitc glass ceramic 1020/1 50 870 542 8.0 milky, < 100 ~
(13) .. 50 translucent Alkali silicate glass 8 3 Apalite glass ceramic Illû()/1 40 910 552 8.8 very < 100 (C) .. 60 translucent Alkali silicate glass S
14 Apalite glass ceramic 1050/1 70 850 539 8.7 slightly milky, < 100 (D) ~ 30 slightly opal, Alkali silicate glass 6 Ir,~ r"~
Claims (24)
1. Alkali silicate glass, which contains the following components:
Component Wt. %
SiO2 55.0 to 71.0 Al2O3 5.0 to 16.0 B2O3 0.2 to 10.0 K2O 4.5 to 10.0 Na2O 3.0 to 14.0 TiO2 + ZRO2 0.2 to 5.0
Component Wt. %
SiO2 55.0 to 71.0 Al2O3 5.0 to 16.0 B2O3 0.2 to 10.0 K2O 4.5 to 10.0 Na2O 3.0 to 14.0 TiO2 + ZRO2 0.2 to 5.0
2. Glass according to claim 1, which additionally contains at least one of the following components:
Component Wt. %
CaO 0 to 3.0 F 0 to 3.0 P2O5 0 to 0.6 Li2O 0 to 4.0 BaO 0 to 5.0 ZnO 0 to 4.0 CeO2 0 to 2.0
Component Wt. %
CaO 0 to 3.0 F 0 to 3.0 P2O5 0 to 0.6 Li2O 0 to 4.0 BaO 0 to 5.0 ZnO 0 to 4.0 CeO2 0 to 2.0
3. Glass according to claim 1 or 2, wherein quantities of some components, independently of one another, are as follows:
Component Wt. %
SiO2 60.0 to 65.0 Ai2O3 6.0 to 10.0 B2O3 0.5 to 8.1 K2O 5.5 to 9.0 Na2O 3.5 to 10.0 CaO 0.5 to 3.0 F 0.2 to 2.0
Component Wt. %
SiO2 60.0 to 65.0 Ai2O3 6.0 to 10.0 B2O3 0.5 to 8.1 K2O 5.5 to 9.0 Na2O 3.5 to 10.0 CaO 0.5 to 3.0 F 0.2 to 2.0
4. Glass according to claim 2 or 3 wherein the quantities of some components, independently of one another, are as follows:
Component Wt.%
SiO2 61.0 to 64.0 Al2O3 7.0 to 9.0 B2O3 0.5 to 4.0 Na2O 7.0 to 9.0 CaO 0.5 to 1.5 F 1.0 to 2.0 Li2O 0 to 3.0 BaO 1.5 to 3.5 ZnO 2.0 to 3.5
Component Wt.%
SiO2 61.0 to 64.0 Al2O3 7.0 to 9.0 B2O3 0.5 to 4.0 Na2O 7.0 to 9.0 CaO 0.5 to 1.5 F 1.0 to 2.0 Li2O 0 to 3.0 BaO 1.5 to 3.5 ZnO 2.0 to 3.5
5. Glass according to any one of claims 1 to 4, which does not crystallise during a heat treatment at temperatures from 600°C to 1000°C for one minute to 2 hours.
6. Glass according to any one of claims 1 to 5, which has a sintering temperature of 650°C to 1150°C.
7. Glass according to any one of claims 1 to 5, which has a sintering temperature of 700°C to 1050°C.
8. Dental material, which contains the glass according to any one of claims 1 to 7.
9. Dental material according to claim 8, which additionally captains an apatite glass ceramic.
10. Dental material comprising an apatite glass ceramic and an alkali silicate glass, the alkali silicate glass comprising:
Component Wt.%
SiO2 55.0 to 71.0 Al2O3 5.0 to 16.0 B2O3 0.2 to 10.0 K2O 4.5 to 10.0 Na2O 3.0 to 14.0
Component Wt.%
SiO2 55.0 to 71.0 Al2O3 5.0 to 16.0 B2O3 0.2 to 10.0 K2O 4.5 to 10.0 Na2O 3.0 to 14.0
11. Dental material according to claim 9 or 10, wherein the apatite glass ceramic contains CaO, P2O5 and F in a molar ratio of:
CaO:P2O5: F 1: 0.020 to 1.5: 0.03 to 4.2 and contains apatite crystals as the main crystal phase.
CaO:P2O5: F 1: 0.020 to 1.5: 0.03 to 4.2 and contains apatite crystals as the main crystal phase.
12. Dental material according to any one of claims 9 to 11 wherein the apatite glass ceramic contains at least one of the following components:
Component Wt.%
SiO2 45.0 to 70.0 Al2O3 5.0 to 22.0 P2O5 0.5 to 6.5 K2O 3.0 to 8.5 Na2O 4.0 to 13.0 CaO 1.5 to 11.0 F 0.1 to 2.5 and contains apatite crystals as the main crystal phase.
Component Wt.%
SiO2 45.0 to 70.0 Al2O3 5.0 to 22.0 P2O5 0.5 to 6.5 K2O 3.0 to 8.5 Na2O 4.0 to 13.0 CaO 1.5 to 11.0 F 0.1 to 2.5 and contains apatite crystals as the main crystal phase.
13. Dental material according to claim 12 wherein the apatite glass ceramic additionally contains at least one of the following components:
Component Wt.%
B2O3 0 to 8.0 La2O3 0 to 5.0 Li2O 0 to 5.0 BaO 0 to 5.0 MgO 0 to 5.0 ZnO 0 to 5.0 SrO 0 to 7.0 TiO2 0 to 4.0 ZrO2 0 to 4.0 CeO2 0 to 3.0
Component Wt.%
B2O3 0 to 8.0 La2O3 0 to 5.0 Li2O 0 to 5.0 BaO 0 to 5.0 MgO 0 to 5.0 ZnO 0 to 5.0 SrO 0 to 7.0 TiO2 0 to 4.0 ZrO2 0 to 4.0 CeO2 0 to 3.0
14. Dental material according to any one of claims 8 to 13 which has a linear thermal expansion coefficient of 5.5 to 12.5 x 10-6K-1, measured in the temperature range of from 100 to 400°C.
15. Use of the dental material according to any one of claims 8 to 14 for coating a substrate.
16. Use of the dental material according to any one of claims 8 to 14 for coating a dental restoration.
17. Use according to claim 15, wherein a substrate based on ceramic or glass ceramic material is employed.
18. Use according to claim 15 wherein a substrate based on lithium disilicate glass ceramic is employed.
19. Use according to claim 18, wherein the lithium disilicate glass ceramic contains the following components:
Component Wt.%
SiO2 57.0 to 80.0 Al2O3 0 to 5.0 La2O3 0.1 to 6.0 MgO 0 to 5.0 ZnO 0 to 8.0 K2O 0 to 13.5 Li2O 11.0 to 19.0 P2O5 0 to 11.0 with the proviso that (a) Al2O3 + La2O3 is 0.1 to 7.0 wt.% and (b) MgO + ZnO is 0.1 to 9.0 wt.%.
Component Wt.%
SiO2 57.0 to 80.0 Al2O3 0 to 5.0 La2O3 0.1 to 6.0 MgO 0 to 5.0 ZnO 0 to 8.0 K2O 0 to 13.5 Li2O 11.0 to 19.0 P2O5 0 to 11.0 with the proviso that (a) Al2O3 + La2O3 is 0.1 to 7.0 wt.% and (b) MgO + ZnO is 0.1 to 9.0 wt.%.
20. Use according to any one of claims 15 to 19 wherein the dental material is applied to the substrate and sintered at temperatures of 650°C to 1150°C.
21. A shaped dental product, which contains the alkali silicate glass according to any one of claims 1 to 7 or the dental material according to any one of claims 8 to 14.
22. Shaped dental product according to claim 21, which is a dental restoration.
23. Shaped dental product according to claim 21 or 22, which has a core based on ceramic or glass ceramic material and a coating applied thereto containing the alkali silicate glass.
24. Shaped dental product according to claim 23, wherein the glass ceramic material is a lithium disilicate glass ceramic.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19725552A DE19725552A1 (en) | 1997-06-12 | 1997-06-12 | Alkali silicate glass |
| DE19725552.3 | 1997-06-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2239861A1 CA2239861A1 (en) | 1998-12-12 |
| CA2239861C true CA2239861C (en) | 2002-11-12 |
Family
ID=7832716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002239861A Expired - Fee Related CA2239861C (en) | 1997-06-12 | 1998-06-08 | Alkali silicate glass |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0885606B1 (en) |
| JP (1) | JP2983961B2 (en) |
| AT (1) | ATE245964T1 (en) |
| CA (1) | CA2239861C (en) |
| DE (2) | DE19725552A1 (en) |
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| DE19750794A1 (en) * | 1997-11-10 | 1999-06-17 | Ivoclar Ag | Process for the preparation of shaped translucent lithium disilicate glass-ceramic products |
| US6420288B2 (en) | 1997-11-10 | 2002-07-16 | Ivoclar Ag | Process for the preparation of shaped translucent lithium disilicate glass ceramic products |
| EP0962213B1 (en) * | 1998-05-29 | 2006-10-25 | Tokuyama Corporation | Dental porcelain |
| JP4716633B2 (en) * | 1999-07-02 | 2011-07-06 | ジェネリック／ペントロン インコーポレイテッド | Porcelain composition for low expansion all porcelain cores and alloys |
| DE19939771B4 (en) * | 1999-08-21 | 2004-04-15 | Schott Glas | Process for refining glass melts |
| WO2001050464A1 (en) * | 2000-01-05 | 2001-07-12 | Schott Glass Technologies, Inc. | Glass substrates for magnetic media and magnetic media based on such glass substrates |
| DE10031430A1 (en) * | 2000-06-28 | 2002-01-17 | Ivoclar Vivadent Ag | Deep-sintered apatite glass-ceramic |
| DE10031431B4 (en) * | 2000-06-28 | 2008-03-13 | Ivoclar Vivadent Ag | Deep-sintering potassium-zinc-silicate glass and its use |
| JP2002087896A (en) * | 2000-09-12 | 2002-03-27 | Mitsubishi Heavy Ind Ltd | Self-repairing high heat resistant and oxidation resistant coating film, and laminated body |
| DE10133963B4 (en) * | 2001-07-17 | 2006-12-28 | Schott Ag | Boroalkali silicate glass and its uses |
| EP1396237A1 (en) * | 2002-09-05 | 2004-03-10 | Elephant Dental B.V. | Strengthened ceramic restoration |
| DE10340597B4 (en) * | 2003-09-01 | 2007-11-08 | Ivoclar Vivadent Ag | Translucent and radio-opaque glass ceramics, process for their preparation and their use |
| JP2007516932A (en) | 2003-12-30 | 2007-06-28 | コーニング インコーポレイテッド | High strain point glass |
| DE102004010138B4 (en) * | 2004-02-27 | 2006-04-06 | Heraeus Kulzer Gmbh | Reinforced, pressable ceramic compositions for dental purposes |
| DE102004013455B3 (en) * | 2004-03-18 | 2005-09-08 | Ivoclar Vivadent Ag | Apatite glass-ceramic useful for making dental materials comprises a glass phase and a phosphate- and fluorine-free silicate-based oxyapatite phase |
| DE102005026269A1 (en) * | 2005-06-08 | 2006-12-14 | Ivoclar Vivadent Ag | Dental glass-ceramics |
| EP1905412B1 (en) * | 2006-09-29 | 2011-05-11 | Ivoclar Vivadent AG | Glass for dental uses |
| DE102009008954B4 (en) | 2009-02-13 | 2010-12-23 | Schott Ag | X-ray opaque barium-free glass and its use |
| DE102009008953B4 (en) | 2009-02-13 | 2010-12-30 | Schott Ag | X-ray opaque barium-free glass and its use |
| DE102009008951B4 (en) | 2009-02-13 | 2011-01-20 | Schott Ag | X-ray opaque barium-free glass and its use |
| JP4559523B2 (en) | 2009-02-24 | 2010-10-06 | 株式会社オハラ | Glass substrate for information recording medium and manufacturing method thereof |
| DE102010007796B3 (en) | 2010-02-12 | 2011-04-14 | Schott Ag | X-ray opaque barium-free glass and its use |
| ES2581452T3 (en) | 2010-04-16 | 2016-09-05 | Ivoclar Vivadent Ag | Vitroceramic glass and lithium silicate glass with transition metal oxide |
| DE102010035545A1 (en) | 2010-08-24 | 2012-03-01 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Veneering ceramics for dental restorations made of yttrium-stabilized zirconium dioxide and methods for their application |
| DE102011084501B3 (en) * | 2011-10-14 | 2013-03-21 | Schott Ag | X-ray opaque barium-free glass and its use |
| CN104108872B (en) * | 2013-04-18 | 2019-09-17 | 成都光明光电股份有限公司 | Environmental protection optical glass, gas preform, optical element and optical instrument |
| AU2015285456B2 (en) | 2014-06-30 | 2018-08-02 | Gc Corporation | Fluoroaluminosilicate glass powder |
| CN105936588A (en) | 2015-02-28 | 2016-09-14 | 肖特玻璃科技(苏州)有限公司 | Glass ceramics capable of being mechanically processed and chemically tempered |
| US10301212B2 (en) | 2016-07-29 | 2019-05-28 | Schott Ag | Radiopaque glass and uses thereof |
| US11136260B2 (en) | 2016-07-29 | 2021-10-05 | Schott Ag | Radiopaque glass and use thereof |
| JP7025427B2 (en) * | 2016-11-30 | 2022-02-24 | コーニング インコーポレイテッド | Fusion moldable automotive glass compositions, articles, and laminates |
| JP7129782B2 (en) * | 2018-01-26 | 2022-09-02 | 株式会社松風 | Low-melting-point glass composition with excellent water resistance |
| DE102018102301B4 (en) | 2018-02-01 | 2019-08-14 | Schott Ag | X-ray opaque glass and its use |
| DE102018010246A1 (en) | 2018-02-01 | 2019-08-01 | Schott Ag | X-ray opaque glass and its use |
| EP3696150A1 (en) | 2019-02-14 | 2020-08-19 | Ivoclar Vivadent AG | Fluorescent glass ceramics and glasses containing europium |
| EP3696149A1 (en) | 2019-02-14 | 2020-08-19 | Ivoclar Vivadent AG | Fluorescent glass ceramics and glasses containing cerium and tin |
| CN110699685A (en) * | 2019-09-05 | 2020-01-17 | 华庚新材料科技(嘉兴)有限公司 | Method for producing composite material |
| CN110592578A (en) * | 2019-09-05 | 2019-12-20 | 华庚新材料科技(嘉兴)有限公司 | Composite material |
| CN114853337B (en) * | 2022-06-22 | 2023-08-25 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element, and optical instrument |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4249946A (en) * | 1979-11-02 | 1981-02-10 | Corning Glass Works | Detergent-durable glasses |
| EP0240643A1 (en) * | 1986-04-11 | 1987-10-14 | Tyszblat Sadoun, Michèle | Method for producing dental prosthesis |
| JPH01212248A (en) * | 1988-02-20 | 1989-08-25 | Nippon Electric Glass Co Ltd | Glaze composition for artificial tooth |
| US5232878A (en) * | 1989-06-30 | 1993-08-03 | Hoya Corporation | Process for producing inorganic biomaterial |
| DE4428839C2 (en) * | 1994-08-01 | 1997-01-23 | Ivoclar Ag | Alkali-zinc-silicate glass-ceramics and glasses and process for producing the glass-ceramics |
| ATE186286T1 (en) * | 1996-09-05 | 1999-11-15 | Ivoclar Ag | SINTERABLE LITHIUM DISILICATE GLASS CERAMIC |
-
1997
- 1997-06-12 DE DE19725552A patent/DE19725552A1/en not_active Ceased
-
1998
- 1998-05-28 DE DE59809132T patent/DE59809132D1/en not_active Expired - Lifetime
- 1998-05-28 EP EP98250188A patent/EP0885606B1/en not_active Expired - Lifetime
- 1998-05-28 AT AT98250188T patent/ATE245964T1/en not_active IP Right Cessation
- 1998-06-08 CA CA002239861A patent/CA2239861C/en not_active Expired - Fee Related
- 1998-06-12 JP JP10165739A patent/JP2983961B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE59809132D1 (en) | 2003-09-04 |
| EP0885606B1 (en) | 2003-07-30 |
| DE19725552A1 (en) | 1998-12-24 |
| ATE245964T1 (en) | 2003-08-15 |
| EP0885606A2 (en) | 1998-12-23 |
| JPH1121145A (en) | 1999-01-26 |
| EP0885606A3 (en) | 1999-07-28 |
| CA2239861A1 (en) | 1998-12-12 |
| JP2983961B2 (en) | 1999-11-29 |
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