CN107235628B - Glass composition and preparation method and application thereof - Google Patents

Glass composition and preparation method and application thereof Download PDF

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CN107235628B
CN107235628B CN201610186669.3A CN201610186669A CN107235628B CN 107235628 B CN107235628 B CN 107235628B CN 201610186669 A CN201610186669 A CN 201610186669A CN 107235628 B CN107235628 B CN 107235628B
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glass composition
zirconia
glass
porcelain
bao
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CN107235628A (en
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彭练
朱庆山
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • 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
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/836—Glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials

Abstract

The invention provides a glass composition, a preparation method and an application thereof, wherein the glass composition is mainly prepared from the following components in percentage by mol: 0 to 19% SiO2、41％～70％B2O3And 20-40% of BaO. The glass composition has a thermal expansion coefficient of 9.5 × 10‑6℃‑1～10.8×10‑6℃‑1When the glass composition is used as a bonding ceramic, the glass and the zirconia are subjected to chemical reaction at the interface to form BaZrO after the zirconia coated with the glass composition is subjected to heat preservation at 800-1100 ℃ for 1-30 min3The crystal enables the glass and the zirconia to generate chemical combination at the interface, and the interface combination strength between the facing porcelain and the zirconia substrate is improved to be more than 40 MPa.

Description

Glass composition and preparation method and application thereof
Technical Field
The invention belongs to the field of biological materials, and relates to a glass composition, and a preparation method and application thereof.
Background
Teeth are human body vulnerable tissues, and if large-area defects of teeth are caused due to lesions or trauma, the functions of the teeth need to be restored through the artificial crowns. Currently, the artificial dental crown is mainly classified into two types, namely a metal fused to metallic restoration (PFM) and a zirconia full ceramic restoration (PFZ). The metal ceramic crown uses metal as a substrate and the zirconia all ceramic crown uses zirconia as a substrate, both of which require the fusion of facing ceramics to provide aesthetic properties. For a long time, the metal ceramic crown has been the mainstream of dental repair materials, but the advent of CAD/CAM (computer aided design and processing) technology has led to zirconia having processing advantages that metal cannot match. The traditional metal coping is prepared by a casting method, and the preparation method is not only troublesome but also has poor precision. The CAD/CAM technology enables the zirconia inner crown to be machined, the whole process is simple and fast like machining a key, and the prepared zirconia inner crown is good in precision and high in yield, so that the zirconia inner crown is rapidly welcomed by the masses of technicians. Furthermore, the color of zirconia is closer to that of natural teeth than the color of metal, which is why zirconia all-ceramic crowns are liked by doctors and patients.
However, one of the most important problems faced by zirconia all-ceramic crowns is the peeling of the facer from the zirconia substrate. According to the report of the literature, the probability of the shedding of the facing porcelain is 15.2% after the zirconia all-porcelain crown is used for 5 years, and the probability of the shedding of the facing porcelain is 5.5% after the metal porcelain crown is used for 15 years. From the above data, it can be seen that the porcelain collapse probability of the zirconia all-ceramic crown is far higher than that of the metal porcelain crown, and the reliability is poor. The metal ceramic crown has a good clinical life because the bonding ceramic used therein can be chemically bonded to the metal substrate well. The bonding porcelain is generally located between the facing porcelain and the base material and functions to enhance the interfacial bonding strength between the facing porcelain and the base material. The bonding porcelain for the metal ceramic crown can enable the interface bonding strength between the facing porcelain and the metal substrate to reach more than 40MPa, and the value far exceeds 25MPa specified by ISO9693 for the interface bonding strength of gold porcelain. In contrast, the interface bonding strength of the zirconia and the facing porcelain is often lower than 20MPa, which is the root cause of high porcelain collapse rate of the zirconia all-porcelain crown. The reason why the interface bonding strength of the zirconium porcelain is so low is mainly because no chemical bonding is generated between the facing porcelain and the zirconia. In the case of commercially available decorative porcelain, VM9 decorative porcelain from VITA (VITA) is applied directly to a zirconia substrate, so that no chemical bonding at all occurs at the interface of the zirconia porcelain. Although the ziga corporation (Ivoclar) used a bonded porcelain (IPS e.max CAD crystall./Connect) in the preparation of the zirconia full porcelain crown, no chemical bonding occurred at all between the bonded porcelain and zirconia as seen from the photograph of the interfacial microstructure of the bonded porcelain and zirconia reported by the ziga corporation.
DE102010012453A1 discloses a low-temperature sintered glass comprising 0 to 20% by weight of silica, 4 to 25% by weight of boron oxide, 0 to 40% by weight of niobium pentoxide + tantalum pentoxide, 30 to 55% by weight of lanthanum oxide + yttrium oxide + aluminum oxide, 0 to 22% by weight of a metal oxide ((Me (II) O), (Me (I))2O)0-10 wt%, titanium oxide, tin oxide and germanium oxide 0-10 wt%. The low-temperature sintered glass has complex components, is not suitable for being used as zirconia all-ceramic crown combined ceramic, and cannot form chemical combination with zirconia.
Therefore, the development of a bonded ceramic capable of chemically bonding with zirconia is a problem to be solved in the art.
Disclosure of Invention
In view of the prior art, the present invention aims to provide a glass composition, a preparation method and an application thereof. The present invention achieves the goal of chemically bonding the glass composition to the zirconia at the interface by providing a glass composition that chemically reacts with the zirconia. When the glass composition is used as a zirconia bonded porcelain, the interface bonding strength of the facing porcelain and zirconia can be remarkably improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a method of forming BaZrO by chemical reaction with zirconia3The glass composition used as the zirconia bonded porcelain comprises the following components in percentage by mol:
SiO 20～19％
B2O341％～70％
BaO 20％～40％。
in the glass composition of the present invention, SiO2Is 0 to 19%, for example 0%, 1%, 3%, 5%, 7%, 9%, 10%, 12%, 14%, 16%, 18% or 19%.
In the glass composition of the present invention, B2O3Is 41% to 70%, for example 42%, 44%, 45%, 47%, 49%, 50%, 53%, 55%, 58%, 60%, 62%, 64%, 66%, 68% or 69%.
In the glass composition of the present invention, BaO is contained in an amount of 20% to 40%, for example, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 35%, or 38%.
Preferably, the glass composition comprises the following components in percentage by mole:
SiO26％～10％
B2O350％～70％
BaO 20％～30％。
preferably, the glass composition of the present invention may further comprise an alkali metal oxide Li2O、Na2O or K2Any one or a combination of at least two of O in a total mole percent content of no more than 10%, e.g., 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.8%, 0.5%, 0.1%, 0.8%, etc.
Preferably, the glass composition of the present invention may further comprise any one or a combination of at least two of the alkaline earth metal oxides MgO, CaO, or SrO in a total mole percent content of no more than 10%, e.g., 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.8%, 0.5%, 0.1%, or 0%, etc.
Preferably, the glass composition of the present invention may further comprise Al2O3And its mole percentage content is not more than 10%, for example 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.8%, 0.5%, 0.1% or 0%, etc.
In order to improve the efficiency of denture fabrication and follow the conventional porcelain process, the bonded porcelain glass needs to undergo interfacial chemical reaction with zirconia in the shortest possible time (e.g., 1min to 30min) in the conventional porcelain temperature range (e.g., 800 ℃ to 1100 ℃) to achieve interfacial chemical bonding. In the present invention, BaO is BaCO3Is introduced in the form that BaO as an active component in the glass can react with zirconia to generate BaZrO3. In order to ensure rapid occurrence of the interfacial reaction, the glass composition of the present invention should have a high content of BaO, because increasing the concentration of BaO is advantageous for accelerating the reaction speed. However, if the content of BaO is not so high, the better, and if the content of BaO is too high, a stable glass cannot be formed. In the invention, the mol percentage of BaO is selected to be 20-40%, and when the mol percentage of BaO is lower than 20%, the BaO can not chemically react with zirconia at an interface. Furthermore, the reaction also occurs more readily when the glass composition has a lower viscosity at the porcelain temperature, since a low viscosity means thatThe resistance to the reaction is relatively small. In order to ensure that the glass composition has lower viscosity at the porcelain baking temperature, the invention designs a high-B glass2O3Low content, low SiO2Glass in an amount of less than one percent. B is2O3And SiO2Both glasses form oxides and the higher the borosilicate ratio the lower the viscosity of the glass. But the borosilicate ratio is not too high, otherwise, the viscosity of the combined porcelain glass at the porcelain baking temperature is very low, so that the fluidity is generated, and the manufacture of the later-stage decorative porcelain is influenced. In the present invention, SiO2The mole percentage of B is 0-19 percent2O3The mol percentage content of the raw materials is 41 to 70 percent. The coefficient of thermal expansion of the bonded porcelain glass of the present invention is preferably set to the coefficient of thermal expansion of the facing porcelain (9.5X 10)-6℃-1) And coefficient of thermal expansion of zirconia (10.8X 10)-6℃-1) Besides the interface chemical reaction, BaO can also improve the thermal expansion coefficient of the combined porcelain glass. Further, alkali metal oxide Li2O、Na2O、K2O and the alkaline earth metal oxides MgO, CaO, SrO may also be added as additional components to increase the coefficient of thermal expansion of the bonded porcelain glass. In the adjustment of the viscosity of the bonded porcelain glass, Al may be added2O3To adjust the viscosity of the glass. Generated BaZrO3The crystal has a thermal expansion coefficient of 8.7X 10-6℃-1The coefficient of thermal expansion of the ceramic glass is relatively close to that of the combined porcelain glass and that of the zirconia, but the BaZrO is reduced to the maximum extent3Thermal stress formed at the interface of the crystal, the bonded ceramic and the zirconia, BaZrO3The size of the crystals should not be too large. In the invention, BaZrO is prepared by matching the components and controlling the dosage of the components3The length of the crystal is not more than 6 μm, and the width is not more than 3 μm.
Preferably, the glass composition of the present invention has a coefficient of thermal expansion of 9.5X 10 between room temperature and 500 deg.C-6℃-1～10.8×10-6℃-1E.g. 9.5 x 10-6℃-1、9.6×10-6℃-1、9.8×10-6℃-1、10.0×10-6℃-1、10.2×10-6℃-1、10.4×10-6℃-1、10.6×10-6℃-1Or 10.8X 10-6℃-1。
In another aspect, the present invention provides a method of making the glass composition, the method comprising the steps of:
(1) crushing raw material components of the glass composition, fully mixing and drying;
(2) and (2) placing the mixture obtained in the step (1) into a reactor, heating and melting, and water-quenching the glass melt to obtain the glass composition.
In the present invention, the raw material components are components used in the preparation of the glass composition, for example, for the preparation of a composition containing SiO2、B2O3And BaO, the raw material component may be SiO2、B2O3And BaCO3。
In the preparation method, the ball milling in the step (1) is carried out in a planetary ball mill.
Preferably, the ball milling pulverization of the step (1) is to 200 mesh to 300 mesh, for example, 210 mesh, 220 mesh, 230 mesh, 240 mesh, 250 mesh, 260 mesh, 270 mesh, 280 mesh or 290 mesh.
Preferably, the reactor in step (2) can be any reactor capable of being used for completing the melting process, and can be a platinum alloy crucible or a corundum crucible suitable for a small amount of sample experiments, and a suitable reactor can be selected according to needs in industrial production.
Preferably, the temperature increase in step (2) is to 1100 ℃ to 1300 ℃, such as 1100 ℃, 1110 ℃, 1130 ℃, 1150 ℃, 1180 ℃, 1200 ℃, 1220 ℃, 1240 ℃, 1260 ℃, 1280 ℃ or 1300 ℃.
Preferably, the melting time in step (2) is 2 to 5 hours, such as 2.2 hours, 2.5 hours, 2.8 hours, 3 hours, 3.4 hours, 3.8 hours, 4 hours, 4.2 hours, 4.5 hours, 4.8 hours or 5 hours.
Preferably, as a preferred embodiment of the present invention, the method for preparing the glass composition of the present invention comprises the following steps:
(1) crushing raw material components of the glass composition in a planetary ball mill to 200-300 meshes, fully mixing and drying;
(2) and (2) placing the mixture obtained in the step (1) in a reactor, heating to 1100-1300 ℃, melting for 2-5 hours, and water-quenching the glass melt to obtain the glass composition.
In another aspect, the present invention provides a zirconia all-ceramic dental crown comprising the glass composition according to the first aspect of the present invention coated on a zirconia surface as a bonding ceramic. Namely, the glass composition is ball-milled and crushed into powder of 200-300 meshes, and then the powder is coated on the surface of zirconia to be used as bonding porcelain.
According to the layered plastic-stacking process of the dental veneer porcelain, the glass powder is uniformly mixed with deionized water, then the mixture is uniformly coated on the surface of a zirconia substrate, and a thin layer is coated. Then according to the conventional porcelain baking procedure, the zirconia coated with the glass powder is subjected to heat preservation for 1min to 30min at 800 ℃ to 1100 ℃ such as 810 ℃, 830 ℃, 850 ℃, 880 ℃, 900 ℃, 920 ℃, 950 ℃, 980 ℃, 1000 ℃, 1020 ℃, 1040 ℃, 1060 ℃, 1080 ℃ or 1100 ℃, such as 2min, 5min, 8min, 10min, 13min, 15min, 18min, 20min, 22min, 25min or 28min, then the glass powder can be sintered into a layer of compact transparent porcelain, and the glass and the zirconia are subjected to chemical reaction at an interface to form BaZrO 23Crystal, so that the aim of generating chemical combination between the zirconia and the combined porcelain at the interface is fulfilled. On the basis of the combined porcelain, the facing porcelain is continuously layered and piled to form the zirconia all-porcelain crown with high interface bonding strength.
When the glass composition is used as a combined ceramic, the glass and the zirconium oxide can generate chemical reaction at the interface to form BaZrO after the zirconium oxide coated with the glass composition is kept at the temperature of 800-1100 ℃ for 1-30 min3The crystal enables the glass and the zirconia to generate chemical combination at the interface, and the interface combination strength between the facing porcelain and the zirconia substrate is improved to be more than 40 MPa. And the glassWhen the glass composition is used in combination with porcelain, it remains amorphous after being fired by a porcelain firing procedure, without significantly altering the existing porcelain firing process.
In another aspect, the invention provides the use of the glass composition for the preparation of an artificial dental crown material. The glass compositions of the present invention are suitable for use in the manufacture of artificial dental crown materials, such as zirconia full-ceramic crowns.
Compared with the prior art, the invention has the following beneficial effects:
the invention applies SiO with the following components of 0-19% by mol percentage2、41％～70％B2O320 to 40 percent of BaO, and the coefficient of thermal expansion of the glass composition from room temperature to 500 ℃ can reach 9.5 multiplied by 10-6℃-1～10.8×10-6℃-1When the glass composition is used as a bonding ceramic, the glass and the zirconia are subjected to chemical reaction at the interface to form BaZrO after the zirconia coated with the glass composition is subjected to heat preservation at 800-1100 ℃ for 1-30 min3The crystal enables the glass and the zirconia to generate chemical combination at the interface, and the interface combination strength between the facing porcelain and the zirconia substrate is improved to be more than 40 MPa. And when the glass composition is used as combined porcelain, after being fired by a porcelain firing procedure, the glass composition is still amorphous, and the existing porcelain firing process cannot be obviously changed.
Drawings
FIG. 1 is an interface microstructure of zirconia coated with the glass composition of example 1 after incubation at 1000 ℃ for 10 min;
FIG. 2 is an interface microstructure of zirconia coated with the glass composition of example 3 after 1min incubation at 1100 deg.C;
FIG. 3 is an XRD pattern of the glass composition of example 3 after incubation at 820 ℃ for 30 min;
fig. 4 is a graph showing thermal expansion per unit length of glass composition samples corresponding to examples 1, 2 and 4.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Examples 1 to 5 and comparative examples 1 to 4
According to the mole percentage of each component in each example listed in table 1, a certain amount of analytically pure SiO was weighed out separately2、B2O3And BaCO3Fully mixing and grinding by a planetary ball mill respectively, and taking out and drying; respectively putting the powder into a platinum alloy crucible, putting the platinum alloy crucible into a box-type resistance furnace, heating to 1100-1300 ℃ in air atmosphere, keeping the temperature for 2-5 hours, and then performing water quenching to obtain the glass composition.
TABLE 1
Figure GDA0002280292450000081
Figure GDA0002280292450000091
Example 6
After the glass composition of example 1 and the glass composition of example 3 were ball-milled and pulverized into 200-300 mesh powders, the glass composition powder of example 1 and the glass composition powder of example 3 were respectively and uniformly blended with water, and then respectively coated on the surface of a zirconia substrate, and only a thin layer was coated. The zirconia coated with the glass composition powder of example 1 and the glass composition powder of example 3, respectively, was placed in a porcelain oven and porcelain baked to a target temperature according to the conventional veneer porcelain baking procedure. The zirconia coated with the glass composition powder of example 1 was held at 1000 ℃ for 10min, while the zirconia coated with the glass composition powder of example 3 was held at 1100 ℃ for 1 min. After the sample is cooled to room temperature, the sample is taken out, and the microstructure of the cross sections of the two samples is observed by grinding and polishing the cross sections of the sample, as shown in fig. 1 and 2.
It is clearly observed from FIGS. 1 and 2 that the glass compositions of examples 1 and 3 chemically react with zirconia at the interface, respectively, and the results of the point spectra show that the reactionThe corresponding phase is BaZrO3. BaZrO formed3The length is not more than 6 μm and the width is not more than 3 μm.
The same tests were carried out on the glass compositions obtained in the other examples, which also demonstrated that the glass compositions reacted chemically with zirconia at the interface, and the results of the point spectroscopy indicated that the reaction phase was BaZrO3. BaZrO formed3The length is not more than 6 μm and the width is not more than 3 μm. Comparative example 2 failed to form a stable glass and thus the above test could not be performed. Comparative example 4 due to SiO2Is 0 and B2O380% by mole, the viscosity of the glass at 800 ℃ is so small that the fluidity is very good, which is very disadvantageous for the production of the post-facing porcelain, and therefore the above-mentioned interfacial observation is not necessary. The same test was conducted on the glass compositions obtained in comparative examples 1 and 3, and the results showed that the glass compositions of comparative examples 1 and 3 did not chemically react with zirconia at the interface.
Example 7
The facing porcelain/zirconia double-layer porcelain was prepared according to the test method for interface bonding strength of gold porcelain described in ISO9693 to test the change in the interface bonding strength between the facing porcelain and zirconia before and after coating the bonding porcelain. VM9 facing from other company was used. Firstly, VM 9/zirconia double-layer porcelain is prepared, and the interface bonding strength of the double-layer porcelain is 21.3 +/-2.3 MPa through testing. A double layer porcelain is then prepared after the addition of the bonding porcelain (i.e. the glass composition according to the invention): firstly, the surfaces of zirconia are respectively coated with the glass composition powder of examples 1-5 or comparative examples 1 and 3, then the zirconia coated with the glass composition powder is respectively placed in a porcelain oven for porcelain baking, and after heat preservation is carried out for 1 min-30 min at 800 ℃ -1100 ℃, the glass composition is sintered into transparent combined porcelain. After the combined porcelain is fired, VM9 decorative porcelain is piled and molded on the surface of the combined porcelain and porcelain is baked, and the preparation of VM 9/combined porcelain/zirconia double-layer porcelain is completed. The results of the interface bonding strength of the double-layer porcelain with the bonding porcelain added are shown in table 2.
TABLE 2
Figure GDA0002280292450000101
As can be seen from the results in Table 2, the interface bonding strength of the double-sided porcelain is remarkably improved from 21.3. + -. 2.3MPa to 41.0. + -. 1.0MPa to 62.1. + -. 1.5MPa after the addition of the bonding porcelain glass of the present invention (examples 1 to 5), and it can be seen from the comparison between the examples and the comparative examples that when the BaO content is too small (comparative example 1) or when the SiO in the glass composition is too small2And B2O3The interface bonding strength was not significantly improved when the contents of (c) were close to (comparative example 3).
Example 8
The glass composition powders of examples 1-5 were each subjected to conventional facing porcelain-firing procedures at 820-920 ℃ for 30min and then removed, and they were all found to have sintered into dense transparent glass. The glasses were pulverized and then subjected to XRD (X-ray diffraction analysis) measurement. The XRD test results of the glass composition of example 3 after incubation at 820 ℃ for 30min are shown in FIG. 3.
The results in FIG. 3 show that the glass composition of example 3 remains amorphous after firing through the porcelain program and does not precipitate any crystalline phases.
The glass compositions of examples 1-2 and 4-5 were also amorphous after the porcelain firing procedure, and did not precipitate any crystalline phases.
Example 9
Corresponding glass samples having dimensions of 4mm × 4mm × 12mm were prepared for the determination of the thermal expansion coefficient according to the glass compositions of example 1, example 2 and example 4, respectively. The thermal expansion coefficient of the above samples was measured using a high temperature thermal expansion instrument (L75/1550, LINSEIS, Germany), and the results are shown in FIG. 4.
FIG. 4 shows the thermal expansion curves per unit length for the three different glass samples, with the coefficient of thermal expansion of the glass composition sample of example 2 being 9.5X 10 measured over a temperature range from room temperature to 500 deg.C-6℃-1The sample of the glass composition of example 1 had a coefficient of thermal expansion of 10.2X 10-6℃-1The sample of the glass composition of example 4 had a coefficient of thermal expansion of 10.8X 10-6℃-1。
The thermal expansion coefficients of the glass composition samples of example 3 and example 5 were measured in the same manner, and found to be 10.6X 10, respectively-6℃-1And 10.4X 10-6 deg.C-1。
The applicant states that the present invention is illustrated by the above examples of the glass composition of the present invention and the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (15)

1. BaZrO generated by chemical reaction with zirconia3The glass composition used as the zirconia bonded porcelain is characterized by comprising the following components in percentage by mol:
SiO21～19％
B2O341％～70％
BaO 20％～40％。
2. the glass composition according to claim 1, wherein the glass composition comprises the following components in mole percent:
SiO26％～10％
B2O350％～70％
BaO 20％～30％。
3. the glass composition of claim 1 or 2, wherein the glass composition further comprises an alkali metal oxide Li2O、Na2O or K2And any one or combination of at least two of O, wherein the molar percentage content of O is not more than 10%.
4. The glass composition of claim 1, further comprising any one or a combination of at least two of the alkaline earth oxides MgO, CaO, or SrO in a molar percentage of no more than 10%.
5. The glass composition of claim 1, wherein the glass composition further comprises Al2O3The mol percentage content of the compound does not exceed 10 percent.
6. The glass composition of claim 1, wherein the glass composition has a coefficient of thermal expansion from room temperature to 500 ℃ of 9.5 x 10-6℃-1～10.8×10-6℃-1。
7. The glass composition of claim 1, wherein the BaO is BaCO in the glass composition3Introduced as a raw material component.
8. A method for producing a glass composition according to any one of claims 1 to 7, characterised in that it comprises the following steps:
(1) crushing raw material components of the glass composition, fully mixing and drying;
(2) and (2) placing the mixture obtained in the step (1) into a reactor, heating and melting, and water-quenching the glass melt to obtain the glass composition.
9. The method according to claim 8, wherein the pulverization of step (1) is carried out in a planetary ball mill.
10. The method according to claim 8, wherein the pulverization of the step (1) is to 200 to 300 mesh.
11. The method according to claim 8, wherein the temperature rise in the step (2) is a temperature rise to 1100 ℃ to 1300 ℃.
12. The method according to claim 8, wherein the melting time in the step (2) is 2 to 5 hours.
13. The method for preparing according to claim 8, characterized in that it comprises the following steps:
(1) crushing raw material components of the glass composition in a planetary ball mill to 200-300 meshes, fully mixing and drying;
(2) and (2) placing the mixture obtained in the step (1) in a reactor, heating to 1100-1300 ℃, melting for 2-5 hours, and water-quenching the glass melt to obtain the glass composition.
14. A zirconia all-ceramic dental crown comprising the glass composition of any of claims 1 to 7 coated on a zirconia surface as a bonding ceramic.
15. Use of a glass composition according to any of claims 1 to 7 for the preparation of an artificial dental crown material.
CN201610186669.3A 2016-03-29 2016-03-29 Glass composition and preparation method and application thereof Active CN107235628B (en)

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