CN107235628A - A kind of glass composition and its preparation method and application - Google Patents
A kind of glass composition and its preparation method and application Download PDFInfo
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- CN107235628A CN107235628A CN201610186669.3A CN201610186669A CN107235628A CN 107235628 A CN107235628 A CN 107235628A CN 201610186669 A CN201610186669 A CN 201610186669A CN 107235628 A CN107235628 A CN 107235628A
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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
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
The present invention provides a kind of glass composition and its preparation method and application, and the glass composition is mainly prepared by the following component of molar content：0~19%SiO2, 41%~70%B2O3, 20%~40%BaO.The glass composition thermal coefficient of expansion is up to 9.5 × 10‑6℃‑1~10.8 × 10‑6℃‑1, the glass composition is as combination porcelain in use, being coated with the zirconium oxide of the glass composition after 800 DEG C~1100 DEG C are incubated 1min~30min, you can the glass is occurred chemical reaction in interface with zirconium oxide and forms BaZrO3Crystal so that the glass produces chemical bond with zirconium oxide in interface, makes the interface bond strength between facing porcelain and zirconium oxide substrate be promoted to more than 40MPa.
Description
Technical field
The invention belongs to technical field of biological material, it is related to a kind of glass composition and its preparation method and application.
Background technology
Tooth is human body susceptible disease tissue, if because lesion or wound cause tooth large defect, it is necessary to pass through
Artificial corona recovers the function of tooth.Current artificial corona is broadly divided into PFM (Porcelain fused to
Metal restoration, PFM) and zirconium oxide all-ceramic crown (Porcelain fused to zirconia restoration,
PFZ) two class.Metal-porcelain is titled with metal as substrate, and zirconium oxide all-ceramic crown, then using zirconium oxide as substrate, they are both needed to melt
Decoation-attaching surface porcelain is to provide aesthetic properties.For a long time, PFM is always the main flow of materials of bone tissue, but CAD/
The appearance of CAM (CAD and processing) technology causes zirconium oxide to be provided with the incomparable processed edge of metal.Pass
Hat is prepared by the method for casting in the metal of system, and this preparation method is not only troublesome but also precision is poor.And CAD/CAM
Technology make it that hat can be by machining in zirconium oxide, and whole process is simple, quick as processing key, prepares
Not only precision is good but also high yield rate for hat in zirconium oxide, therefore is welcome by numerous skilled workers rapidly.In addition, the color of zirconium oxide
Color than metal is more nearly the color of nature tooth, and this is also the reason for zirconium oxide all-ceramic crown is liked by doctor and patient.
However, the main problem that zirconium oxide all-ceramic crown faces is exactly that facing porcelain comes off from zirconium oxide substrate.Root
According to document, zirconium oxide all-ceramic crown is after using 5 years, and the probability that facing porcelain comes off is 15.2%, and PFM exists
After 15 years, the probability that facing porcelain comes off is 5.5%.As can be seen from the above data, zirconium oxide all-ceramic crown collapses porcelain probability
Significantly larger than PFM, shows very poor reliability.PFM why have good clinical life, be because
Good chemical bond can be produced for its combination porcelain used with metallic substrates.Facing porcelain and base material are usually located at reference to porcelain
Between, it is to strengthen the interface bond strength between facing porcelain and base material that it, which is acted on,.Combination porcelain energy for PFM
The interface bond strength between facing porcelain and metallic substrates is set to reach more than 40MPa, this numerical value is considerably beyond ISO9693 to gold
25MPa as defined in porcelain interface bond strength.By contrast, the interface bond strength of zirconium oxide and facing porcelain is often below 20MPa,
This exactly zirconium oxide all-ceramic crown collapses the high basic reason of porcelain rate.Cause zircon porcelain interface bond strength so it is low the reason for mainly because
Chemical bond is produced to be no between facing porcelain and zirconium oxide.By taking the facing porcelain of commercial goods as an example, the only VM9 of his company (VITA)
Facing porcelain is directly coated in zirconium oxide substrate, therefore zircon porcelain interface does not just produce chemical bond at all.Although adopted Huojia County
Company (Ivoclar) used when preparing zirconium oxide all-ceramic crown with reference to porcelain (IPS e.max CAD Crystall./
Connect), but according to adopted company of Huojia County report this combine the Interface Microstructure photo of porcelain and zirconium oxide from the point of view of, the knot
Close and just do not produce chemical bond at all between porcelain and zirconium oxide.
DE102010012453A1 discloses a kind of low-temperature sintering glass, including silica 0-20%, boron oxide 4-
25wt%, niobium pentaoxide+tantalum pentoxide 0-40wt%, lanthana+yittrium oxide+aluminum oxide 30-55%, metal oxide
((Me (II) O) 0-22wt%, (Me (I)2O) 0-10wt%, titanium oxide+tin oxide+germanium oxide 0-10wt%.The invention it is low
Warm sintered glass complicated component, and be not suitable for as zirconium oxide all-ceramic crown combination porcelain, it is impossible to zirconium oxide formation chemical bond.
Therefore, it is this area urgent need to resolve that one kind is developed in this area and can produce chemically combined combination porcelain with zirconium oxide
The problem of.
The content of the invention
For prior art, it is an object of the invention to provide a kind of glass composition and its preparation method and application.This
Invention is by providing a kind of glass composition that can be chemically reacted with zirconium oxide, so as to realize glass composition and zirconium oxide
Occurs chemically combined purpose in interface.When the glass composition is used as zirconium oxide combination porcelain, facing can be obviously improved
The interface bond strength of porcelain and zirconium oxide.
To reach this goal of the invention, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of glass composition, and the glass composition is following comprising molar content
Component：
SiO20~19%
B2O341%~70%
BaO 20%~40%.
In glass composition of the present invention, SiO2Content be 0~19%, such as 0%, 1%, 3%, 5%, 7%,
9%th, 10%, 12%, 14%, 16%, 18% or 19%.
In glass composition of the present invention, B2O3Content be 41%~70%, such as 42%, 44%, 45%,
47%th, 49%, 50%, 53%, 55%, 58%, 60%, 62%, 64%, 66%, 68% or 69%.
In glass composition of the present invention, BaO content is 20%~40%, such as 20%, 22%, 24%,
26%th, 28%, 30%, 32%, 34%, 35% or 38%.
Preferably, the glass composition includes the following component of molar content：
SiO26%~10%
B2O350%~70%
BaO 20%~30%.
Preferably, glass composition of the present invention can also include alkali metal oxide Li2O、Na2O or K2Appointing in O
Meaning it is a kind of or at least two combinations, their total moles percentage composition be no more than 10%, such as 10%, 9%, 8%, 7%,
6%th, 5%, 4%, 3%, 2%, 1%, 0.8%, 0.5%, 0.1% or 0% etc..
Preferably, glass composition of the present invention can also include appointing in alkaline earth oxide MgO, CaO or SrO
Meaning it is a kind of or at least two combinations, their total moles percentage composition be no more than 10%, such as 10%, 9%, 8%, 7%,
6%th, 5%, 4%, 3%, 2%, 1%, 0.8%, 0.5%, 0.1% or 0% etc..
Preferably, glass composition of the present invention can also include Al2O3, its molar content be no more than 10%,
Such as 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.8%, 0.5%, 0.1% or 0%.
In order to improve the producing efficiency of artificial tooth and follow traditional porcelain technique, needed with reference to porcelain glass in traditional porcelain
With time (for example 1min~30min) as short as possible and zirconium oxide interface occurs for temperature range (for example 800 DEG C~1100 DEG C)
Chemical reaction, so as to realize that surface chemistry is combined.In the present invention, BaO is with BaCO3Form introduce, BaO is as in glass
Chemical reaction generation BaZrO can occur with zirconium oxide for active component3.In order to ensure in the quick generation of interfacial reaction, the present invention
Glass composition need to have the BaO of high content because the concentration for improving BaO is conducive to accelerating reaction speed.But BaO's
Content is not that the higher the better, when BaO content is too high, just can not form stable glass.In the present invention, moles the hundred of BaO
Divide content selection 20%~40%, when BaO molar content is less than 20%, it is impossible to occur chemistry at interface with zirconium oxide
Reaction.In addition, when glass composition has relatively low viscosity at a temperature of porcelain, reaction is also easier to occur, because low viscous
Degree means that the comparison of resistance of reaction is small.In order to ensure that glass composition has relatively low viscosity, the present invention at a temperature of porcelain
Devise a kind of high B2O3Content, low SiO2The glass of content.B2O3And SiO2All it is network former, borosilicate is than more Gao Ze
The viscosity of glass is smaller.But borosilicate should not be too high than also, and otherwise the viscosity with reference to porcelain glass at a temperature of porcelain can be very low, so that
Mobility is produced, the making of later stage facing porcelain is influenceed.In the present invention, SiO2Molar content select 0~19%, B2O3
Molar content selection 41%~70%.The thermal coefficient of expansion of combination porcelain glass in the present invention is preferably in the warm of facing porcelain
The coefficient of expansion (9.5 × 10-6℃-1) and zirconium oxide thermal coefficient of expansion (10.8 × 10-6℃-1) between, BaO is except for occurring
Outside interfacial chemical reaction, the thermal coefficient of expansion with reference to porcelain glass can also be improved.In addition, alkali metal oxide Li2O、Na2O、K2O
And alkaline earth oxide MgO, CaO, SrO can also improve the thermal coefficient of expansion with reference to porcelain glass as addO-on therapy.
And in terms of combining porcelain glass viscosity regulation, Al can also be added2O3To adjust the viscosity of glass.The BaZrO of generation3Crystal
Thermal coefficient of expansion be 8.7 × 10-6℃-1, compare with the thermal coefficient of expansion of combination porcelain glass and the thermal coefficient of expansion of zirconium oxide
It is closer to, but in order to farthest reduce BaZrO3Crystal, the heat formed with reference to porcelain and zirconium oxide three in interface are answered
Power, BaZrO3The size of crystal should not be too big.In the present invention, pass through the cooperation between each composition and the consumption of each composition of control
So that BaZrO3Of length no more than 6 μm of crystal, width is no more than 3 μm.
Preferably, the thermal coefficient of expansion of glass composition of the present invention is 9.5 × 10 between room temperature~500 DEG C-6
℃-1~10.8 × 10-6℃-1, such as 9.5 × 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 10.8 × 10-6℃-1。
On the other hand, the invention provides the preparation method of the glass composition, it the described method comprises the following steps：
(1) raw material components of glass composition are crushed, be sufficiently mixed, dried；
(2) mixture for obtaining step (1) is put in reactor, heating melting, by glass melt water quenching to obtain
State glass composition.
In the present invention, the raw material components are the component used when preparing glass composition, for example in order to prepare containing
SiO2、B2O3With BaO glass composition, then its raw material components can be SiO2、B2O3And BaCO3。
In preparation method of the present invention, step (1) described ball milling is carried out in planetary ball mill.
Preferably, step (1) described ball mill grinding is is crushed to the mesh of 200 mesh~300, such as 210 mesh, 220 mesh, 230 mesh,
240 mesh, 250 mesh, 260 mesh, 270 mesh, 280 mesh or 290 mesh.
Preferably, step (2) described reactor can be any reactor that can be used in completing melting process, Ke Yiwei
The platinum alloy crucible or corundum crucible of a small amount of sample experiments are applicable, can select suitable as needed in the industrial production certainly
Reactor.
Preferably, step (2) heating is is warming up to 1100 DEG C~1300 DEG C, such as 1100 DEG C, 1110 DEG C, 1130
DEG C, 1150 DEG C, 1180 DEG C, 1200 DEG C, 1220 DEG C, 1240 DEG C, 1260 DEG C, 1280 DEG C or 1300 DEG C.
Preferably, the time of step (2) described melting be 2~5 hours, such as 2.2 hours, 2.5 hours, 2.8 hours, 3
Hour, 3.4 hours, 3.8 hours, 4 hours, 4.2 hours, 4.5 hours, 4.8 hours or 5 hours.
Preferably as the preferred technical solution of the present invention, the preparation method of glass composition of the present invention include with
Lower step：
(1) raw material components of glass composition are crushed to the mesh of 200 mesh~300 in planetary ball mill, are sufficiently mixed,
Drying；
(2) mixture for obtaining step (1) is put in reactor, is warming up to 1100 DEG C~1300 DEG C, melting 2~5 is small
When, by glass melt water quenching to obtain the glass composition.
On the other hand, the present invention provides a kind of Zirconium oxide full-porcelain hat, and the Zirconium oxide full-porcelain hat, which is included, is coated on oxygen
Change zirconium surface as the glass composition as described in the first aspect of the invention for combining porcelain.I.e. described glass composition is through ball milling powder
It is broken be the mesh of 200 mesh~300 powder after, the surface for being coated on zirconium oxide is used as with reference to porcelain.
According to the layering heap modeling technique of dentistry facing porcelain, above-mentioned glass powder and deionized water are reconciled uniformly, Ran Houjun
The surface of zirconium oxide substrate is coated in evenly, coats very thin one layer.Afterwards according to conventional porcelain program, it is coated with
The zirconium oxide of the glass powder 800 DEG C~1100 DEG C such as 810 DEG C, 830 DEG C, 850 DEG C, 880 DEG C, 900 DEG C, 920 DEG C, 950
DEG C, 980 DEG C, 1000 DEG C, 1020 DEG C, 1040 DEG C, 1060 DEG C, 1080 DEG C or 1100 DEG C, insulation 1min~30min after, for example protect
After warm 2min, 5min, 8min, 10min, 13min, 15min, 18min, 20min, 22min, 25min or 28min, you can make this
Glass powder sinters one layer of fine and close transparent porcelain into, and makes the glass that chemical reaction formation occur in interface with zirconium oxide
BaZrO3Crystal, so as to realize zirconium oxide with combining porcelain in the chemically combined purpose of interface generation.The basis of porcelain is combined herein
On, it is further continued for layering heap modeling facing porcelain, you can prepare the zirconium oxide all-ceramic crown with high interfacial bonding strength.
Glass composition of the present invention is as combination porcelain in use, being coated with the zirconium oxide of the glass composition 800
DEG C~1100 DEG C, it is incubated after 1min~30min, you can the glass is occurred chemical reaction in interface with zirconium oxide and formed
BaZrO3Crystal so that the glass produces chemical bond with zirconium oxide in interface, makes between facing porcelain and zirconium oxide substrate
Interface bond strength is promoted to more than 40MPa.And the glass composition is as combination porcelain in use, experience porcelain program is fired
Afterwards, it is still unbodied, will not substantially change existing porcelain technique.
On the other hand, the application the invention provides described glass composition in artificial corona material is prepared.This hair
Bright glass composition is suitable for manufacturing artificial corona material, and such as Zirconium oxide full-porcelain is preced with.
Relative to prior art, the invention has the advantages that：
Following 0~the 19%SiO of component of present invention application molar content2, 41%~70%B2O3, 20%~40%
BaO prepares glass composition, and the glass composition is from room temperature to 500 DEG C of thermal coefficient of expansion up to 9.5 × 10-6℃-1~
10.8×10-6℃-1, the glass composition is as combination porcelain in use, being coated with the zirconium oxide of the glass composition at 800 DEG C
After~1100 DEG C of insulation 1min~30min, you can the glass is occurred chemical reaction in interface with zirconium oxide and form BaZrO3
Crystal so that the glass produces chemical bond with zirconium oxide in interface, ties the interface between facing porcelain and zirconium oxide substrate
Strength enhancing is closed to more than 40MPa.And after the glass composition is as porcelain is combined in use, experience porcelain program fires, its
It is still unbodied, will not substantially changes existing porcelain technique.
Brief description of the drawings
Fig. 1 is to be coated with the microcosmic knot in interface after the zirconium oxide of the glass composition of embodiment 1 is incubated 10min at 1000 DEG C
Structure；
Fig. 2 is to be coated with the microcosmic knot in interface after the zirconium oxide of the glass composition of embodiment 3 is incubated 1min at 1100 DEG C
Structure；
Fig. 3 is XRD of the glass composition of embodiment 3 after 820 DEG C of insulation 30min；
Fig. 4 is the unit length thermal dilatometry of embodiment 1, embodiment 2 and the corresponding glass composition sample of embodiment 4
Figure.
Embodiment
Technical scheme is further illustrated below by embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.
Embodiment 1-5 and comparative example 1-4
The molar content of each component of each embodiment according to listed by table 1, is weighed a certain amount of analytically pure respectively
SiO2、B2O3And BaCO3, respectively with after the abundant mix grinding of planetary ball mill, take out drying；Powder is placed on platinum alloy earthenware respectively
In pot, it is placed in chamber type electric resistance furnace, is warming up to 1100 DEG C~1300 DEG C under air atmosphere, constant temperature 2~5 hours, then water quenching is obtained
Obtain glass composition.
Table 1
| SiO2 | B2O3 | BaO | |
| Embodiment 1 | 0.5 | 69.1 | 30.4 |
| Embodiment 2 | 11.2 | 68.5 | 20.3 |
| Embodiment 3 | 18.6 | 42.2 | 39.2 |
| Embodiment 4 | 18.7 | 41.3 | 40.0 |
| Embodiment 5 | 9.3 | 56.4 | 34.3 |
| Comparative example 1 | 15.2 | 69.2 | 15.6 |
| Comparative example 2 | 3.6 | 48.1 | 48.3 |
| Comparative example 3 | 32.6 | 32.6 | 34.8 |
| Comparative example 4 | 0 | 80.0 | 20.0 |
Embodiment 6
By ball mill grinding it is the mesh of 200 mesh~300 by the glass composition of embodiment 1 and the glass composition of embodiment 3
Powder after, the glass combination powder of embodiment 1 and the glass combination powder of embodiment 3 are reconciled with water respectively it is uniform,
Then it is respectively coated in the surface of zirconium oxide substrate, only coats very thin one layer.The glass composition of embodiment 1 will be respectively coated
The zirconium oxide of powder and the glass combination powder of embodiment 3 is placed in porcelain furnace, according to traditional facing porcelain porcelain temperature programming
To target temperature porcelain.The zirconium oxide for being wherein coated with the glass combination powder of embodiment 1 is incubated 10min at 1000 DEG C, and applies
The zirconium oxide for having covered the glass combination powder of embodiment 3 is incubated 1min at 1100 DEG C.Taken out after sample is down to room temperature, pass through mill
The section for throwing sample observes the microstructure of two sample sections, as depicted in figs. 1 and 2.
Can be clearly observed from Fig. 1 and Fig. 2 glass composition in embodiment 1 and embodiment 3 respectively with oxidation
Zirconium is chemically reacted at interface, and the result of point power spectrum shows that the reaction is mutually BaZrO3.The BaZrO of formation3Length does not surpass
6 μm are crossed, width is no more than 3 μm.
The glass composition obtained to other embodiment carries out same test, is also demonstrated that glass composition and zirconium oxide
Chemically reacted at interface, the result of point power spectrum shows that the reaction is mutually BaZrO3.The BaZrO of formation3It is of length no more than
6 μm, width is no more than 3 μm.Comparative example 2 can not form stable glass therefore can not carry out above-mentioned test.In comparative example 4 due to
SiO2Molar content for 0 and B2O3Molar content be 80%, the glass is very small in 800 DEG C of viscosity so that
Very good in mobility, this making to later stage facing porcelain is very unfavorable, therefore is not necessarily to do above-mentioned interface observation.To contrast
The glass composition that example 1 and 3 is obtained carries out same test, and as a result the glass composition of display comparison example 1 and 3 exists with zirconium oxide
Interface does not chemically react.
Embodiment 7
Method of testing according to the golden porcelain interface bond strength described by ISO9693 prepares the double-deck porcelain of facing porcelain/zirconium oxide,
To test the change for combining facing porcelain and zirconium oxide interface bond strength before and after porcelain is coated.Using the VM9 facing porcelain of only his company.
The double-deck porcelain of VM9/ zirconium oxides is prepared first, and after tested, the interface bond strength of the double-deck porcelain is 21.3 ± 2.3MPa.Then prepare
It with the addition of with reference to the double-deck porcelain after porcelain (glass composition i.e. of the present invention)：Reality is respectively coated on the surface of zirconium oxide first
The glass combination powder of a 1-5 or comparative example 1 and 3 is applied, then puts the zirconium oxide for being coated with glass combination powder respectively
Porcelain in porcelain furnace is placed in, after 800 DEG C~1100 DEG C are incubated 1min~30min into, glass composition is sintered to transparent knot
Close porcelain.After combination porcelain is fired and finished, then combining the surface heap modeling VM9 facings porcelain and porcelain, completion VM9/ combinations porcelain/oxygen of porcelain
Change the preparation of the double-deck porcelain of zirconium.After tested, the interface bond strength result that with the addition of the double-deck porcelain for combining porcelain is as shown in table 2.
Table 2
After with the addition of combination porcelain glass (embodiment 1-5) of the present invention it can be seen from the result of table 2, two-sided porcelain
Interface bond strength improved by 21.3 ± 2.3MPa to 41.0 ± 1.0MPa~62.1 ± 1.5MPa, interface bond strength is notable
Improve, it can be seen from the comparison of embodiment and comparative example when BaO contents are very few (comparative example 1) or when in glass composition
SiO2With B2O3Content it is close when (comparative example 3), interface bond strength is not all significantly improved.
Embodiment 8
By embodiment 1-5 glass combination powder respectively according to traditional facing porcelain porcelain program at 820 DEG C~920 DEG C
It is incubated after 30min and takes out, it is found that they have sintered the clear glass of densification into.XRD (X will be carried out after these glass grinds
X ray diffraction analysis x) test.XRD test result such as Fig. 3 institute of the glass composition of embodiment 3 after 820 DEG C of insulation 30min
Show.
Fig. 3 result shows that the glass composition of embodiment 3 is still amorphous, do not had after the firing of porcelain program
Separate out any crystalline phase.
Embodiment 1-2 and embodiment 4-5 glass composition are also still amorphous after the firing of porcelain program,
Any crystalline phase is not separated out.
Embodiment 9
Corresponding glass sample is not prepared according to the glass composition of embodiment 1, embodiment 2 and embodiment 4, the hyaloid
The size of product is 4mm × 4mm × 12mm, the measure for thermal coefficient of expansion.Using high-temperature heat expansion instrument (L75/1550,
LINSEIS, Germany) the above-mentioned sample of test thermal coefficient of expansion, as a result as shown in Figure 4.
Fig. 4 shows the unit length thermal dilatometry of these three different glass samples, the temperature model in room temperature~500 DEG C
The thermal coefficient of expansion that the glass composition sample of embodiment 2 is measured under enclosing is 9.5 × 10-6℃-1, the glass composition of embodiment 1
The thermal coefficient of expansion of sample is 10.2 × 10-6℃-1, the thermal coefficient of expansion of the glass composition sample of embodiment 4 is 10.8 × 10-6℃-1。
The thermal coefficient of expansion of the glass composition sample of testing example 3 and embodiment 5, obtains them in the same way
Thermal coefficient of expansion be respectively 10.6 × 10-6℃-1With 10.4 × 10-6℃-1。
Applicant states, the present invention illustrated by above-described embodiment the present invention glass composition and preparation method thereof and
Using, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention has to rely on above-described embodiment and could implemented.
Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, is replaced to the equivalent of raw material selected by the present invention
Change and auxiliary element addition, the selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of glass composition, it is characterised in that the glass composition includes the following component of molar content：
SiO20~19%
B2O341%~70%
BaO 20%~40%.
2. glass composition according to claim 1, it is characterised in that the glass composition includes molar content
Following component：
SiO26%~10%
B2O350%~70%
BaO 20%~30%.
3. glass composition according to claim 1 or 2, it is characterised in that the glass composition also includes alkali metal
Oxide Li2O、Na2O or K2In O any one or at least two combination, its molar content be no more than 10%；
Preferably, the glass composition also includes any one in alkaline earth oxide MgO, CaO or SrO or at least two
The combination planted, its molar content is no more than 10%；
Preferably, the glass composition also includes Al2O3, its molar content is no more than 10%.
4. the glass composition according to any one of claim 1-3, it is characterised in that the glass composition is from room temperature
It is 9.5 × 10 to 500 DEG C of thermal coefficient of expansions-6℃-1~10.8 × 10-6℃-1；
Preferably, BaO is with BaCO in the glass composition3Introduced as raw material components.
5. the preparation method of the glass composition according to any one of claim 1-4, it is characterised in that methods described bag
Include following steps：
(1) raw material components of glass composition are crushed, be sufficiently mixed, dried；
(2) mixture for obtaining step (1) is put in reactor, heating melting, by glass melt water quenching to obtain the glass
Glass composition.
6. preparation method according to claim 5, it is characterised in that step (1) crushing is in planetary ball mill
Carry out；
Preferably, step (1) is described crushes to be crushed to the mesh of 200 mesh~300.
7. the preparation method according to claim 5 or 6, it is characterised in that step (2) heating is to be warming up to 1100 DEG C
~1300 DEG C；
Preferably, the time of step (2) described melting is 2~5 hours.
8. the preparation method according to claim 5-7, it is characterised in that the described method comprises the following steps：
(1) raw material components of glass composition are crushed to the mesh of 200 mesh~300 in planetary ball mill, be sufficiently mixed, dried
It is dry；
(2) mixture for obtaining step (1) is put in reactor, is warming up to 1100 DEG C~1300 DEG C, is melted 2~5 hours, will
Glass melt water quenching is to obtain the glass composition.
9. a kind of Zirconium oxide full-porcelain hat, it is characterised in that the Zirconium oxide full-porcelain hat is made comprising zirconium surface is coated on
For the glass composition as any one of claim 1-4 with reference to porcelain.
10. application of the glass composition in artificial corona material is prepared according to any one of claim 1-4.
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| CN201610186669.3A CN107235628B (en) | 2016-03-29 | 2016-03-29 | Glass composition and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112759422A (en) * | 2021-02-01 | 2021-05-07 | 云南省第一人民医院 | Method for preparing dental zirconia-veneer porcelain with high-bonding-force interface |
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Cited By (2)
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| CN112759422A (en) * | 2021-02-01 | 2021-05-07 | 云南省第一人民医院 | Method for preparing dental zirconia-veneer porcelain with high-bonding-force interface |
| CN112759422B (en) * | 2021-02-01 | 2022-12-27 | 云南省第一人民医院 | Method for preparing dental zirconia-veneer porcelain with high-bonding-force interface |
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