CN108069611A - The lithium metasilicate devitrified glass of high permeability and lithium bisilicate devitrified glass, preparation method and use - Google Patents
The lithium metasilicate devitrified glass of high permeability and lithium bisilicate devitrified glass, preparation method and use Download PDFInfo
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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
- 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
- C03C10/0018—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 containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—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 containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
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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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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
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Abstract
The present invention relates to a kind of lithium metasilicate devitrified glass of high permeability and lithium bisilicate devitrified glass, preparation method and the usages.The size of silicic acid crystalline lithium is less than 50nm in the lithium metasilicate devitrified glass of the present invention, and the size of lithium bisilicate crystal is less than 200nm in lithium bisilicate devitrified glass.The present invention prepares parent glass by providing specific composition, controls SiO2、Li2The matching relationship of O and other components, particularly control SiO2With Li2The proportionate relationship of O, by being once heat-treated, obtain the lithium metasilicate devitrified glass that size is less than 50nm, prepared by lithium bisilicate devitrified glass to lithium metasilicate devitrified glass heat treatment again, the crystalline size of obtained lithium bisilicate devitrified glass is in below 200nm, 20%~95%, intensity can meet clinic to the high permeability of lithium bisilicate devitrified glass and the demand of superior strength in 360MPa~450MPa for light transmittance at 550nm wavelength.
Description
Technical field
The invention belongs to technical field of biological material, are related to lithium metasilicate devitrified glass, lithium bisilicate devitrified glass and its preparation side
The lithium metasilicate devitrified glass of method and purposes more particularly to high permeability, high permeability lithium bisilicate devitrified glass and its repaiied in dentistry
The purposes of multiple Material Field.
Background technology
Lithium bisilicate (Li2Si2O5) devitrified glass is by Li2O-SiO2Glass system carries out Controlled Crystallization and obtains,
Its principal crystalline phase being precipitated is lithium bisilicate crystal.Due to Li2O-SiO2Glass system can be real by special heat treating regime
Now whole crystallization, and then obtain excellent mechanical property, therefore it is subject to that scholars' is widely studied.Adopted company of Huojia County
(Ivoclar) by Li2O-SiO2Glass system is successfully applied to dental prosthesis field, and representative products are exactly lithium bisilicate
Devitrified glass.
Although lithium bisilicate devitrified glass as a kind of dental prosthetic material in clinical practice for many years, light transmittance
It is relatively low always, so as to limit its application as veneer and corona.The patent of open report is concentrated mainly on two silicic acid at present
The mechanical property of lithium devitrified glass, substep are cut in control and manufacturing process.For example CN102741186A and US2015/
0246843A1 reports the substep crystallization control of lithium bisilicate devitrified glass, and CN104108883A reports lithium bisilicate crystallite
The mechanics activeness and quietness of glass, CN104909571A report the work that lithium bisilicate devitrified glass is prepared using powder sintering
Skill.As people are for the higher and higher pursuit of denture aesthetics performance, and the aesthetic properties of artificial tooth cease manner of breathing with its light transmittance
It closes, thus the light transmittance for improving artificial tooth material is extremely important, but the research of the prior art is difficult to take into account extraordinary mechanics
Performance and high transparency, thus develop that the lithium bisilicate devitrified glass with high transparency and excellent mechanical performances has very much must
It will.
In order to improve the translucency of lithium bisilicate devitrified glass, scholars have carried out substantial amounts of research, are mainly reflected in and subtract
In the size of small lithium bisilicate crystal, because the size of lithium bisilicate crystal is smaller, the light transmittance of lithium bisilicate devitrified glass is got over
It is high.For example P is worked as in F.Wang et al. discoveries2O5Molar content be 2% when, the size of lithium bisilicate crystal can control
200nm~400nm (F.Wang, J.Gao, H.Wang, J.H.Chen, Flexural strength and translucent
characteristics of lithium disilicate glass-ceramics with different
P2O5content,Mater.Des.31,2010,3270-3274).For another example P.Zhang et al. is had found first in 650 DEG C of heat treatments
72h is heat-treated 3h at 830 DEG C again, in obtained devitrified glass the size of lithium bisilicate crystal for 400nm (P.Zhang,
X.H.Li,J.F.Yang,S.C.Xu,Effect of heat treatment on the microstructure and
properties of lithium disilicate glass-ceramics,J.Non-Cryst.Solids 402,2014,
101-105).But the translucency of the lithium bisilicate devitrified glass of the prior art is still very low, to commercial two silicon of the prior art
The translucency of sour lithium devitrified glass is tested, using light transmission of the spectrophotometer test sample at 380nm~780nm wavelength
Rate, result are：Thickness is that light transmittance of the lithium bisilicate devitrified glass of 0.8mm at 550nm wavelength is less than 10%, and existing skill
Art is not disclosed to adjust the research of the light transmittance of lithium bisilicate devitrified glass.
Thus, study the size of lithium bisilicate crystal and the power of lithium bisilicate devitrified glass in lithium bisilicate devitrified glass
The relation of performance and translucency is learned, there is important positive meaning to take into account extraordinary mechanical property and excellent translucency
Justice.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of lithium metasilicate of high permeability is micro-
The lithium bisilicate devitrified glass and its preparation method and application of crystal glass, high permeability.The lithium metasilicate devitrified glass of the present invention exists
Light transmittance at 550nm wavelength is more than 75%, and intensity is in 110MPa~220MPa；The lithium bisilicate devitrified glass of the present invention exists
20%~95%, intensity has both good light transmittance and excellent power in 360MPa~450MPa for light transmittance at 550nm wavelength
The lithium metasilicate devitrified glass and lithium bisilicate devitrified glass for learning intensity can meet the needs of clinically dental prosthetic material.
In the present invention, " the lithium metasilicate devitrified glass of high permeability " refers to light transmission of the lithium metasilicate devitrified glass at 550nm wavelength
Rate is more than 75%.
In the present invention, " the lithium bisilicate devitrified glass of high permeability " refers to：Lithium bisilicate devitrified glass is at 550nm wavelength
Light transmittance is 20%~95%.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of lithium metasilicate devitrified glass, the lithium metasilicate devitrified glass by glass parent phase and
The silicic acid crystalline lithium composition being dispersed in glass parent phase, the size of the silicic acid crystalline lithium are less than 50nm, such as 48nm, 46nm,
45nm, 42nm, 40nm, 35nm, 30nm, 25nm or 20nm etc..
The pattern of the silicic acid crystalline lithium in lithium metasilicate devitrified glass in the present invention for spherical shape, it is described " silicic acid crystalline lithium
Size " refers to the diameter of spherical silicic acid crystalline lithium.
Light transmittance of the lithium metasilicate devitrified glass at 550nm wavelength of the present invention more than 75%, such as 75%, 77%,
80%th, 85%, 87%, 90%, 92% or 95% etc..
The intensity of the lithium metasilicate devitrified glass of the present invention for 110MPa~220MPa, such as 110MPa, 120MPa,
130MPa, 140MPa, 150MPa, 160MPa, 170MPa, 180MPa, 190MPa, 200MPa, 210MPa or 220MPa etc..
Second aspect, the present invention provide a kind of lithium bisilicate devitrified glass, and the lithium bisilicate devitrified glass is female by glass
Phase and the lithium bisilicate crystal composition being dispersed in glass parent phase, the lithium bisilicate devitrified glass is by first aspect institute
Obtained from the lithium metasilicate devitrified glass stated is heat-treated, the ruler of the lithium bisilicate crystal in the lithium bisilicate devitrified glass
It is very little be less than 200nm, such as 195nm, 190nm, 185nm, 180nm, 175nm, 170nm, 165nm, 160nm, 155nm, 150nm,
145nm、140nm、135nm、130nm、125nm、120nm、110nm、105nm、100nm、90nm、80nm、75nm、70nm、
60nm, 50nm, 40nm, 30nm or 20nm etc..
The lithium bisilicate crystal in lithium bisilicate devitrified glass in the present invention has fusiformis and spherical two kinds of patterns, when two silicon
For the size of sour crystalline lithium in 100nm~200nm, pattern is fusiformis, and described at this time " size of lithium bisilicate crystal " refers to shuttle
The length of the long axis of the lithium bisilicate crystal of shape.When the size of lithium bisilicate crystal is less than 100nm, pattern is spherical shape, this
Shi Suoshu " size of lithium bisilicate crystal " refers to the diameter of spherical lithium bisilicate crystal.
Preferably, it is described during preparing lithium bisilicate devitrified glass using the lithium metasilicate devitrified glass of first aspect
The temperature of heat treatment is 800 DEG C~900 DEG C, such as 800 DEG C, 825 DEG C, 830 DEG C, 840 DEG C, 850 DEG C, 880 DEG C or 900 DEG C etc.,
The time of the heat treatment is preferably 5min~60min, for example, 5min, 10min, 13min, 16min, 20min, 25min,
35min, 40min, 45min, 50min or 60min etc..
The light transmittance of the lithium bisilicate devitrified glass of the present invention is 20%~95%, such as 20%, 23%, 25%, 26%,
28%th, 29%, 30%, 32%, 34%, 35%, 37%, 40%, 43%, 45%, 50%, 55%, 60%, 65%, 68%,
70%th, 75%, 80%, 85%, 90% or 95% etc..
It is a discovery of the invention that the side of the size for reducing silicic acid crystalline lithium and the size for reducing lithium bisilicate crystal can be passed through
Formula is respectively increased the light transmittance of lithium metasilicate devitrified glass and lithium bisilicate devitrified glass, and will not cause under mechanical property
Drop.When the size of silicic acid crystalline lithium is less than 50nm, the light transmittance of lithium metasilicate devitrified glass is more than 75%；When lithium bisilicate is brilliant
When the size of body is less than 200nm, the light transmittance of lithium bisilicate devitrified glass is 20%~95%.
Further study show that when the size of lithium bisilicate crystal is when 100nm is less than 200nm, lithium bisilicate
Light transmittance of the devitrified glass at 550nm wavelength is 20%~30%, saturating at 550nm wavelength such as when size is in 100nm
Light rate is 27.3%；When the size of lithium bisilicate crystal is less than 100nm, lithium bisilicate devitrified glass is at 550nm wavelength
Light transmittance is more than 30% and below 95%.
The intensity of the lithium bisilicate devitrified glass of the present invention in 360MPa~450MPa, such as 360MPa, 380MPa,
390MPa, 400MPa, 410MPa, 420MPa, 430MPa, 430MPa or 440MPa etc..
The third aspect, the present invention provide the preparation method of lithium metasilicate devitrified glass as described in relation to the first aspect, the method
For：Parent glass is once heat-treated, obtains lithium metasilicate devitrified glass；
Wherein, the parent glass includes following components with weight：
The sum of weight percentage of each component is 100% in glass of the present invention, and SiO2With Li2The mass ratio of O
For (4~5):1, such as 4:1、4.2:1、4.5:1、4.7:1、4.8:1 or 5:1 etc., if ratio SiO2/Li2O is more than 5:1, then
The big quartzy phase of coefficient of thermal expansion can be precipitated, cause to generate thermal stress in devitrified glass body, reduce translucency and reduce mechanical property
Energy；If SiO2/Li2O is less than 4:1, it can cause lithium metasilicate crystalline phase that cannot be fully converted to lithium bisilicate crystalline phase, cause lithium bisilicate
The intensity of devitrified glass is greatly reduced, and can also reduce light transmittance.
In the parent glass of the present invention, SiO2Weight percentage for 50%~80%, may be, for example, 50%, 52%,
55%th, 58%, 60%, 63%, 65%, 67%, 70%, 72%, 75%, 77% or 80% etc..
In the parent glass of the present invention, Li2The weight percentage of O is 10%~20%, may be, for example, 10%, 12%,
14%th, 16%, 18% or 20% etc..
In the parent glass of the present invention, K2The weight percentage of O is 0.5%~10%, may be, for example, 0.5%, 1%,
2%th, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% etc..
In the parent glass of the present invention, Al2O3Weight percentage for 0.5%~15%, may be, for example, 0.5%, 1%,
1.5%th, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%,
9%th, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% or 15%
Deng.
In the parent glass of the present invention, the weight percentage of nucleating agent is 0.2%~10%, may be, for example, 0.2%,
0.5%th, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%,
8%th, 8.5%, 9%, 9.5% or 10% etc..
Preferably, the nucleating agent in phosphorus pentoxide, zirconium dioxide or titanium dioxide any one or at least
Two kinds of combination.
In the parent glass of the present invention, the weight percentage of colorant is 0~5%, may be, for example, 0,0.5%, 1%,
1.5%th, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% etc..The mass percentage of the colorant represents for 0：No
Add colorant.
Preferably, the colorant is the oxide and/or pigment that can make glass coloration, can make the oxide of glass coloration
Selected from iron oxide, titanium oxide, cerium oxide, copper oxide, chromium oxide, nickel oxide, manganese oxide, selenium oxide, silver oxide, indium oxide, oxygen
Change gold or rare earth oxide in any one or at least two combination.The rare earth oxide is preferably neodymia, oxidation
In praseodymium or samarium oxide any one or at least two combination.
The present invention is had found by a large number of experiments, by adjusting the SiO of parent glass2、Li2O、K2O、Al2O3, nucleating agent and
The content matching relationship of the components such as toner controls SiO2With Li2The mass ratio of O is in (4~5):1, it can be obtained by being once heat-treated
To the lithium metasilicate devitrified glass of high permeability.
Below as currently preferred technical solution, but not as the limitation to technical solution provided by the invention, lead to
Following preferred technical solution is crossed, can preferably reach and realize the technical purpose and advantageous effect of the present invention.
Preferably, the parent glass includes following components with weight：
The sum of weight percentage of each component is 100% in the glass, and SiO2With Li2The mass ratio of O for (4~
5):1。
It is further preferred that the parent glass includes following components with weight：
The sum of weight percentage of each component is 100% in the glass, and SiO2With Li2The mass ratio of O for (4~
5):1。
Preferably, the temperature being once heat-treated be 500 DEG C~750 DEG C, such as 500 DEG C, 520 DEG C, 540 DEG C, 560
DEG C, 580 DEG C, 600 DEG C, 620 DEG C, 640 DEG C, 660 DEG C, 680 DEG C, 700 DEG C, 720 DEG C, 740 DEG C or 750 DEG C etc..
Preferably, the time being once heat-treated be 5min~60min, be, for example, 5min, 10min, 15min,
20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min etc..
Parent glass is once heat-treated, substantial amounts of nucleus can be generated, single crystalline phase lithium metasilicate is precipitated, is prepared into
To the lithium metasilicate devitrified glass containing single crystalline phase silicic acid crystalline lithium.
As the optimal technical scheme of the method for the invention, the parent glass is prepared via a method which：
With SiO2、Li2CO3、K2CO3、Al2O3, nucleating agent raw material and colorant as raw material, raw material is mixed first, into
Row ball milling, then melting obtain parent glass.
Preferably, when nucleating agent is P2O5When, nucleating agent raw material is ammonium dihydrogen phosphate and/or diammonium hydrogen phosphate；Work as nucleating agent
For zirconium dioxide and/or titanium dioxide when, nucleating agent raw material is identical with nucleating agent.
" zirconium dioxide and/or titanium dioxide " of the present invention refers to：Can be zirconium dioxide or titanium dioxide,
It can also be the mixture of zirconium dioxide and titanium dioxide.
Preferably, ball milling is carried out using planetary ball mill.
Preferably, the time of the ball milling be 1min~60min, be, for example, 1min, 5min, 10min, 15min, 20min,
25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min etc..
Preferably, the mixture obtained after ball milling is put into platinum alloy crucibles and melted.
Preferably, the temperature of the melting be 1200 DEG C~1600 DEG C, be, for example, 1200 DEG C, 1250 DEG C, 1300 DEG C, 1350
DEG C, 1400 DEG C, 1450 DEG C, 1500 DEG C, 1550 DEG C or 1600 DEG C etc..
Preferably, the time of the melting be 1h~5h, be, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or
5h etc..
Parent glass in the method for the invention can be through melting obtained parent glass or through continuing to pour
Note obtained parent glass block.
Preferably, the parent glass that the melting obtains further is cast into parent glass block.
Gained parent glass is used to prepare lithium metasilicate devitrified glass and lithium bisilicate devitrified glass, and the present invention is to parent glass
The shape of block has no specific limitation, can be designed as needed, such as can make the shape of corona.
In the lithium metasilicate devitrified glass being prepared by the preparation method of lithium metasilicate devitrified glass of the present invention
Silicic acid crystalline lithium is very tiny and is dispersed in glass parent phase, and size is less than 50nm, so that can not be differentiated under scanning electron microscope
(referring to Fig. 1), although the size of silicic acid crystalline lithium can not be told from SEM figures, by carrying out XRD (referring to figure to it
2) analysis is understood, silicic acid crystalline lithium is implicitly present in lithium metasilicate devitrified glass, illustrates to exist in lithium metasilicate devitrified glass very thin
Small silicic acid crystalline lithium.
Fourth aspect, the present invention provide the preparation method of the lithium bisilicate devitrified glass as described in second aspect, the side
Method is：The lithium metasilicate devitrified glass of first aspect is heat-treated, obtains lithium bisilicate devitrified glass.
Preferably, during lithium bisilicate devitrified glass is prepared using lithium metasilicate devitrified glass, the heat treatment
Temperature is 800 DEG C~900 DEG C, is, for example, 800 DEG C, 820 DEG C, 840 DEG C, 860 DEG C, 880 DEG C or 900 DEG C etc..The heat treatment
Time is preferably 5min~60min, be, for example, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min,
45min, 50min, 55min or 60min etc..By the heat treatment of this step, single crystalline phase lithium metasilicate is converted into single crystalline phase two
Lithium metasilicate, and the size of the lithium bisilicate crystal in obtained lithium bisilicate devitrified glass is less than 200nm, since the size is less than
The wavelength (380nm~780nm) of visible ray, therefore, the lithium bisilicate devitrified glass have very high light transmittance, up to 20%~
95%, which can be used as dental prosthetic material, such as corona, veneer be made, intensity 360MPa~
450MPa can meet clinical requirement completely in intensity and translucency.
5th aspect, the present invention provide such as the lithium metasilicate devitrified glass of first aspect and the lithium bisilicate crystallite of second aspect
The purposes of glass, the lithium metasilicate devitrified glass and lithium bisilicate devitrified glass are used equally for dental restorative area.
Compared with the prior art, the present invention has the advantages that：
Since parent glass forms cooperation selection and SiO2/Li2The restriction of O, then it is equipped with the suitable of two-step thermal processing system
Selection so that the parent glass can generate a large amount of core positions after experience is once heat-treated, and obtain the lithium metasilicate crystallite of high transparency
Glass, light transmittance is more than 75%；Big take measurements can be precipitated by continuing after being heat-treated to lithium metasilicate devitrified glass is less than
The lithium bisilicate crystal of 200nm makes the lithium bisilicate devitrified glass of acquisition not only with excellent mechanical strength also with very high
Light transmittance, light transmittance is 20%~95%.
Description of the drawings
Fig. 1 is the micro-structure diagram of 1 gained lithium metasilicate devitrified glass of embodiment；
Fig. 2 is the XRD diagram of 1 gained lithium metasilicate devitrified glass of embodiment；
Fig. 3 is the micro-structure diagram of 1 gained lithium bisilicate devitrified glass of embodiment；
Fig. 4 is light transmittance curve of the 1 gained lithium bisilicate devitrified glass of embodiment to 380nm~780nm scope visible rays
Figure.
Specific embodiment
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
The present invention is to the test method of devitrified glass light transmittance：Using spectrophotometer to test sample 380nm~
It is tested in 780nm wave-length coverages, the thickness of test sample of the invention is in 2mm.
Examples 1 to 5
The preparation of parent glass block：
The weight percentage of glass each component, weighs analytically pure respectively described in each embodiment listed according to table 1
SiO2、Li2CO3、K2CO3、Al2O3、TiO2And CeO2, after the abundant mix grinding of planetary ball mill, take out drying；It will be obtained after drying
To powder be placed in platinum alloy crucible, be placed in chamber type electric resistance furnace, 1200 DEG C~1600 DEG C be warming up under air atmosphere, constant temperature
Then 1h~5h takes out at 1400 DEG C and is cast into parent glass block.About 30 grams or so of parent glass block obtained by casting.
The preparation of lithium metasilicate devitrified glass containing nanometer silicic acid crystalline lithium：
By the glass block obtained by each embodiment after 500 DEG C~750 DEG C are heat-treated 5min~60min, it is precipitated single
Lithium metasilicate crystalline phase, obtain lithium metasilicate devitrified glass, which has very high light transmittance and very thin
Small crystalline size, crystalline size is less than 50nm, so that its microstructure is observed under scanning electron microscope can not see lithium metasilicate
The size of crystal (referring to Fig. 1).It and is heat-treated by this step so that inside glass generates a large amount of nucleus.
The preparation of lithium bisilicate devitrified glass containing nanometer lithium bisilicate crystal：
Continue by lithium metasilicate devitrified glass after 800 DEG C~900 DEG C are heat-treated 5min~60min, lithium metasilicate crystalline phase is whole
Lithium bisilicate crystalline phase is changed into, obtains lithium bisilicate devitrified glass.Lithium bisilicate crystal ruler in the lithium bisilicate devitrified glass
It is very little to be less than 200nm, therefore with very high light transmittance.
Fig. 1 is the micro-structure diagram of 1 gained lithium metasilicate devitrified glass of embodiment, can only see glass parent phase by figure, this is
Since the size of silicic acid crystalline lithium in the devitrified glass is extremely tiny so that being difficult to recognize under scanning electron microscope.
Fig. 2 is the XRD diagram of 1 gained lithium metasilicate devitrified glass of embodiment, as seen from the figure, the crystal in the devitrified glass
Only silicic acid crystalline lithium.
Fig. 3 is the micro-structure diagram of 1 gained lithium bisilicate devitrified glass of embodiment, as seen from the figure, the devitrified glass
In lithium bisilicate crystal size be less than 200nm.
Fig. 4 is light transmittance of the 1 gained lithium bisilicate devitrified glass of embodiment to visible ray, as seen from the figure, as wavelength increases
Greatly, online light transmittance becomes larger, which is 27.3%.
Glass block prepared by embodiment 1-5 casting is without occurring split-phase and crystallization, and according to two-step thermal processing
Lithium bisilicate devitrified glass made from system has very high light transmittance, and the size of wherein lithium bisilicate crystal is respectively less than
200nm。
The crystalline size of the lithium bisilicate devitrified glass obtained to each embodiment is detected, as a result as follows：
The size of lithium bisilicate crystal in lithium bisilicate devitrified glass made from embodiment 1-5 be followed successively by 100nm,
120nm, 160nm, 180nm and 130nm.
Light transmittance of the lithium bisilicate devitrified glass obtained to each embodiment at 550nm wavelength is detected, as a result
It is as follows：
Light transmittance of the lithium bisilicate devitrified glass at 550nm wavelength made from embodiment 1-5 be followed successively by 27.3%,
26.2%th, 24.3%, 21.5% and 25.8%.
In the present invention, when being detected to the translucency of lithium metasilicate devitrified glass and lithium bisilicate devitrified glass,
For 2mm, the method for test is the thickness of the sample used：It is examined using spectrophotometer in visible-range 380nm~780nm
It surveys.
The intensity of the lithium bisilicate devitrified glass obtained to each embodiment is detected, as a result as follows：
The intensity of lithium bisilicate devitrified glass made from embodiment 1-5 be followed successively by 365MPa, 386MPa, 421MPa,
446MPa and 402MPa.
Comparative example 1
Except SiO2The weight percentage of component is 81.6%, and Li2The weight percentage of O components for outside 6.4%,
The content and preparation method and condition of his each component are same as Example 2.
It is easily calculated, the SiO of this comparative example2/Li2O=12.75.
Glass block prepared by the casting of this comparative example 1 is after two-step thermal processing system, except lithium bisilicate oikocryst is precipitated
Outside phase, apparent quartz crystal has also been precipitated.Since the precipitation of quartz crystal causes huge thermal stress, obtained two
There are many strength reduction of lithium metasilicate devitrified glass, and intensity is only 183MPa, and the precipitation of quartz crystal also results in light transmittance
Decline.The size of lithium bisilicate crystal is more than 1 μm in devitrified glass obtained, light transmission of the devitrified glass at 550nm wavelength
Rate is reduced to 8.2%.
Comparative example 2
Except SiO2The weight percentage of component is 77.5%, and Li2The weight percentage of O components for outside 21.3%,
The content and preparation method and condition of his each component are same as Example 3.
It is easily calculated, the SiO of this comparative example2/Li2O=3.64.
Glass block prepared by the casting of this comparative example 2 is after two-step thermal processing system, and there is no turn lithium metasilicate crystalline phase completely
Lithium bisilicate crystalline phase is turned to, there are many strength reduction for causing lithium bisilicate devitrified glass, intensity 226MPa, and reduce
Light rate, light transmittance of the devitrified glass at 550nm wavelength are reduced to 14.3%.
Comparative example 3
Except SiO2The weight percentage of component is 48.6%, and Li2The weight percentage of O components for outside 12.7%,
The content and preparation method and condition of his each component are same as Example 4.
It is easily calculated, the SiO of this comparative example2/Li2O=3.83.
Glass block prepared by the casting of this comparative example 3 is after two-step thermal processing system, and there is no turn lithium metasilicate crystalline phase completely
Lithium bisilicate crystalline phase is turned to, there are many strength reduction for causing lithium bisilicate devitrified glass, intensity 241MPa, and reduce
Light rate, light transmittance of the devitrified glass at 550nm wavelength are reduced to 14.6%.
Comparative example 4
Except SiO2The weight percentage of component is 66.2%, and Li2The weight percentage of O components for outside 9.2%,
The content and preparation method and condition of his each component are same as Example 5.
It is easily calculated, the SiO of this comparative example2/Li2O=7.20.
Glass block prepared by the casting of this comparative example 4 is after two-step thermal processing system, except lithium bisilicate oikocryst is precipitated
Outside phase, apparent quartz crystal has also been precipitated.Since the precipitation of quartz crystal causes huge thermal stress, obtained two
There are many strength reduction of lithium metasilicate devitrified glass, and intensity is only 165MPa, and also reduces light transmittance, devitrified glass obtained
For the size of middle lithium bisilicate crystal more than 1 μm, light transmittance of the devitrified glass at 550nm wavelength is reduced to 9.2%.
Comparative example 5
Except the two-step thermal processing in embodiment 2 is become only 860 DEG C carry out a steps heat treatment in addition to, other each component contents
And preparation method and condition it is same as Example 2.
The size of lithium bisilicate crystal is 300nm in the devitrified glass that this comparative example 5 is prepared, and devitrified glass exists
Light transmittance at 550nm wavelength is 18.2%.
Comparative example 6
Except the two-step thermal processing in embodiment 3 is become only 910 DEG C carry out a steps heat treatment in addition to, other each component contents
And preparation method and condition it is same as Example 3.
The size of lithium bisilicate crystal is 1.5 μm in the devitrified glass that this comparative example 6 is prepared, and devitrified glass exists
Light transmittance at 550nm wavelength is 8.1%.
1 parent glass of table composition table (weight percentage)
| SiO2 | Li2O | K2O | Al2O3 | TiO2 | CeO2 | |
| Embodiment 1 | 65.4 | 15 | 4.6 | 14.2 | 0.6 | 0.2 |
| Embodiment 2 | 72.8 | 15.2 | 0.6 | 0.6 | 9.2 | 1.6 |
| Embodiment 3 | 79.1 | 19.7 | 0.5 | 0.5 | 0.2 | 0 |
| Embodiment 4 | 50.5 | 10.8 | 9.5 | 14.6 | 9.8 | 4.8 |
| Embodiment 5 | 62.6 | 12.8 | 8.6 | 7.6 | 5.6 | 2.8 |
Parent glass prepared by the composition provided according to the present invention is can be seen that by embodiment 1-5, due to controlling
SiO2、Li2The matching relationship of O and other components, particularly control SiO2With Li2The proportionate relationship of O, then coordinate at two steps heat
Reason so that the size of lithium bisilicate crystal is less than 200nm in the lithium bisilicate devitrified glass being prepared, so as in 550nm ripples
Strong point obtains 20%~95% light transmittance.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of lithium metasilicate devitrified glass, which is characterized in that the lithium metasilicate devitrified glass is by glass parent phase and is dispersed in described
Silicic acid crystalline lithium composition in glass parent phase, the size of the silicic acid crystalline lithium are less than 50nm.
2. lithium metasilicate devitrified glass as described in claim 1, which is characterized in that the lithium metasilicate devitrified glass is in 550nm ripples
The light transmittance of strong point is more than 75%；
Preferably, the intensity of the devitrified glass is 110MPa~220MPa.
3. a kind of lithium bisilicate devitrified glass, which is characterized in that the lithium bisilicate devitrified glass is by claim 1 institute
Obtained from the devitrified glass stated is heat-treated, the lithium bisilicate devitrified glass is by glass parent phase and is dispersed in the glass
Lithium bisilicate crystal composition in parent phase, the size of the lithium bisilicate crystal are less than 200nm；
Preferably, the temperature of the heat treatment is 800 DEG C~900 DEG C, and the time of the heat treatment is preferably 5min~60min；
Preferably, the light transmittance of the lithium bisilicate devitrified glass is 20%~95%；
Preferably, when the lithium bisilicate crystal in the lithium bisilicate devitrified glass size in 100nm less than 200nm
When, light transmittance of the lithium bisilicate devitrified glass at 550nm wavelength is 20%~30%；
When the size of the lithium bisilicate crystal in the lithium bisilicate devitrified glass is less than 100nm, the lithium bisilicate crystallite
Light transmittance of the glass at 550nm wavelength is more than 30% and below 95%；
Preferably, the intensity of the lithium bisilicate devitrified glass is 360MPa~450MPa.
4. the preparation method of lithium metasilicate devitrified glass as claimed in claim 1 or 2, which is characterized in that the method is：
Parent glass is once heat-treated, obtains lithium metasilicate devitrified glass；
Wherein, the parent glass includes following components with weight：
The sum of weight percentage of each component is 100% in the glass, and SiO2With Li2The mass ratio of O is (4~5):
1。
5. according to the method described in claim 4, it is characterized in that, the parent glass with weight include it is following
Component：
The sum of weight percentage of each component is 100% in the glass, and SiO2With Li2The mass ratio of O is (4~5):
1。
6. method according to claim 4 or 5, which is characterized in that the parent glass is included with weight
Following components：
The sum of weight percentage of each component is 100% in the glass, and SiO2With Li2The mass ratio of O is (4~5):
1。
7. according to claim 4-6 any one of them methods, which is characterized in that the temperature being once heat-treated is 500 DEG C
~750 DEG C；
Preferably, the time being once heat-treated is 5min~60min.
8. according to claim 4-7 any one of them methods, which is characterized in that the colorant is oxide and/or pigment；
Preferably, the oxide is selected from iron oxide, titanium oxide, cerium oxide, copper oxide, chromium oxide, nickel oxide, manganese oxide, oxygen
Change in selenium, silver oxide, indium oxide, gold oxide or rare earth oxide any one or at least two combination；
Preferably, the rare earth oxide is any one in neodymia, praseodymium oxide or samarium oxide or at least two combination；
Preferably, the nucleating agent in phosphorus pentoxide, zirconium dioxide or titanium dioxide any one or at least two
Combination.
9. according to claim 4-8 any one of them methods, which is characterized in that the parent glass is made by the following method
It is standby：
With SiO2、Li2CO3、K2CO3、Al2O3, nucleating agent raw material and colorant as raw material, raw material is mixed first, carries out ball
Mill, then melting obtain parent glass；
Preferably, when nucleating agent is P2O5When, nucleating agent raw material is ammonium dihydrogen phosphate and/or diammonium hydrogen phosphate；When nucleating agent is two
When zirconium oxide and/or titanium dioxide, nucleating agent raw material is identical with nucleating agent；
Preferably, ball milling is carried out using planetary ball mill；
Preferably, the time of the ball milling is 1min~60min；
Preferably, the temperature of the melting is 1200 DEG C~1600 DEG C；
Preferably, the time of the melting is 1h~5h；
Preferably, the glass that the melting obtains further is cast into glass block.
10. the preparation method of lithium bisilicate devitrified glass according to claim 3, which is characterized in that the method is：It is right
Devitrified glass described in claim 1 or 2 is heat-treated, and obtains lithium bisilicate devitrified glass；
Preferably, the temperature of the heat treatment is 800 DEG C~900 DEG C, and the time of the heat treatment is preferably 5min~60min.
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