CN106927682A - A kind of negative expansion devitrified glass and preparation method thereof - Google Patents
A kind of negative expansion devitrified glass and preparation method thereof Download PDFInfo
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- CN106927682A CN106927682A CN201511011585.8A CN201511011585A CN106927682A CN 106927682 A CN106927682 A CN 106927682A CN 201511011585 A CN201511011585 A CN 201511011585A CN 106927682 A CN106927682 A CN 106927682A
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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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C03C10/0054—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 PbO, SnO2, B2O3
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- Engineering & Computer Science (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a kind of negative expansion devitrified glass and preparation method thereof, including following component and content：The SiO of 30-80wt%2；The Al of 35-40wt%2O3；The Li of 5-10wt%2O；The B of 2-10wt%2O3；The R of 2-5wt%2O, wherein R2O is Li2O、Na2O、K2O、Cu2One or more in O；The RO of 2-10wt%, wherein RO are one or more in MgO, CaO, SrO, BaO, ZnO；Preparation method is：The weight of raw material, is then placed in being sufficiently stirred in agitator needed for weighing first；Put into melting furnace again, be heated beyond 1800 DEG C and keep more than 24h, be high temp glass stoste by solid glass dissolution of raw material, stoste is made original sheet glass by float glass process or die mould method；Original sheet glass is put into high temperature furnace and is heat-treated, generate homogeneous negative expansion β-quartz solid solution crystallite by being heat-treated after terminating in original sheet glass, obtain satisfactory devitrified glass.
Description
Technical field
Hot thermal expansion devitrified glass and preparation method thereof is born the present invention relates to one kind, negative expansion devitrified glass refers to one
Its linear expansion coefficient (α T) or the coefficient of volume expansion (β T) are the devitrified glass of negative value within the scope of fixed temperature.According to its characteristic
Can be used for the high-tech areas such as Aero-Space, photoelectron, manufacture precision optics etc., have broad application prospects.
Background technology
Devitrified glass is chemical analysis and the exigent specific composition glass of fusing, after heat treatment at a certain temperature
Become have microcrystal composite mutually equally distributed with glass, also referred to as glass-ceramic.Glass phase and knot in devitrified glass
The distribution situation of both crystalline phases changes with its ratio, and when the ratio that glass is mutually accounted for is big, glass is mutually continuous matrix, crystalline phase
It is evenly distributed in isolation wherein；When such as glass is mutually less, glass is mutually dispersed between crystal rack, in continuous net-shaped；If
Glass phase amount is very low, then glass is distributed between crystal with filminess.Devitrified glass has low-expansion coefficient, machinery strong
Degree is high, chemical stability and heat endurance is good, temperature in use is high and the premium properties such as hard wear resistant.
Lot of domestic and international mechanism and enterprise are to the composition of negative expansion devitrified glass, properity, research situation and its hair
Exhibition have also been made more research, but because composition is complicated, glass melting temperature is high, melting technology condition is more harsh and for big chi
Very little integrally crystallization control is more difficult, so the difficulty for preparing ultra-low-expansion glass ceramic is larger.
Up to the present, for the application of devitrified glass, domestic many enterprises are only confined to construction material, micro-wave oven material
Deng low-end product.
The content of the invention
The defect that the present invention exists for prior art, there is provided a kind of heat shock resistance temperature is high, melt temperature is low, pressure resistance
The devitrified glass that degree is high, transmission of visible light is high with Preparation Method, the devitrified glass prepared with the method can be used for Aero-Space,
The high-tech areas such as photoelectron, for manufacturing precision optics.
A kind of negative expansion devitrified glass, it is characterised in that including following component and content：The SiO of 30-80wt%2；35-
The Al of 40wt%2O3；The Li of 5-10wt%2O；The B of 2-10wt%2O3；The R of 2-5wt%2O, wherein R2O is Li2O、Na2O、K2O、
Cu2One or more in O；The RO of 2-10wt%, wherein RO are one or more in MgO, CaO, SrO, BaO, ZnO.
A kind of preparation method of negative expansion devitrified glass, comprises the following steps：
1）It is prepared by raw material：The weight of raw material needed for weighing according to the above ratio, makees after being then placed in being thoroughly mixed in agitator
It is solid glass raw material；
2）Raw materials melt：In the solid glass raw material input melting furnace that will be prepared, heating exceedes the temperature in melting furnace
1800 DEG C and more than 24h is kept, be high temp glass stoste by solid glass dissolution of raw material, while removing solid glass dissolution of raw material
When the bubble and foreign matter that produce；
3）Glass is molded：The high temp glass stoste that will have been melted is made original sheet glass by float glass process or die mould method；
4）Heat treatment：Original sheet glass is put into high temperature furnace and is heat-treated, it is raw in original sheet glass by being heat-treated after terminating
Into homogeneous negative expansion β-quartz solid solution crystallite, satisfactory devitrified glass is obtained.
Beneficial effects of the present invention：
1st, negative expansion devitrified glass can produce controllable thermal expansion material using its negative expansion, reduce to greatest extent high
The internal stress of adiabator, increases the heat shock resistance and mechanical strength of material, improves electrical insulation capability so that dielectric constant, resistance to
The characteristic such as mill, corrosion-resistant.
2nd, by crystallization and thermal treatment, the problems such as can thoroughly eliminate bubble, striped.
3rd, melt temperature is reduced, the production time has been saved, production cost is reduced.
4th, in the range of 1000-1200 °C, bending strength is 240MPA, spectrum to the coefficient of negative expansion devitrified glass
Transmitance more than 97%, thermal coefficient of expansion is -2*10-8, devitrified glass surface and film layer are firmly combined with after plated film, increase its hardness
And abrasion resistance.The high-tech areas such as Aero-Space, photoelectron, precision optical machinery, optics and electronic device etc. can be met completely.
Specific embodiment
Embodiment 1
Negative expansion devitrified glass composition of raw materials, constitutes according to following percentage：30% SiO2, 35% Al2O3, 5% Li2O、
2% B2O3, 2% Li2O and K2The mixture of O, the mixture of 2% MgO and CaO and 1.5% TiO2, 1% ZrO2、
2.5% P2O5F with 1%.Then its whole is put into after V-type agitator is thoroughly mixed as solid glass raw material；Then
In the solid glass raw material input electric furnace or crucible furnace that will be prepared, heating make temperature in stove for 1800 DEG C and keep 24h with
On, you can by solid glass dissolution of raw material it is high temp glass stoste, while the bubble that produces when removing solid glass dissolution of raw material
And foreign matter；Then the high temp glass stoste that will have been melted is made original sheet glass by float glass process or die mould method；Finally will be obtained
Original sheet glass is put into high temperature furnace and is heat-treated, and the heat treatment process includes that microcrystals is separated out and crystallite is grown up two stages,
Wherein in microcrystals precipitation phase, the temperature in high temperature furnace is set to be maintained at 600 DEG C, and it is most to continue generation during 2.5h makes original sheet glass
Possible polycrystallite core, is then increased to the temperature in high temperature furnace 750 DEG C and enters into the crystallite stage of growth and persistently 1.5h, you can
Homogeneous negative expansion β-quartz solid solution crystallite is generated in original sheet glass, satisfactory devitrified glass is obtained, in this stage
The devitrified glass that original sheet glass will be then converted into based on microstructure by parent glass, its be contained within β-quartz solid solution into
It is divided into Li2O-Al2O3-2SiO2。
Embodiment 2
Negative expansion devitrified glass composition of raw materials, constitutes according to following percentage：50% SiO2, 38% Al2O3, 7.5%
Li2O, 6% B2O3, 3.5% Na2O and K2The mixture of O, the mixture of 6% SrO and CaO and 3% TiO2, 1.5%
ZrO2, 4% P2O5F with 1.5%.Then its whole is put into after V-type agitator is thoroughly mixed former as solid glass
Material；Then in the solid glass raw material input electric furnace or crucible furnace that will be prepared, heating makes the temperature in stove for 1900 DEG C and protects
Hold more than 24h, you can by solid glass dissolution of raw material be high temp glass stoste, while remove solid glass dissolution of raw material when produce
Bubble and foreign matter；Then the high temp glass stoste that will have been melted is made original sheet glass by float glass process or die mould method；Finally will
Obtained original sheet glass is put into high temperature furnace and is heat-treated, and the heat treatment process includes that microcrystals is separated out and crystallite is grown up two
In stage, wherein microcrystals precipitation phase, make the temperature in high temperature furnace be maintained at 700 DEG C, and continue 3h to make to be produced in original sheet glass
Raw polycrystallite core as far as possible, is then increased to the temperature in high temperature furnace 900 DEG C and enters into the crystallite stage of growth and persistently 2h, i.e.,
Homogeneous negative expansion β-quartz solid solution crystallite can be generated in original sheet glass, satisfactory devitrified glass is obtained, in this rank
The devitrified glass that section original sheet glass will be then converted into based on microstructure by parent glass, it is contained within β-quartz solid solution
Composition is Li2O-Al2O3-2SiO2。
Embodiment 3
Negative expansion devitrified glass composition of raw materials, constitutes according to following percentage：80% SiO2, 40% Al2O3, 10%
Li2O, 10% B2O3, 5% Cu2O and K2The mixture of O, the mixture of 10% ZnO and CaO and 5% TiO2, 3%
ZrO2, 4% P2O5F with 3%.Then its whole is put into after V-type agitator is thoroughly mixed as solid glass raw material；
Then in the solid glass raw material input electric furnace or crucible furnace that will be prepared, heating makes the temperature in stove for 2000 DEG C and keeps
More than 24h, you can by solid glass dissolution of raw material be high temp glass stoste, while being produced when removing solid glass dissolution of raw material
Bubble and foreign matter；Then the high temp glass stoste that will have been melted is made original sheet glass by float glass process or die mould method；Finally will system
The original sheet glass for obtaining is put into high temperature furnace and is heat-treated, and the heat treatment process includes that microcrystals is separated out and crystallite two ranks of growth
Section, wherein in microcrystals precipitation phase, makes the temperature in high temperature furnace be maintained at 1000 DEG C, and continues 4h and make to be produced in original sheet glass
Polycrystallite core, is then increased to the temperature in high temperature furnace 1200 DEG C and enters into the crystallite stage of growth and persistently 2.5h as far as possible,
Homogeneous negative expansion β-quartz solid solution crystallite can be generated in original sheet glass, satisfactory devitrified glass is obtained, herein
The devitrified glass that staged glass original piece will be then converted into based on microstructure by parent glass, it is contained within β-quartz solid solution
Composition be Li2O-Al2O3-2SiO2。
Concrete application approach of the present invention is a lot, and the above is only the preferred embodiment of the present invention, it is noted that for
For those skilled in the art, under the premise without departing from the principles of the invention, some improvement can also be made, this
A little improvement also should be regarded as protection scope of the present invention.
Claims (2)
1. a kind of negative expansion devitrified glass, it is characterised in that including following component and content：The SiO of 30-80wt%2；35-
The Al of 40wt%2O3；The Li of 5-10wt%2O；The B of 2-10wt%2O3；The R of 2-5wt%2O, wherein R2O is Li2O、Na2O、K2O、
Cu2One or more in O；The RO of 2-10wt%, wherein RO are one or more in MgO, CaO, SrO, BaO, ZnO.
2. the preparation method of negative expansion devitrified glass described in a kind of claim 1, it is characterised in that comprise the following steps：
1）It is prepared by raw material：The weight of raw material needed for weighing according to the above ratio, makees after being then placed in being thoroughly mixed in agitator
It is solid glass raw material；
2）Raw materials melt：In the solid glass raw material input melting furnace that will be prepared, heating makes the temperature in melting furnace 1800
DEG C -2000 DEG C and more than 24h is kept, be high temp glass stoste by solid glass dissolution of raw material, while removing solid glass raw material
The bubble and foreign matter produced during dissolving；
3）Glass is molded：The high temp glass stoste that will have been melted is made original sheet glass by float glass process or die mould method；
4）Heat treatment：Original sheet glass is put into high temperature furnace and is heat-treated, it is raw in original sheet glass by being heat-treated after terminating
Into homogeneous negative expansion β-quartz solid solution crystallite, satisfactory devitrified glass is obtained.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511011585.8A CN106927682A (en) | 2015-12-30 | 2015-12-30 | A kind of negative expansion devitrified glass and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201511011585.8A CN106927682A (en) | 2015-12-30 | 2015-12-30 | A kind of negative expansion devitrified glass and preparation method thereof |
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| CN106927682A true CN106927682A (en) | 2017-07-07 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111302633A (en) * | 2018-12-12 | 2020-06-19 | 佛山市顺德区美的电热电器制造有限公司 | Negative expansion coefficient microcrystalline glass, preparation method thereof, glass product and cooking utensil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432181A (en) * | 2010-09-06 | 2012-05-02 | 株式会社正贯 | Crystallized glass with negative coefficient of thermal expansion and method for manufacturing the same |
| CN102838278A (en) * | 2012-09-18 | 2012-12-26 | 江苏宜达光电科技有限公司 | Negative thermal expansion microcrystalline glass and preparation method thereof |
-
2015
- 2015-12-30 CN CN201511011585.8A patent/CN106927682A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432181A (en) * | 2010-09-06 | 2012-05-02 | 株式会社正贯 | Crystallized glass with negative coefficient of thermal expansion and method for manufacturing the same |
| CN102838278A (en) * | 2012-09-18 | 2012-12-26 | 江苏宜达光电科技有限公司 | Negative thermal expansion microcrystalline glass and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111302633A (en) * | 2018-12-12 | 2020-06-19 | 佛山市顺德区美的电热电器制造有限公司 | Negative expansion coefficient microcrystalline glass, preparation method thereof, glass product and cooking utensil |
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