CN101693597B - Novel transparent glass ceramics and preparation process thereof - Google Patents
Novel transparent glass ceramics and preparation process thereof Download PDFInfo
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- CN101693597B CN101693597B CN2009102103868A CN200910210386A CN101693597B CN 101693597 B CN101693597 B CN 101693597B CN 2009102103868 A CN2009102103868 A CN 2009102103868A CN 200910210386 A CN200910210386 A CN 200910210386A CN 101693597 B CN101693597 B CN 101693597B
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Abstract
Disclosed are novel Na2O-CaO-SiO2 based transparent glass ceramics materials and the preparation process thereof. Compositions and mass percentage content of the glass ceramics raw materials are: 19.2% Na2O, 27.5% CaO, 48.3% SiO2, 2.5% TiO2+ZrO2, 0.5% Sb2O3 and 2% NH4NO3. The materials have high crystallinity (crystalline phase content is larger than 95%), zero porosity and micron-scale crystal grain size, and transmittance in a visible range is larger than 75%. The preparation process of the materials is: (1) glass smelting; (2) glass annealing; (3) glass cutting; (4) glass heat treatment; (5) glass ceramics cold working; (6) performance test. The transparent glass ceramics materials have simple production technology and low cost.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, a kind of high-crystallinity (crystal content is greater than 95%) be provided especially, zero void content, the micron order grain-size, in the visible-range transmitance greater than novel transparent glass ceramics material of 75% and preparation method thereof.
Background technology
Transparent glass ceramics (Glass-ceramics, also claim devitrified glass) be a class new function material that grew up in recent years, compare with crystalline material, it is low except having preparation cost, can mass production, be easy to prepare outside the conspicuous advantages such as complicated shape and large-sized sample, also because the characteristics of technology of preparing itself make it possess active ions doping height, microstructure is easy to advantages such as regulation and control; In addition, compare with the transparent ceramic material for preparing with sintering processing, it is not easy in the inner generation of polycrystalline defective, colour center, absorption, scattering etc., these significant advantages make transparent glass ceramics be expected to obtain widespread use, as civil areas such as solid laser medium material, scintillation material and information, illuminations.The research of transparent glass ceramics obtained the extensive concern of Chinese scholars in recent years, the nearly 3 years SCI about transparent glass ceramics research include paper and reach nearly hundred pieces, from the chemical constitution of these transparent glass-ceramics, mainly concentrate on oxyfluoride system, sulfur halide system, oxide-nitride objects system etc.With substrate glass bigger difference is arranged mutually owing to separate out chemical constitution, the physicals of crystalline phase, the common trait of these transparent glass-ceramics is crystal content lower usually (less than 70%), and control the crystalline phase grain-size tens nanometers, otherwise the transmitance of glass can be very undesirable.
Summary of the invention
The object of the present invention is to provide a kind of novel Na
2O-CaO-SiO
2It is transparent glass ceramics and preparation method thereof.This Na
2O-CaO-SiO
2Be that the transparent glass ceramics material is owing to precipitated phase (Na in crystallization process
2Ca
2Si
3O
9) change continuously with glass basis chemical ingredients mutually, the chemical ingredients of promptly separating out crystalline phase is similar to parent glass, thereby makes that the refractive index difference between the two-phase is minimum, thereby can obtain the transparent glass ceramics sample of height crystallization, big grain-size.
The present invention realizes by following technical scheme:
The main raw material(s) of the host glass of transparent glass ceramics of the present invention is Na
2O, CaO, SiO
2, add a spot of ZrO
2, TiO
2Improve the crystallization property of material; The NH of trace
4NO
3, Sb
2O
3The main clarification that rises guarantees that glass melting is even, does not have bubble.Na
2O-CaO-SiO
2Be that the transparent glass ceramics composition proportion is as shown in the table:
The feed composition of described glass-ceramic and best in quality degree are: 19.2%Na
2O, 27.5%CaO, 48.3%SiO
2, 2.5%TiO
2+ ZrO
2, 0.5%Sb
2O
3, 2%NH
4NO
3
Na of the present invention
2O-CaO-SiO
2Be that the technology that the preparation of transparent glass ceramics is adopted comprises following flow process: design of components-batching-ball milling mixing-high temperature melting-casting-controlled crystallization-cold working (sample).
In above-mentioned technology, adopt traditional fusion integrally crystallization legal system to be equipped with Na
2O-CaO-SiO
2It is transparent glass ceramics, press the mentioned component proportioning and form batching, ball milling after 2～3 hours in the silicon molybdenum rod furnace of 1400-1450 fusion 2～3h, the glass metal cast molding that fusion is good, 450 ℃～500 ℃ back 700 ℃～800 ℃ crystallization of annealing are handled, obtain the transparent glass ceramics sample of height crystallization, big grain-size, Fig. 2 is the scanning electron microscope pattern of the transparent laser glass for preparing of the present invention, shows sample grain-size of the present invention.
Concrete processing step is:
(1) glass melting: by described Na
2O-CaO-SiO
2It is the configuration material of the component of transparent laser glass-ceramic raw material and content even batch mixing after 3 hours in planetary ball mill, pour corundum crucible into, in silicon molybdenum resistance furnace,, inject the stainless steel mould of preheating, make the melt curing molding of lowering the temperature rapidly in 1450 ℃ of fusions 3 hours;
(2) glass annealing: the vitreum after the moulding is placed in 500 ℃ of retort furnaces insulation 2 hours rapidly, reduce to room temperature with stove then, obtain the block transparent glass;
(3) glass cutting: with cutting machine the glasswork for preparing is cut into fritter, be used for follow-up crystallization and thermal treatment;
(4) glass heat is handled: determine the glass crystallization heat treating regime according to differential thermal analysis curve, with the fritter sample after the cutting 675 ℃ of coring after 2 hours 725 ℃ of crystallization 2 hours, obtain transparent glass ceramics;
(5) glass-ceramic cold working: carry out twin grinding and polishing with the silicon carbide powder of the varying particle size glass-ceramic sample after with thermal treatment, grinding and polishing reaches the optical accuracy requirement, and finally obtaining the transparent glass ceramics thickness of sample is 2mm;
(6) performance measurement: employing ultraviolet-near infrared spectrometer measurement thickness is that the transmitance of the transparent laser glass-ceramic of 2mm is about 75%.
Description of drawings
Fig. 1 is the differential thermal analysis curve that utilizes the glass powder of method preparation of the present invention;
Fig. 2 is the scanning electron microscope pattern of the transparent laser glass for preparing of the present invention;
The transmittance curve of glass-ceramic after Fig. 3 pristine glass and the thermal treatment;
Fig. 4 is a transparent glass ceramics process flow sheet of the present invention.
Embodiment
Embodiment 1
A kind of Na
2O-CaO-SiO
2The raw material that is the transparent laser glass-ceramic is formed batching 100g, wherein measures 19.2%Na
2O, 27.5%CaO, 48.3%SiO
2, 2.5%TiO
2+ ZrO
2, 0.5%Sb
2O
3, 2%NH
4NO
3
Its preparation method comprises according to transparent glass ceramics process flow sheet shown in Figure 4:
(1) glass melting: by above-mentioned Na
2O-CaO-SiO
2Be the component of transparent laser glass-ceramic raw material and content configuration material in planetary ball mill evenly batch mixing pour corundum crucible into after 3 hours, in silicon molybdenum resistance furnace,, inject the stainless steel mould of preheating, the melt curing molding of lowering the temperature rapidly in 1450 ℃ of fusions 3 hours.
(2) glass annealing: the vitreum after the moulding is placed in 500 ℃ of retort furnaces insulation 2 hours rapidly, reduce to room temperature with stove then, obtain the block transparent glass;
(3) glass cutting: with cutting machine the glasswork for preparing is cut into fritter, be used for follow-up crystallization and thermal treatment;
(4) glass heat is handled: determine the glass crystallization heat treating regime according to differential thermal analysis curve, with the fritter sample after the cutting 675 ℃ of coring after 2 hours 725 ℃ of crystallization 2 hours, obtain transparent glass ceramics, Fig. 1 is the differential thermal analysis curve that utilizes the glass powder of method preparation of the present invention; Wherein, Tg is a glass transformation temperature, and Tc is the glass crystallization temperature.
(5) glass-ceramic cold working: carry out twin grinding and polishing with the silicon carbide powder of the varying particle size glass-ceramic sample after with thermal treatment, grinding and polishing reaches the optical accuracy requirement, and obtaining the transparent glass ceramics thickness of sample is 2mm;
(6) performance measurement: employing ultraviolet-near infrared spectrometer measurement thickness is that the transmitance of the transparent laser glass-ceramic of 2mm is about 75%.The transmittance curve of glass-ceramic after Fig. 3 pristine glass and the thermal treatment; Among the figure, top curve is the non-crystallized glass sample transmittance curve at 300～1200nm wave band; Below curve be that glass-ceramic sample after the crystallization is at the transmittance curve of 300～1200nm wave band.
Embodiment 2
A kind of Na
2O-CaO-SiO
2The raw material that is the transparent laser glass-ceramic is formed batching 100g, wherein 18.6%Na
2O, 26.9%CaO, 47.5%SiO
2, 4.5%TiO2+ZrO
2, 0.5%Sb
2O
3, 2%NH
4NO
3
The preparation method:
Glass heat is handled: sample obtains transparent glass ceramics 720 ℃ of crystallization 2 hours;
Other is with embodiment 1.
Claims (3)
1. Na
2O-CaO-SiO
2Be transparent glass ceramics, it is characterized in that the feed composition of described glass-ceramic and mass percentage content are: 17.5～20.0%Na
2O, 26.5～28.0%CaO, 45.5～50.0%SiO
2, 1.0～5.0%ZrO
2+ TiO
2, 0.1～0.5%Sb
2O
3, 1.0～2.0%NH
4NO
3
2. Na according to claim 1
2O-CaO-SiO
2Be transparent glass ceramics, it is characterized in that the feed composition of described glass-ceramic and mass percentage content are: 19.2%Na
2O, 27.5%CaO, 48.3%SiO
2, 2.5%TiO
2+ ZrO
2, 0.5%Sb
2O
3, 2%NH
4NO
3
3. Na according to claim 1
2O-CaO-SiO
2Be the preparation method of transparent glass ceramics, it is characterized in that comprising processing step:
(1) glass melting: by described Na
2O-CaO-SiO
2Be the configuration material of the component of transparent glass ceramics raw material and content in planetary ball mill evenly batch mixing pour corundum crucible into after 3 hours, in silicon molybdenum resistance furnace,, inject the stainless steel mould of preheating in 1450 ℃ of fusions 3 hours, make the melt curing molding of lowering the temperature rapidly;
(2) glass annealing: the vitreum after the moulding is placed in 500 ℃ of retort furnaces insulation 2 hours rapidly, reduce to room temperature with stove then, obtain the block transparent glass;
(3) glass cutting: with cutting machine the glasswork for preparing is cut into fritter, be used for follow-up crystallization and thermal treatment;
(4) glass heat is handled: determine the glass crystallization heat treating regime according to differential thermal analysis curve, with the fritter sample after the cutting 675 ℃ of coring after 2 hours 725 ℃ of crystallization 2 hours, obtain transparent glass ceramics;
(5) glass-ceramic cold working: carry out twin grinding and polishing with the silicon carbide powder of the varying particle size glass-ceramic sample after with thermal treatment, grinding and polishing reaches the optical accuracy requirement, and finally obtaining the transparent glass ceramics thickness of sample is 2mm;
(6) performance measurement: employing ultraviolet-near infrared spectrometer measurement thickness is that the transmitance of the transparent glass ceramics of 2mm is 75%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102103868A CN101693597B (en) | 2009-11-02 | 2009-11-02 | Novel transparent glass ceramics and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102103868A CN101693597B (en) | 2009-11-02 | 2009-11-02 | Novel transparent glass ceramics and preparation process thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101693597A CN101693597A (en) | 2010-04-14 |
| CN101693597B true CN101693597B (en) | 2011-06-08 |
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ID=42092612
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107601902B (en) * | 2017-09-20 | 2020-07-10 | 中南大学 | Rubidium-containing bioglass ceramic and preparation method thereof |
| CN110204324B (en) * | 2019-05-15 | 2020-11-20 | 浙江大学 | Preparation method and application of green fluorescent transparent ceramic |
| CN113698082B (en) * | 2021-09-10 | 2023-03-21 | 成都光明光电股份有限公司 | Method for producing glass-ceramic molded body |
| CN116693173A (en) * | 2023-06-08 | 2023-09-05 | 咸宁南玻光电玻璃有限公司 | Microcrystalline glass forming equipment |
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