CN103723926A

CN103723926A - Low-expansion lithium aluminum silicon transparent glass ceramic

Info

Publication number: CN103723926A
Application number: CN201310701075.8A
Authority: CN
Inventors: 田瑞平; 赵会峰; 吴建玉; 张振华; 姜宏; 潘国治; 崔永红; 周莉; 陈垂昌; 谭惠
Original assignee: HAINAN AVIC SPECIAL GLASS MATERIALS CO Ltd
Current assignee: Xinyi Glass (Hainan) Co.,Ltd.
Priority date: 2013-12-19
Filing date: 2013-12-19
Publication date: 2014-04-16
Anticipated expiration: 2033-12-19
Also published as: CN103723926B

Abstract

The invention belongs to the technical field of special glass production and manufacturing and provides low-expansion lithium aluminum silicon transparent glass ceramic. The low-expansion lithium aluminum silicon transparent glass ceramic comprises the following basic ingredients by mass percentage: 6-9% of B2O3, 5-10% of K2O+Na2O, 56-64% of SiO2, 13-18% of Al2O3, 2-4% of Li2O, and 1-3.5% of MgO, wherein clarifiers and nucleation agents are added into the basic ingredients of the transparent nucleated glass; the clarifiers are Sb2O3 and CeO2; the additions of Sb2O3 and CeO2 are 1.6% and 0.35% respectively; the nucleation agents are TiO2 and ZrO2; and the additions of TiO2 and ZrO2 are 2.5% and 0.8% respectively. The transparent nucleated glass has excellent light transmittance and chemical stability, high strength and low expansion coefficient.

Description

Low bulk lithium aluminium silicon series transparent glass-ceramics

Technical field

The invention belongs to special glass manufacturing technology field, relate generally to a kind of low bulk lithium aluminium silicon series transparent glass-ceramics.

Background technology

Devitrified glass, be a kind of glass particle by suitably forming through coalescent and crystallization, hard, the closely knit uniform composite diphase material of the quality being formed by crystallization phases and glassy phase of making.The formal name used at school of devitrified glass is glass-ceramic, there is glass and ceramic dual nature, devitrified glass is higher than ceramic brightness, stronger than glass toughness, can be used for building curtain wall and indoor high-grade decoration, also can be used as structured material mechanically, the insulating material on electronics, electrician, the baseboard material of large-scale integrated circuit, chemical industry and impregnating material and mine high-abrasive material etc.

In prior art, devitrified glass does not generally possess the transparency, uses the lithium silicon aluminum micro-crystal glass of tailings of high silicon iron as a kind of, and this has just limited the range of application of devitrified glass; In order to make devitrified glass there is certain transparency, in devitrified glass, add As ₂o ₃as finings, however As ₂o ₃all be there is to potentially dangerous in safety in production and environmental protection aspect.

Summary of the invention

For solving the problems of the technologies described above, the object of the invention is to propose a kind of low bulk lithium aluminium silicon series transparent glass-ceramics.

The present invention adopts following technical scheme for completing above-mentioned purpose:

A low bulk lithium aluminium silicon series transparent glass-ceramics, the basic components of described transparent glass-ceramics and mass percent are: B ₂o ₃6～9% K ₂o+ Na ₂o 5～10% SiO ₂56～64% A1 ₂o ₃13～18% Li ₂o 2～4% MgO 1～3.5%; And in the basic components of transparent glass-ceramics, add finings and Nucleating Agent; Described finings is Sb ₂o ₃and CeO ₂; Sb ₂o ₃and CeO ₂add-on be respectively 1.6% and 0.35%; Described Nucleating Agent is TiO ₂and ZrO ₂; TiO ₂and ZrO ₂add-on be respectively 2.5% and 0.8%.

Obtain excellent over-all properties, must make devitrified glass separate out the crystalline phase that a large amount of hope obtains, and make the crystalline size of separating out arrive micron-sized controlled range at nano level; The heat treated nucleation temperature of parent glass of described devitrified glass between 610～630 ℃, nucleation time 60min, crystallization temperature is between 830～850 ℃, crystallization time is 40min.

The crystallite of the devitrified glass obtaining by above-mentioned processing be take β-quartz solid solution as principal crystalline phase, the spherical particle that crystal grain diameter is 20～50nm; The coefficient of expansion α of devitrified glass _{20～400 ℃}be 15～20 * 10 ^-7/ ℃.

The specified range that low-expansion coefficient transparent microcrystal glass material of the present invention limits has directly determined the performance that glass board material possesses; Therefore the content analysis of each composition is as follows:

At the SiO that guaranteed minimizing suitable under the enough conditions of Network former ₂content, SiO ₂content when too much, the melting of glass, difficult forming; On the other hand, SiO ₂content when very few, vitrifying difficulty, it is large that the thermal expansivity of glass becomes, the resistance to sudden heating of glass reduces, the poor chemical stability of glass; So SiO in the present invention ₂content is decided to be 56%～64%.

The present invention has improved Al ₂o ₃content, adopt Al ₂o ₃replace part SiO ₂after, the Si in β-quartz ⁴⁺well-regulated quilt (Li ⁺+ Al ³⁺) ionic replacement, just generate the β-quartz solid solution with heterogeneity and character; By generate β-quartz solid solution in devitrified glass, obtain and make transparent glass-ceramics there is low-expansion coefficient and high transparent; So Al ₂o ₃content is decided to be 13～18%.

Li ₂the Li of O ⁺be filled in Al ³⁺near network space in and make electrically to reach neutralization, work as Li ₂o/Al ₂o ₃mol ratio < 1 time, crystallization amount Al ₂o ₃/ SiO ₂mol ratio reduce and reduce, and work as Li ₂o/Al ₂o ₃mol ratio be about at 1 o'clock, crystallization amount increases to some extent; So Li ₂o content is decided to be 2～4%.

Na ₂o has high temperature viscosity, raising meltbility and the formability that reduces glass, reduces the function of cracking frequency, improves the devitrification resistance of glass simultaneously; On the other hand, Na ₂when O content is too much, the thermal expansivity of glass becomes large, and the resistance to sudden heating of glass reduces; In addition, in composition design, improve K ₂the content of O contributes to SiO ₂fusing, increase the glossiness of glass, improve the chemical stability of glass; But K ₂when the content of O is too much, it is large that the thermal expansivity of glass becomes; Considering under the considering of glass component balance, so K ₂o and Na ₂o component sum interval is set to 5～10%.

Suitable MgO can improve chemical stability and the physical strength of glass, but the content of MgO is when high, and the strain point of glass is lower; Therefore the component content of MgO is 1～3.5%.

With B ₂o ₃the increase of content, the mobility of melten glass improves, and refining quality improves; B ₂o ₃introducing make glass there are many good performances: as good thermostability, chemical stability, mechanical property, processing performance and good optical property; But devitrified glass after treatment, with B ₂o ₃the increase of content, transparent variation; So B ₂o ₃component content be set as 6～9%.

Sb ₂o ₃and CeO ₂in body series, play finings effect, Sb ₂o ₃and CeO ₂at low temperature absorption oxygen, when high temperature, decomposing goes out oxygen, plays clarification, due to Sb ₂o ₃and CeO ₂clarifying temp different, the compound clarifier of its composition can play better clarification; The a small amount of Sb adding in composition design ³⁺, Ce ⁴⁺ion is in cyberspace, and silicon-oxy tetrahedron is around played to the effect of gathering, and improves contiguity and the tap density of network structure, increases the compactness of structure, reduces the coefficient of expansion, Sb ₂o ₃add-on be 1.6% and CeO ₂add-on be 0.35%.

Nucleating Agent Zr0 ₂and Ti0 ₂indispensable in devitrified glass components system; Ti0 ₂add again Zr0 outward ₂contribute to increase the stability of the β-quartz solid solution forming; As there is no a Zr0 ₂, β-quartz solid solution crystallite of separating out is easy to change into β-triphane crystallite, makes glass devitrification; Therefore the present invention adopts Zr0 ₂and Ti0 ₂composite Nucleation Agents, both mixing is used and can be made devitrified glass have a large amount of thin and microcrystals of size uniform; The amount of Nucleating Agent plays an important role to the size of nucleus, and the number of add-on directly affects the size of nucleus, also just affects the transparency of the finished product, adds 2.5% TiO in the present invention ₂add-on be 2.5%; ZrO ₂add-on be 0.8%.

A kind of low bulk lithium aluminium silicon series transparent glass-ceramics that the present invention proposes, by add finings and Nucleating Agent in glass ingredient, and parent glass is carried out to coring and crystallization and thermal treatment obtain and there is good light permeability, good chemical stability, high strength and low-expansion transparent glass-ceramics, the coefficient of expansion of devitrified glass is not more than 2.0 * 10 ^-6/ ℃, greatly reduce the coefficient of expansion of parent glass.

Embodiment

In conjunction with the following example, the present invention is illustrated, but does not form any limitation of the invention: (component content in embodiment is all by percentage to the quality):

Embodiment 1:

B ₂o ₃6%; K ₂o+ Na ₂o 8%; SiO ₂56%; A1 ₂o ₃18%; Li ₂o 3.25%; MgO 3.5%; Add 1.6% Sb ₂o ₃with 0.35% CeO ₂for finings; Add 2.5% TiO ₂with 0.8% ZrO ₂for Nucleating Agent.

By the glass of design, form and take various raw materials, and fully mix; The admixtion mixing is put into 1550 ℃ of corundum crucibles and founds, pour into piece after 600 ℃ of annealing be cooled to room temperature; Cooled parent glass is put in electric furnace and heat-treated, be first warming up to 610 ℃ of insulation 60min of nucleation temperature, then continue to be heated to 830 ℃ of insulation 40min of crystallization temperature and carry out crystallization processing; After thermal treatment finishes, control electric furnace cooling by sample temperature-reduction at constant speed, can obtain coefficient of expansion α _{20～400 ℃}be 18 * 10 ^-7/ ℃, grain size is only 20～50nm, 5.0mm sample transmitance Tvis (%) within the scope of 380～780nm test wavelength is 81.5%.

Embodiment 2:

B ₂o ₃9%; (K ₂o+ Na ₂o) 5%; SiO ₂62.75%; A1 ₂o ₃15.8%; Li ₂o 2%; MgO 1%; Add 1.6% Sb ₂o ₃with 0.35% CeO ₂for finings; Add 2.5% TiO ₂with 0.8% ZrO ₂for Nucleating Agent.

By the glass of design, form and take various raw materials, and fully mix.The admixtion mixing is put into 1550 ℃ of corundum crucibles and founds, pour into piece after 600 ℃ of annealing be cooled to room temperature; Cooled parent glass is put in electric furnace and heat-treated, be first warming up to 610 ℃ of insulation 60 min of nucleation temperature, then continue to be heated to 830 ℃ of insulation 40min of crystallization temperature and carry out crystallization processing; After thermal treatment finishes, control electric furnace cooling by sample temperature-reduction at constant speed, can obtain coefficient of expansion α _{20～400 ℃}be 15 * 10 ^-7/ ℃, grain size is only 20～50nm, 5.0mm sample transmitance Tvis (%) within the scope of 380～780nm test wavelength is 81.7%.

Embodiment 3:

B ₂o ₃7%; (K ₂o+ Na ₂o) 5.75%; SiO ₂64%; A1 ₂o ₃13%; Li ₂o 4%; MgO 1%; Add 1.6% Sb ₂o ₃with 0.35% CeO ₂for finings; Add 2.5% TiO ₂with 0.8% ZrO ₂for Nucleating Agent.

By the glass of design, form and take various raw materials, and fully mix; The admixtion mixing is put into 1550 ℃ of corundum crucibles and founds, pour into piece after 600 ℃ of annealing be cooled to room temperature; Cooled parent glass is put in electric furnace and heat-treated, be first warming up to 610 ℃ of insulation 60min of nucleation temperature, then continue to be heated to 830 ℃ of insulation 40min of crystallization temperature and carry out crystallization processing; After thermal treatment finishes, control electric furnace cooling by sample temperature-reduction at constant speed, can obtain coefficient of expansion α _{20～400 ℃}be 20 * 10 ^-7/ ℃, grain size is only 20～50nm, 5.0mm sample transmitance Tvis (%) within the scope of 380～780nm test wavelength is 82.1%.

Claims

1. a low bulk lithium aluminium silicon series transparent glass-ceramics, is characterized in that: the basic components of described transparent glass-ceramics and mass percent are: B ₂o ₃6～9% K ₂o+ Na ₂o 5～10% SiO ₂56～64% A1 ₂o ₃13～18% Li ₂o 2～4% MgO 1～3.5%; And in the basic components of transparent glass-ceramics, add finings and Nucleating Agent; Described finings is Sb ₂o ₃and CeO ₂; Sb ₂o ₃and CeO ₂add-on be respectively 1.6% and 0.35%; Described Nucleating Agent is TiO ₂and ZrO ₂; TiO ₂and ZrO ₂add-on be respectively 2.5% and 0.8%.

2. low bulk lithium aluminium silicon series transparent glass-ceramics according to claim 1, it is characterized in that: the heat treated nucleation temperature of parent glass of described devitrified glass is between 610～630 ℃, nucleation time 60min, crystallization temperature is between 830～850 ℃, and crystallization time is 40min.

3. low bulk lithium aluminium silicon series transparent glass-ceramics according to claim 1, is characterized in that: the crystallite of described transparent glass-ceramics be take β-quartz solid solution as principal crystalline phase, the spherical particle that crystal grain diameter is 20～50nm; The coefficient of expansion α of devitrified glass _{20～400 ℃}be 15～20 * 10 ^-7/ ℃.