CN106277800A

CN106277800A - Li2o Al2o3siO2the preparation method and application of system glass ceramics

Info

Publication number: CN106277800A
Application number: CN201610735292.2A
Authority: CN
Inventors: 李亮
Original assignee: HUBEI GEBIJIA PHOTOELECTRIC TECHNOLOGY CO LTD
Current assignee: HUBEI GEBIJIA PHOTOELECTRIC TECHNOLOGY CO LTD
Priority date: 2016-08-26
Filing date: 2016-08-26
Publication date: 2017-01-04
Anticipated expiration: 2036-08-26
Also published as: CN106277800B

Abstract

The invention discloses a kind of Li₂O‑Al₂O₃‑SiO₂The preparation method and application of system glass ceramics；This glass include by oxide on the basis of following components in parts by weight: SiO₂58 68 parts, Al₂O₃14 parts, ZrO₂13 parts, P₂O₅0.5 1 parts, K₂O 0.5 2 parts, CeO₂0.5 1 parts and Li₂O 25 28 parts.When specifically preparing, proportionally weigh the material of each component, mix homogeneously；Then at 1,450 1480 DEG C, found 2 5h, obtain the vitreous humour of high uniformity；Again vitreous humour is eliminated bubble and striped, finally enter cooling molding in mould；Wherein with ZrO₂And P₂O₅As mixing Nucleating Agent, the former main induced synthesis principal crystalline phase in glass system is β quartz solid solution, and the latter mainly promotes ZrO₂Dissolving in glass, improves nucleation rate, and the two is mutually promoted, thus obtains the devitrified glass that crystal grain is thinner, and the devitrified glass intensity so obtained is high, and good biocompatibility is with a wide range of applications.

Description

Li2O- Al2O3- SiO2The preparation method and application of system glass ceramics

Technical field

The invention belongs to bioglass material technical field, be specifically related to a kind of Li₂O- Al₂O₃- SiO₂System crystallite glass Glass and its preparation method and application.

Background technology

Li₂O- Al₂O₃- SiO₂The topmost characteristic of system glass ceramics is that thermal coefficient of expansion is in the biggest temperature range Adjustable, say, that can even zero thermal expansion coefficient the highest, the lowest or negative expansion at the biggest temperature range thermal expansion coefficient Coefficient, additionally, this kind of devitrified glass has highly desirable optical characteristics, such as good translucence or the highest transmitance, this A little performances make this kind of glass have to be widely applied very much.This Li₂O- Al₂O₃- SiO₂System glass ceramics mainly generates two Lithium metasilicate crystal, lithium bisilicate crystal has suitable thermal coefficient of expansion and optical refractive index, can reach good mutually with glass Thermodynamics and optical match so that lithium bisilicate glass ceramics, while possessing relatively high-mechanical property, remains to keep outstanding Semi-transparent characteristic.

At existing Li₂O- Al₂O₃- SiO₂In system crystallite, the single Nucleating Agent nucleation of many employings, obtained is micro- Crystal glass crystal grain is relatively big, and the intensity of glass is relatively low, and the sintering of glass and crystallize second-rate, some affect devitrified glass arrange Performance.

Summary of the invention

It is an object of the invention to provide the preparation method and application of Li2O-Al2O3-SiO2 system glass ceramics, obtain crystalline substance The devitrified glass that grain is thinner.

For solving above-mentioned technical problem, the technical solution adopted in the present invention is: a kind of Li₂O- Al₂O₃- SiO₂System Devitrified glass, including by the following components in parts by weight on the basis of oxide: SiO₂58-68 part, Al₂O₃1-4 part, ZrO₂ 1-3 part, P₂O₅0.5-1 part, K₂O 0.5-2 part, CeO₂0.5-1 part and Li₂O 25-28 part.

Preferably in scheme, including by the following components in parts by weight on the basis of oxide: SiO₂63 parts, Al₂O₃ 3 parts, ZrO₂3 parts, P₂O₅1 part, K₂O 2 parts, CeO₂0.8 part and Li₂O 27.2 parts.

Further, described K₂O is with carbonate (K₂CO₃) form introducing；Li₂O is with carbonate (Li₂CO₃) form introducing Du Absolutely KNO₃Decompose produced NO, NO₂Dusty gas；Al₂O₃With hydroxide (Al (OH)₃) form introducing, contribute to former Material preferably fusing.

The method preparing described glass, comprises the following steps:

Proportionally weigh the material of each component, mix homogeneously；Then at 1450-1480 DEG C, found 2-5h, obtain high uniform The vitreous humour of property；Again vitreous humour is eliminated bubble and striped, finally enter cooling molding in mould；Obtain Li₂O- Al₂O₃- SiO₂System glass ceramics.

Further, using V shape batch mixer during the mixing of described raw material, the time is 10-30 minute.

Further, the raw material of mix homogeneously is added in the platinum crucible being warming up to more than 1450 DEG C when founding, Found at being subsequently placed in 1450-1480 DEG C；Melting process uses platinum bubbler continuously bottom melting tank Bubbling in melting tank.

The invention still further relates to described Li₂O- Al₂O₃- SiO₂System glass ceramics application in full porcelain aesthetic orthopaedics.

K₂O is with K₂CO₃Form introduces, and has stopped KNO₃Decompose produced NO, NO₂Dusty gas.K₂O is cosolvent, Reduce the viscosity of vitreous humour, promote fusing and the clarification of vitreous humour, moreover it is possible to be substantially reduced the tendency towards devitrification of glass.

Al₂O₃The tendency towards devitrification of glass can be reduced, improve chemical stability and mechanical strength, improve heat stability.But contain Amount can not be the highest, otherwise can increase tendency towards devitrification, and easily make the defects such as brush line occur on glass raw sheet.

ZrO₂It is intermidate oxide, the viscosity of glass, hardness, elasticity, refractive index, chemical stability can be improved, reduce glass The thermal coefficient of expansion of glass.But content not can exceed that the 6% of effective oxide component, otherwise can cause crystallize.ZrO₂It it is nucleus simultaneously Agent, it is considered that separated out the crystallization rich in zirconium oxygen, and then induction mother glass nucleation before this from parent phase, at Li₂O- Al₂O₃- SiO₂In devitrified glass, ZrO₂Main induced synthesis principal crystalline phase is β-quartz solid solution, and paracrystalline phase is fine grain cube ZrO₂ Solid solution.

P₂O₅It is the oxide that can form glass network, silicate glass is had good nucleation capability, P₂O₅Make glass The reason producing nucleation is that he can promote split-phase, reduces interface energy, is that nucleation activation energy reduces.

CeO₂Can improve glass ultraviolet absorption ability and insolation proof effect, he is a kind of strong oxidizer, at high temperature adds Heat can release oxygen, shares with nitrate, can play certain clarification.

Wherein, ZrO₂And P₂O₅As mixing Nucleating Agent.SiO₂For forming the key component of glass, and glass is made to have one Series premium properties, such as transparency, mechanical strength, chemical stability and heat stability etc..

Li₂O is network modifying oxide, the most predominantly scission of link effect, and fluxing action is strong, is strong flux； Li₂O can make the coefficient of expansion of glass reduce, and crystallization tendency diminishes, and can reduce glass smelting temperature in glass, improves glass Quality.

Li₂O- Al₂O₃- SiO₂The topmost characteristic of system glass ceramics is that thermal coefficient of expansion is in the biggest temperature range Adjustable, say, that can even zero thermal expansion coefficient the highest, the lowest or negative expansion at the biggest temperature range thermal expansion coefficient Coefficient, additionally, this kind of devitrified glass has highly desirable optical characteristics, such as good translucence or the highest transmitance, this A little performances make this kind of glass have to be widely applied very much.

This Li₂O- Al₂O₃- SiO₂Mainly generating lithium bisilicate crystal in system glass ceramics, lithium bisilicate crystal has Suitable thermal coefficient of expansion and optical refractive index, can reach good thermodynamics and optical match mutually so that two silicon with glass Acid lithium glass pottery while possessing relatively high-mechanical property, remain to keep outstanding semi-transparent characteristic, it is achieved that high intensity and The unification of aesthetic effect, has broad application prospects in full porcelain aesthetic orthopaedics field.

Beneficial effects of the present invention is as follows:

1, with ZrO₂And P₂O₅As mixing Nucleating Agent, the former main induced synthesis principal crystalline phase in glass system is that β-quartz is solid Solution, the latter mainly promotes ZrO₂Dissolving in glass, improves nucleation rate, and the two is mutually promoted, thus obtains crystal grain more Thin devitrified glass, the properties for devitrified glass improves more obvious, improves the quality of devitrified glass

2, by ZrO₂And P₂O₅Additional proportion and other stream components ratios, preparation method technological parameter are controlled, system For the Li gone out₂O- Al₂O₃- SiO₂System glass ceramics intensity is high, and good biocompatibility has the highest using value.

Detailed description of the invention

Below in conjunction with specific embodiment, it is further elucidated with the present invention.These embodiments are interpreted as being merely to illustrate this Bright rather than be used for limiting the scope of the invention.After having read the content that the present invention records, those skilled in the art Can make various changes or modifications the present invention, these equivalence changes and modification fall into claims of the present invention equally and are limited Scope.

Embodiment 1

A kind of Li₂O- Al₂O₃- SiO₂System glass ceramics, including by parts by weight following group on the basis of oxide Point:

SiO₂63 parts；

Al₂O₃3 parts；

ZrO₂3 parts；

P₂O₅1 part；

K₂O 2 parts；

CeO₂0.8 part；

Li₂O 27.2 parts.

Embodiment 2

SiO₂65 parts；

Al₂O₃2 parts；

ZrO₂3 parts；

P₂O₅1 part；

K₂O 2 parts；

CeO₂0.5 part；

Li₂O 26.5 parts

Embodiment 3

SiO₂65 parts；

Al₂O₃4 parts；

ZrO₂1.5 part；

P₂O₅0.8 part；

K₂O 2 parts；

CeO₂1 part；

Li₂O 25.7 parts.

Embodiment 4

SiO₂61 parts；

Al₂O₃4 parts；

ZrO₂3 parts；

P₂O₅1 part；

K₂O 2 parts；

CeO₂1 part；

Li₂O 28 parts.

Embodiment 5

SiO₂68 parts；

Al₂O₃2 parts；

ZrO₂1 part；

P₂O₅1 part；

K₂O 2 parts；

CeO₂1 part；

Li₂O 25 parts.

In above example, K₂O is with carbonate (K₂CO₃) form introducing；Li₂O is with carbonate (Li₂CO₃) form introducing； Al₂O₃With hydroxide (Al (OH)₃) form introducing.

Comparative example 1: specially press the following components in parts by weight on the basis of oxide: SiO₂63 parts, Al₂O₃ 3 Part, ZrO₂0 part, P₂O₅1 part, K₂O 2 parts, CeO₂0.8 part and Li₂O 27.2 parts.

Comparative example 2: specially press the following components in parts by weight on the basis of oxide: SiO₂63 parts, Al₂O₃ 3 Part, ZrO₂3 parts, P₂O₅0 part, K₂O 2 parts, CeO₂0.8 part and Li₂O 27.2 parts.

The concrete preparation method of above devitrified glass, comprises the following steps that

1) proportionally weighing the material of each component, each component raw material mixed with V shape batch mixer, incorporation time is 20 points Clock, the raw material being uniformly mixed；

2) raw material of described step 1) mix homogeneously is joined in the platinum crucible being warming up to more than 1450 DEG C, 1450 Founding 2 h at DEG C, platinum bubbler continuously bubbling in melting tank bottom melting tank in melting process, by melting tank Interior glass mix homogeneously, obtains the vitreous humour of high uniformity；

3) described step 2) vitreous humour flowed into by the melting tank vomit pipe bottom melting tank rear wall in the platinum dish of rear end Carry out eliminating bubble and striped, the vitreous humour of be eliminated bubble and striped；

4) described step 3) eliminates the discharge nozzle that the vitreous humour of bubble and striped heats through platinum direct-electrifying, enters into molding Cooling in mould；Obtain Li₂O- Al₂O₃- SiO₂System glass ceramics.

Carry out the sample that comparative example 1,2 and embodiment 1 prepare including flexural strength, chemical solubility, the coefficient of expansion, turning Temperature and hardness (exerting formula) are in interior performance test test, and result is as shown in table 1:

The performance test data of table 1 each sample

In comparative example 1 and comparative example 2, use P respectively₂O₅And ZrO₂For Nucleating Agent, comparative example 1 is not added ZrO₂, comparative example P is not added in 2₂O₅.With P₂O₅Compare, ZrO₂The density of raw material is big, and refractive index is high, obvious for improving strength of glass effect. As shown in Table 1, ZrO is used₂The flexural strength of comparative example 2 sample, transition temperature, density and refractive index number for independent Nucleating Agent Value is above P₂O₅For the sample of the comparative example 1 of independent Nucleating Agent, and thermal coefficient of expansion is less than the sample of comparative example 1.

In embodiment 1, use ZrO₂And P₂O₅For Nucleating Agent, the performance data of sample and two kinds of raw materials are for for glass The impact of character is consistent, and the former main induced synthesis principal crystalline phase in glass system is β-quartz solid solution, and the latter mainly promotees Enter ZrO₂Dissolving in glass, improves nucleation rate, and the two is mutually promoted, and obtains a kind of Li₂O- Al₂O₃- SiO₂System is micro- Crystal glass.

The above embodiments are only the preferred technical solution of the present invention, and are not construed as the restriction for the present invention, this Shen Embodiment in please and the feature in embodiment, can mutual combination in any in the case of not conflicting.The protection model of the present invention Enclose the technical scheme should recorded with claim, including the equivalent side of technical characteristic in the technical scheme that claim is recorded Case is protection domain.Equivalent the most in this range is improved, also within protection scope of the present invention.

Claims

1. a Li₂O- Al₂O₃- SiO₂System glass ceramics, it is characterised in that: on the basis of including by oxide with weight The following components of part meter: SiO₂58-68 part, Al₂O₃1-4 part, ZrO₂1-3 part, P₂O₅0.5-1 part, K₂O 0.5-2 part, CeO₂ 0.5-1 part and Li₂O 25-28 part.

Glass the most according to claim 1, it is characterised in that: on the basis of including by oxide in parts by weight below Component: SiO₂63 parts, Al₂O₃3 parts, ZrO₂3 parts, P₂O₅1 part, K₂O 2 parts, CeO₂0.8 part and Li₂O 27.2 parts.

Glass the most according to claim 1, it is characterised in that: described K₂O is with carbonate (K₂CO₃) form introducing；Li₂O with Carbonate (Li₂CO₃) form introducing；Al₂O₃With hydroxide (Al (OH)₃) form introducing.

4. the method for glass described in preparation claim 1-3 any one, it is characterised in that comprise the following steps:

Method the most according to claim 4, it is characterised in that: using V shape batch mixer during the mixing of described raw material, the time is 10-30 minute.

Method the most according to claim 4, it is characterised in that: when founding, the raw material of mix homogeneously is added and be warming up to In the platinum crucible of more than 1450 DEG C, found at being subsequently placed in 1450-1480 DEG C；Melting process is adopted bottom melting tank With platinum bubbler continuously bubbling in melting tank.

7. the Li described in claim 1-3 any one₂O- Al₂O₃- SiO₂System glass ceramics is in full porcelain aesthetic orthopaedics Application.