CN109678341A

CN109678341A - Alkali-free glass compositions and alkali-free glass and application

Info

Publication number: CN109678341A
Application number: CN201811512297.4A
Authority: CN
Inventors: 张广涛; 李青; 郑权; 王丽红; 闫冬成; 安利营; 王俊峰; 田鹏
Original assignee: Tunghsu Group Co Ltd; Tunghsu Technology Group Co Ltd
Current assignee: Dongxu Optoelectronic Technology Co Ltd
Priority date: 2018-12-11
Filing date: 2018-12-11
Publication date: 2019-04-26
Anticipated expiration: 2038-12-11
Also published as: CN109678341B

Abstract

The present invention relates to glass art, a kind of alkali-free glass compositions and alkali-free glass and preparation method thereof are disclosed.The alkali-free glass compositions include: on the basis of the total weight of alkali-free glass compositions, which contains the SiO of 58-64wt%₂, 16-19wt% Al₂O₃, 7-13wt% B₂O₃+P₂O₅, 0.5-3.5wt% MgO, 4-8wt% CaO, 0.1-4wt% SrO, 0-2.5wt% BaO, 0-4wt% ZnO, the R less than 0.05wt%₂O, wherein R₂O is Li₂O、Na₂O、K₂The sum of content of O.Glass mechanical strength with higher, the lesser density of composition preparation of the present invention, higher chemical corrosion resistance (i.e. high chemical stability), low thermal expansion coefficient (are lower than 38 × 10^‑7/ DEG C), the excellent properties such as higher strain point temperature, can be used for preparing display device and/or area of solar cell, have a good application prospect.

Description

Alkali-free glass compositions and alkali-free glass and application

Technical field

The present invention relates to glass arts, and in particular to alkali-free glass compositions and alkali-free glass and application.

Background technique

LCD technology has become the key technology of modern most important picture transmission and reproduction.Liquid crystal display Principle is imaged, is to be placed in liquid crystal between two panels electro-conductive glass, by the driving of two electric field between electrodes, causes twisted liquid crystal molecules The field effect of nematic generates light and shade between power supply pass is opened and shows image to control lit transmissive or shielding function Come, if adding colored filter, can show chromatic image.TFT liquid crystal display mode, with 600 times faster than old-fashioned LCD screen Pixel response speed.Advanced silicon electrode is added, and greatly accelerates the pixel response speed of LCD screen, reduces what picture occurred Delay phenomenon.Higher technical requirements are proposed to glass substrate, the geometric dimension of the substrate after processing must not heating condition Influence, i.e., the thermal expansion coefficient of this kind of glass substrate wants small, according to glass substrate make in the stress resultant of production consider, Best thermal expansion coefficient is 28 × 10^-7/ DEG C or so.

For the glass substrate of TFT-LCD, need through technologies such as sputtering, chemical vapor depositions (CVD) in underlying substrate Glass surface forms transparent conductive film, insulating film, semiconductor (polysilicon, amorphous silicon etc.) film and metal film, then passes through light Etching (Photo-etching) technology forms various circuits and figure, if glass contains alkali metal oxide (Na₂O, K₂O, Li₂O), alkali metal ion diffuses into deposited semiconductor material during heat treatment, damages semiconductor film characteristic, therefore, glass Glass should be free of alkali metal oxide, it is necessary to use alkali-free glass, it is preferred that with SiO₂、Al₂O₃、B₂O₃And alkaline earth oxide RO (RO=Mg, Ca, Sr, Ba) etc. is the silicate glass containing boron and aluminium without alkali of principal component.

Now with the quick universal of portable electronic device (such as laptop, smart phone, PDA), to accessory Lightweight proposes requirements at the higher level.Thus to the composition of glass substrate, more stringent requirements are proposed, to guarantee to adapt to modern liquid crystal The needs of display.Glass substrate must have the property that containing alkali metal oxide less than 1000ppm；Has chemical resistance； Thermal expansion coefficient must be close with the silicon of thin film transistor (TFT)；Strain point of glass is improved, to reduce thermal shrinking quantity；With lesser close Degree, in order to carry and hold.

In addition to lightweight, the glass substrate for portable electronic device also needs to meet people and executes and enjoy all the time By the requirement of commercial affairs and the recreation of higher level.Such demand requires also to be continuously improved to display performance, especially The image quality of intelligent movable equipment, visual performance requirement outdoors are also being promoted.Under the guidance of this trend, Display panel develops to the direction that lightening, ultra high-definition is shown, on the one hand, it is required that glass substrate should have it is lesser close Degree；On the other hand, panel making technology manages temperature development to higher height；Monolithic glass passes through process simultaneously, and thickness reaches 0.25mm, 0.2mm, 0.1mm, 0.05mm are even more thin.

The mode for keeping glass thinning is presently mainly chemical reduction, specifically, uses hydrofluoric acid or buffered hydrofluoric acid solution Glass substrate is corroded, thinning principle is as follows:

Main chemical reactions: 4HF+SiO₂=SiF₄+2H₂O；

Secondary chemical reaction: RO+2H⁺=R²⁺+H₂O (R represents alkaline-earth metal etc.).

Surface quality and parent glass composition after chemical reduction technique and thinning glass substrate have certain relationship, existing TFT-LCD base plate glass frequently occurs the bad deficient point such as " pit ", " sags and crests " during chemical reduction, increases and is produced into This.Glass with high chemical stability has better surface quality after being thinned, therefore researches and develops high chemical stability TFT-LCD base plate glass, it is possible to reduce the production costs such as second polishing promote product quality and yields, for large scale industry Metaplasia production has larger benefit.And excessively slow hydrofluoric acid or buffered hydrofluoric acid solution corrosion rate can reduce thinning factory production efficiency.

According to the technical standard of liquid crystal display, it is special that the glass substrate of TFT-LCD must have basic physics below Property:

1, the thermal expansion coefficient of glass substrate must be enough low, is not higher than 38 × 10^-7/℃；

2, the strain point temperature of glass substrate should be higher than that 640 DEG C；

3, density is lower than 2.6g/cm³, and it is more lighter better.

But with the progress of LCD technology, curved-surface display, advanced lines panel propose one to the performance of glass substrate A little new requirements require for example, can bear smaller radius of curvature in bending without rupturing, and large-size substrate is passing Occurs sag of chain small as far as possible during defeated.This just needs glass substrate to improve bending strength, Young's modulus or than machines such as moduluses Tool performance.And under normal conditions, the improvement (enhancing) of mechanical performance often brings middle warm area viscosity (strain point, annealing point, softening Near point) and the undesirable variation of high-temperature region viscosity (forming temperature, fusion temperature etc.) appearance.Such as in practical alkali-free liquid-crystalline glasses In composition, Al₂O₃, the oxides such as MgO, SrO, BaO increase improve Young's modulus, but deposit physics and chemistry in other respects The drawbacks of capable of being deteriorated, for example, promoting Al₂O₃Content will lead to liquidus temperature and be substantially improved；Content of MgO is promoted, will lead to point Mutually tendency increases, liquidus temperature is substantially improved and declines to a great extent with low temperature viscosity；SrO content and/or BaO content are promoted, can be led It causes high temperature viscosity of glass to increase to be substantially increased with density, is unfavorable for improving than modulus.

CN105392743A discloses the alkali-free glass of a kind of high Young's modulus and Gao Bi elasticity modulus, and Young's modulus is 94.5GPa or more, than elasticity modulus be 34.5GPa/ (g/cm³) more than, but have the excessively high coefficient of expansion, 50-350 DEG C it Between mean thermal expansion coefficients be all larger than 38 × 10^-7/ DEG C, it is unable to satisfy TFT LCD technology requirement；

CN104211300A discloses a kind of alkali-free glass formula of high specific modulus, and elasticity modulus is higher than 82GPa, compares mould Number is higher than 33GPa/ (g/cm³), while middle warm area viscosity with higher, strain point are higher than 720 DEG C.In order to reach above-mentioned mesh Mark, this application have used more Al in composition₂O₃With less B₂O₃, to provide mechanical strength and Heat-resistant stable simultaneously Property.But the compositing characteristic will lead to declining to a great extent for chemical-resistant stability, particularly hydrofluoric acid corrosion resistance, be unfavorable for current The demand of lightening substrate manufacture.

Therefore, it needs a kind of while having both improved mechanical performance and the glass of other performances, to be suitble to TFT liquid crystal display The requirement of technology.

Summary of the invention

The purpose of the invention is to overcome improvement glass machinery performance of the existing technology that can damage other performances (such as Heat-resistant stability, chemical corrosion resistance) the problem of making it not be able to satisfy TFT LCD technology requirement, alkali-free glass group is provided Close object and alkali-free glass and application.

To achieve the goals above, first aspect present invention provides a kind of alkali-free glass compositions, comprising: with alkali-free glass On the basis of the total weight of glass composition, which contains the SiO of 58-64wt%₂, 16-19wt% Al₂O₃、7- The B of 13wt%₂O₃+P₂O₅, 0.5-3.5wt% MgO, 4-8wt% CaO, 0.1-4wt% SrO, 0-2.5wt% BaO, The ZnO of 0-4wt%, the R less than 0.05wt%₂O, wherein R₂O is Li₂O、Na₂O、K₂The sum of content of O.

Second aspect of the present invention provides the glass made of glass composition of the present invention.

Third aspect present invention provides the method that the glass composition as described in first aspect present invention prepares glass, the party Method includes: to melt glass composition described in first aspect present invention, form, making annealing treatment, and machining processes.

The alkali-free glass made of glass composition of the present invention has high mechanical strength, suitable resistant to chemical etching Property, excellent heat-resistant stability, specifically, the alkali-free glass have following performance standard:

A. crooked test maximum stress value σ_max≥80MPa；And

B. crooked test maximum strain amount ε_max≥1500×10^-6。

In addition, other physical characteristics of the alkali-free glass can be stable reach:

(1) density≤2.49g/cm³；

(2) thermal expansion coefficient within the scope of 50-350 DEG C is lower than 38 × 10^-7/℃；

(3) Young's modulus >=72GPa, than modulus >=30GPa (g/cm³)；

(4) strain point T_stIt is 650 DEG C -730 DEG C；

(5) liquidus temperature T_L≤1200℃；

(6) viscosity is the corresponding temperature T of 200 pools₂₀₀≤1630℃；

(7) hydrofluoric acid corrosion rate is 4mg/cm²-6.5mg/cm²；

(8) wavelength is transmitance >=50% at 308nm；

(9) 1200 DEG C of surface tension≤370mN/m；

(10) Vickers hardness >=580kgf/cm²；

(11) refractive index nD≤1.53.

Preferably, what the characteristic of the alkali-free glass can be stable reaches:

(1) crooked test maximum stress value σ_max≥100MPa；And

(2) crooked test maximum strain amount ε_max≥1600×10^-6；

(3) density≤2.42g/cm³；

(4) thermal expansion coefficient within the scope of 50-350 DEG C is lower than 36 × 10^-7/℃；

(5) Young's modulus >=73GPa, than modulus >=30.5GPa (g/cm³)；

(6) strain point T_stIt is 680 DEG C -700 DEG C；

(7) liquidus temperature T_L≤1130℃；

(8) viscosity is the corresponding temperature T of 200 pools₂₀₀≤1627℃；

(9) hydrofluoric acid corrosion rate is 4.5mg/cm²-5.2mg/cm²；

(10) wavelength is transmitance >=70% at 308nm；

(11) 1200 DEG C of surface tension≤360mN/m

(12) Vickers hardness >=620kgf/cm²；

(13) refractive index nD≤1.52.

Fourth aspect present invention provides the glass as described in second aspect of the present invention in display device and/or solar battery In application.

Glass mechanical strength with higher (the i.e. high crooked test maximum stress value of composition preparation of the present invention With crooked test maximum strain amount), higher chemical corrosion resistance (i.e. high chemical stability), low thermal expansion coefficient is (low In 38 × 10^-7/ DEG C), the excellent properties such as higher strain point temperature.The glass can be used for preparing display device and/or the sun Energy battery, is particularly suitable for preparing the substrate glass substrate material of flat panel display product and/or screen surface protection glass-film Layer material, the substrate glass substrate material of Flexible Displays product and/or surface encapsulation glass material and/or screen surface protection are used Glass film layers material, the substrate glass substrate material of flexible solar battery, safety glass, bulletproof glass, intelligent automobile glass, Intelligent transportation display screen, intelligent show window and smart card ticket and high thermal stability and mechanical stability glass material are needed for other The application field of material.

Specific embodiment

The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.

First aspect present invention provides a kind of alkali-free glass compositions, comprising: with the total weight of alkali-free glass compositions On the basis of, which contains the SiO of 58-64wt%₂, 16-19wt% Al₂O₃, 7-13wt% B₂O₃+P₂O₅、 The ZnO of BaO, 0-4wt% of SrO, 0-2.5wt% of CaO, 0.1-4wt% of MgO, 4-8wt% of 0.5-3.5wt%, it is less than The R of 0.05wt%₂O, wherein R₂O is Li₂O、Na₂O、K₂The sum of content of O.

According to the present invention, on the basis of the total weight of alkali-free glass compositions, which contains: 58-64wt% SiO₂, such as SiO₂Content can for 58wt%, 58.4wt%, 58.5wt%, 58.9wt%, 59.5wt%, 59.7wt%, 59.8wt%, 60wt%, 61.4wt%, 61.7wt%, 61.8wt%, 61.9wt%, 62wt%, 62.1wt%, 62.2wt%, 62.3wt%, 62.4wt%, 62.5wt%, 62.6wt%, 62.7wt%, 62.8wt%, 62.9wt%, Appointing in 63wt%, 63.3wt%, 63.6wt%, 63.7wt%, 63.8wt%, 63.9wt%, 64wt% and these point values Arbitrary value in two ranges constituted of anticipating；

The Al of 16-19wt%₂O₃, such as Al₂O₃Content can for 16wt%, 16.3wt%, 16.8wt%, 17.1wt%, 17.2wt%, 17.3wt%, 17.4wt%, 17.5wt%, 17.6wt%, 17.7wt%, 17.8wt%, 17.9wt%, 18wt%, 18.1wt%, 18.3wt%, 18.5wt%, 18.8wt%, 18.9wt%, 19wt% and these points The arbitrary value in range that any two in value are constituted；

The B of 7-13wt%₂O₃+P₂O₅, such as B₂O₃、P₂O₅The sum of content can for 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%, 10wt%, 10.5wt%, 11wt%, 11.5wt%, 12wt%, 12.5wt%, 13wt% And the arbitrary value in the range that is constituted of any two in these point values；

The MgO of 0.5-3.5wt%, for example, MgO content can for 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2.1wt%, 2.4wt%, 2.6wt%, 2.8wt%, 3wt%, 3.1wt%, 3.3wt%, 3.5wt% And the arbitrary value in the range that is constituted of any two in these point values；

The CaO of 4-8wt%, for example, CaO content can for 4.1wt%, 4.4wt%, 4.8wt%, 5wt%, 5.2wt%, 5.3wt%, 5.4wt%, 5.5wt%, 5.6wt%, 5.7wt%, 5.8wt%, 5.9wt%, 6wt%, 6.1wt%, 6.2wt%, 6.3wt%, 6.4wt%, 6.6wt%, 6.8wt%, 7.1wt%, 7.2wt%, 7.3wt%, The arbitrary value in range that any two in 7.5wt%, 7.7wt%, 8wt% and these point values are constituted；

The SrO of 0.1-4wt%, for example, SrO content can for 0.1wt%, 0.2wt%, 0.4wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, Any two in 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt%, 4wt% and these point values The arbitrary value in range constituted；

The BaO of 0-2.5wt%, for example, BaO content can for 0wt%, 0.2wt%, 0.4wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt% And the arbitrary value in the range that is constituted of any two in these point values；

The ZnO of 0-4wt%, for example, ZnO content can for 0wt%, 0.1wt%, 0.2wt%, 0.26wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 2wt%, 2.5wt%, Appointing in the range that any two in 2.8wt%, 3wt%, 3.3wt%, 3.7wt%, 4wt% and these point values are constituted Meaning value.

In the present invention, the alkali-free glass compositions are interpreted as not needing in the composition in addition adding alkali metal group Point, the alkaline components can be added in the form of any simple substance or compound containing alkali metal element.The alkali metal Including Li, Na and/or K.

In alkali-free glass compositions of the present invention, SiO₂For glass former, if SiO₂Content it is too low, be unfavorable for The enhancing of endurance and corrosion resistance, it is excessively high to will cause the coefficient of expansion, and glass is caused to be easy devitrification；If SiO₂Content increase, Although facilitating glass lightweight, thermal expansion coefficient reduces, and strain point increases, and endurance increases, SiO₂Too high levels The high temperature viscosity that will cause alkali-free glass obtained increases, i.e., fusion temperature increases, and is unfavorable for melting in this way, and general kiln is difficult To meet conventional high capacity smelting technology for material melt batch.It is therefore preferred that SiO₂Content be 58-64wt%, this Sample is conducive to endurance, mechanical strength and the high temperature viscosity of further taking into account gained alkali-free glass.

In alkali-free glass compositions of the present invention, work as Al₂O₃Content it is too low when, glass heat resistance is difficult to be promoted, It is easy the erosion by extraneous aqueous vapor and chemical reagent；Work as Al₂O₃Content increase when, although facilitating strain point of glass, machinery Intensity increases, but Al₂O₃Too high levels be easy to appear crystallization, while can glass be difficult to melt.Preferably, with alkali-free On the basis of the total weight of glass composition, Al₂O₃Content be 17-18wt%, be conducive to advanced optimize gained alkali-free glass in this way Heat resistance, endurance and the mechanical strength of glass, and improve crystallization property.

In alkali-free glass compositions of the present invention, B₂O₃、P₂O₅As the matrix for constituting glass, it can be individually created glass, They be added can reinforcing glass chemical stability, mechanical performance, while B₂O₃、P₂O₅It is also good fluxing agent, high temperature item High temperature viscosity can be reduced under part, and glass melting temperature can be greatly reduced, it is also helpful for During Vitrification in vitro；B, which has, when low temperature takes by force The trend for taking free oxygen makes structure tend to the low temperature difficulty for closely improving glass, prevents the generation of crystallization.But it is excessive B₂O₃Strain point of glass can be made to be greatly reduced.Preferably, on the basis of the total weight of alkali-free glass compositions, B₂O₃With P₂O₅Weight The sum of amount content meets 7wt% < B₂O₃+P₂O₅≤ 13wt%；It is further preferred that 8.8wt%≤B₂O₃+P₂O₅≤ 11wt%.

In alkali-free glass compositions of the present invention, adding appropriate ZnO helps to reduce crystallization temperature, and then inhibits analysis Crystalline substance, and can reduce high temperature viscosity of glass is conducive to eliminate bubble, at the same have below softening point promoted glass intensity, Hardness, endurance, the effect for reducing thermal expansion coefficient of glass.Theoretically, ZnO in alkali-free glass, draws as network outer body After entering glass, generally with [ZnO under high temperature₄] form exist, compared with [ZnO₆] glass structure is more loose, with the glass for being free of ZnO It being compared under same high temperature state, the glass viscosity containing ZnO is smaller, and atomic motion speed is bigger, nucleus can not be formed, It needs to further decrease temperature, is just conducive to the formation of nucleus, thus reduce the crystallization ceiling temperature of glass.And ZnO content Excessively the strain point of glass can be made to be greatly lowered, be unfavorable for the promotion of glass substrate thermal stability.

In alkali-free glass compositions of the present invention, MgO, CaO, SrO, BaO belong to alkaline earth oxide, they The high temperature viscosity that can effectively reduce glass is added to improve the meltbility and formability of glass, and the strain of glass can be improved Point.In addition, MgO, BaO have the characteristics that improve alkali-free glass chemical stability and mechanical stability.But alkaline-earth metal oxide The content of object can excessively be such that the density of alkali-free glass increases, the incidence raising of crackle, devitrification, split-phase.

In a preferred embodiment, which contains the SiO of 61-63wt%₂, 17-18wt% Al₂O₃, 8.8-11wt% B₂O₃+P₂O₅, 1.1-2.7wt% MgO, 5.4-7.7wt% CaO, 1.6-3.6wt% The ZnO of BaO, 0wt% of SrO, 0wt%, the R less than 0.05wt%₂O, wherein R₂O is Li₂O、Na₂O、K₂The sum of content of O.

In alkali-free glass compositions of the present invention, it is further preferred that the total weight with alkali-free glass compositions is Benchmark, SiO₂And Al₂O₃The sum of content Q meets Q > 75wt%；It is further preferred that 75wt% < Q < 82wt%；It is further excellent Selection of land, 78wt% < Q < 81wt%, in this way can the alkali-free glass obtained by improving to the maximum extent chemical resistance, corrosion-resistant Property, heat resistance, machinability and mechanical strength, while reducing the probability for crystallization occur.

In alkali-free glass compositions of the present invention, although B₂O₃、P₂O₅It is all good fluxing agent, so that raw material melts More easily.But B₂O₃/(B₂O₃+P₂O₅) weight percentage than it is too low when, can be to a certain degree such as down to 0.1 or 0.01 Upper raising liquidus temperature, while can also damage chemical corrosion resistance.Preferably, B₂O₃、(B₂O₃+P₂O₅) weight ratio B₂O₃/ (B₂O₃+P₂O₅) > 0.1, such as can be appointing in 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1 and these point values Arbitrary value in two ranges constituted of anticipating；It is further preferred that 0.8 < B₂O₃/(B₂O₃+P₂O₅)≤1。

In composition of the present invention, alkaline earth oxide such as MgO, CaO, SrO, BaO can effectively reduce glass High temperature viscosity, but R ' O/ (B₂O₃+P₂O₅) weight ratio it is too high or too low can all bring undesirable influence, wherein R ' be MgO, The sum of CaO, SrO, BaO and ZnO content.Work as R ' O/ (B₂O₃+P₂O₅) it is lower when, when being, for example, less than 0.5, glass can be significantly reduced Thermal stability is (here, use strain point temperature T_stCharacterize the thermal stability of glass, T_stHigher, the thermal stability of glass is higher), Liquidus temperature can increase simultaneously；And work as R ' O/ (B₂O₃+P₂O₅) it is higher when, such as when higher than 1.9, can also improve the liquid of glass Liquidus temperature, the increase of simultaneous thermal expansion coefficient.It is preferred that 0.5 < R ' O/ (B₂O₃+P₂O₅) < 1.9, such as It can be any one value in 0.6,0.8,1,1.2,1.4,1.6,1.8 and above-mentioned numerical value in any two institute compositing range； Further preferably 0.9 < R ' O/ (B₂O₃+P₂O₅) < 1.3, still more preferably 1.0 < R ' O/ (B₂O₃+P₂O₅) < 1.2, more Further preferably R ' O/ (B₂O₃+P₂O₅)=1.1.

In alkali-free glass compositions of the present invention, the weight ratio of MgO, CaO also will affect glass combination raw material Liquidus temperature, such as when MgO/CaO ratio is excessively high, the liquidus temperature of glass combination raw material can be also obviously improved, no Conducive to the industrialization manufacture of glass.It is preferred that MgO, CaO content ratio, 0.1 < MgO/CaO < 0.9, such as can be 0.2,0.3,0.4,0.5,0.6,0.7,0.8 and these point values in the constituted range of any two in arbitrary value, into one Walk preferably 0.15 < MgO/CaO < 0.5.

In alkali-free glass compositions of the present invention, the weight ratio of SrO, CaO also will affect glass combination raw material Liquidus temperature, such as when SrO/CaO ratio is excessively high, the liquidus temperature of glass combination raw material can be also obviously improved, no Conducive to the industrialization manufacture of glass.It is preferred that SrO, CaO content ratio SrO/CaO > 0.01, for example, can for 0.05, 0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.8 and these point values in it is any Arbitrary value in two constituted ranges；Preferably 0.2 < SrO/CaO < 0.6, more preferably 0.3 < SrO/CaO < 0.45.

According to the present invention, in the alkali-free glass compositions, on the basis of the total weight of alkali-free glass compositions, BaO Content be less than 2wt%；Preferably, the content of BaO is less than 1.5wt%；It is further preferred that the content of BaO is less than 1wt%； It is further preferred that the content of BaO is less than 0.005wt%, it is further preferred that being free of BaO.

According to the present invention, in the alkali-free glass compositions, on the basis of the total weight of alkali-free glass compositions, ZnO Content be less than 2wt%；Preferably, the content of ZnO is less than 1.2wt%；It is further preferred that the content of ZnO is less than 0.8wt%；It is further preferred that the content of ZnO is less than 0.005wt%；It is further preferred that being free of ZnO.

According to the present invention, the alkali-free glass compositions also contain chemical fining agent, with the gross weight of alkali-free glass compositions On the basis of amount, the content of clarifying agent is not more than 1wt%.The chemical fining agent can be selected according to the prior art, such as institute Stating chemical fining agent can be sn-containing compound, such as tin oxide.

Second aspect of the present invention provides glass made of the glass composition described in first aspect present invention, the glass It has the following performance:

A. crooked test maximum stress value σ_max≥80MPa；And

B. crooked test maximum strain amount ε_max≥1500×10^-6。

Preferably, the crooked test maximum stress value σ of the glass_max>=100MPa, it is further preferred that σ_max≥ 120MPa, it is further preferred that σ_max≥130MPa；Preferably, crooked test maximum strain amount ε_max≥1600×10^-6, excellent Selection of land, ε_max≥1700×10^-6, it is highly preferred that ε_max≥1800×10^-6。

Preferably, the glass also has the following performance:

(1) viscosity is the corresponding temperature T of 200 pools₂₀₀≤ 1630 DEG C, preferably T₂₀₀≤1627℃；

(2) liquidus temperature T_L≤ 1200 DEG C, preferably T_L≤1130℃；

(3) strain point T_stIt is 650-730 DEG C, preferably 680 DEG C -700 DEG C, more preferably 680 DEG C -695 DEG C；

(4) Young's modulus >=72GPa and than modulus >=30GPa (g/cm³), it is preferable that Young's modulus >=73GPa and compare mould Number >=30.5GPa/ (g/cm³)；And

(5) hydrofluoric acid corrosion rate is 4-6.5mg/cm², preferably 4.5-5.3mg/cm², more preferably 4.5-5.2mg/ cm²。

According to the present invention, the glass also has the following performance:

(6) density is lower than 2.49g/cm³, it is preferably lower than 2.42g/cm³；

(7) thermal expansion coefficient within the scope of 50-350 DEG C is lower than 38 × 10^-7/ DEG C, it is preferably lower than 36 × 10^-7/℃；

(8) wavelength is transmitance >=50% at 308nm, preferably >=70%；

(9) 1200 DEG C of surface tension≤370mN/m, preferably≤360mN/m；

(10) Vickers hardness >=580kgf/cm², preferably >=620kgf/cm²；

(11) refractive index nD≤1.53, preferably≤1.52.

The mechanical strength with higher of glass described in second aspect of the present invention (i.e. high crooked test maximum stress value and Crooked test maximum strain amount), while having both low-density, higher chemical corrosion resistance (i.e. high chemical stability), low Thermal expansion coefficient (is lower than 38 × 10^-7/ DEG C), the excellent properties such as higher strain point temperature.

Third aspect present invention provides the method that the glass composition as described in first aspect present invention prepares glass, the party Method includes: to melt glass composition described in first aspect present invention, form, making annealing treatment, and machining processes.Institute State the glass finished-product that glass can be any shape, for example, glass plate.

In third aspect present invention the method, before melt composition, first the various components of composition are mixed Uniformly.Melting, molding condition can be selected according to the prior art, such as the condition of melt process includes: temperature lower than 1630 DEG C, the time is greater than 1h.Those skilled in the art can specific temperature and time determines according to actual conditions, it is no longer superfluous herein It states.

In third aspect present invention the method, under preferable case, the condition of annealing includes: that temperature is higher than 720 DEG C, the time is greater than 0.1h.Those skilled in the art can specific annealing temperature and time determines according to actual conditions, herein not It repeats again.

In third aspect present invention the method, for machining processes, there is no particular limitation, can be ability The common various machining modes in domain, such as can be cut for the product for obtaining annealing, grind, polish.

Preferably, this method further include: second melting is carried out to the product that machining processes obtain and draws thin processing.

Preferably, the machining processes are controlled or second melting draws the condition of thin processing to be less than to prepare thickness The glass plate of 0.1mm.

Alkali-free glass of the present invention can be used for preparing display device and/or solar battery, and it is flat to be particularly suitable for preparation Plate shows the substrate glass substrate material of product and/or the lining of screen surface protection glass film layers material, Flexible Displays product Bottom glass substrate material and/or surface encapsulation glass material and/or screen surface protection glass film layers material, flexible solar Substrate glass substrate material, safety glass, bulletproof glass, intelligent automobile glass, intelligent transportation display screen, the intelligent show window of battery The application field of high thermal stability and mechanical stability glass material is needed with smart card ticket and for other.

The present invention will be described in detail by way of examples below.

In following embodiment, unless otherwise instructed, each raw material used can be commercially available, unless otherwise instructed, Used test method is the conventional method of this field.

Glass density, unit g/cm are measured referring to ASTM C-693³。

Referring to the thermal expansion coefficient of glass that ASTM E-228 uses horizontal expander instrument to measure 50-350 DEG C, unit 10^-7/ ℃。

Glass Young's modulus, unit GPa are measured referring to ASTM C-623；It is obtained by the ratio calculation of Young's modulus and density To than modulus, unit is GPa/ (g/cm³)。

Glass high temperature viscosity-temperature curve is measured using rotation high-temperature viscosimeter referring to ASTM C-965, wherein 200P viscosity pair The temperature T answered₂₀₀, unit is DEG C；The corresponding temperature T of 35000P viscosity₃₅₀₀₀, unit is DEG C.

Glass liquidus temperature T is measured using temperature gradient furnace method referring to ASTM C-829_L, unit is DEG C.

Glass annealing point T is measured using annealing point strain point tester referring to ASTM C-336_aWith strain point T_st, unit is ℃。

Glass Vickers hardness, unit kgf/cm are measured using Vickers referring to ASTM E-384²。

Glass 1200 is measured using high temperature surface tension instrument (Beijing Xu Hui new master Science and Technology Ltd., model ZLXS-II) DEG C surface tension, unit mN/m.

Using Shanghai optical instrument factory WAY-2S type Abbe refractometer, the refractive index n of glass is measured at room temperature_D。

Glass transmitance is measured using ultraviolet-visible spectrophotometer, glass sample takes 308nm with a thickness of 0.5mm respectively Locate transmitance, unit %.

Hydrofluoric acid corrosion rate refers to that the alkali-free glass substrate of unit area is in the HF that concentration is 10 weight % at 20 DEG C The weight that 20min loss is impregnated in solution, is denoted as CHF, unit mg/cm²。

Crooked test refers to that three-point bending strength is tested, and thinks carefully Science and Technology Co., Ltd.'s production in length and breadth using Shenzhen The bending strength tester of WAW-500W model measures.Wherein, glass sample length >=120mm, sheet thickness > 0.1mm, lower support and upperpush rod diameter are 3mm, and lower support span L is 110mm, and glass sheet sample load fall off rate is 10mm/min.Crooked test maximum strain amount ε_maxRefer to that glass substrate stress maximal destruction into fracture process strains；Bending Test maximum stress value σ_maxRefer to glass substrate stress maximal destruction stress into fracture process, unit MPa.ε_maxWith σ_maxIt is calculated according to the following equation respectively:Wherein, F is maximum when glass sheet sample is broken Load, unit N；L is lower support span, unit mm；D is maximum displacement when glass sheet sample is broken, unit mm； B is glass sheet sample width, unit mm；H is glass sheet sample thickness, unit mm.

Embodiment 1-24 and comparative example 1-3

According to the compositing formula of alkali-free glass compositions shown in table 1, each component is mixed, then heats 10 at 1600 DEG C Hour, and uniform speed slow stirs.The glass metal melted is poured into stainless steel cast iron grinding tool, defined blocky glass is configured to Glass product, then by glassware corresponding annealing point T in the lehr_aLower annealing 2 hours closes power supply furnace cooling to 25 ℃.Glassware is cut, ground, is polished, is then cleaned up and is dried with deionized water, is made with a thickness of 0.5mm Glass finished-product.The various performances of each glass finished-product are measured respectively, the results are shown in Table 2.

It can be seen that the glass (such as embodiment 1-23) of glass composition preparation of the present invention by the result of table 1-3 Crooked test maximum stress value σ_max≥80MPa；Crooked test maximum strain amount ε_max≥1500×10^-6, and thermally expand and be Number is lower, is not higher than 38 × 10^-7/ DEG C, the strain point temperature of glass is higher than 650 DEG C, and density is lower than 2.49g/cm³, with comparison The example glass phase ratio has obvious better performance.

The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims

1. a kind of alkali-free glass compositions, comprising: on the basis of the total weight of alkali-free glass compositions, which contains The SiO of 58-64wt%₂, 16-19wt% Al₂O₃, 7-13wt% B₂O₃+P₂O₅, 0.5-3.5wt% MgO, 4-8wt% The ZnO of BaO, 0-4wt% of SrO, 0-2.5wt% of CaO, 0.1-4wt%, the R less than 0.05wt%₂O, wherein R₂O is Li₂O、Na₂O、K₂The sum of content of O.

2. composition according to claim 1, wherein the glass composition contains the SiO of 61-63wt%₂, 17-18wt% Al₂O₃, 8.8-11wt% B₂O₃+P₂O₅, 1.1-2.7wt% MgO, 5.4-7.7wt% CaO, 1.6-3.6wt% The ZnO of BaO, 0wt% of SrO, 0wt%, the R less than 0.05wt%₂O, wherein R₂O is Li₂O、Na₂O、K₂The sum of content of O.

3. composition according to claim 1 or 2, wherein B₂O₃/(B₂O₃+P₂O₅) weight ratio > 0.1；Preferably, B₂O₃/(B₂O₃+P₂O₅) weight ratio meet 0.8 < B₂O₃/(B₂O₃+P₂O₅)≤1。

4. composition according to claim 1 or 2, wherein R ' O/ (B₂O₃+P₂O₅) weight ratio meet 0.5 < R ' O/ (B₂O₃+P₂O₅) < 1.9, preferably 0.9 < R ' O/ (B₂O₃+P₂O₅) < 1.3, more preferably 1.0 < R ' O/ (B₂O₃+P₂O₅) < 1.2, wherein R ' O is the sum of MgO, CaO, SrO, BaO and ZnO content.

5. composition according to claim 1 or 2, wherein the weight ratio of MgO/CaO meets 0.1 < MgO/CaO < 0.9, Preferably 0.15 < MgO/CaO < 0.5.

6. composition according to claim 1 or 2, wherein SrO/CaO weight ratio meets SrO/CaO > 0.01；Preferably 0.2 < SrO/CaO < 0.6, more preferably 0.3 < SrO/CaO < 0.45.

7. composition according to claim 1 or 2, wherein SiO₂+Al₂O₃The sum of weight content Q > 75wt%；It is preferred that Ground, Q meet 75wt% < Q < 82wt%, it is highly preferred that 78wt% < Q < 81wt%.

8. glass made of the glass composition described in any one of claim 1-7, the glass is had the following performance:

A. crooked test maximum stress value σ_max≥80MPa；And

B. crooked test maximum strain amount ε_max≥1500×10^-6。

9. glass according to claim 8, wherein the glass has the following performance:

(1) viscosity is the corresponding temperature T of 200 pools₂₀₀≤ 1630 DEG C,

(2) liquidus temperature T_L≤ 1200 DEG C,

(3) strain point T_stIt is 650-730 DEG C,

(4) Young's modulus >=72GPa and than modulus >=30GPa/ (g/cm³), and

(5) hydrofluoric acid corrosion rate is 4mg/cm²-6.5mg/cm²；

Preferably, the glass has the following performance:

(1) viscosity is the corresponding temperature T of 200 pools₂₀₀≤ 1627 DEG C,

(2) liquidus temperature T_L≤ 1130 DEG C,

(3) strain point T_stIt is 680 DEG C -695 DEG C,

(4) Young's modulus >=73GPa and than modulus >=30.5GPa/ (g/cm³), and

(5) hydrofluoric acid corrosion rate is 4.5mg/cm²-5.3mg/cm²。

10. the application of claim 8,9 glass in display device or solar battery.