CN105621882A - Composition for glass, chemically strengthened glass with low brittleness, and preparation method and application of chemically strengthened glass with low brittleness - Google Patents

Abstract

The invention relates to the glass field, and discloses a composition for glass, chemically strengthened glass with low brittleness, a preparation method of the chemically strengthened glass with low brittleness and application of the chemically strengthened glass with low brittleness. The composition is prepared from the following components in percent by weight: 40 weight percent to 60 weight percent of SiO2, 15 weight percent to 35 weight percent of B2O3, 1 weight percent to 7 weight percent of Al2O3, 10 weight percent to 17 weight percent of Na2O, 0 to 4 weight percent of K2O, 8 weight percent to 15 weight percent of MgO, 0 to 6 weight percent of CaO, 0.01 weight percent to 3 weight percent of SrO, 0.01 weight percent to 3 weight percent of BaO and 1 weight percent to 8 weight percent of ZnO. The glass prepared according to the preparation method disclosed by the invention has the advantages of good toughening effect, higher strain point, higher modulus of elasticity, lower melting temperature, higher coefficient of thermal expansion, lower brittleness, excellent strength, excellent toughness, suitability for large-scale industrial production, compatibility for PDP (Plasma Display Panel) substrate production and capability of solving the PDP glass waste recycling problem.

Description

A kind of glass compositions, low fragility chemically reinforced glass and its preparation method and application

Technical field

The present invention relates to glass art, in particular it relates to a kind of glass compositions, low fragility chemically reinforced glass and its preparation method and application.

Background technology

Showing field in plane, touch screen product market development recent years is rapid, and current main product is capacitive touch screen, and its critical piece is the glass substrate that surface shields. Along with the development of Display Technique and touch technology, market is improved day by day for the requirement of glass substrate. Owing to touch-screen applications is more and more extensive, big-and-middle undersized equipment nearly all has touch screen, so the main performance of touch screen is to possess outstanding mechanical performance, anti-scratch and scratch resistance capability, and this performance is to be embodied by the intensity of glass, so the intensity improving glass self is crucial. Strength of glass is except being affected by tempering, and the material side's composition of itself plays the decisive action of key. The cover sheet glass of main flow adopts common sodium-calcium-silicate system or high-alkali high alumina silicate systems to carry out the purpose that chemical tempering reaches to strengthen on the market, and the cover-plate glass of newer type adopts colourless sapphire slices as cover sheet. But all there is bigger defect in above-mentioned system.

After common soda lime glass carries out ion exchange, it is impossible to reaching enough stressor layers degree of depth and higher surface compression stress, the ability (hardness) of opposing mechanically deform is more weak, and anti-scratch ability is poor; High-alkali high alumina silicate glass introduces high-load Al₂O₃Accelerating process and the degree of depth of ion exchange afterwards, anti-scratch ability is improved, but Al₂O₃Substitute SiO₂Reduce the degree of opening of glass structure afterwards, there is rigid structure, deformation can be resisted, cause that the broken screen events of hand-held display such as fracture toughness reduction, fragility increase, mobile phone happen occasionally. On the other hand, high-load Al₂O₃Introducing quickly add the fusing difficulty of glass, viscosity be temperature during 200 pool often beyond 1550 DEG C, even 1600 DEG C, even 1650 DEG C and higher, industry manufacture difficulty is bigger; Sapphire is the material that hardness is only second to diamond; its Mohs' hardness is 9; anti-scratch ability is better than strengthening glass; but fragility is excessive; run into impact to be easily broken; there is frangible risk in the large scale protection surfaces such as current is use, smart mobile phone screen on small size device surfaces such as camera head protecting glass, there is no popularization and application.

In field of flexible display, flexible display device is mainly by substrate, middle display medium, encapsulation up of three layers. Substrate backing material can be prepared by materials such as glass, organic polymer, metals, the current quality that is respectively arranged with, and there is no perfect solution strength and toughness harmonized programme. With flexible material such as polymer compared with metal forming, <ultra-thin glass of 0.1mm is the glass material of a kind of formula height optimization to thickness, it intercepts the excellent performance of steam and oxygen, has excellent endurance and mechanical performance, also has relatively low thermal expansion and higher heat stability. Its maximum advantage is the maturity and the compatibility that are in that coating technique. Current main flow AMLCD, AMOLED make TFT all on the glass substrate, correlation technique, equipment and industrial chain are highly developed, compatible ideal, will be substantially reduced production cost, but as the ultra-thin glass of fragile material, reducing its fragility is one of material side's aspect problem of needing to break through. In flexible package cover plate materials, the low fragility ultrathin flexible cover-plate glass of chemical tempering can far win polymeric material in intensity, air-tightness etc., but equally exist the unavoidable brittleness problems of glass material, be therefore still one of important topic in material side's aspect reduction fragility, raising pliability.

Due to directivity and the saturability of covalent bond, glass, when being subject to external force, is only capable of producing the plastic deformation area of Nano grade, impulsive force is to be distributed on only small area, thus producing heavily stressed, exceedes the strength of glass limit, making glass breakage, this is caused by glass fragility. The fracture toughness K of glass_ICRefer to the ability of its opposing cracks can spread. The extension of crackle is relevant with glass surface crack tip concentration, depends on the size of the energy to failure of glass, crack size and external carbuncle. K_ICReach a certain marginal value, crackle generation unstable propagation, cause brittle fracture. In linear elastic fracture mechanics, fracture toughness K_ICCan be represented by the formula:

K_IC=Y �� (�� c)^1/2=2 (�� E)^1/2

Y is constant; �� is applied stress; C is half crack length; �� is energy to failure; E is Young's modulus. I type refers to put on the tensile stress in perpendicular direction, crackle interface.

Fragility value B_LFor Vickers hardness Hv and fracture toughness K_ICRatio, it may be assumed that

B_L=Hv/K_IC

The glass fragility value of different compositions has bigger difference, and quartz glass fragility value is relatively big, B_LIt is about 8.8 ��m^1/2, soda-lime glass fragility value is about 6.5 ��m^1/2, borosilicate glass fragility value is at 10��4 ��m^1/2Between, there is large change according to composition difference. In quartz glass, Si-O bonding force is strong and longrange disorder, is difficult to produce plasticity shear, therefore hardness is high and fragility is big, replace a part of SiO with boron or alkali metal₂, silica network produces scission of link, and plasticity shear is relatively easily generated, therefore hardness declines to some extent, fragility reduces; Use Al₂O₃Substitute SiO₂Reducing the degree of opening of glass structure afterwards, have rigid structure, can resist deformation, cause that fracture toughness reduces, fragility increases, and current high alumina height alkali silicate cover-plate glass exists the feature that intensity is big, fragility is big.

Plasma display is the display of new generation after CRT. Owing to this device has series of advantages, as wide in visual angle, slim, image is undistorted, fast response time, life-span length, have good luminous efficiency and brightness, have store function, should make large scale etc., what it had once once been well recognized as realizes one of high definition digital television and the most promising device of giant-screen wall hung television. But, flourish due to LCD technology, PDP shows that industry runs into strong impact, and its market share progressively reduces; On the other hand, expiring service life along with having been sold out PDP display device, electron wastes green processes and has begun to bring into schedule. Particularity due to PDP base plate glass composition, it is difficult in the industrialized production of other kinds of glass and recycles, there is more difficulty in electronic glass recycling, if can be used in certain glass ingredient that can carry out tempering, can not only be promoted it to greatest extent and recycle value, and garbage harmless treatment is brought great convenience, be conducive to alleviating ambient pressure.

Summary of the invention

The invention aims to overcome drawbacks described above of the prior art, it is provided that a kind of glass compositions, low fragility chemically reinforced glass and its preparation method and application.

To achieve these goals, first aspect, the invention provides a kind of glass compositions, with the weight of said composition for benchmark, said composition contains the SiO of 40-60wt%₂, 15-35wt% B₂O₃, 1-7wt% Al₂O₃, 10-17wt% Na₂The K of O, 0-4wt%₂The ZnO of BaO and the 1-8wt% of SrO, 0.01-3wt% of CaO, 0.01-3wt% of MgO, 0-6wt% of O, 8-15wt%.

Second aspect, the invention provides a kind of method preparing low fragility chemically reinforced glass, the method includes glass compositions of the present invention is sequentially carried out melt process, forming processes, annealing and machining processes, preferably, the product that the method also includes machining processes is obtained carries out chemical intensification treatment.

The third aspect, the invention provides the low fragility chemically reinforced glass that said method prepares.

Fourth aspect, the invention provides glass compositions of the present invention or the application in preparing display device and/or solaode of the low fragility chemically reinforced glass.

The glass compositions of the present invention, for a kind of low brittle glass material side with good chemical strengthening effect, belong to borosilicate glass system, suitable in various Conventional glassmaking methods such as float glass process, press over system, rolling process, glass tube down-drawings for producing thickness>plate glass of 0.1mm or thickness<flexible glass of 0.1mm (and namely once moulding method obtain thickness<flexible glass of 0.1mm), or draw thin method for producing the thickness<flexible glass of 0.1mm suitable in second melting. The glass that the present invention prepares, tempering is effective, there is higher strain point, higher elastic modelling quantity, relatively low fusion temperature, higher thermal coefficient of expansion, relatively low fragility, and have good intensity and toughness concurrently simultaneously, it is appropriate to large-scale industrial production, simultaneously compatible PDP substrate production solve PDP glass recovery and reuse of waste problem.

A preferred embodiment of the invention, contains the SiO of certain content in glass compositions₂��B₂O₃��Al₂O₃��Na₂O��K₂O, MgO, CaO, SrO, BaO and ZnO, utilize the glass that this glass compositions prepares, and elastic modelling quantity is higher than 75GPa, and density is lower than 2.5g/cm³, the thermal coefficient of expansion within the scope of 50-350 DEG C is between 45 �� 10^-7/��-70��10^-7/ DEG C, strain point temperature is higher than 550 DEG C, and softening point is higher than 790 DEG C, and annealing point is higher than 580 DEG C, the temperature (T that viscosity is corresponding when being 200 pool_2.3) lower than 1450 DEG C; Wherein, before chemical intensification treatment, (draw, corresponding to machining processes or second melting, the glass that thin process obtains), the fragility value B of glass_LLess than 6.0 ��m^1/2, fracture toughness K_ICMore than 0.9MPa m^1/2; The fragility value B of the glass that chemical intensification treatment obtains_LLess than 2.5 ��m^1/2, fracture toughness K_ICMore than 2.5MPa m^1/2, the compression stress that glass surface is formed is at more than 850MPa, and compression stress layer depth, more than 50 ��m, can be effectively prevented the impact of display product glass surface and scratch infringement; Preferably, machining processes or second melting draw the thickness of the glass that thin process obtains less than 0.1mm, and radius of curvature is less than 5cm.

Glass compositions or the low fragility chemically reinforced glass of the present invention can be used for preparing display device and/or solaode, it is particularly useful for preparing the screen surface protection glass material of flat board or Flexible Displays product, the substrate glass substrate material of Flexible Displays product, the substrate glass material of plane and/or flexible solar battery, the cover-plate glass material of plane and/or flexible solar battery, PDP base plate glass material, intelligent automobile glass, intelligent transportation display screen, intelligence show window, smart card ticket and need the field of low fragility high strength glass material for other.

Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.

Detailed description of the invention

Hereinafter the specific embodiment of the present invention is described in detail. It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.

First aspect, the invention provides a kind of glass compositions, and with the weight of said composition for benchmark, said composition contains the SiO of 40-60wt%₂, 15-35wt% B₂O₃, 1-7wt% Al₂O₃, 10-17wt% Na₂The K of O, 0-4wt%₂The ZnO of BaO and the 1-8wt% of SrO, 0.01-3wt% of CaO, 0.01-3wt% of MgO, 0-6wt% of O, 8-15wt%.

In the glass compositions of the present invention, SiO₂As the substrate constituting borosilicate glass, it adds resistance to sudden heating and the chemical durability that can improve glass, and makes glass not easily devitrification, also helpful for During Vitrification in vitro. But too much SiO₂Melt temperature can be made to raise, reduce thermal coefficient of expansion, production technology is proposed excessive demand. Therefore, consider, with the weight of said composition for benchmark, SiO₂Content be 40-60wt%, it is preferred to 45-58wt%.

In the glass compositions of the present invention, B₂O₃As the substrate constituting borosilicate glass, being individually created glass, it adds the fragility that can reduce glass, improves the fracture toughness of glass, simultaneously B₂O₃Also it is good cosolvent, glass melting temperature can be greatly reduced, also helpful for During Vitrification in vitro. There is [BO in glass₄] tetrahedron and [BO₃] two kinds of structures of triangle body, B when high temperature melting₂O₃It is difficult to form [BO₄], it is possible to decrease high temperature viscosity, depends on during low temperature that the quantity of free oxygen preferentially forms tetrahedron or triangle body. In borosilicate glass, [BO₄] tetrahedron can with [SiO₄] tetrahedron forms unified continuous three-dimensional network, and [BO₃] it is that rotary boron ring connects between triangle body, produce sliding after stress, cause plastic flow, there is relatively low fragility and higher fracture toughness; And borosilicate glass has relatively low fusion temperature, the temperature (T that viscosity is corresponding when being 200 pool_2.3) lower than 1450 DEG C and lower, borosilicate glass has relatively low pyrometric scale surface tension relative to high alumina silicate glass simultaneously, is more suitable for high-volume commercial production manufacture. But too much B₂O₃Glass low-temperature decrease in viscosity can be made, be unfavorable for subsequent chemistry steel process adjustment. Therefore, consider, with the weight of said composition for benchmark, B₂O₃Content be 15-35wt%, it is preferred to 17-30wt%.

In the glass compositions of the present invention, Al₂O₃Addition can accelerate ion exchange process and the degree of depth, but its contention free oxygen very capable, introduce Al in a large number₂O₃The degree of opening of glass structure can be reduced, make glass tend to rigidity, increase the fragility of glass. The easy devitrification of glass, thermal coefficient of expansion can be caused to reduce simultaneously and be difficult to mate with periphery material, pyrometric scale surface tension and high temperature viscosity excessive, increasing process of glass difficulty etc. Therefore, consider, with the weight of said composition for benchmark, Al₂O₃Content be 1-7wt%.

In the glass compositions of the present invention, Na⁺With K⁺Being all the composition of ion exchange, appropriate its content of increase can be effectively reduced the high temperature viscosity of glass, thus improving meltbility and formability, and can improve devitrification. But, its too high levels can increase the thermal expansion of glass and reduce the chemical durability of glass, and too high levels has the tendency that increased devitrification resistance worsens on the contrary, the Na for chemical tempering, in glass⁺By the K in solution⁺Displacement, therefore Na in glass⁺Content suitably increases can significantly improve tempering effect. Therefore, consider, with the weight of said composition for benchmark, Na₂The content of O is 10-17wt%, it is preferred to 13-16.5wt%; K₂The content of O is 0-4wt%, it is preferred to 1-3wt%.

In the glass compositions of the present invention, MgO has glass Young's modulus and ratio modulus is substantially improved, and reduces glass fragility, reduces high temperature viscosity, makes glass be prone to the effect of fusing. Relative to other alkaline earth oxides, there is 4 and 6 two kind of coordination in MgO, at Na₂O-MgO-B₂O₃-SiO₂In system, magnesium ion Mg²⁺Tend to promote glass to have higher contiguity in tetrahedron, improve chemically-resistant, strain point, Young's modulus and fracture toughness, reduce the coefficient of expansion. If with the weight of said composition for benchmark, MgO is more than 15wt%, and glass chemically-resistant can be deteriorated, and glass forms stability reduction simultaneously. Therefore, considering, with the weight of said composition for benchmark, the content of MgO is 8-15wt%, it is preferred to 9-12wt%.

In the glass compositions of the present invention, CaO, SrO, BaO belong to alkaline earth oxide, their addition can effectively reduce the high temperature viscosity of glass, thus improving meltbility and formability, the raising ion-exchange performance of glass, and strain point and the Young's modulus of glass can be improved, linear adjustment thermal coefficient of expansion meets PDP base plate glass requirement simultaneously. But its content too much makes density increase, crackle, devitrification, point phase incidence rate all improve, also result in ion-exchange performance and worsen on the contrary. Therefore, considering, with the weight of said composition for benchmark, the content of CaO is 0-6wt%; The content of SrO is 0.01-3wt%, it is preferred to 0.1-2.5wt%; The content of BaO is 0.01-3wt%, it is preferred to 0.1-2.5wt%.

In the glass compositions of the present invention, bivalent metal oxide is different to characteristics influence according to its status in the periodic table of elements, it is possible to be divided into two classes: a class is in the alkaline earth oxide of main group, its ion R²⁺There are 8 exoelectron structures; Equations of The Second Kind is positioned at periodic chart subgroup (such as ZnO, CdO etc.), its ion R²⁺There are 18 outer electronic structures, in glass both configuration states from glass property impact be different. Relative to alkaline-earth metal, there is the Zn of 18 electronics layer structures²⁺Ion is easier to polarized, can reduce glass viscosity (such as 1450 DEG C) under high temperature, is conducive to eliminating bubble; When total alkali content and network intermediate oxide molecule ratio are during more than 1, after introducing glass as network outer body, Zn²⁺Tend to form tetrahedron [ZnO with four-coordination₄] exist, relatively [ZnO₆] glass structure is more loose, is under the identical condition of high temperature with the glass without ZnO and compares, the glass viscosity containing ZnO is less, atomic motion speed is bigger, it is impossible to form nucleus, it is necessary to reduce temperature further, just be conducive to the formation of nucleus, thus, reduce the crystallize ceiling temperature of glass; Below softening point, there is the chemical resistance promoting intensity, hardness, increase glass, reduce fragility value, reduce the effect of thermal expansion coefficient of glass. ZnO content too much can make the strain point of glass be greatly lowered. Therefore, considering, with the weight of said composition for benchmark, the content of ZnO is 1-8wt%, it is preferred to 1.5-6.5wt%.

In the glass compositions of the present invention, the difference according to glass preparation technique, clarifier when compositions can also contain as glass melting, described clarifier is preferably at least one in sulfate, nitrate, stannum oxide and Tin monoxide; With the weight of said composition for benchmark, the content of clarifier is not more than 1wt%. For clarifier specifically chosen, there is no particular limitation, it is possible to for various selections commonly used in the art, for instance sulfate can be sodium sulfate, and nitrate can be one or more in sodium nitrate, potassium nitrate, strontium nitrate and barium nitrate.

In the glass compositions of the present invention, when utilizing it to prepare low fragility chemically reinforced glass, why enable to glass and there is aforementioned excellent combination property, be mainly attributed in compositions cooperating between each component, especially SiO₂��B₂O₃��Al₂O₃��Na₂O��K₂Mating reaction between O, MgO, CaO, SrO, BaO and ZnO, cooperating between each component of more particularly aforementioned certain content.

Second aspect, the invention provides a kind of method preparing low fragility chemically reinforced glass, and the method includes glass compositions of the present invention is sequentially carried out melt process, forming processes, annealing and machining processes.

In the method for the present invention, the concrete restriction for glass compositions refers to the description of aforementioned corresponding contents, does not repeat them here.

Process of the present invention it is preferred in situation, the condition of melt process includes: temperature is for lower than 1450 DEG C, and the time is more than 1h. Those skilled in the art can determine concrete melt temperature and melting time according to practical situation, and this is well known to those skilled in the art, and does not repeat them here.

Process of the present invention it is preferred in situation, the condition of annealing includes: temperature is 600-700 DEG C, and the time is more than 0.1h. Those skilled in the art can determine concrete annealing temperature and annealing time according to practical situation, and this is well known to those skilled in the art, and does not repeat them here.

In the method for the present invention, for machining processes, there is no particular limitation, it is possible to for the various machining modes that this area is common, for instance can be undertaken the product that obtains of annealing cutting, grind, polishing etc.

In order to improve the combination property of glass further and reduce its fragility, it is preferable that in situation, the product that the method also includes machining processes is obtained carries out chemical intensification treatment. It is further preferred that the method for chemical intensification treatment includes: product machining processes obtained is placed in the melted KNO of 350-480 DEG C₃Middle process at least 0.1h. Those skilled in the art can according between practical situation determines the temperature of concrete chemical intensification treatment and moves back, and this is well known to those skilled in the art, and does not repeat them here.

In the method for the present invention, the various Conventional glassmaking methods such as float glass process, press over system, glass tube down-drawing can be passed through and produce the thickness plate glass more than 0.1mm or the thickness < flexible glass (corresponding to once moulding method) of 0.1mm, it is also possible to draw thin method to produce the thickness flexible glass less than 0.1mm by second melting. Therefore, if thickness can be obtained by one-shot forming < during the flexible glass of 0.1mm, can be made directly chemical intensification treatment. If the thickness of glass obtained by one-shot forming is not less than 0.1mm, before then the method is additionally may included in chemical intensification treatment, the product that machining processes is obtained carries out second melting and draws thin process, is drawn by thickness of glass and is as thin as less than 0.1mm, then carries out chemical intensification treatment. Under preferable case, control described machining processes or second melting draws the condition of thin process to prepare the thickness glass less than 0.1mm, that is, machining processes or second melting draw the thickness of the glass that thin process (namely before chemical intensification treatment) obtains less than 0.1mm. There is no particular limitation to draw the concrete grammar of thin process for second melting, can be various methods commonly used in the art, such as, second melting draws the condition of thin process may include that and produces the thickness plate glass less than 1mm by glass-making processes such as float glass process, press over system, glass tube down-drawings, plate glass is transported to succeeding stretch shaped device inlet, with appropriate speed V₀Mm/min inwardly sends in drawing and forming stove, and restrained stretching forming area viscosity is about 10^5.5-10⁷With appropriate speed V within the scope of pool, by stretching-machine and cylinder₁Mm/min carries out volume to volume winding, thus obtaining the thickness ultrathin flexible glass board material less than 0.1mm, described pull speed V₁More than V₀��

The third aspect, the invention provides the low fragility chemically reinforced glass that said method prepares.

Under preferable case, the low fragility chemically reinforced glass of the present invention, elastic modelling quantity is higher than 75GPa, and density is lower than 2.5g/cm³, the thermal coefficient of expansion within the scope of 50-350 DEG C is between 45 �� 10^-7/��-70��10^-7/ DEG C, strain point temperature is higher than 550 DEG C, and softening point is higher than 790 DEG C, and annealing point is higher than 580 DEG C, and the temperature corresponding when being 200 pool of viscosity is lower than 1450 DEG C.

Wherein, the fragility value B of the glass that (namely machining processes or second melting draw thin process) obtains before chemical intensification treatment_LLess than 6.0 ��m^1/2, fracture toughness K_ICMore than 0.9MPa m^1/2��

Wherein, the fragility value B of the glass that chemical intensification treatment obtains_LLess than 2.5 ��m^1/2, fracture toughness K_ICMore than 2.5MPa m^1/2, the compression stress that glass surface is formed is at more than 850MPa, and compression stress layer depth is more than 50 ��m.

As previously mentioned, different technique can prepare the glass of different-thickness, < flexible glass of 0.1mm draws thin method can also produce the thickness flexible glass less than 0.1mm by second melting can to produce the thickness plate glass more than 0.1mm or thickness by various Conventional glassmaking methods such as float glass process, press over system, glass tube down-drawings. Preferably, machining processes or second melting draw the thickness of the glass that thin process obtains less than 0.1mm, and radius of curvature is less than 5cm.

Fourth aspect, the invention provides glass compositions of the present invention or low fragility chemically reinforced glass preparing display device and/or solaode and needing the application in the field of the low brittle glass material of high intensity at other, it is preferably used for preparing the screen surface protection glass material of flat board or Flexible Displays product, the substrate glass substrate material of Flexible Displays product, the substrate glass material of plane and/or flexible solar battery, the cover-plate glass material of plane and/or flexible solar battery, PDP base plate glass material, intelligent automobile glass, intelligent transportation display screen, intelligence show window, smart card ticket and other need the application of the low brittle glass material of high intensity.

Embodiment

Hereinafter will be described the present invention by embodiment. In following example, if no special instructions, each material used all can pass through commercially available, and if no special instructions, method used is the conventional method of this area.

In following example and comparative example, measuring glass density with reference to ASTMC-693, unit is g/cm³��

Use the thermal expansion coefficient of glass of horizontal expander instrument mensuration 50-350 DEG C with reference to ASTME-228, unit is 10^-7/ shelves

Using material mechanical test machine to measure glass Young's modulus with reference to ASTMC-623, unit is GPa.

Using Vickers to measure glass Vickers hardness with reference to ASTME-384, unit is GPa.

Universal testing machine and Vickers is used to measure glass breakage toughness K with reference to ASTME-1820_IC, unit is MPa m^1/2, and obtain glass fragility value B by calculating_L, unit is ��m^1/2��

Using 3 testers to measure glass softening points, annealing point and strain point with reference to ASTMC-336 and ASTMC-338, unit is DEG C.

Use with reference to ASTMC-965 and rotate high-temperature viscosimeter mensuration glass high temperature viscosity-temperature curve, wherein, temperature T corresponding during 200P viscosity_2.3, unit is DEG C.

The measurement of FSM-6000LE surface stress is used determine glass surface compression stress (unit is MPa) and compression stress layer depth (unit be ��m).

Embodiment 1-9

Shown in table 1, weigh each component, mixing, compound is poured in platinum crucible, then heat 4 hours in 1430 DEG C of resistance furnaces, and use platinum rod to stir to discharge bubble. The vitreous humour melted is poured in rustless steel cast iron grinding tool, is configured to the both bulk glasses goods of regulation, then by glass in the lehr, anneals 2 hours, close power supply furnace cooling to 25 DEG C. Being undertaken glass cutting, grind, polish, the surface deionized water of the glass of 50*50*1mm polishing obtained puts into the melted KNO of 420 DEG C after cleaning up₃Middle process 3h, then takes out and is cooled to 25 DEG C, clean up with deionized water and dry, prepare glass finished-product. Respectively the various performances of each glass finished-product being measured, result is in Table 1.

Table 1

Embodiment 10-17

According to the method for embodiment 1, the difference is that, compound composition and the performance measurement result of product that obtains are in Table 2.

Table 2

Comparative example 1-3

According to the method for embodiment 1, the difference is that, compound composition and the performance measurement result of product that obtains are in Table 3.

Table 3

Data in table 1-2 and table 3 are compared it can be seen that the method for the present invention utilizes the SiO containing certain content₂��B₂O₃��Al₂O₃��Na₂O��K₂O, MgO, CaO, SrO, BaO and ZnO the glass for preparing of glass compositions, elastic modelling quantity is higher than 75GPa, and density is lower than 2.5g/cm³, the thermal coefficient of expansion within the scope of 50-350 DEG C is between 45 �� 10^-7/��-70��10^-7/ DEG C, strain point temperature is higher than 550 DEG C, and softening point is higher than 790 DEG C, and annealing point is higher than 580 DEG C, the temperature (T that viscosity is corresponding when being 200 pool_2.3) lower than 1450 DEG C; Wherein, before chemical intensification treatment, the fragility value B of glass_LLess than 6.0 ��m^1/2, fracture toughness K_ICMore than 0.9MPa m^1/2; The fragility value B of the glass that chemical intensification treatment obtains_LLess than 2.5 ��m^1/2, fracture toughness K_ICMore than 2.5MPa m^1/2, the compression stress that glass surface is formed is at more than 850MPa, and compression stress layer depth, more than 50 ��m, can be effectively prevented the impact of display product glass surface and scratch infringement. The glass compositions of the present invention or low fragility chemically reinforced glass can be used for preparing display device and/or solaode and other need the field of low fragility high strength glass material, to be particularly useful for preparing the screen surface protection glass material of flat board or Flexible Displays product, the substrate glass substrate material of Flexible Displays product, plane and/or the cover-plate glass material of the substrate glass material of flexible solar battery, plane and/or flexible solar battery, PDP base plate glass material, intelligent automobile glass, intelligent transportation display screen, intelligence show window and smart card ticket etc.

Radius of curvature measures

Glass is prepared according to the method for embodiment 1-17, then carry out second melting and draw thin process and chemical intensification treatment, wherein, second melting draws the method for thin process to include: by cutting, grind, the thickness that obtains of polishing is 0.7mm, width is 50mm plate glass is transported to succeeding stretch shaped device inlet, with V₀The speed of mm/min is inwardly sent in drawing and forming stove, restrained stretching forming area viscosity P, by stretching-machine and cylinder with speed V₁Mm/min carries out volume to volume winding, obtains thickness to be d1, width be the flexible glass goods of d2. The method of chemical intensification treatment includes: put into the melted KNO of 420 DEG C after being cleaned up by the surface deionized water of flexible glass goods₃Middle process 2h, then takes out and is cooled to 25 DEG C, clean up with deionized water and dry, prepare glass finished-product. Using surface stress meter and radius of curvature tester chemical enhanced effect and radius of curvature to each glass finished-product to be respectively measured, the radius of curvature of the condition of embodiment 1-17, chemical enhanced effect and correspondence is in Table 4.

Table 4

By upper result it can be seen that the method for the present invention can prepare the thickness low fragility chemically reinforced glass less than 0.1mm, and its radius of curvature is less than 5cm.

The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.

It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.

Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (10)

1. a glass compositions, it is characterised in that with the weight of said composition for benchmark, said composition contains the SiO of 40-60wt%₂, 15-35wt% B₂O₃, 1-7wt% Al₂O₃, 10-17wt% Na₂The K of O, 0-4wt%₂The ZnO of BaO and the 1-8wt% of SrO, 0.01-3wt% of CaO, 0.01-3wt% of MgO, 0-6wt% of O, 8-15wt%.

2. compositions according to claim 1, wherein, with the weight of said composition for benchmark, B₂O₃Content be 17-30wt%.

3. compositions according to claim 1 and 2, wherein, with the weight of said composition for benchmark, the content of MgO is 9-12wt%.

4. the compositions according to any one in claim 1-3, wherein, with the weight of said composition for benchmark, SiO₂Content be 45-58wt%;

Preferably, with the weight of said composition for benchmark, Na₂The content of O is 13-16.5wt%;

Preferably, with the weight of said composition for benchmark, K₂The content of O is 1-3wt%;

Preferably, with the weight of said composition for benchmark, the content of SrO is 0.1-2.5wt%;

Preferably, with the weight of said composition for benchmark, the content of BaO is 0.1-2.5wt%;

Preferably, with the weight of said composition for benchmark, the content of ZnO is 1.5-6.5wt%.

5. compositions according to claim 1, wherein, described compositions is possibly together with clarifier, and described clarifier is preferably at least one in sulfate, nitrate, stannum oxide and Tin monoxide; With the weight of said composition for benchmark, the content of clarifier is not more than 1wt%.

6. the method preparing low fragility chemically reinforced glass, it is characterized in that, the method includes the glass compositions described in any one in claim 1-5 is sequentially carried out melt process, forming processes, annealing and machining processes, preferably, the product that the method also includes machining processes is obtained carries out chemical intensification treatment.

7. method according to claim 6, wherein, the method also includes: before chemical intensification treatment, and the product that machining processes is obtained carries out second melting and draws thin process;

Preferably, control described machining processes or second melting draws the condition of thin process to prepare the thickness glass less than 0.1mm.

8. the low fragility chemically reinforced glass that the method described in claim 6 or 7 prepares.

9. low fragility chemically reinforced glass according to claim 8, wherein, the elastic modelling quantity of described low fragility chemically reinforced glass is higher than 75GPa, and density is lower than 2.5g/cm³, the thermal coefficient of expansion within the scope of 50-350 DEG C is between 45 �� 10^-7/��-70��10^-7/ DEG C, strain point temperature is higher than 550 DEG C, and softening point is higher than 790 DEG C, and annealing point is higher than 580 DEG C, and the temperature corresponding when being 200 pool of viscosity is lower than 1450 DEG C;

Preferably, the fragility value B of the glass obtained before described chemical intensification treatment_LLess than 6.0 ��m^1/2, fracture toughness K_ICMore than 0.9MPa m^1/2;

Preferably, the fragility value B of the glass that described chemical intensification treatment obtains_LLess than 2.5 ��m^1/2, fracture toughness K_ICMore than 2.5MPa m^1/2, the compression stress that glass surface is formed is at more than 850MPa, and compression stress layer depth is more than 50 ��m;

Preferably, machining processes or second melting draw the thickness of the glass that thin process obtains less than 0.1mm, and radius of curvature is less than 5cm.

10. the glass compositions described in any one or the low fragility chemically reinforced glass described in claim 8 or 9 application in preparing display device and/or solaode in claim 1-5, it is preferably and is preparing the screen surface protection glass material of flat board or Flexible Displays product, the substrate glass substrate material of Flexible Displays product, the substrate glass material of plane and/or flexible solar battery, the cover-plate glass material of plane and/or flexible solar battery, PDP base plate glass material, intelligent automobile glass, intelligent transportation display screen, application in intelligence show window and smart card ticket.