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CN108821566A - Alumina silicate glass, preparation method and application - Google Patents

Alumina silicate glass, preparation method and application Download PDF

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Publication number
CN108821566A
CN108821566A CN201810592003.7A CN201810592003A CN108821566A CN 108821566 A CN108821566 A CN 108821566A CN 201810592003 A CN201810592003 A CN 201810592003A CN 108821566 A CN108821566 A CN 108821566A
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glass
alumina silicate
silicate glass
oxide
equal
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赵得翔
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CSG Holding Co Ltd
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CSG Holding Co Ltd
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Priority to CN201810592003.7A priority Critical patent/CN108821566A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
    • G02F1/133331—Cover glasses

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses a kind of alumina silicate glass and preparation methods.Wherein, it for alumina silicate glass, is indicated with the mass percentage of following oxide benchmarks, including following component：56.0%~68.0% silica, 10.0%~22.0% aluminum oxide, 9.0%~15.0% sodium oxide molybdena, 2.0%~8.0% magnesia, 0%~9.0% potassium oxide and 0%~1.5% zirconium dioxide；Wherein, the gross mass percentage composition of the silica and the aluminum oxide is more than or equal to 70% and less than or equal to 85%, and the gross mass percentage composition of the sodium oxide molybdena and the potassium oxide is more than or equal to 9% and is less than or equal to 23%；Containing the sulfur trioxide no more than 0.08% in the alumina silicate glass, the di-iron trioxide no more than 0.018%.By reducing sulphur and iron content in above-mentioned alumina silicate glass, to obtain the glass of muted color.

Description

Alumina silicate glass, preparation method and application
Technical field
The present invention relates to a kind of alumina silicate glass, preparation method, the reinforcings strengthened by the alumina silicate glass Glass, glass plate and application.
Background technique
In recent years, it touches in class equipment in mobile phone and tablet computer, wearing etc. more and more using protection Glass is beautiful to protect display and increase.This portable display device requires weight saving, thickness thinning.Therefore, equally Also it requires for protecting the cover glasses of display very thin.However, if the thickness of cover glasses is made to very thin, intensity meeting It reduces, and if display apparatus is fallen in use or carrying process, and cover glasses itself may also can be crushed sometimes.Cause This, will have that cover glasses are unable to reach the primary objective of protection display apparatus.
To solve the above-mentioned problems, it is contemplated that the intensity for improving cover glasses, it is notorious to be as such method The method of compressive stress layers is formed on the glass surface.As the method for forming compressive stress layers on the glass surface, typically Method is：With a kind of chemical strengthening method, that is, it is being lower than glass transition point temperature hereinafter, by ion exchange, with larger ion half The alkali metal ion (usually K+ ion) of diameter replaces the alkali metal ion compared with small ionic radii that has in glass pane surface (to lead to It is often lithium ion, sodium ion).For the method for improving chemical strengthening velocity of ion exchange, high basic metal content is mainly used Alumina silicate glass.In addition, people require the aesthetic conceptions of display device higher and higher, this glass surface of requirement for its surface Plate ontology generally present it is colourless, and it is high thoroughly, do not influence its touch-sensitive.
Various glass raw materials (such as processing, transport) during industrialized production, hold with ironware by all more or less meetings Device contact, thus can also bring a small amount of iron in glass into.During industrialized production, being melted is the reduction in fossil fuel again Property combustion atmosphere in, and reducing atmosphere is also in using float glass process moulding process, easily causes sulphur remaining in glass in this way Valence state change, even if the sulphur of positive valence state is easily reduced into the sulphur of negative divalent in glass, and the sulphur of negative divalent can in glass Iron reaction, generate more iron sulfide (FeSx), and make glass that amber or sulphur color or brown be presented.
Summary of the invention
Based on this, it is necessary to provide a kind of alumina silicate glass that muted color can be presented, preparation method, by the manosil AS The glass reinforced obtained strengthened glass of salt, glass plate and application.
A kind of alumina silicate glass is indicated with the mass percentage of following oxide benchmarks, including following component：
56.0%~68.0% silica, 10.0%~22.0% aluminum oxide, 9.0%~15.0% oxygen Change sodium, 2.0%~8.0% magnesia, 0%~9.0% potassium oxide and 0%~1.5% zirconium dioxide；
Wherein, the gross mass percentage composition of the silica and the aluminum oxide is more than or equal to 70% and is less than etc. In 85%, the gross mass percentage composition of the sodium oxide molybdena and the potassium oxide more than or equal to 9% and is less than or equal to 23%；
Three oxidations two containing the sulfur trioxide no more than 0.08% in the alumina silicate glass, no more than 0.018% Iron.
Not calcic in the alumina silicate glass in one of the embodiments,；Or contain in the alumina silicate glass Calcium oxide no more than 0.1%.
Contain the sulfur trioxide no more than 0.08% in the alumina silicate glass in one of the embodiments,.
Contain the di-iron trioxide no more than 0.018% in the alumina silicate glass in one of the embodiments,.
Se, Co, Nd, Cr or Ce are free of in the alumina silicate glass in one of the embodiments,；Or the manosil AS At least one of oxide in salt glass containing Se, Co, Nd, Cr and Ce, and in the oxide of Se, Co, Nd, Cr and Ce The mass percentage of any one is no more than 0.001%.
Not boracic in the alumina silicate glass in one of the embodiments,.
A kind of preparation method of alumina silicate glass, which is characterized in that claim by the mass percentage of each oxide benchmark It takes corresponding raw material to be mixed and heated after melting obtains glass metal to form, wherein oxide includes：The two of 56.0%~68.0% Silica, 10.0%~22.0% aluminum oxide, 9.0%~15.0% sodium oxide molybdena, 2.0%~8.0% magnesia, 0%~9.0% potassium oxide and 0%~1.5% zirconium dioxide；Wherein, the silica and the aluminum oxide Gross mass percentage composition is more than or equal to 70% and less than or equal to 85%, and the gross mass percentage of the sodium oxide molybdena and the potassium oxide contains Amount is more than or equal to 9% and is less than or equal to 23%, wherein aluminum oxide, sodium oxide molybdena in the alumina silicate glass, oxidation At least one of magnesium, potassium oxide and zirconium dioxide are introduced at least partially by the form of nitrate in the preparation, or are being added Ammonium nitrate carries out heating melting together with other raw materials and obtains glass metal.
A kind of strengthened glass, the strengthened glass are strengthened to obtain by above-mentioned alumina silicate glass.
A kind of glass plate, the glass plate are made by above-mentioned alumina silicate glass or by above-mentioned strengthened glass.
Application of the above-mentioned glass plate in display device, touch device and mobile device.
Above-mentioned alumina silicate glass, be converted into CIE Lab color shades index under the equivalent thickness of 1.1mm be T value >= 91.60%, L* value >=96.70%, a* value are that 0 ± 0.05%, b* value is 0.05~0.17, and alumina silicate glass chromatic value is presented Neutralc tint；And the gross mass percentage composition of the content of alkali metal oxide be more than or equal to 9% and be less than or equal to 23%, convenient for into Row chemical intensification treatment；Each component is introduced in the preparation by way of nitrate or ammonium nitrate, nitrate or ammonium nitrate is added For element sulphur valence state in stabilized glass, by Fe when can melt during the preparation process2+It is oxidized to Fe3+, Fe in glass3+? Color ratio Fe2+It is much weaker, to obtain the glass of muted color.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.But the present invention can be to be permitted Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes It is more thorough and comprehensive to the understanding of the disclosure.
The alumina silicate glass of one embodiment indicates with the mass percentage of following oxide benchmarks, including as follows Component：
56.0%~68.0% silica, 10.0%~22.0% aluminum oxide, 9.0%~15.0% oxygen Change sodium, 2.0%~8.0% magnesia, 0%~9.0% potassium oxide and 0%~1.5% zirconium dioxide.Wherein, dioxy The gross mass percentage composition of SiClx and aluminum oxide is more than or equal to 70% and is less than or equal to 85%, sodium oxide molybdena and potassium oxide it is total Mass percentage is more than or equal to 9% and is less than or equal to 23%；Alumina silicate glass is converted under the equivalent thickness of 1.1mm It is -0.05~0.05, b* value is 0.05~0.17 that CIE Lab color shades index, which is L* value >=96.70%, a* value, light transmittance >=91.60%, neutralc tint is presented in alumina silicate glass chromatic value.
Silica (SiO2) it is important network former, moreover, it is steady to improve the mechanical strength of glass, chemistry Qualitative, thermal stability etc..But SiO2It is more infusibilized substance, therefore SiO2Content has its optimum value.If content is lower than 56.0% (mass percentage, content below are mass percentage unless otherwise specified), forming and chemical resistance can reduce, There is crystallization tendency；Content is more than 68.0%, and glass melting and clarifying temp can be higher, and viscosity rises, it is difficult to make glass It homogenizes, is unsuitable for floating process manufacture, so SiO of the invention2Content range is 56.0~68.0%.
Aluminum oxide (Al2O3) can participate in network serve network generate body, and can reduce glass crystallization be inclined to, Improve chemical stability, thermal stability, mechanical strength, the hardness of glass, and improve drawn glass elasticity modulus it is necessary at Point, but can increase glass viscosity, if Al2O3Excessively, it is just difficult to obtain the long glass of material property, makes float glass operating difficulties. In addition, the Al in glass3+Tend to form aluminum-oxygen tetrahedron network [AlO4], this is big than oxygen-octahedron [SiO4] network It is more, leave the channel that biggish gap is spread as ion, therefore Al high in glass2O3Content can promoteFrom Son exchange, facilitates ion exchange process in lower temperature and carries out under the shorter time, and such as 370~430 DEG C, 0.5h~ 8h.However, Al2O3Content is greater than 22.0%, increases the crystallization tendency and viscosity of glass, thus must avoid.In the present invention Al2O3Content be 10~22%, preferably 12~20%, more preferable 15~19%.
If SiO2And Al2O3Gross mass percentage composition be more than 85%, then the viscosity of glass at high temperature will increase, and make Glass melting is difficult to carry out.Usual SiO2And Al2O3Gross mass percentage composition be up to 85%.If SiO2+Al2O3Total content Less than 70%, then resistance to fragility can reduce.Usual SiO2+Al2O3Total content be at least 70%.
Magnesia (MgO) is a kind of network modifying oxide, when the content of MgO is not more than 8.0%, helps to reduce glass Glass fusing point improves uniformity, increases hydrolytic resistance.MgO can also make glass tend towards stability, and improve the durability of glass, prevent glass Glass generates crystallization, inhibits the movement of alkali metal ion in glass, similarly has the function of improving glass modulus.Its content Range is 2.0~8.0%, preferably 3.5~7.0%, most preferably 3.9~6.5%.
Sodium oxide molybdena (Na2It O is) for forming surface compression stressor layers by ion exchange and for improving glass melting The component of property, is necessary.If Na2The content of O is less than 9%, then is difficult to form required surface pressure by ion exchange Stress under compression layer.Usual Na2The content of O is at least 9%.If Na2O content is more than 15%, then weatherability can reduce.Na2The content of O It is preferably up to 15%.
Potassium oxide (K2O) although be not alumina silicate glass carried out when carrying out chemical intensification treatment ion exchange institute it is required Ingredient, but with a small amount of K2O replaces Na2O can play " mixed alkali effect ", so that a series of performances of glass is improved, be for mentioning High melting property and for improving ion exchange ratio in chemical strengthening to obtain required surface compression stress and stress layer depth Component.If K2The content of O is more than 9%, then weatherability can reduce.K2The content of O preferably up to 7% is usually up to 6%.
If Na2O and K2The total content Na of O2O+K2O is less than 9%, then can not obtain required ion exchange property.Na2O and K2The total content of O is at least 9%, usually above 9.5% or higher than 13.5%.If Na2O+K2The total content of O is more than 23%, then glass The chemical durability of glass such as weatherability can reduce.Na2O and K2The total content of O preferably up to 18% is usually up to 17%.
Zirconium dioxide (ZrO2) ion-exchange performance of alumina silicate glass can be dramatically increased and improve strain point, but it is excessive When cause devitrification resistance to be remarkably decreased.ZrO2Though not being necessary, ZrO2Content be up to 1.5% with reduce at high temperature Viscosity or increase surface compression stress.If ZrO2Content be more than 1.5%, then ZrO2It is likely to remain in glass as particle Rubble.Moreover, crush resistance can also reduce.Containing ZrO2In the case where, content is generally at least 0.2%.
Calcium oxide (CaO) makes oxygen-octahedron [SiO4] it is formed by network relaxation, fracture, improve glass at high temperature Melting property makes glass be not easy devitrification, but content excessively will affect the weatherability of alumina silicate glass, and hinder ion exchange Progress, therefore preferably do not introduce calcium oxide, if containing calcium oxide, can at most contain the CaO less than 0.1%.
Lower iron-content is designed in component, in order to improve the transmitance of glass itself, while improve glass metal fusing, Diathermancy when clarification and molding, annealing.For guarantee glass liquid stream stabilization is consistent with diathermancy and optical color one Cause property, the iron oxide content of strict control glass and the content of ferrous oxide.By to the iron content and full iron/ferrous iron in component Strict control, improve the inherent quality and external quality of glass, iron oxide content is too low can increase considerably raw material at This, excessively high influence transmitance.The present invention is by adjusting raw material composition, iron oxide Fe2O3Content is not more than 0.018%, for by other Brought into the impurity of component, is not added individually.
Element sulphur is mainly brought into saltcake, soda ash, fossil fuel etc. in glass, and sulphur not only results in clarification in glass metal Bubble quality problem, and can bring glass colour problem especially will cause the unsightly beautiful face such as Huang, palm fibre of glass Color, therefore, by adjusting raw material composition, with oxide S O in this glass metal3It counts highest and is not more than 0.08%.
Preferably, without Se, Co, Nd, Cr or Ce, these make the element of glass coloration or colour killing in alumina silicate glass；Or At least one of oxide in alumina silicate glass containing Se, Co, Nd, Cr and Ce, and the oxidation of Se, Co, Nd, Cr and Ce The mass percentage of any one in object is no more than 0.001%.The elements such as Se, Co, while making glass carry out colour killing, It also reduces the visible light transmittance of glass, simultaneously because it does not consider sulphur remaining in glass to the shadow of glass colour It rings, the decolorising agent of addition is also very unstable to the decoloration of glass.Display device class touch panel is used in such glass in this way When, the brightness of screen is not only reduced, beautiful color can be reduced after ink printing, the touch for influencing to touch class equipment is rung Sensitivity is answered, simultaneously because its decoloration is influenced and unstable, different time sections life by fusing atmosphere and raw material oxidation-reduction quality The color of the glass product of output has certain color difference also and will affect its using effect.
Preferably, not boracic in alumina silicate glass.B2O3Addition can reduce fusing point, improve the meltbility of glass, still B is added2O3A very big disadvantage be can bring serious negative effect to chemical strengthening, reduce the speed of ion exchange, with And it is unable to reach high bearing stress.The reason of leading to this negative effect is that boron oxide forms fine and close boron oxygen tetrahedron [BO4] network, to limit the migration of ion in glass.
In above-mentioned alumina silicate glass, the CIE Lab color shades index being converted under the equivalent thickness of 1.1mm is T value >=91.60%, L* value >=96.70%, a* value are that 0 ± 0.05%, b* value is 0.05~0.17, and alumina silicate glass chromatic value is in Existing neutralc tint；And the gross mass percentage composition of the content of alkali metal oxide is convenient for more than or equal to 9% and less than or equal to 23% Carry out chemical intensification treatment.
When prepared by above-mentioned alumina silicate glass, corresponding raw material is weighed by the mass percentage of each oxide benchmark and is mixed And heating melting obtain glass metal after form.Wherein, the aluminum oxide in the alumina silicate glass, sodium oxide molybdena, magnesia, At least one of potassium oxide and zirconium dioxide are introduced at least partially by the form of nitrate in the preparation, or nitric acid is being added Ammonium carries out heating melting together with other raw materials and obtains glass metal.
Preferably, the mass ratio of ammonium nitrate and glass metal is 0.1~5.5: 100.
Preferably, the heating melting by the way of electric smelting.
Preferably, in the preparation, progress heating melting obtains glass metal after clarifying agent is added into raw material, wherein described Clarifying agent is selected from SnO2And SnCl2At least one of.Further, in glass metal clarifying agent mass percentage be 0.1~ 0.6%.Certainly, in other examples, clarifying agent further includes sodium sulphate, and the mass ratio of sodium sulphate and glass metal is 0.1~ 2.0∶100。
Preferably, in the preparation, be additionally added carbon dust and carry out heating melting together with other raw materials and obtain glass metal, carbon dust with The mass ratio of glass metal is 0.0001~0.25: 100.
It should be noted that weighing corresponding raw material by the mass percentage of each oxide benchmark is mixed and heated melting Deaeration, stirring etc. can also further be passed through after glass metal by, which obtaining, makes glass metal homogenize；Glass metal passes through floating process, drop-down Method or roll-in method etc. are molded into glass plate, or passing through cast molding is glass blocks.
Raw material draws by way of containing the corresponding raw mineral materials of above-mentioned glass oxide benchmark (such as silica sand, zircon) Enter, or passes through soda ash (Na2CO3), silica, zirconium dioxide, potassium carbonate, magnesia, aluminium hydroxide, magnesium hydroxide, oxidation Aluminium, Na2O、K2O, the form of the industrial chemicals such as potassium nitrate, magnesium nitrate, sodium nitrate introduces.
The various raw materials of alumina silicate glass (such as processing is transported) during industrialized production, it is all more or less It can be contacted with ironware container, thus can also bring a small amount of iron in glass into, use fossil fuel and saltcake clear during glass preparation Clear agent and soda ash raw material etc. all inevitably introduce element sulphur.The alumina silicate glass of high basic metal content, due to its glass Alkali metal oxide content is high, and oxidisability is strong.It is well known that the solubility of sulphur remaining in oxidisability glass is than general reproducibility Glass wants high, and during industrialized production, being melted is to be in the reproducibility combustion atmosphere of fossil fuel, and use floating again Method moulding process is also in reducing atmosphere, easily causes the valence state of sulphur remaining in glass to change in this way, even if glass The sulphur of positive valence state is easily reduced into the sulphur of negative divalent in glass, and the sulphur of negative divalent can be reacted with the iron in glass, generate more iron sulfide (FeSx), and glass presentation is made to make us the inaesthetic amber or sulphur color not liked or dark brown or brown color, in this way, right For the panel for touching class equipment, in silk-screen printing process, inaesthetic appearance color will form.
Preferably, at least one of aluminum oxide, sodium oxide molybdena, magnesia, potassium oxide and zirconium dioxide be in the preparation It is introduced at least partially by the form of nitrate, or during the preparation process, ammonium nitrate is added and is melted together with other raw materials Melt, clarify and obtain glass metal.It is further preferred that the mass ratio of ammonium nitrate and glass metal is 0.1~5.5: 100.Pass through addition Nitrate, can be when glass raw material be melted by Fe2+It is oxidized to Fe3+, Fe in glass3+Coloring ratio Fe2+It is much weaker, it can Obtain the better product of color.In addition, decomposed under nitrate high temperature, will not remaining influence glass properties new component；It is another Aspect, can be to avoid the soda ash for using introducing sulfur impurity.
In order to avoid by heating the element sulphur inevitably brought into using combustion of fossil fuel, it is preferred that use The mode fused raw material of electric smelting.
Clarifying agent can also be added in glass melting process to be clarified, it is preferred that SnO is added2And SnCl4In at least It is a kind of to be used as clarifying agent.It is further preferred that the mass percentage of clarifying agent is 0.1~0.6% in glass metal.It avoids using Sodium sulphate is as clarifying agent, to reduce the content of sulphur in glass.Even if using sodium sulphate (saltcake) as clarifying agent, sodium sulphate Mass ratio with glass metal is 0.1~2.0: 100.
Since the solubility of sulphur in glass enhances with the enhancing of the oxidisability of glass, carbon dust, which is added, can be used as reduction Agent, however, the sulphur some or all of in glass can be reduced into the sulphur (S of negative valency state by excessive carbon dust2-), in glass Fe ion (Fe2+Or Fe3+) it is combined into FeSx, finally make glass it is dark brown or pale brown at the amber or sulphur color of needs Color, therefore a small amount of carbon dust can be added as strong reductant, it is preferred that the mass ratio of carbon dust and glass metal is 0.0001~ 0.25：100.
The preparation method of above-mentioned alumina silicate glass, by adjusting raw material composition, the clarifying agent and heating method of addition, greatly Width reduces or controls the introducing of coloring element Fe and S, make glass amber or sulphur color or brown color or the coloring factor (FeSx) content reduces, and keeps the visible light transmittance of glass high, glass colour index is substantially close to muted color, and visible light-transmissive Rate is high.
The strengthened glass of one embodiment is strengthened to obtain using above-mentioned alumina silicate glass.
Preferably, strengthened by way of chemical strengthening.Due to alkali metal oxide in above-mentioned alumina silicate glass Content gross mass percentage composition be more than or equal to 9% and be less than or equal to 23%, the content of alkali metal oxide is higher, convenient for into Row chemical intensification treatment.
The glass plate of one embodiment is made of above-mentioned alumina silicate glass or above-mentioned strengthened glass.
In a preferred embodiment, the thickness of glass plate is no more than 1.5mm, so as to apply glass plate in movement In the display devices such as phone, vehicle mounted guidance, tablet computer, touch device and mobile device as cover glasses, glass substrate or Glass panel.
Since the glass plate general thickness such as display device is less than 1.5mm, it is required that glass visible light transmittance is high, increase The brightness of display device, or display device electricity consumption can be saved when same brightness is shown, extend the mobile class that touches and produces Product stand-by time；On the other hand, because glass itself is very thin, the ferrous components content in glass is few, and the visible light transmittance of glass is high, Human eye can significantly be felt to obtain to the extremely fraction of color difference of the presentation in glass body, especially the amber in glass Color not only influences beauty, and in systems such as its ink printing (especially print white glaze), the UV lamp drying that are fabricated to touch panel It can significantly be showed during work, influence the aesthetic appearance for showing class device.Above-mentioned glass plate be converted into 1.1mm etc. It is 0 ± 0.05%, b* that CIE Lab color shades index under valence thickness, which is T value >=91.60%, L* value >=96.70%, a* value, Value is 0.05~0.17, and neutralc tint is presented in alumina silicate glass chromatic value, and aesthetics is strong and light transmission rate is high.
Above-mentioned alumina silicate glass is described in detail below in conjunction with specific embodiment.
Examples 1 to 20
The alumina silicate glass of Examples 1 to 10 weighs corresponding raw material according to the proportion in table 1, embodiment 11~20 Alumina silicate glass weighs corresponding raw material according to the proportion in table 2, after being sufficiently mixed, is put into platinum crucible, and 1620 DEG C high-temperature electric resistance furnace under carry out 6 hours fusing, clarification.Glass metal is poured into graphite jig and is formed, and is kept the temperature at 650 DEG C Half an hour cools to room temperature with the furnace later, obtains glass blocks.Using machine cuts and roughly grind, fine grinding, be polished to 1.1mm thickness The foliated glass of degree.Ingredient (including the Fe of its final glass2O3With SO3) tested using XRF, with the matter of oxide benchmark Amount percentage composition expression the results are shown in Table 3 and table 4；Visible light transmittance and glass colour chromatic value are surveyed using spectrophotometer Examination, the results are shown in Table 3 and table 4.
Table 1
Table 2
Table 3
Note：Fe × S is the product of Fe2O3 and SO3 mass percentage in glass.
Table 4
The Fe from the alumina silicate glass that table 3~4 can be seen that Examples 1 to 7 and embodiment 11~202O3And SO3's Content is lower, and the muted color of pleasant is presented in color.
One or more of embodiments of the invention above described embodiment only expresses, description are more specific and detailed Carefully, but it cannot be understood as limitations on the scope of the patent of the present invention.It should be pointed out that for the common skill of this field For art personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to this hair Bright protection scope.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (12)

1. a kind of alumina silicate glass, which is characterized in that indicated with the mass percentage of following oxide benchmarks, including as follows Component：
56.0%~68.0% silica, 10.0%~22.0% aluminum oxide, 9.0%~15.0% oxidation Sodium, 2.0%~8.0% magnesia, 0%~9.0% potassium oxide and 0%~1.5% zirconium dioxide；
Wherein, the gross mass percentage composition of the silica and the aluminum oxide is more than or equal to 70% and is less than or equal to 85%, the gross mass percentage composition of the sodium oxide molybdena and the potassium oxide more than or equal to 9% and is less than or equal to 23%；
Containing the sulfur trioxide no more than 0.08% in the alumina silicate glass, the di-iron trioxide no more than 0.018%.
2. alumina silicate glass according to claim 1, which is characterized in that during the alumina silicate glass chromatic value is presented Property tone, the alumina silicate glass be converted into the CIE Lab color shades index under the equivalent thickness of 1.1mm be L* value >= 96.70%, a* value are that -0.05~0.05, b* value is 0.05~0.17, light transmittance >=91.60%.
3. alumina silicate glass according to claim 1, which is characterized in that the alumina silicate glass in the preparation, aluminium At least one of silicate glass raw material introduces in the preparation at least partially by nitrate or alumina silicate glass Central Plains Material carries out heating melting together with ammonium nitrate and obtains glass metal.
4. alumina silicate glass according to claim 1, which is characterized in that the alumina silicate glass in the preparation, to Progress heating melting obtains glass metal after carbon dust and clarifying agent are added in raw material.
5. alumina silicate glass according to claim 1, which is characterized in that not calcic in the alumina silicate glass；Or Contain the calcium oxide no more than 0.1% in the alumina silicate glass.
6. alumina silicate glass according to claim 1, which is characterized in that in the alumina silicate glass without Se, Co, Nd, Cr or Ce；Or at least one of oxide in the alumina silicate glass containing Se, Co, Nd, Cr and Ce, and Se, The mass percentage of any one in the oxide of Co, Nd, Cr and Ce is no more than 0.001%.
7. alumina silicate glass according to claim 1, which is characterized in that not boracic in the alumina silicate glass.
8. a kind of preparation method of alumina silicate glass, it is characterised in that：
Corresponding raw material is weighed by the mass percentage of following each oxide benchmarks to be mixed and heated after melting obtains glass metal Molding, wherein oxide includes：56.0%~68.0% silica, 10.0%~22.0% aluminum oxide, 9.0% ~15.0% sodium oxide molybdena, 2.0%~8.0% magnesia, 0%~9.0% potassium oxide and 0%~1.5% titanium dioxide Zirconium；Wherein, the gross mass percentage composition of the silica and the aluminum oxide is more than or equal to 70% and is less than or equal to 85%, the gross mass percentage composition of the sodium oxide molybdena and the potassium oxide more than or equal to 9% and is less than or equal to 23%；
Wherein, in the aluminum oxide in the alumina silicate glass, sodium oxide molybdena, magnesia, potassium oxide and zirconium dioxide extremely It is few a kind of in the preparation at least partially by the form introducing of nitrate, or ammonium nitrate is added and is heated together with other raw materials Melting obtains glass metal.
9. preparation method according to claim 8, wherein further include, when preparing glass metal, carbon dust being added into raw material And carry out heating melting after clarifying agent and obtain glass metal, the clarifying agent is selected from SnO2And SnCl2At least one of, the carbon The mass ratio of powder and glass metal is 0.0001~0.25: 100.
10. a kind of strengthened glass, which is characterized in that the strengthened glass is by the described in any item aluminosilicates of claim 1~7 It is glass reinforced to obtain.
11. a kind of glass plate, which is characterized in that the glass plate by the described in any item alumina silicate glasses of right 1~7 or by Strengthened glass described in any one of claim 10 is made.
12. application of the glass plate as claimed in claim 11 in display device, touch device and mobile device.
CN201810592003.7A 2016-04-28 2016-04-28 Alumina silicate glass, preparation method and application Pending CN108821566A (en)

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Application publication date: 20181116