CN108658452A - Color tone adjustment agents, alumina silicate glass and preparation method thereof - Google Patents

Color tone adjustment agents, alumina silicate glass and preparation method thereof Download PDF

Info

Publication number
CN108658452A
CN108658452A CN201710210655.5A CN201710210655A CN108658452A CN 108658452 A CN108658452 A CN 108658452A CN 201710210655 A CN201710210655 A CN 201710210655A CN 108658452 A CN108658452 A CN 108658452A
Authority
CN
China
Prior art keywords
alumina silicate
silicate glass
mass ratio
glass
ceo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710210655.5A
Other languages
Chinese (zh)
Other versions
CN108658452B (en
Inventor
何浩波
肖子凡
邓臻禄
戴斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Csg Application Technology Co Ltd
CSG Holding Co Ltd
Original Assignee
Shenzhen Csg Application Technology Co Ltd
CSG Holding Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Csg Application Technology Co Ltd, CSG Holding Co Ltd filed Critical Shenzhen Csg Application Technology Co Ltd
Priority to CN201710210655.5A priority Critical patent/CN108658452B/en
Publication of CN108658452A publication Critical patent/CN108658452A/en
Application granted granted Critical
Publication of CN108658452B publication Critical patent/CN108658452B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

A kind of color tone adjustment agents of present invention offer, alumina silicate glass and preparation method thereof.A kind of color tone adjustment agents for alumina silicate glass, the color tone adjustment agents include carbon dust, SnO2、CeO2And ZnO, the SnO2、CeO2And the mass ratio of ZnO is 0.06~1：0.01~1：0.05~1, and 1≤C/ (0.08SnO2+0.0349CeO2)≤42, in formula, C represents carbon dust, and each molecular formula represents respective quality.Above-mentioned color tone adjustment agents can easily adjust alumina silicate glass tone.

Description

Color tone adjustment agents, alumina silicate glass and preparation method thereof
Technical field
The present invention relates to a kind of color tone adjustment agents, alumina silicate glass and preparation method thereof.
Background technology
In recent years, it is touched in class equipment more and more using protection in mobile phone and tablet computer, wearing etc. 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 for forming compressive stress layers on the glass surface.As the method for forming compressive stress layers on the glass surface, typically It is：With a kind of chemical strengthening method, i.e., less than glass transition point temperature hereinafter, by ion exchange, with larger ionic radius Alkali metal ion (is typically K+Ion) instead of (being typically with the alkali metal ion compared with small ionic radii in glass pane surface Lithium ion, sodium ion).The method of chemical strengthening velocity of ion exchange is improved, the glass of high basic metal content is mainly used.
Various glass raw materials (such as processing, transport) during industrialized production, with ironware hold by all more or less meetings Device contacts, thus can also bring a small amount of iron in glass into.During industrialized production, it is the reduction in fossil fuel again to be melted 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.
For alumina silicate glass, since its alkali content is higher, it is conducive to retain the sulphur for bearing divalent in glass, therefore And the tone of the inclined yellow of this fixation is more readily formed, and this single tone is insufficient for all sense organ needs.It is existing When having technology to adjust plexiglass tint, the simple content for changing coal dust influences whether the clarification of saltcake in glass, to The quality of glass is influenced, furnace pressure and glass melting temperature and control Wind-oil ratio is changed or general mood ratio, this several person is mutually related Parameter is very difficult to be adjusted to suitable parameter in production to control the tone of glass.
Invention content
Based on this, it is necessary to provide a kind of color tone adjustment agents for the tone that can easily adjust alumina silicate glass, aluminium silicon Silicate glass and preparation method thereof.
A kind of color tone adjustment agents for alumina silicate glass, the color tone adjustment agents include carbon dust, SnO2、CeO2And ZnO, the SnO2、CeO2And the mass ratio of ZnO is 0.06~1：0.01~1：0.05~1, and 1≤C/ (0.08SnO2+ 0.0349CeO2)≤42, in formula, C represents carbon dust, and each molecular formula represents respective quality.
Above-mentioned color tone adjustment agents contain 0.001%~0.012% Fe in alumina silicate glass2O3In the case of, it is added Color tone adjustment agents can effectively adjust the coloration of alumina silicate glass, obtain the glass of muted color or the glass of other tones；It adjusts The content for saving several components in color tone adjustment agents, can further adjust the tone of alumina silicate glass, SnO2、CeO2And ZnO Mass ratio is 0.08~0.15：0.08~0.15：0.05~1, and 1≤C/ (0.08SnO2+0.0349CeO2When)≤5.34, aluminium Silicate glass be converted into the CIE Lab color shades indexs under the equivalent thickness of 1.1mm be T values >=91.60%, L* value >= 96.70%, a* value are that -0.04~-0.01, b* values are 0.1~0.16；If SnO2、CeO2And the mass ratio of ZnO is 0.06~1： 0.01~0.1：0.1~0.15, and 5.34≤C/ (0.08SnO2+0.0349CeO2)≤20.83, alumina silicate glass is converted into It is 0.06 that CIE Lab color shades indexs under the equivalent thickness of 1.1mm, which are T values >=91.60%, L* value >=96.70%, a* value, ~0.1, b* value are 0.07~0.1；If SnO2、CeO2And the mass ratio of ZnO is 0.06~1：0.01~0.05：0.2~1, and 20.83≤C/(0.08SnO2+0.0349CeO2)≤32.38, alumina silicate glass are converted into the CIE under the equivalent thickness of 1.1mm It is -0.01~0.06, b* values is 0~0.07 that Lab color shades indexs, which are T value >=91.60%, L* value >=96.70%, a* values,； If SnO2、CeO2And the mass ratio of ZnO is 0.06~1：0.15~1：0.05~1, and 32.38≤C/ (0.08SnO2+ 0.0349CeO2)≤42, it is T values that alumina silicate glass, which is converted into the CIE Lab color shades indexs under the equivalent thickness of 1.1mm, >=91.60%, L* value >=96.70%, a* value are that -0.1~-0.04, b* values are 0.16~0.2, to realize alumino-silicate glass Glass tone is adjustable.
The SnO in one of the embodiments,2、CeO2And the mass ratio of ZnO is 0.08~0.15：0.08~0.15： 0.05~1, and 1≤C/ (0.08SnO2+0.0349CeO2)≤5.34。
The SnO in one of the embodiments,2、CeO2And the mass ratio of ZnO is 0.06~1：0.01~0.1：0.1~ 0.15, and 5.34≤C/ (0.08SnO2+0.0349CeO2)≤20.83。
The SnO in one of the embodiments,2、CeO2And the mass ratio of ZnO is 0.06~1：0.01~0.05：0.2 ~1, and 20.83≤C/ (0.08SnO2+0.0349CeO2)≤32.38。
The SnO in one of the embodiments,2、CeO2And the mass ratio of ZnO is 0.06~1：0.15~1：0.05~ 1, and 32.38≤C/ (0.08SnO2+0.0349CeO2)≤42。
A kind of alumina silicate glass, the raw material of the alumina silicate glass include main material and above-mentioned color tone adjustment agents, Wherein, the mass ratio of the color tone adjustment agents and the main material is 0.12：100~3：100, in the alumina silicate glass with Mass percentage meter contains 0.001%~0.012% Fe2O3。
The main material includes by percentage to the quality in one of the embodiments,：52%~67% SiO2, 9% ~21% Al2O3, 2.5%~7% MgO, 11.5%~17% Na2O, 0~4% K2O's and 0.1%~1.5% ZrO2。
The SiO in one of the embodiments,2With the Al2O3Gross mass percentage composition be less than 85%.
1≤C/ (0.08SnO in one of the embodiments,2+0.0349CeO2)≤5.34, the CeO2With the main original The mass ratio of material is 0.08：100~0.15：100, the SnO2Mass ratio with the main material is 0.08：100~0.15： The mass ratio of 100, the ZnO and the main material is 0.05~1：100, the alumina silicate glass be converted into 1.1mm etc. It is -0.04~-0.01 that CIE Lab color shades indexs under valence thickness, which are T value >=91.60%, L* value >=96.70%, a* values, B* values are 0.1~0.16.
5.34≤C/ (0.08SnO in one of the embodiments,2+0.0349CeO2)≤20.83, the CeO2With it is described The mass ratio of main material is 0.01~0.1：100, the SnO2Mass ratio with the main material is 0.06~1：100, it is described The mass ratio of ZnO and the main material is 0.1：100~0.15：100, the alumina silicate glass is converted into the equivalence of 1.1mm It is 0.06~0.1, b* values that CIE Lab color shades indexs under thickness, which are T values >=91.60%, L* value >=96.70%, a* value, It is 0.07~0.1.
20.83≤C/ (0.08SnO in one of the embodiments,2+0.0349CeO2)≤32.38, the CeO2With institute The mass ratio for stating main material is 0.01~0.05：100, the SnO2Mass ratio with the main material is 0.06~1：100, institute The mass ratio for stating ZnO and the main material is 0.2：100~1：100, the equivalence that the alumina silicate glass is converted into 1.1mm is thick It is -0.01~0.06, b* values that CIE Lab color shades indexs under degree, which are T value >=91.60%, L* value >=96.70%, a* values, It is 0~0.07.
32.38≤C/ (0.08SnO in one of the embodiments,2+0.0349CeO2)≤42, the CeO2With the master The mass ratio of raw material is 0.15：100~1：100, the SnO2Mass ratio with the main material is 0.06~1：100, it is described The mass ratio of ZnO and the main material is 0.05：100~1：100, the equivalence that the alumina silicate glass is converted into 1.1mm is thick It is -0.1~-0.04, b* values that CIE Lab color shades indexs under degree, which are T value >=91.60%, L* value >=96.70%, a* values, It is 0.16~0.2.
A kind of alumina silicate glass indicates with the mass percentage of oxide benchmark, including：50.48%~66.92% SiO2, 8.74%~20.97% Al2O3, 2.43%~6.99% MgO, 11.16%~16.98% Na2O, 0~ 4%K2O, 0.1%~1.5% ZrO2, 0.001%~0.012% Fe2O3, 0.058%~0.999% SnO2, 0.01% ~0.999% CeO2And 0.049%~0.999% ZnO, light transmittance >=91.60% of the alumina silicate glass.
A kind of preparation method of alumina silicate glass, above-mentioned color tone adjustment agents are mixed with the main material of alumina silicate glass And it heats melting and obtains glass metal aftershaping.
Specific implementation mode
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.Make on the contrary, purpose of providing these embodiments is It is more thorough and comprehensive to the understanding of the disclosure.
The alumina silicate glass of one embodiment, raw material include main material, color tone adjustment agents.
The mass ratio of color tone adjustment agents and main material is 0.12：100~3：100.
Color tone adjustment agents include carbon dust, SnO2、CeO2And ZnO, SnO2、CeO2And the mass ratio of ZnO is 0.06~1：0.01 ~1：0.05~1, and 1≤C/ (0.08SnO2+0.0349CeO2)≤42, in formula, C represents carbon dust, and each molecular formula represents respective Quality.
(as without particularly pointing out, the percentage composition in text is quality hundred in terms of mass percentage in alumina silicate glass Divide content) contain 0.001%~0.012% Fe2O3.It should be strongly noted that for most of alumina silicate glass, Fe2O3It is as existing for inevitable impurity, is not to be intentionally added.The various raw materials of glass are in industrialized production (such as processing, transport) in journey, all more or less meeting is contacted with ironware container, thus can also bring a small amount of iron in glass into, glass Element sulphur is all inevitably introduced using fossil fuel and saltcake fining agent and soda ash raw material etc. in preparation process.High basic metal The glass of content, since its glass alkali metal oxide content is high, oxidisability is strong.It is well known that remaining in oxidisability glass The solubility of sulphur is higher than general reproducibility glass, and during industrialized production, being melted is gone back in fossil fuel again In originality combustion atmosphere, and reducing atmosphere is also in using float glass process moulding process, easily caused so remaining in glass The valence state of sulphur changes, even if the sulphur of positive valence state is easily reduced into the sulphur of negative divalent in glass, and bears sulphur meeting and the glass of divalent In iron reaction, generate more iron sulfide (FeSx), and make glass that amber or sulphur color or dark brown or brown color be presented.
As the Fe contained in alumina silicate glass2O3Mass percentage be 0.001%~0.012% when, use is above-mentioned Color tone adjustment agents can effectively adjust tone, make glass that the tone needed be presented.Carbon dust, SnO2, CeO2, ZnO relative amounts Variation can change the valence state of the sulphur in glass metal, iron determination and the combination between them, to realize change glass The purpose of tone.
SnO in one of the embodiments,2、CeO2And the mass ratio of ZnO is 0.08~0.15：0.08~0.15：0.05 ~1, and 1≤C/ (0.08SnO2+0.0349CeO2)≤5.34.Adjust CeO2Mass ratio with main material is 0.08：100~ 0.15：100, SnO2Mass ratio with main material is 0.08：100~0.15：100, ZnO and main material mass ratio be 0.05： 100~1：100, it is T values that alumina silicate glass, which is converted into the CIE Lab color shades indexs under the equivalent thickness of 1.1mm, at this time >=91.60%, L* value >=96.70%, a* value are that -0.04~-0.01, b* values are 0.1~0.16.
SnO in one of the embodiments,2、CeO2And the mass ratio of ZnO is 0.06~1：0.01~0.1：0.1~ 0.15, and 5.34≤C/ (0.08SnO2+0.0349CeO2)≤20.83.Adjust CeO2Mass ratio with main material is 0.01：100 ~0.1：100, SnO2Mass ratio with main material is 0.06：100~1：100, ZnO and main material mass ratio be 0.1：100 ~0.15：100, it is T values that alumina silicate glass, which is converted into the CIE Lab color shades indexs under the equivalent thickness of 1.1mm, at this time >=91.60%, L* value >=96.70%, a* value are that 0.06~0.1, b* values are 0.07~0.1.
SnO in one of the embodiments,2、CeO2And the mass ratio of ZnO is 0.06~1：0.01~0.05：0.2~1, And 20.83≤C/ (0.08SnO2+0.0349CeO2)≤32.38.Adjust CeO2Mass ratio with main material is 0.01：100~ 0.05：100, SnO2Mass ratio with main material is 0.06：100~1：100, ZnO and main material mass ratio be 0.2：100~ 1：100, at this time alumina silicate glass be converted into the CIE Lab color shades indexs under the equivalent thickness of 1.1mm be T values >= 91.60%, L* value >=96.70%, a* value are that -0.01~0.06, b* values are 0~0.07.
SnO in one of the embodiments,2、CeO2And the mass ratio of ZnO is 0.06~1：0.15~1：0.05~1, and 32.38≤C/(0.08SnO2+0.0349CeO2)≤42.Adjust CeO2Mass ratio with main material is 0.15：100~1：100, SnO2Mass ratio with main material is 0.06：100~1：100, ZnO and main material mass ratio be 0.05：100~1：100, this When, it is T values >=91.60%, L* that alumina silicate glass, which is converted into the CIE Lab color shades indexs under the equivalent thickness of 1.1mm, It is 0.16~0.2 that value >=96.70%, a* values, which are -0.1~-0.04, b* values,.
Main material includes by percentage to the quality in one of the embodiments,：52%~67% SiO2, 9%~ 21% Al2O3, 2.5%~7% MgO, 11.5%~17% Na2O, 0~4% K2The ZrO of O and 0.1%~1.5%2。
Silica (SiO2) be glass network forming component, be required.SiO2Can improve glass mechanical strength, Chemical stability, thermal stability etc..If SiO2Content it is too low, then the stability of glass declines, but SiO2It is more infusibilized Substance, if SiO2Too high levels, then the fusion temperature of glass increase, fusing and the difficulty that can all become of clarification, therefore SiO2Contain Amount is 52%~67%.
Alundum (Al2O3) (Al2O3) it is the ingredient for making weatherability improve, the crystallization tendency of glass can be reduced, glass is improved Chemical stability, thermal stability, mechanical strength, hardness, in alumina silicate glass, Al2O3It can participate in network and play network generation body Effect.Due to [AlO4] tetrahedral space is more than [SiO4] tetrahedral space, so the raising of alumina content is to be conducive to Ion exchange.If Al2O3Too high levels, then meltability be significantly deteriorated, contain Al2O3It can then embody on improved weathering Effect, contain suitable Al2O3It can be so that glass weatherability be good.But if Al2O3Too high levels, then the melting of glass Property is significantly deteriorated.Therefore, in alumina silicate glass, Al2O3Content is 9%~21%.
Magnesia (MgO) is also a kind of required component, is network modifying oxide.MgO helps to reduce glass melting point, Improve uniformity, increases hydrolytic resistance.MgO can also make glass tend towards stability, and improve the durability of glass, prevent glass from generating knot Crystalline substance improves glass modulus, inhibits the generation of crackle.But if content of MgO is excessively high, then glass may be made to be easy devitrification, If content of MgO is too low, the viscosity of glass melt will increase, meltbility can reduce.Therefore, the content range of MgO is 2.5% ~7%.
Sodium oxide molybdena (Na2O it is) ingredient for promoting glass raw material melting, is required.If Na2The too high levels of O, then glass The weatherability and bad stability of glass, and be easy to be combined with the sulphur in glass, so that the sulphur in glass is remained, to make glass It is easier yellow, if Na2The content of O is too low, then the fusing of glass becomes difficult.Therefore, Na2The content of O be 11.5%~ 17%.
Preferably, SiO2With Al2O3Gross mass percentage composition be less than 85%.
Potassium oxide (K2O) same to Na2O is the component of same nature, and and Na2O is compared, and the ability for preserving sulphur in glass is weaker, It is advantageous when being adjusted toward inclined blue color to glass.K2The too high levels of O, then the water resistance and weatherability of glass can become Difference, and the ion exchange of glass can significantly be hindered；If not adding K2O, then glass smelting effect and to glass toward yellow Color hue adjustment is unfavorable.Therefore, the K no more than 4% is contained in alumina silicate glass2O。
Zirconium oxide (ZrO2) it is a kind of ingredient that can increase glass surface compression stress, glass hard (HRC65Yi Shang) is improved, glass is improved The weatherability and stability of glass, and zirconium ion is easier to be combined with the sulphur of the negative valency state in glass than iron ion, to change Yellow caused by kind carbon sulphur coloring, its addition is conducive to glass and is adjusted toward blue color direction, but excessive ZrO2It can make The possibility that crackle occurs from impression for glass increases.Therefore ZrO in glass2Content be 0.1~1.5%.
Preferably, CaO is not contained in alumina silicate glass.The addition of CaO can reduce the fusing point of glass, improve glass Material property, but if CaO is added in the alumina silicate glass of the present invention, since it is in glass to Na+Suppression And space steric effect, ion exchange will be unfavorable for.
Preferably, B is not contained in alumina silicate glass2O3。B2O3Addition can reduce fusing point, improve the meltbility of glass, But cause glass ingredient uneven since its is volatile if being added in soda lime glass, and can cause Glass have brush line, furnace wall the great number of issues such as erosion, be not appropriate in manufacture.
Carbon dust, SnO2、CeO2And ZnO collective effects, play the role of clarification and adjusts coloration.
Zinc oxide (ZnO) is a kind of glass fluxing agent, is conducive to the decline of glass melting point and viscosity, when meeting certain condition When, ZnO can constitute glass network, form similar [SiO4] tetrahedron stablize network structure, help to improve the weather-proof of glass Property and chemical stability, and zinc ion is easier to be combined with the sulphur of the negative valency state in glass than iron ion, and it is past to help plexiglass tint Yellow direction adjusts, but excessive ZnO can make the ZnO of some that can not form network structure, to reduce glass Weatherability and chemical stability.
Cerium oxide (CeO2) it is a kind of strong oxidizer and fining agent, it can will be born by the ferrous oxidation in glass at ferric iron The sulphur of valence state is oxidized to the sulphur of nominal price, and zirconium ion is easier to be combined with the sulphur of the negative valency state in glass than iron ion, integrate and Speech, its addition are conducive to glass and are adjusted toward yellow tone direction, but due to CeO2Itself is colored as yellow tone, so excessively CeO2Addition, the coloring of glass can be made to deepen, transmitance decline.
Stannic oxide (SnO2) and CeO2Property is similar and a kind of strong oxidizer and fining agent and the sulphur of negative valency state combine Ability it is stronger than iron, but and CeO2Difference, itself is not colored, so, its addition is conducive to glass toward blue color side To adjustment, but as fining agent for, excessive SnO2Instead to clarify it is unfavorable, cause glass gas rate promoted, and glass at Increasing for bubble can cause to scatter and significantly reduce light transmittance in product.
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-), and in glass Fe ions (Fe2+Or Fe3+) it is combined into FeSx, finally make the amber or sulphur color that glass into needs dark brown or pale brown Color, therefore a small amount of carbon dust can be added as strong reductant, the mass ratio of carbon dust and main material is 0.001~0.5：100.
Above-mentioned alumina silicate glass contains 0.001%~0.012% Fe in alumina silicate glass2O3In the case of, add The tone of alumina silicate glass can effectively be adjusted by entering color tone adjustment agents, adjust the content of several components in color tone adjustment agents, can Further to adjust the tone of alumina silicate glass.
The preparation method of the alumina silicate glass of one embodiment mixes above-mentioned main material, above-mentioned color tone adjustment agents simultaneously Heating melting obtains glass metal aftershaping.
Further, by main material, color tone adjustment agents obtain after thawing and clarification in 6 hours glass metal carry out at Type.
Further, further glass metal can also be made to homogenize by deaeration, stirring etc. after glass metal；Glass metal passes through Floating process, glass tube down-drawing or roll-in method etc. are molded into glass plate, or by cast molding are glass blocks.
Further, excellent in order to avoid the element sulphur inevitably brought by using combustion of fossil fuel to heat Choosing, the fused raw material by the way of electric smelting.
The preparation method of above-mentioned alumina silicate glass is simple for process, and the alumina silicate glass being prepared has center color It adjusts.
The alumina silicate glass of another embodiment indicates with the mass percentage of oxide benchmark, including： 50.48%~66.92% SiO2, 8.74%~20.97% Al2O3, 2.43%~6.99% MgO, 11.16%~ 16.98% Na2O, 0~4%K2O, 0.1%~1.5% ZrO2, 0.001%~0.012% Fe2O3, 0.058%~ 0.999% SnO2, 0.01%~0.999% CeO2And 0.049%~0.999% ZnO, the light transmission of alumina silicate glass Rate >=91.60%.
The alumina silicate glass is mixed by above-mentioned main material, clarification and coloration conditioning agent in one of the embodiments, It prepares.It should be noted that main material is by containing above-mentioned glass oxide benchmark corresponding raw mineral materials (such as silica sand, zirconium English Stone etc.) form introduce, or pass through soda ash (Na2CO3), silica, potassium carbonate, magnesia, aluminium hydroxide, magnesium hydroxide, The form of the industrial chemicals such as aluminium oxide, potassium nitrate, sodium nitrate introduces, it is only necessary to ensure finally obtained alumina silicate glass In the content range that is obtained with the content calculation of oxide benchmark meet above range.
Alumina silicate glass contains 0.0777%~0.1498% SnO in one of the embodiments,2, 0.0777% ~0.1498% CeO2, 0.0485%~0.9988% ZnO, alumina silicate glass is converted under the equivalent thickness of 1.1mm CIE Lab color shades indexs be T value >=91.60%, L* value >=96.70%, a* values be that -0.04~-0.01, b* values are 0.1~0.16.
Alumina silicate glass contains 0.0582%~0.9988% SnO in one of the embodiments,2, 0.0097% ~0.0999% CeO2, 0.0971%~0.1498% ZnO, alumina silicate glass is converted under the equivalent thickness of 1.1mm CIE Lab color shades indexs be T values >=91.60%, L* value >=96.70%, a* value be 0.06~0.1, b* values be 0.07 ~0.1.
Alumina silicate glass contains 0.0582%~0.9988% SnO in one of the embodiments,2, 0.0097% ~0.0499% CeO2, 0.1942%~0.9988% ZnO, alumina silicate glass is converted under the equivalent thickness of 1.1mm CIE Lab color shades indexs be T value >=91.60%, L* value >=96.70%, a* values be -0.01~0.06, b* values be 0~ 0.07。
Alumina silicate glass contains 0.0582%~0.9988% SnO in one of the embodiments,2, 0.1456% ~0.9988% CeO2, 0.0485%~0.9988% ZnO, alumina silicate glass is converted under the equivalent thickness of 1.1mm CIE Lab color shades indexs be T value >=91.60%, L* value >=96.70%, a* values be that -0.1~-0.04, b* values are 0.16~0.2.
Although containing 0.001%~0.012% Fe in above-mentioned alumina silicate glass2O3, but light transmittance >=91.60%, By adjusting SnO2、CeO2, ZnO content can adjust the tone of glass.
It is described in detail below in conjunction with specific embodiment.
Unless otherwise specified, then other for not containing in addition to the inevitable impurity are not known and point out following embodiment Component.
Examples 1 to 25
The alumina silicate glass of Examples 1 to 25 weighs main material according to raw material proportioning in table 1~5 respectively, tone is adjusted Agent (the corresponding numerical value of each raw material is parts by weight in table 1~5), is sufficiently mixed to obtain mixture in mixing machine.It needs to illustrate , because being Laboratory Production, the pure raw material that each component uses completely can be to avoid containing Fe, therefore Examples 1 to 25 In be intentionally added Fe2O3。
Mixture is put into platinum crucible, and carries out the fusing and clarification of 6h under 1620 DEG C of high temperature furnace.By glass Liquid is poured into graphite jig and is molded, and keeps the temperature half an hour at 650 DEG C, and furnace cooling later obtains glass blocks.
Glass blocks by machine cuts and roughly grind, fine grinding, the foliated glass for being polished to 1.1mm thickness.
The glass prepared to Examples 1 to 25 is tested, glass ingredient (including Fe2O3) tested using XRF, with The mass percentage expression of oxide benchmark the results are shown in Table 6~10, and foliated glass is put into spectrophotometer, is measured Visible light transmittance within the scope of its 380nm~780nm of 1.1mm glass finds out the CIE (states using D65 light sources using color meter Border illuminate the committee) L*, a*, b* chromatic value, the results are shown in Table 6~10.
Table 1
Table 2
Embodiment 6 7 8 9 10
SiO2 66.40 66.40 66.40 66.40 66.40
Al2O3 13.00 13.00 13.00 13.00 13.00
MgO 2.50 2.50 2.50 2.50 2.50
Na2O 17.00 17.00 17.00 17.00 17.00
K2O 1.00 1.00 1.00 1.00 1.00
ZrO2 0.10 0.10 0.10 0.10 0.10
CeO2 0 0.09 0.06 0.05 0.18
SnO2 0 0.14 0.11 0.07 0.08
ZnO 0 0.48 0.12 0.71 0.07
Carbon dust 0 0.06 0.17 0.19 0.45
Fe2O3 0.010 0.010 0.010 0.010 0.010
Table 3
Table 4
Embodiment 16 17 18 19 20
SiO2 52.00 52.00 52.00 52.00 52.00
Al2O3 21.00 21.00 21.00 21.00 21.00
MgO 5.85 5.85 5.85 5.85 5.85
Na2O 17.00 17.00 17.00 17.00 17.00
K2O 4.00 4.00 4.00 4.00 4.00
ZrO2 0.15 0.15 0.15 0.15 0.15
CeO2 0.00 0.15 0.10 0.05 0.26
SnO2 0.00 0.15 0.12 0.09 0.06
ZnO 0.00 1.00 0.15 0.20 1.00
Carbon dust 0.00 0.03 0.23 0.25 0.50
Fe2O3 0.0040 0.0040 0.0040 0.0040 0.0040
Table 5
Table 6
Embodiment 1 2 3 4 5
SiO2(wt%) 60.4952 60.0528 60.0627 60.0032 60.2842
Al2O3(wt%) 15.9987 15.8817 15.8844 15.8686 15.9429
MgO (wt%) 4.9996 4.9630 4.9639 4.9589 4.9822
Na2O (wt%) 15.6987 15.5840 15.5865 15.5711 15.6440
K2O (wt%) 1.9998 1.9852 1.9855 1.9836 1.9929
ZrO2(wt%) 0.7999 0.7941 0.7942 0.7934 0.7971
CeO2(wt%) 0 0.1158 0.0496 0.0198 0.1594
SnO2(wt%) 0 0.1092 0.5361 0.1785 0.1096
ZnO (wt%) 0 0.5062 0.1291 0.6149 0.0797
Fe2O3(wt%) 0.0080 0.0080 0.0080 0.0080 0.0080
TVisible light(%) 91.8 91.9 92.1 92.3 91.8
L* 96.72 96.73 96.81 96.92 96.71
a* -0.04 -0.03 0.08 0.03 -0.06
b* 0.12 0.13 0.09 0.04 0.18
Table 7
Table 8
Embodiment 11 12 13 14 15
SiO2(wt%) 66.4960 65.9291 66.1536 65.9395 66.2714
Al2O3(wt%) 10.9993 10.9056 10.9427 10.9073 10.9622
MgO (wt%) 6.9996 6.9399 6.9635 6.9410 6.9759
Na2O (wt%) 13.9992 13.8798 13.9271 13.8820 13.9519
K2O (wt%) 0 0 0 0 0
ZrO2(wt%) 1.4999 1.4871 1.4922 1.4874 1.4948
CeO2(wt%) 0 0.1487 0.0995 0.0397 0.1893
SnO2(wt%) 0 0.1487 0.3060 0.1329 0.0887
ZnO (wt%) 0 0.5552 0.1094 0.6644 0.0598
Fe2O3(wt%) 0.006 0.006 0.006 0.006 0.006
TVisible light(%) 91.9 91.9 92.1 92.3 91.8
L* 96.71 96.74 96.79 96.97 96.73
a* -0.02 -0.01 0.06 0.01 -0.04
b* 0.11 0.12 0.07 0.02 0.17
Table 9
Table 10
Embodiment 21 22 23 24 25
SiO2(wt%) 66.9920 66.8049 66.7227 66.4679 66.8183
Al2O3(wt%) 8.9989 8.9738 8.9627 8.9285 8.9756
MgO (wt%) 6.9992 6.9796 6.9710 6.9444 6.9810
Na2O (wt%) 11.4986 11.4665 11.4524 11.4087 11.4688
K2O (wt%) 3.9995 3.9884 3.9834 3.9682 3.9891
ZrO2(wt%) 1.4998 1.4956 1.4938 1.4881 1.4959
CeO2(wt%) 0 0.0798 0.0996 0.0496 0.1496
SnO2(wt%) 0 0.1496 0.1530 0.2367 0.0598
ZnO (wt%) 0 0.0499 0.1494 0.4960 0.0499
Fe2O3(wt%) 0.0120 0.0120 0.0120 0.0120 0.0120
TVisible light(%) 91.4 91.5 91.7 91.9 91.40
L* 96.70 96.73 96.78 96.88 96.71
a* -0.07 -0.04 0.10 0.05 -0.08
b* 0.15 0.15 0.10 0.06 0.20
It can be seen that the alumina silicate glass of embodiment 2~5,7~10,12~15,17~20 and 21~25 from table 6-10 Although containing Fe2O3, but by the way that color tone adjustment agents are added, the tone of glass can be adjusted.
One or more of embodiments of the invention above described embodiment only expresses, description are more specific and detailed Carefully, but it cannot be construed as a limitation to the scope 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 domain.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (14)

1. a kind of color tone adjustment agents for alumina silicate glass, which is characterized in that the color tone adjustment agents include carbon dust, SnO2、 CeO2And ZnO, the SnO2、CeO2And the mass ratio of ZnO is 0.06~1：0.01~1：0.05~1, and 1≤C/ (0.08SnO2 +0.0349CeO2)≤42, in formula, C represents carbon dust, and each molecular formula represents respective quality.
2. color tone adjustment agents according to claim 1, which is characterized in that the SnO2、CeO2And the mass ratio of ZnO is 0.08~0.15：0.08~0.15：0.05~1, and 1≤C/ (0.08SnO2+0.0349CeO2)≤5.34。
3. color tone adjustment agents according to claim 1, which is characterized in that the SnO2、CeO2And the mass ratio of ZnO is 0.06~1：0.01~0.1：0.1~0.15, and 5.34≤C/ (0.08SnO2+0.0349CeO2)≤20.83。
4. color tone adjustment agents according to claim 1, which is characterized in that the SnO2、CeO2And the mass ratio of ZnO is 0.06~1：0.01~0.05：0.2~1, and 20.83≤C/ (0.08SnO2+0.0349CeO2)≤32.38。
5. color tone adjustment agents according to claim 1, which is characterized in that the SnO2、CeO2And the mass ratio of ZnO is 0.06~1：0.15~1：0.05~1, and 32.38≤C/ (0.08SnO2+0.0349CeO2)≤42。
6. a kind of alumina silicate glass, which is characterized in that the raw material of the alumina silicate glass includes main material and claim 1 ~5 any one of them color tone adjustment agents, wherein the mass ratio of the color tone adjustment agents and the main material is 0.12：100~ 3：100,0.001%~0.012% Fe is contained in terms of mass percentage in the alumina silicate glass2O3。
7. alumina silicate glass according to claim 6, which is characterized in that the main material wraps by percentage to the quality It includes：52%~67% SiO2, 9%~21% Al2O3, 2.5%~7% MgO, 11.5%~17% Na2O, 0~4% K2The ZrO of O and 0.1%~1.5%2。
8. alumina silicate glass according to claim 6, which is characterized in that the SiO2With the Al2O3Gross mass hundred Content is divided to be less than 85%.
9. alumina silicate glass according to claim 6, which is characterized in that 1≤C/ (0.08SnO2+0.0349CeO2)≤ 5.34, the CeO2Mass ratio with the main material is 0.08：100~0.15：100, the SnO2With the matter of the main material Amount is than being 0.08：100~0.15：The mass ratio of 100, the ZnO and the main material is 0.05~1：100, the manosil AS Salt glass be converted into the CIE Lab color shades indexs under the equivalent thickness of 1.1mm be T values >=91.60%, L* value >= 96.70%, a* value are that -0.04~-0.01, b* values are 0.1~0.16.
10. alumina silicate glass according to claim 6, which is characterized in that 5.34≤C/ (0.08SnO2+ 0.0349CeO2)≤20.83, the CeO2Mass ratio with the main material is 0.01~0.1：100, the SnO2With it is described The mass ratio of main material is 0.06~1：The mass ratio of 100, the ZnO and the main material is 0.1：100~0.15：100, institute It is T value >=91.60%, L* values to state the CIE Lab color shades indexs that alumina silicate glass is converted under the equivalent thickness of 1.1mm >=96.70%, a* value are that 0.06~0.1, b* values are 0.07~0.1.
11. alumina silicate glass according to claim 6, which is characterized in that 20.83≤C/ (0.08SnO2+ 0.0349CeO2)≤32.38, the CeO2Mass ratio with the main material is 0.01~0.05：100, the SnO2With it is described The mass ratio of main material is 0.06~1：The mass ratio of 100, the ZnO and the main material is 0.2：100~1：100, it is described Alumina silicate glass be converted into the CIE Lab color shades indexs under the equivalent thickness of 1.1mm be T values >=91.60%, L* value >= 96.70%, a* value are that -0.01~0.06, b* values are 0~0.07.
12. alumina silicate glass according to claim 6, which is characterized in that 32.38≤C/ (0.08SnO2+ 0.0349CeO2)≤42, the CeO2Mass ratio with the main material is 0.15：100~1：100, the SnO2With the master The mass ratio of raw material is 0.06~1：The mass ratio of 100, the ZnO and the main material is 0.05：100~1：100, the aluminium Silicate glass be converted into the CIE Lab color shades indexs under the equivalent thickness of 1.1mm be T values >=91.60%, L* value >= 96.70%, a* value are that -0.1~-0.04, b* values are 0.16~0.2.
13. a kind of alumina silicate glass, which is characterized in that it is indicated with the mass percentage of oxide benchmark, including： 50.48%~66.92% SiO2, 8.74%~20.97% Al2O3, 2.43%~6.99% MgO, 11.16%~ 16.98% Na2O, 0~4%K2O, 0.1%~1.5% ZrO2, 0.001%~0.012% Fe2O3, 0.058%~ 0.999% SnO2, 0.01%~0.999% CeO2And 0.049%~0.999% ZnO, the alumina silicate glass Light transmittance >=91.60%.
14. a kind of preparation method of alumina silicate glass, which is characterized in that by Claims 1 to 5 any one of them tone tune The main material of section agent and alumina silicate glass is mixed and heated melting and obtains glass metal aftershaping.
CN201710210655.5A 2017-03-31 2017-03-31 Color tone regulator, aluminosilicate glass and preparation method thereof Active CN108658452B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710210655.5A CN108658452B (en) 2017-03-31 2017-03-31 Color tone regulator, aluminosilicate glass and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710210655.5A CN108658452B (en) 2017-03-31 2017-03-31 Color tone regulator, aluminosilicate glass and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108658452A true CN108658452A (en) 2018-10-16
CN108658452B CN108658452B (en) 2021-07-02

Family

ID=63784505

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710210655.5A Active CN108658452B (en) 2017-03-31 2017-03-31 Color tone regulator, aluminosilicate glass and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108658452B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1034526A (en) * 1988-01-25 1989-08-09 秦皇岛耀华玻璃厂 Silver-free photochromic glass
JP3204500B2 (en) * 1999-07-21 2001-09-04 花王株式会社 Full color toner
CN102892723A (en) * 2010-02-26 2013-01-23 肖特公开股份有限公司 Lithium aluminosilicate glass having a high e-module and method for the production thereof
CN105985018A (en) * 2016-04-28 2016-10-05 中国南玻集团股份有限公司 Aluminosilicate glass, and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1034526A (en) * 1988-01-25 1989-08-09 秦皇岛耀华玻璃厂 Silver-free photochromic glass
JP3204500B2 (en) * 1999-07-21 2001-09-04 花王株式会社 Full color toner
CN102892723A (en) * 2010-02-26 2013-01-23 肖特公开股份有限公司 Lithium aluminosilicate glass having a high e-module and method for the production thereof
CN105985018A (en) * 2016-04-28 2016-10-05 中国南玻集团股份有限公司 Aluminosilicate glass, and preparation method and application thereof

Also Published As

Publication number Publication date
CN108658452B (en) 2021-07-02

Similar Documents

Publication Publication Date Title
CN105985018B (en) Alumina silicate glass, preparation method and application
JP2005075665A (en) Optical glass, press-moldable glass body, optical element, and method for producing the optical element
TW399031B (en) Bronze glass composition
TW201311601A (en) Glass to be chemically reinforced and glass housing
WO2002059052A1 (en) Grey glass composition including erbium
US10611671B2 (en) Heat-ray- and ultraviolet-absorbent glass sheet, and method for manufacturing same
WO2003027036A1 (en) Grey glass composition including erbium, holmium, and/or yttrium
WO2004018375A2 (en) Glass composition with low visible and ir transmission
WO2016017558A1 (en) High-transparency glass
WO2019153845A1 (en) Glass composition, low inclusion content glass, preparation method therefor and application thereof
JP2007070156A (en) Method of manufacturing optical glass
WO2007021432A2 (en) Grey glass composition including erbium, neodymium and/or praseodymium
JP6566024B2 (en) Glass article and light guide
WO2017185288A1 (en) Aluminosilicate glass and preparation method therefor, and glass plate
TW201700427A (en) Glass article
CN108314315B (en) Glass, preparation method thereof, tempered glass, glass plate and application
WO2015170759A1 (en) Heat ray-absorbing glass plate and method for producing same
JP2019182719A (en) Reinforced crystallized glass
CN108658452A (en) Color tone adjustment agents, alumina silicate glass and preparation method thereof
JP2005132709A (en) Ultraviolet and infrared absorbing green glass
WO2015118964A1 (en) Near-infrared absorbing/high-contrast glass lens
JPH10297934A (en) Colored glass absorbing ultraviolet and infrared rays
CN114014538A (en) Silicate glass and preparation method and application thereof
US11066318B2 (en) Green glass composition
CN108947238B (en) Light guide plate glass, preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant