CN101012104A - Method of manufacturing alkali-free aluminosilicate base plate glass - Google Patents
Method of manufacturing alkali-free aluminosilicate base plate glass Download PDFInfo
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- CN101012104A CN101012104A CNA2007100539178A CN200710053917A CN101012104A CN 101012104 A CN101012104 A CN 101012104A CN A2007100539178 A CNA2007100539178 A CN A2007100539178A CN 200710053917 A CN200710053917 A CN 200710053917A CN 101012104 A CN101012104 A CN 101012104A
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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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
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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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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Abstract
The invention discloses a manufacturing method of non-alkaline aluminosilicate base glass with less evolved crystal, which comprises the following steps: (1) allocating; dissolving; (2) clarifying; evening; (3) cooling; (4) moulding; (5) annealing; cutting; detecting; packing; controlling air wetness; keeping steam pressure between 0.8kPa and 12.5kPa.
Description
Technical field
The present invention relates to a kind of method that reduces the production alkali-free aluminosilicate base plate glass of glass liquidus temperature, minimizing devitrification of glass by control air humidity.
Background of invention
Liquid-crystal display (LCD) is the class in the flat-panel monitor, can be divided into two kinds of passive matrix type LCD and active-matrix formula LCD according to the control mode difference.Passive matrix type LCD can be divided into TN-LCD (TwistedNematic-LCD), STN-LCD (Super TN-LCD) and DSTN-LCD (Double layer STN-LCD) again, passive matrix type LCD is being subjected to bigger restriction aspect brightness and the angle of visibility, speed of response is also slower.Using at present is active-matrix formula LCD (AMLCD) more widely, also claim TFT-LCD (Thin FilmTransistor-LCD), the TFT liquid-crystal display is each the pixel integrated transistor in picture, can make that brightness is brighter, color is abundanter and broader apparent area.A slice LCD panel need use two sheet glass substrates, is used separately as the base plate of bottom glass substrate and colored filter (Color Filter).The used glass substrate of LCD can be divided into alkali-containing glass and non-alkali glass two big classes, and alkali-containing glass is used for passive matrix type LCD such as TN and STN LCD; The glass substrate that is used for TFT-LCD, need forming nesa coating, insulating film, semi-conductor (polysilicon, amorphous silicon etc.) film and metallic membrane on bottom base plate glass surface by technology such as sputter, chemical vapor deposition (CVD)s, form various circuit and figure by photoetch (Photo-etching) technology then, if glass contains alkalimetal oxide (Na
2O, K
2O, Li
2O), alkalimetal ion diffuses into deposited semiconductor material in heat treatment process, infringement semiconductor film characteristic, and therefore, glass is answered the alkali-free metal oxide, must adopt non-alkali glass, and first-selected is with SiO
2, Al
2O
3, B
2O
3And alkaline earth metal oxide RO (R=Mg, Ca, Sr, Ba) grade is the aluminiu-boron silicate glass without alkali of principal constituent (Aluminoborosilicate Glass).Up to the present, the production flat-panel screens has three kinds of main manufacturing technologies with glass substrate, is respectively float glass process (Float Technology), slot draw method (Slot DownDraw) and overflow scorification (Overflow Fusion Technology).The glass baseplate surface that float glass process is produced can produce scar and concavo-convex, needs to polish through surface grinding again, and polishing process is expensive and time-consuming, can produce broad glassy product and the bigger advantage of output but have; The production of small area substrate during the slot draw method only is applicable to; The overflow fusion technology can output has the ultra-thin glass substrate on two pristine glasses surface, compare with the slot draw method with float glass process, can exempt post-treatment processes such as grinding or polishing, simultaneously in the flat-panel screens manufacturing processed, do not note because of having original simultaneously and the different glass surface that contacts being arranged with liquid tin yet, or contact to some extent with grinding medium and cause glass surface nature difference etc., become the main flow of ultra-thin flat glass moulding.
The production of glass substrate generally comprises step: (1) batching and dissolving; (2) clarification and homogenization; (3) cooling; (4) moulding; (5) annealing, cutting, check and packing etc.Produce the synoptic diagram of aluminiu-boron silicate glass without alkali substrate as Fig. 1 for the overflow scorification, mainly contain following steps: batching and dissolving, the admixtion that mixes are dissolved in 1500～1650 ℃ in glass furnace 1, and carry out clarification and homogenization; The glass melt that forms in the clarification and homogenization, step 1 enters in the finer of being made by precious metal material 2 further to be clarified, and removes the bubble in the glass; Carry out further homogenizing by 3 pairs of glass of agitator, eliminate striped; Cooling, the glass melt of finishing clarification and homogenization enters feed device 5 by cooling tube 4, and glass is cooled to the required viscosity of moulding in this process; Moulding, glass enter formed body 6, carry out the drawing moulding of sheet glass; Annealing, cutting, check and packing, the sheet glass that drawing is finished enters annealing furnace and carries out fine annealing, and enters operations such as cutting, check and packing.Wherein, in step 4, fused glass has also downward convergent formed body (overflow brick) surface of wedge shape section along one and flows downward, and be integral at the interflow, below of the lower edge portion of formed body (be labeled as among Fig. 17 position), make the traction downwards simultaneously of its refrigerative form sheet glass then.In this forming method, glass in case moulding process is just finished immediately in the interflow, must make it later on no longer to deform under the formed body lower edge portion of wedge shape section.Near the viscosity of the glass the formed body lower edge portion of wedge shape section is too high or too low, all will seldom arrive high-quality sheet glass.When adopting the moulding of overflow scorification, the glass melt viscosity of lower edge portion that must formed body is in the manufacturing of carrying out sheet glass in 30000～1000000 scopes of mooring.When adopting the moulding of overflow scorification, because the glass viscosity of the lower edge portion of cross section wedge shape formed body is restricted, then the crystallization viscosity of formed glass (corresponding to the viscosity of devitrification of glass temperature) is restricted.For guaranteeing not produce at glass the situation compacted under of crystallization, the initial crystallization viscosity of glass (be liquid phase viscosity, corresponding temperature is called liquidus temperature) must be more than 30000 pools.Because being used for the glass material of TFT type plate of flat liquid crystal display is to belong to the aluminoborosilicate P series glass with higher recrystallization temperature, therefore just the glass of using is formed and had higher requirement, glass must have beyond the character such as desired physics, chemistry and machinery, and the liquidus temperature of glass or liquid phase viscosity must be as the important indicators of investigating glass formula.Obtain high liquid phase viscosity by adjusting glass formula, may impact or increase cost to other character of glass,, contain Ta as U.S. Pat 5374595 disclosed a kind of non-alkali glasss with high liquid phase viscosity
2O
5Deng rare metal oxide, will increase product cost.Be to solve the problem of devitrification of glass, application number be 02124968.7 and the Chinese patent of 02824902.X special production equipment is disclosed respectively, these devices have increased the complicacy and the fund input of equipment greatly.
In traditional TFT liquid crystal glass base is produced, use As usually
2O
3Make finings, consider environmental requirement, need to use no arsenic finings.Use more As at present
2O
3Substitute is SnO
2, as Chinese patent 00128604.8 disclosed a kind of non-alkali glass.A large amount of SnO in the actual production
2The adding of finings can reduce the crystallization stability of glass, and the liquidus temperature of glass is raise.
Summary of the invention
The present invention is directed to above-mentioned problems of the prior art and a kind of method of passing through to reduce the non-alkali glass liquidus temperature and reducing the production alkali-free aluminosilicate base plate glass of devitrification of glass is provided.
The object of the present invention is achieved like this:
The spontaneous crystallization of this type of alkali-free aluminoborosilicate mainly shows as surperficial crystallization, glass inside seldom produces spontaneous crystallization, by increasing this crystallization that steam partial pressure (being atmospheric moisture) in the glass ambient air of living in can suppress glass, reduce the glass liquidus temperature.
One of purpose of the present invention is achieved in that provides a kind of method of producing alkali-free aluminosilicate base plate glass, may further comprise the steps: (1), batching and dissolving; (2) clarification and homogenization; (3) cooling; (4) moulding; (5) annealing, cutting, check and packing in (4) step therein, by increasing the humidity of formed glass ambient air of living in, reduce the liquidus temperature of glass, reduce the crystallization of glass.Control air humidity remains on the steam partial pressure in the formed glass ambient air of living in more than the 0.8kPa, better remains on more than the 1.0kPa, preferably remains on more than the 1.5kPa the highest 12.5kPa that is no more than.
This method especially is fit to comprise the non-alkali glass (representing with weight percentage) of following composition: the SiO of 50-70%
2, 12-25%Al
2O
3, the B of 7-14%
2O
3, the ∑ RO (MgO+CaO+SrO+BaO) of 10-20%, 0-2%As
2O
3, 0-1%Sb
2O
3, 0-2%SnO
2, 0-1%CeO
2, 0-3%Cl.
Aforesaid method is suitable for glass to be adopted in the overflow scorification moulding process.
One of purpose of the present invention also can be achieved like this: a kind of method of producing alkali-free alumina silicate glass is provided, a kind of method of producing alkali-free aluminosilicate base plate glass is provided, may further comprise the steps: (1), batching and dissolving; (2) clarification and homogenization; (3) cooling; (4) moulding; (5) annealing, cutting, check and packing in (4) step therein, by increasing the atmospheric moisture of shaping area space outerpace, reduce the liquidus temperature of glass, reduce the crystallization of glass.The atmospheric moisture of control shaping area space outerpace remains on more than the 0.8kPa airborne steam partial pressure, better remains on more than the 1.0kPa, preferably remains on more than the 1.5kPa the highest 12.5kPa that is no more than.The envrionment temperature of shaping area space outerpace should be not less than 10 ℃, better is not less than 15 ℃, preferably is not less than 18 ℃.
This method is particularly suitable for producing the non-alkali glass (representing with weight percentage) that comprises following composition: 50-70%SiO2,12-25%Al
2O
3, 7-14%B
2O
3, 10-20% ∑ RO (MgO+CaO+SrO+BaO), 0-2%As
2O
3, 0-1%Sb
2O
3, 0-2%SnO
2, 0-1%CeO
2, 0-3%Cl.
Aforesaid method is suitable for glass to be adopted in the overflow scorification moulding process.
The present invention can reduce the liquidus temperature of alkali-free alumina silicate glass effectively, reduces the requirement of moulding to the glass liquidus temperature, suppresses the crystallization of glass.The present invention is suitable for the production of alkali-free alumina silicate sheet glass, especially is fit to adopt the overflow scorification to produce alkali-free glass substrate, is suitable for float glass process and slot draw method simultaneously and produces alkali-free glass substrate.
Before describing the present invention, at first key concept and the mechanism that the present invention relates to is described.
Absolute humidity is a kind of method for expressing of atmospheric moisture, is the weight of water vapour contained in the gas mixture of the water vapor of unit volume and air (or other gas), shows with the gram or the kilogram numerical table of institute's containing water vapor in one cubic metre of wet air (or other gas).The also available water vapour pressure that is present in the air (or other gas) is represented.Relative humidity then is the another kind of method for expressing of atmospheric moisture.Relative humidity is meant under uniform temp and pressure, the ratio of absolute humidity and saturated humidity ratio, the i.e. ratio of the ratio of the actual water vapour weight that contains and saturated steam weight in the air (or other gas), or actual water vapour pressure and saturation vapor pressure.It is generally represented with per-cent.In absolutely dry air (or other gas), the numerical value of relative humidity is 0; By water vapour in the saturated air (or other gas), relative humidity is 100%.Because water saturation vapour pressure and temperature are closely related, therefore, when adopting relative humidity to represent atmospheric moisture, must spell out the air themperature when measuring humidity, the atmospheric moisture method for expressing is to adopt absolute humidity more intuitively, as the dividing potential drop P water of water in air steam.Table 1 has been listed water saturation vapour pressure under the differing temps.
The data of the water saturation vapour pressure (mmhg) that table 1 is listed are meant the pressure of steam when water contacts with its vapor phase.The air of vapor pressure when contacting with to(for) water when the temperature t ℃ must add that is then revised a number.When temperature was lower than 40 ℃, its correction number was
P
Full(0.0775-3.13 * 10
-4T)/100
Water saturation vapour pressure (seeing Table 1) when P satisfies for t ℃ in the formula.
The liquidus temperature of glass is meant the ceiling temperature of devitrification of glass, is equivalent to the solid, liquid equilibrium temperature of crystalline phase material, and when this temperature, the solubleness of certain solid (crystal) in solution reaches capacity and begins to separate out.
Glass is often referred to and is incubated certain hour in thermal gradient furnace, begins to occur the top temperature of crystallization when setting up solid-liquid equilibrium between crystal and the glass, and the glass viscosity under this temperature is called liquid phase viscosity.The liquidus temperature of glass is low more, liquid phase viscosity is high more, and glass is difficult to crystallization more.Liquidus temperature is low more, and then far away more apart from the mold temperature upper limit (working point), the crystallization district of glass may be in rapid cooling zone more, helps fast making glass be not easy crystallization by the crystallization district.Liquid phase viscosity is big more, glass ionic when crystallization reset and velocity of diffusion slow more, the dynamic conditions of crystal growth is not easy to satisfy more, crystal growth is slower, causes the crystallization difficulty, helps uniform glass formation.
According to the present invention, a kind of method of producing alkali-free alumina silicate glass is provided, following steps are arranged: (1) batching and dissolving; (2) clarification and homogenization; (3) cooling; (4) moulding; (5) annealing, cutting, check and packing.In (4) step therein, glass adopts the moulding of overflow scorification, it is characterized in that, by increasing the atmospheric moisture of formed glass environment of living in, reduces the liquidus temperature of glass, reduces the crystallization of glass.Control air humidity remains on the steam partial pressure in the formed glass ambient air of living in more than the 0.8kPa, better remains on more than the 1.0kPa, preferably remains on more than the 1.5kPa the highest 12.5kPa that is no more than.This method especially is fit to comprise the non-alkali glass (representing with weight percentage) of following composition: the SiO of 50-70%
2, 12-25%Al
2O
3, the B of 7-14%
2O
3, the ∑ RO (MgO+CaO+SrO+BaO) of 10-20%, 0-2%As
2O
3, 0-1%Sb
2O
3, 0-2%SnO
2, 0-1%CeO
2, 0-3%Cl.
SiO
2Be the main glass-former of TFT liquid-crystalline glasses, SiO
2Can reduce the thermal expansivity and the density of glass, improve strain point of glass, SiO
2Content is limited to the 50-70wt% scope.SiO
2When content is lower than 50wt%, be difficult for obtaining the glass of low bulk, low density and high strain-point, can reduce the chemical stabilities such as acid resistance of glass; SiO
2When content surpassed 70wt%, the high temperature viscosity of glass increased, and makes the glass smelting temperature too high.B
2O
3Itself being glass network former, is again a kind of fusing assistant, and it can reduce glass viscosity and improve stability, glass.B
2O
3Content is limited at 7-14wt% scope, B
2O
3Content is lower than 7wt%, can't play fluxing action, is unfavorable for reducing glass density, and the ability of anti-buffered hydrofluoric acid (BHF) solution of glass is relatively poor simultaneously; B
2O
3When content surpassed 14wt%, strain point of glass reduced, and makes glass heat impedance variation, and reduced the resistance to acid of glass, and the phase-splitting tendency of glass is increased, and reduced stability, glass.Al
2O
3Can significantly improve the strain point of glass, increase the chemical stability and the Young's modulus of glass.Al
2O
3Content is limited to 12-25wt%, Al
2O
3Content is lower than 12wt%, is difficult for obtaining the non-alkali glass of high strain-point, and glass chemistry stability is not enough; Al
2O
3Content will significantly increase the high temperature viscosity of glass greater than 25wt%, and glass melting temperature is raise, and can increase the liquidus temperature of glass simultaneously, and stability, glass is descended.
In the non-alkali glass that the present invention relates to, adopt alkaline earth metal oxide as solubility promoter, and be used for adjusting the physicochemical property of glass.MgO has the effect that reduces the glass high temperature viscosity, increases low temperature viscosity; CaO has the effect that reduces the glass high temperature viscosity, increases low temperature viscosity equally, plays the fusing assistant effect, and increases the glass acid resistance.SrO and BaO all have the effect that increases glass chemistry stability and improve the anti-devitrification of glass, and can improve the anti-BHF solvent ability of glass.The summation of MgO+CaO+SrO+BaO is defined as 10-20wt%, and when MgO+CaO+SrO+BaO total content during less than 10wt%, glass is difficult to found.When MgO+CaO+SrO+BaO content during greater than 20wt%, the glass liquidus temperature is too high, and tendency towards devitrification increases.
The non-alkali glass that the present invention relates to also can contain at least a finings to improve melting quality of glass, and finings can be selected from As
2O
3, Sb
2O
3, CeO
2, SnO
2, Cl etc., wherein As
2O
3Use separately or and Sb
2O
3Be used in combination As
2O
3Content range be 0-2wt%, Sb
2O
3Content range be 0-1wt%; SnO
2Separately or and CeO
2Be used in combination, its content is respectively 0-2wt% and 0-1wt%; Cl is by muriate such as CaCl
2Deng introducing, help reducing the viscosity and the clarification of glass, its content range is 0-3wt%.
The crystallization that the present invention is suitable as the TFT liquid crystal display substrate, comprise the non-alkali glass of mentioned component mainly shows as surperficial crystallization, rare inner crystallization, Fig. 2 is an example of this class devitrification of glass, and the surperficial degree of crystallization of glass is relevant with glass composition and glass condition of living in.Because crystal grain makes glass surface present opalescence to the absorption and the scattering of light, influenced by grain-size and crystallization layer thickness, it is translucent, even not transparent to white to present slight opalescence in appearance.The present invention finds that also top temperature (liquidus temperature) and degree of crystallization that this class glass produces crystallization are obviously relevant with atmospheric moisture, and the liquidus temperature of glass changes with atmospheric moisture.
The spontaneous crystallization of homogeneous glass generally is divided into two kinds of whole crystallization and surperficial crystallizatioies, and the two all forms the mechanism of (nucleation) and crystal growth based on nucleus, and the surface nucleation of glass is mainly derived from surface imperfection and tiny crack.A distinguishing feature of borosilicate glass is to be easy to generate phase-splitting, this phase-splitting is mainly from glass-former ion Si4+ and the B3+ competition to O, the phase-splitting that can provide free 0 basic metal and alkaline earth metal oxide can suppress glass, wherein, alkalimetal oxide is more effective than alkaline-earth metal; On the other hand, the TFT liquid-crystalline glasses that the present invention relates to is an alkali-free, alkali-free metal oxide in the glass.Therefore, the surface of this class glass is except having the common surface imperfection and tiny crack that has of glass, because the phase-splitting of glass, cause surface imperfection and little inhomogeneous district to increase, therefore the high temperature nucleation of glass takes place easily and originates in glass surface, along with the glass growth of the residence time at high temperature, the nucleus quantity and the crystalline size of glass surface increase gradually, and extend to internal layer gradually.
H
2O may reside in the glass internal structure, also can enter glass structure from the surface of glass.During low temperature, because glass structure can't be adjusted airborne H
2O can only be adsorbed on the surface of glass; And at high temperature,, have adjustment capability, H because glass structure is more loose
2O can cut off the glass structure network by reaction, progressively to the glass internal penetration.
H
2O is relevant with the kind of glass to the influence of glass, concerning the alkali-free alumina silicate glass that the present invention relates to, with the airborne H of glass contact
2O comprises following several respects to the influence of glass surface crystallization:
Under the high temperature, H
2O combines with Si4+ and B3+ that glass surface has unsaturated link(age), reduces the energy on surface, suppresses surperficial homogeneous nucleation; H
2The effect of H+ among the O is similar to alkalimetal ion, enters the skin glass structure, suppresses the phase-splitting of upper layer; H
2O reduces the viscosity of surface layer of glass to the suspension effect of glass structure, is lower than the viscosity of inner glass, makes the nucleus on surface be difficult to form.H
2O can be expressed as the suspension effect of glass structure:
According to the present invention, by increasing airborne H
2O content promptly increases atmospheric moisture, can suppress the crystallization of aluminiu-boron silicate glass without alkali, reduces the liquidus temperature of glass, and 2 couples of the present invention of embodiment 1 and embodiment are fully described and verify.Because the water saturation vapour pressure varies with temperature, with the dividing potential drop P H of water in air steam
2O represents the absolute humidity of air.Particularly, according to the present invention,, should keep airborne steam partial pressure P H for crystallization that reduces aluminiu-boron silicate glass without alkali and the liquidus temperature that reduces glass
2O better remains on more than the 1.0kPa more than 0.8kPa, preferably remains on more than the 1.5kPa the highest 12.5kPa that is no more than.
The present invention also provides a kind of method of producing alkali-free alumina silicate glass, and following steps are arranged: (1) batching and dissolving; (2) clarification and homogenization; (3) cooling; (4) moulding; (5) annealing, cutting, check and packing.In (4) step therein, glass adopts the moulding of overflow scorification, it is characterized in that reducing by the atmospheric moisture that increases the shaping area space outerpace liquidus temperature of glass, reduces the crystallization of glass.The atmospheric moisture of control shaping area space outerpace remains on more than the 0.8kPa airborne steam partial pressure, better remains on more than the 1.0kPa, preferably remains on more than the 1.5kPa the highest 12.5kPa that is no more than.
If to the direct humidification in forming part internal space, then may produce disturbance to the air-flow of forming part internal space, the angularity of sheet glass is exerted an influence, be unfavorable for producing qualified product.According to the present invention, keep the atmospheric moisture of shaping area space outerpace, make water make the atmospheric moisture that contacts with formed glass reach requirement by spontaneous diffusion and air flowing.Particularly, airborne steam partial pressure PH20 remains on more than the 0.8kPa with the shaping area space outerpace, better remains on more than the 1.0kPa, preferably remains on more than the 1.5kPa.Considering the factors such as influence of humidity to equipment, is the upper limit of PH20 with 12.5kPa (water saturation vapour pressure when being equivalent to 50 ℃ approximately).Under specific temperature, the relative humidity of air is 100% to the maximum, and promptly the water in air vapor partial pressure can not surpass water saturation vapour pressure under this temperature.For steam partial pressure PH20 is remained on more than the 0.8kPa, better remain on more than the 1.0kPa, preferably remain on more than the 1.5kPa, the envrionment temperature of shaping area space outerpace should be not less than 10 ℃, better is not less than 15 ℃, preferably is not less than 18 ℃.
This method especially is fit to produce the non-alkali glass (weight fraction) that comprises following composition: 50-70%SiO
2, 12-25%Al
2O
3, 7-14%B
2O
3, 10-20% ∑ RO (MgO+CaO+SrO+BaO), 0-2%As
2O
3, 0-1%Sb
2O
3, 0-2%SnO
2, 0-1%CeO
2, 0-3%Cl.
Description of drawings
Fig. 1 produces the schematic flow sheet of alkali-free glass substrate for the overflow scorification.
Figure denote represents meaning as follows among the figure: 1 kiln; 2 precious metal finer; 3 whipping apptss; 4 cooling tubes; 5 feed devices; 6 formed bodys (overflow brick); 7 formed body lower edge.
Fig. 2 is the surperficial crystallization real scene shooting figure of glass D (seeing Table 1).
Glass specimen was handled 24 hours 1050 ℃ of insulations, and the air medial humidity of representing with steam partial pressure is about 0.4kPa.White portion is the crystallization of glass among the figure.
Embodiment
Below for being used to illustrate embodiments of the invention, its purpose is example and explanation, and does not limit the present invention in any way.
Embodiment 1
Table 2 is some embodiment of glass involved in the present invention.Form according to the glass in the table 1, prepare burden by producing 300g glass, glass batch is founded in the platinum rhodium crucible, founds 2 hours in 1600 ℃, promotes homogenization of glass by hand mixing during founding, and the glass casting that melts becomes piece and annealing.
Listed the liquidus temperature of glass under different condition in the table 2.Adopt reference liquid phase collimation method to measure the liquidus temperature of glass, the glass particle of chunky shape is placed in the platinum boat, insulation is 4 hours in thermal gradient furnace, and the liquidus temperature of the top temperature of spontaneous crystallization as glass appears in glass.Under three kinds of ambient air humidity, measure the liquidus temperature of glass respectively, the absolute humidity of the atmospheric moisture that provides in the table 2 for representing with steam partial pressure PH20, the unit of water in air vapor partial pressure is kPa, and humidity data is the average air humidity during measuring in the table.
Listed file names with the following character of glass in the table 2
20/300[10-7/ ℃ of the average coefficient of linear expansion α of-20-300 ℃ of scope];
-density d [g/cm3];
-strain point Ts[℃]
Embodiment 2
The glass liquidus temperature has reflected the difference of devitrification of glass temperature, can reflect the crystallization property of glass, because the difference of composition will influence crystalline growth velocity, causes the difference of devitrification of glass degree, though some glass crystallization, crystallization is less, degree is lighter.Table 3 listed glass A, B and D (seeing Table 2) 24 hours crystallization states of 1050 ℃ of insulations and with the relation of atmospheric moisture.
In the table 3, symbol represents devitrification of glass serious, that sample is in is translucent ~ opaque between; Symbol represents devitrification of glass medium, and this class crystallization shows as the surface and presents obvious opalescence phenomenon; Symbol ⊙ represents devitrification of glass lighter, and the surface presents slight opalescence phenomenon; On behalf of glass, symbol zero do not have obvious spontaneous crystallization.
Embodiment 3
The overflow scorification is made in the alkali-free glass substrate process, usually need in the range of viscosities of 105-106 pool, draw moulding to glass, if near the viscosity of the glass ribbon formed body (overflow brick) lower end edge portion is low excessively, because of rapid stretching, extension takes place in the effect of the deadweight of glass ribbon self or drawing force downwards, cause glass ribbon to rupture easily midway, the excessive attenuation of thickness of glass etc. can be do not caused even do not rupture yet, the uniform moulding of thickness can't be carried out; Simultaneously, glass is longer in the residence time of shaping area, and glass liquidus temperature and crystallization property are had higher requirement, requires glass at its liquidus temperature quite high viscosity to be arranged, and the glass that is used to produce should have the liquid phase viscosity that is not less than 106 pools.
Composition according to glass D adopts the overflow scorification to carry out the production of alkali-free glass substrate, and near the temperature of the glass the overflow brick lower end edge portion is controlled at 1120 ℃, and corresponding glass viscosity is about 105.65 pools.When the overflow scorification is produced alkali-free glass substrate, load is low, glass flow is slow, glass is long in the residence time of shaping area, in exsiccant season, is lower than at steam partial pressure under the atmospheric moisture of 0.8kPa, the long-time glass that stops is easy to produce crystallization near the overflow brick lower edge portion, its reason is under this condition, and the liquidus temperature of glass is more than 1120 ℃, and the glass metal phase viscosity is less than 105.65 pools.By to forming part space outerpace humidification, airborne steam partial pressure is remained on more than the 1.0kPa, through the time of a couple of days, by the spontaneous diffusion of convection of air and water vapor slowly, the atmospheric moisture of forming part internal space increases, and the crystallization of glass fades away.
According to the present invention, can reduce the liquidus temperature of alkali-free alumina silicate glass effectively, reduce the requirement of moulding to the glass liquidus temperature, suppress the crystallization of glass.The present invention is suitable for the production of alkali-free alumina silicate glass substrate, especially is fit to adopt the overflow scorification to produce alkali-free glass substrate, is suitable for float glass process and slot draw method simultaneously and produces alkali-free glass substrate.
Do not departing from goal of the invention, surmounting under the prerequisite of invention scope, those skilled in the art can carry out multiple modification and conversion to the present invention.Therefore, the present invention includes based on of the present invention, in the claim scope to modification of the present invention and conversion etc.
Table 1 water saturation vapour pressure
| Temperature (℃) | Water saturation vapour pressure (mmHg) | Temperature (℃) | Water saturation vapour pressure (mmHg) | Temperature (℃) | Water saturation vapour pressure (mmHg) |
| 0 | 4.579 | 15 | 12.788 | 30 | 31.824 |
| 1 | 4.926 | 16 | 13.634 | 31 | 33.695 |
| 2 | 5.294 | 17 | 14.530 | 32 | 35.663 |
| 3 | 5.635 | 18 | 15.477 | 33 | 37.729 |
| 4 | 6.101 | 19 | 16.477 | 34 | 39.898 |
| 5 | 6.543 | 20 | 17.535 | 35 | 42.175 |
| 6 | 7.013 | 21 | 18.650 | 36 | 44.563 |
| 7 | 7.513 | 22 | 19.827 | 37 | 47.067 |
| 8 | 8.045 | 23 | 21.068 | 38 | 49.692 |
| 9 | 8.609 | 24 | 22.377 | 39 | 52.442 |
| 10 | 9.209 | 25 | 23.756 | 40 | 55.324 |
| 11 | 9.844 | 26 | 25.209 | ||
| 12 | 10.518 | 27 | 26.739 | ||
| 13 | 11.231 | 28 | 28.349 | ||
| 14 | 11.987 | 29 | 30.043 |
Unit conversion: 1mmHg=0.133322KPa=0.00135951kg/cm
2=0.00133232bar
Table 2
| Oxide | The composition of glass (wt%) | ||||||
| A | B | C | D | E | F | ||
| SiO 2 | 61.0 | 60.0 | 60.0 | 61.0 | 57.5 | 57.9 | |
| B 2O 3 | 9.5 | 9.5 | 9.0 | 9.2 | 9.5 | 9.2 | |
| Al 2O 3 | 14.5 | 14.7 | 14.7 | 14.5 | 16.6 | 16.4 | |
| MgO | 0.4 | 0.5 | 0.5 | 0.5 | 0.5 | ||
| CaO | 6.3 | 6.3 | 6.0 | 7.0 | 5.1 | 5.3 | |
| SrO | 1.5 | 2.7 | 2.6 | 2.0 | 2.9 | 3.2 | |
| BaO | 6.0 | 6.0 | 6.4 | 5.0 | 7.1 | 6.5 | |
| CeO 2 | 0.3 | ||||||
| SnO 2 | 0.5 | 0.8 | |||||
| Cl 2 | 1.0 | ||||||
| Sb 2O 3 | 0.3 | 0.2 | |||||
| As 2O 3 | 0.5 | 0.8 | 0.6 | 1.0 | |||
| α 20/300[10 -7/℃] | 37.2 | 38.0 | 38.2 | 37.9 | 37.8 | 37.6 | |
| d[g/cm 3] | 2.49 | 2.50 | 2.51 | 2.48 | 2.53 | 2.52 | |
| T s[℃] | 658 | 658 | 660 | 660 | 662 | 663 | |
| The liquidus temperature of different atmospheric moisture lower-glass (℃) | |||||||
| P H2O (kPa) | 0.4 | 1150 | 1150 | 1140 | 1160 | 1090 | 1100 |
| 0.8 | 1110 | 1110 | 1100 | 1115 | 1060 | 1070 | |
| 1.8 | 1085 | 1085 | 1080 | 1090 | 1040 | 1040 | |
Table 3
| The glass numbering | Glass is at different atmospheric moisture P H2OUnder surperficial crystallization state | ||
| 0.4kPa | 0.8kPa | 1.8kPa | |
| A | | | ⊙ |
| D | | | ⊙ |
| E | | ⊙ | ○ |
Claims (8)
1, a kind of method of producing alkali-free aluminosilicate base plate glass may further comprise the steps: (1) batching and dissolving; (2) clarification and homogenization; (3) cooling; (4) moulding; (5) annealing, cutting, check and packing, it is characterized in that: in (4) step therein, by increasing the humidity of formed glass ambient air of living in, reduce the liquidus temperature of glass, reduce the crystallization of glass, keep steam partial pressure in the formed glass ambient air of living in more than 0.8kPa, the highest 12.5kPa that is no more than.
2, the method for production alkali-free aluminosilicate base plate glass according to claim 1 is characterized in that: aforesaid method is used to contain the non-alkali glass (representing with weight percentage) of following composition: the SiO of 50-70%
2, the Al of 12-25%
2O
3, the B of 7-14%
2O
3, the ∑ RO (MgO+CaO+SrO+BaO) of 10-20%, the As of 0-2%
2O
3, the Sb of 0-1%
2O
3, the SnO of 0-2%
2, the CeO of 0-1%
2, the Cl of 0-3%.
3, the method for production alkali-free aluminosilicate base plate glass according to claim 1 is characterized in that: glass adopts the moulding of overflow scorification.
4, a kind of method of producing alkali-free alumina silicate glass may further comprise the steps: (1) batching and dissolving; (2) clarification and homogenization; (3) cooling; (4) moulding; (5) annealing, cutting, check and packing.It is characterized in that, in (4) step therein, this method adopts the moulding of overflow scorification, and reduce the liquidus temperature of glass by the atmospheric moisture that increases the shaping area space outerpace, reduce the crystallization of glass, keep shaping area space outerpace water in air partial vapor pressure more than 0.8kPa, the highest 12.5kPa that is no more than.
5, the method for production alkali-free aluminosilicate base plate glass according to claim 4 is characterized in that: the envrionment temperature of shaping area space outerpace is not less than 10 ℃.
6, the method for production alkali-free aluminosilicate base plate glass according to claim 4 is characterized in that: aforesaid method is used to contain the non-alkali glass (representing with weight percentage) of following composition: 50-70%SiO
2, 12-25%Al
2O
3, 7-14%B
2O
3, 10-20% ∑ RO (MgO+CaO+SrO+BaO), 0-2%As
2O
3, 0-1%Sb
2O
3, 0-2%SnO
2, 0-1%CeO
2, 0-3%Cl.
7, the method for production alkali-free aluminosilicate base plate glass according to claim 4 is characterized in that: keep shaping area space outerpace water in air partial vapor pressure more than 1.0kPa, the highest 12.5kPa that is no more than.
8, the method for production alkali-free aluminosilicate base plate glass according to claim 4 is characterized in that: glass adopts the moulding of overflow scorification.
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|---|---|---|---|
| CNA2007100539178A CN101012104A (en) | 2007-01-31 | 2007-01-31 | Method of manufacturing alkali-free aluminosilicate base plate glass |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100539178A CN101012104A (en) | 2007-01-31 | 2007-01-31 | Method of manufacturing alkali-free aluminosilicate base plate glass |
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| Publication Number | Publication Date |
|---|---|
| CN101012104A true CN101012104A (en) | 2007-08-08 |
Family
ID=38699850
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|---|---|---|---|
| CNA2007100539178A Pending CN101012104A (en) | 2007-01-31 | 2007-01-31 | Method of manufacturing alkali-free aluminosilicate base plate glass |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103201228A (en) * | 2010-11-08 | 2013-07-10 | 日本电气硝子株式会社 | Alkali-free glass |
| CN108878593A (en) * | 2018-07-23 | 2018-11-23 | 成都中建材光电材料有限公司 | A kind of preparation method and production system of cadmium telluride solar battery |
| CN110776254A (en) * | 2019-11-16 | 2020-02-11 | 中建材蚌埠玻璃工业设计研究院有限公司 | Glass composition for liquid crystal display and preparation method of glass |
| CN113735450A (en) * | 2021-09-09 | 2021-12-03 | 温州市康尔微晶器皿有限公司 | Transparent high-hardness magnesium-aluminum-silicon microcrystalline glass and preparation method thereof |
| US11319241B2 (en) * | 2016-12-30 | 2022-05-03 | Tunghsu Group Co., Ltd. | Composition for preparing glass, glass article and use thereof |
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2007
- 2007-01-31 CN CNA2007100539178A patent/CN101012104A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103201228A (en) * | 2010-11-08 | 2013-07-10 | 日本电气硝子株式会社 | Alkali-free glass |
| US9061938B2 (en) | 2010-11-08 | 2015-06-23 | Nippon Electric Glass Co., Ltd. | Alkali-free glass |
| CN103201228B (en) * | 2010-11-08 | 2015-11-25 | 日本电气硝子株式会社 | Non-alkali glass |
| US11319241B2 (en) * | 2016-12-30 | 2022-05-03 | Tunghsu Group Co., Ltd. | Composition for preparing glass, glass article and use thereof |
| CN108878593A (en) * | 2018-07-23 | 2018-11-23 | 成都中建材光电材料有限公司 | A kind of preparation method and production system of cadmium telluride solar battery |
| CN110776254A (en) * | 2019-11-16 | 2020-02-11 | 中建材蚌埠玻璃工业设计研究院有限公司 | Glass composition for liquid crystal display and preparation method of glass |
| CN113735450A (en) * | 2021-09-09 | 2021-12-03 | 温州市康尔微晶器皿有限公司 | Transparent high-hardness magnesium-aluminum-silicon microcrystalline glass and preparation method thereof |
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