CN106673422A - Glass for air-quench tempering and air-quenched tempered glass - Google Patents

Glass for air-quench tempering and air-quenched tempered glass Download PDF

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Publication number
CN106673422A
CN106673422A CN201610082301.2A CN201610082301A CN106673422A CN 106673422 A CN106673422 A CN 106673422A CN 201610082301 A CN201610082301 A CN 201610082301A CN 106673422 A CN106673422 A CN 106673422A
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China
Prior art keywords
glass
air
content
less
cooled
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CN201610082301.2A
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Chinese (zh)
Inventor
土屋博之
前田枝里子
永井研辅
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AGC Inc
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Asahi Glass Co Ltd
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Publication of CN106673422A publication Critical patent/CN106673422A/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
    • C03C3/087—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 containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B27/00—Tempering or quenching glass products
    • C03B27/04—Tempering or quenching glass products using gas
    • 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
    • C03C4/00—Compositions for glass with special properties

Abstract

Provided is a glass that is for air-quench tempering and that, even when the glass is thin glass that has a thickness of 2.5 mm or less, can have ample residual stress added thereto by air-quench tempering. In the glass for air-quench tempering, the Fe<3+> content, in terms of Fe2O3 is 0.8 mass% or more but less than 2.2 mass%, the Fe<2+> content, in terms of Fe2O3, is 0.45 mass% or less, the Fe-Redox value is 20% or lower, an average thermal expansion coefficient [alpha]50-350 at 50-350 DEG C is 75*10<-7>/DEG C-90*10<-7>/DGE C, a glass transition point is 500 -600 DGE C, and a maximum [alpha]max thermal expansion coefficient between the glass transition point and the yield point thereof is 410*10<-7>/DEG C or higher.

Description

Air-cooled reinforcing glass and air-quench toughened glass
Technical field
Even if the present invention relates in the case where the thin glass that thickness is below 2.5mm is made, it is also possible to logical Cross the air-cooled reinforcing glass that air-cooled reinforcing gives enough residual stress.
Additionally, the present invention relates to the air-cooled reinforcing of the present invention with air-cooled strong obtained by glass carries out air-cooled reinforcing Change glass.
Background technology
Strengthens glass is technical problem, the improved glass of i.e. crackly defect that usual glass is present Glass, is used for the vehicles, building etc..As the vehicles, passenger car, truck, public vapour can be enumerated Car, railway, ship, airborne vehicle etc., strengthens glass is used for window, headlight, taillight etc..Additionally, conduct Building, can enumerate building, house etc., and strengthens glass is used for door, partition wall etc..Additionally, being widely used in The electrification product such as the furniture such as bookshelf, show cabinet, cooking apparatus, office appliance etc..
Strengthens glass is manufactured for example, by the method for being referred to as heat reinforcing.Heat reinforcing is using glass during cooling Thermal contraction, cooled down after the temperature that glass is heated near softening point or yield point.Now, because The temperature drop on surface is faster than internal temperature drop, so temperature difference is produced in a thickness direction, on surface Produce tensile stress and internally produce compression stress, by the reversion based on stress mitigation phenomenon thereafter Compression stress is produced on surface and internally produce tensile stress and remnants.Because should in surface residual compression Power, so intensity is improved, the progress damaged in addition is inhibited, and marresistance improves.As heat reinforcing, Representational is following air-cooled reinforcings：The glass of tabular is manufactured by float glass process etc., the glass plate after cutting is added Heat carries out chilling to the temperature near softening point or yield point to surface spray cooling medium.
In recent years, it is desirable to the lightweight of the strengthens glass in the vehicles, building etc..The light weight of strengthens glass Change can for example be required for thickness to be made as below 2.5mm by the way that the thinning slimming of its thickness is realized.But It is that heat is strengthened because being the temperature difference using surface during cooling and inside, if thickness is thinning, The temperature difference of surface and inside cannot then be increased, it is difficult to realize real reinforcing.
As the manufacture method of slim strengthens glass, it is known to use for example with regulation glass composition and And average coefficient of linear expansion when 50～350 DEG C is 80～110 × 10-7/ DEG C glass composition (referring for example to Patent document 1).
But, it is only capable of controlling the average coefficient of linear expansion of low temperature side by such manufacture method, so differing Surely the slim glass effectively to thickness for below 2.5mm gives residual stress.
Additionally, as the solar module that patent document 2 is recorded, there are two surfaces by glass clamp In the solar module of the structure, the weight of glass substrate accounts for the more than half of module weight, so by glass Glass substrate attenuation, make the benefit that it lightens very big.Accordingly, as light panel and backplate, using by The glass substrate that chemically reinforced glass is constituted.This is because, if chemically reinforced glass, even if then thickness Enough residual stress can be also given for below 2.5mm.
But, chemically reinforced glass price compared with air-quench toughened glass is higher, so having used chemical enhanced The price of the solar module that glass is recorded as the patent document 2 of light panel and backplate is high.
Prior art literature
Patent document
Patent document 1：Japanese Patent Laid-Open 2003-119048 publication
Patent document 2：Japanese Patent Laid-Open 2013-247238 publication
The content of the invention
Invent technical problem to be solved
The present invention is in view of above-mentioned technical problem and the invention that completes, even if its objective is that providing one kind is making In the case of thin glass of the thickness for below 2.5mm, also can give enough remnants by air-cooled reinforcing should The air-cooled reinforcing glass of power, and to air-cooled reinforcing with air-cooled reinforcing glass obtained by glass carries out air-cooled reinforcing Glass.
Solve the technical scheme that technical problem is adopted
In order to achieve the above object, the present invention provides a kind of air-cooled reinforcing glass, wherein, Fe3+Content with Fe2O3Conversion is calculated as 0.8 mass % less than 2.2 mass %, Fe2+Content is with Fe2O3Conversion is calculated as Below 0.45 mass %, the value of Fe-Redox is less than 20%, the mean thermal expansion coefficients at 50～350 DEG C α50～350For 75 × 10-7/ DEG C more than and 90 × 10-7/ DEG C below, vitrification point be more than 500 DEG C and 600 Below DEG C, maximum α of the thermal coefficient of expansion between vitrification point and yield pointmaxFor 410 × 10-7/℃ More than.
In the air-cooled reinforcing glass of the present invention, represented with quality % of oxide benchmark, preferably comprised：
Additionally, the present invention provides the air-cooled reinforcing to the present invention with air-cooled strong obtained by glass carries out air-cooled reinforcing Change glass.
The air-quench toughened glass preferred surface compression stress value of the present invention is more than 60MPa.
The air-quench toughened glass of the present invention preferably thickness with below 2.5mm.
The air-quench toughened glass of the present invention is preferred for mobile applications.
The air-quench toughened glass of the present invention is preferred for building occupancy.
The air-quench toughened glass of the present invention is preferred for solar module.
Invention effect
Even if the air-cooled reinforcing glass of the present invention is in the feelings for making the thin glass that thickness is below 2.5mm Under condition, it is also possible to give enough residual stress by air-cooled reinforcing.
Description of the drawings
Fig. 1 is the vertical view at the position for being provided with cooling nozzle of the air-cooled strengthening device used in embodiment Figure.
Specific embodiment
Hereinafter, the air-cooled reinforcing to the present invention is illustrated with glass.
The vitrification point of the air-cooled reinforcing glass of the present invention is more than 500 DEG C.As described above, air-cooled strong During change is processed, in the glass by the manufacture tabular such as float glass process, by the glass plate after cutting be heated to softening point or After temperature near yield point, by carrying out chilling to surface spray cooling medium, so as to give glass residual Stress, it is difficult by above-mentioned heating process and refrigerating work procedure in the case where vitrification point is less than 500 DEG C So that surface and inside have temperature difference, it is impossible to effectively give residual stress.Vitrification point is preferably 530 More than DEG C, more preferably more than 540 DEG C.In addition, the upper limit of temperature during heating process is preferably vitrifying + 200 DEG C of temperature.If the upper limit of temperature during heating process is higher than+200 DEG C of vitrification point, under high temperature The easy VISCOUS FLOW deformation of glass, the optical quality of final strengthens glass is possible to be deteriorated.
On the other hand, if vitrification point is excessively high, need to be heated to high temperature in heating process, use High temperature is exposed in surrounding member for keeping glass etc., so their life-span is possible to significantly reduce, is In the prolongation life-span, need the high price component for using excellent heat resistance.So, vitrification point is set to 600 DEG C Below.Vitrification point is preferably less than 590 DEG C, more preferably less than 580 DEG C.
In the air-cooled reinforcing glass of the present invention, the thermal coefficient of expansion between vitrification point and yield point is most Big value αmax(it is recited as " high-temperature heat expansion factor alpha in this manual belowmax") it is 410 × 10-7/℃ More than.High-temperature heat expansion factor alphamaxLess than 410 × 10-7/ DEG C when, making thickness for below 2.5mm In the case of thin glass, it is possible to effectively give remaining answering using common air-cooled intensifying device Power.Generally, air-cooled reinforcing carries out chilling to implement by the temperature from 100 DEG C higher than vitrification point or so. By by high-temperature heat expansion factor alphamaxIt is set to 410 × 10-7/ DEG C more than, even if making thickness for 2.5mm In the case of following thin glass, temperature that also can be more than, had using common air-cooled intensifying device Effect ground gives residual stress.
Here, high-temperature heat expansion factor alphamaxRefer to, in being located that utilization dilatometer as described below is determined In the coefficient of expansion curve of reason glass, maximum of the thermal coefficient of expansion between vitrification point and yield point. From from the viewpoint of imparting residual stress, high-temperature heat expansion factor alphamaxIt is the bigger the better, as long as but generally 600 ×10-7/ DEG C i.e. enough.If additionally, high-temperature heat expansion factor alphamaxIncrease, it is possible to due to cooling down the initial stage Occur temporary transient deformation and cause the rupture of glass, make yield rate be deteriorated, so high-temperature heat expansion factor alphamax Preferably 410 × 10-7/ DEG C more than and 600 × 10-7/ DEG C below.
For the air-cooled reinforcing of the present invention is not necessarily limited with the yield point of glass, but preferably greater than 600 ℃.In the case that yield point is less than 600 DEG C, the glass plate after by cutting is heated to softening point or surrender When putting neighbouring temperature, heating-up temperature, i.e. reinforcing started temperature step-down, it is possible to cannot effectively give residual Residue stress.Yield point is preferably less than 750 DEG C.If yield point is more than 750 DEG C, need heating paramount Temperature, the surrounding member etc. for keeping glass is exposed to high temperature, so their life-span is possible to significantly to drop It is low, in order to extend the life-span, need the high price component for using excellent heat resistance.The air-cooled reinforcing glass of the present invention The yield point of glass is more preferably less than 700 DEG C.
From from the viewpoint of imparting residual stress, at 50～350 DEG C of the air-cooled reinforcing glass of the present invention Mean thermal expansion coefficients α50～350It is more big more preferred, but if excessively big, it is likely that occur with it is existing its The unmatched problem of expansion or the patience to thermal shock of his component dies down.Therefore, the present invention's is air-cooled strong Mean thermal expansion coefficients α at 50～350 DEG C of change glass50～350For 75 × 10-7/ DEG C more than, more preferably For 77 × 10-7/ DEG C more than, further preferred 79 × 10-7/ DEG C more than.On the other hand, the present invention's is air-cooled Mean thermal expansion coefficients α at 50～350 DEG C of reinforcing glass50～350For 110 × 10-7/ DEG C below, more Preferably 100 × 10-7/ DEG C below, further preferred 95 × 10-7/ DEG C below.
The high-temperature heat expansion factor alpha of the air-cooled reinforcing glass of the present inventionmaxWith the evenly heat at 50～350 DEG C Coefficient of expansion α50～350Coefficient of thermal expansion differences (Δ α (=αmax-α50～350)) it is preferably 345 × 10-7/ DEG C with On.Increase thermal coefficient of expansion, the i.e. high-temperature heat expansion factor alpha from low temperature to high temperature merelymaxWith 50～350 Average coefficient of linear expansion α at DEG C50～350In the case of, in heating process and refrigerating work procedure, it is susceptible to Because of the rupture that thermal shock causes, the mismatch with the thermal expansion of other components is inadaptable etc. with current technology.
By the way that coefficient of thermal expansion differences (Δ α) is set into 345 × 10-7/ DEG C more than, i.e., by by 50～350 Mean thermal expansion coefficients α at DEG C50～350It is set in the state of certain value, increases high-temperature heat expansion coefficient relatively αmaxEven if in the case where the thin glass that thickness is below 2.5mm is made, could be used that common wind Cold intensifying device effectively gives residual stress, and the generation of the rupture that can suppress to be caused by thermal shock etc.. Coefficient of thermal expansion differences (Δ α) is more preferably 360 × 10-7/ DEG C more than, further preferred 370 × 10-7/ DEG C with On.It is substantially more big more preferred with regard to coefficient of thermal expansion differences (Δ α), as long as but being generally 500 × 10-7/ DEG C it is sufficient that.
Here, vitrification point, yield point, thermal coefficient of expansion (αmax、α50～350) to be ushered into according to following Row is determined.That is, diameter 5mm, the cylindric sample of long 20mm are made, using dilatometer at 5 DEG C/minute Thermal expansion is determined under the conditions of the programming rate of clock, the loading of 10g, vitrification point, yield point, heat is obtained The coefficient of expansion (αmax、α50～350)。
With regard to air-quench toughened glass, because being to utilize to be produced by the above-mentioned heating process of enforcement and refrigerating work procedure Raw surface and the temperature difference of inside, become if thickness cannot be made the temperature difference of surface and inside if thinning Greatly, the residual stress enough so as to be difficult to imparting.With regard to this point, present inventor is conscientiously ground Study carefully, as a result find the iron (Fe of the trivalent in air-cooled reinforcing glass3+) content, the iron (Fe of divalence2+) Content and Fe-Redox value meet specific condition in the case of, α can be increasedmax, its result is The residual stress of the glass after air-cooled reinforcing is improved.
In the air-cooled reinforcing glass of the present invention, by making Fe3+Content is with Fe2O3Conversion is calculated as 0.8 mass % less than 2.2 mass %, even if make thickness be below 2.5mm thin glass in the case of, Also residual stress can effectively be given using common air-cooled intensifying device.Fe3+Content is with Fe2O3Conversion When meter is less than 0.8 mass %, in the case where the thin glass that thickness is below 2.5mm is made, make It is possible to effectively give residual stress with common air-cooled intensifying device.Fe3+Content is with Fe2O3Change When calculating for more than 2.2 mass %, become yellowing, degraded appearance, so not preferred.
In the air-cooled reinforcing glass of the present invention, preferred Fe3+Content is with Fe2O3Conversion is calculated as 0.9 mass Below more than % and 2.1 mass %, more than more preferably 1.0 mass % and below 2.0 mass %.
In the air-cooled reinforcing glass of the present invention, Fe2+Content is with Fe2O3Conversion is calculated as below 0.45 mass %. If Fe2+Content is with Fe2O3Conversion meter is higher than 0.45 mass %, then melt the temperature step-down of kiln, glass Melting declines.
In the air-cooled reinforcing glass of the present invention, preferred Fe2+Content is with Fe2O3Conversion is calculated as 0.43 mass % Hereinafter, more preferably below 0.41 mass %.
In the air-cooled reinforcing glass of the present invention, the value of Fe-Redox is less than 20%.Here, Fe-Redox is referred to Fe2O3The Fe of conversion meter2+Content is relative to Fe2O3The all iron content of conversion meter Ratio.If the value of Fe-Redox is more than 20%, there is solarization (day because of sunshine Text：ソ ラ リ ゼ ー シ ョ Application), cause tone variations, so color occurs when there is Long-Time Service becoming The problem of change.
The value of the preferred Fe-Redox of air-cooled reinforcing glass of the present invention is less than 16%, more preferably 13 Below %, further preferred less than 10%.
In the air-cooled reinforcing glass of the present invention, represented with quality % of oxide benchmark, preferably comprised：
Hereinafter quality % of oxide benchmark is represented simply as into %.
If using such composition, because being the soda-lime glass being usually used in the manufacture with strengthens glass The essentially identical constituent of constituent, so productivity is good.If additionally, using the composition, Vitrification point is obtained for less than more than 500 DEG C 600 DEG C and high-temperature heat expansion factor alphamaxFor 410 × 10-7/ DEG C more than glass.The scope of the composition of each composition is illustrated below.
SiO2Content be preferably more than 66% and less than 75%.If fewer than 66%, then glass can occur Density increase, thermal coefficient of expansion increase, marresistance be deteriorated etc. unfavorable condition.SiO2Content it is preferred For more than 67%, more preferably more than 68%.If additionally, SiO2Content more than 75%, then viscosity increase High, glass is difficult to melt.SiO2Content be preferably less than 73%.
Al can as needed be contained2O3, its content is below 15%.If Al2O3Content more than 15%, Thermal coefficient of expansion when being then possible to more than vitrification point is difficult increase, it is difficult to increase residual stress.Al2O3 Content be preferably less than 10%, more preferably less than 5%.
B can as needed be contained2O3, its content is below 20%.If B2O3Content more than 20%, Thermal coefficient of expansion when being then possible to more than vitrification point is difficult increase, it is difficult to increase residual stress.B2O3 Content be preferably less than 15%, more preferably less than 10%.
The content of alkaline-earth metals oxide, i.e. MgO, CaO, SrO and BaO it is total (MgO+CaO+SrO+BaO) it is more than 1%.If MgO+CaO+SrO+BaO is less than 1%, in order to maintain The thermal coefficient of expansion of melting at a high temperature of glass and appropriateness, needs a large amount of addition alkali metal oxides, i.e. Li2O、Na2O、K2O, its result is possible to that the temperature difference of DEFORMATION POINTS and yield point diminishes, residual stress becomes It is little.MgO+CaO+SrO+BaO is preferably more than 3%, more preferably more than 5%, further preferred 10% with On.MgO+CaO+SrO+BaO is preferably less than 30%.If it exceeds 30%, then the tendency towards devitrification increasing of glass Plus, productivity is deteriorated.MgO+CaO+SrO+BaO is preferably less than 25%.
The content of MgO is more than 0.1%.MgO is required composition in order to appropriateness maintains thermal coefficient of expansion, Marresistance can also be improved.The content of MgO is preferably more than 2%, more preferably more than 3%.Additionally, MgO Content be less than 25%.If the content of MgO is more than 25%, the tendency towards devitrification of glass increases, raw Producing property is deteriorated.The content of MgO is preferably less than 23%, more preferably less than 21%, further preferred 20% Below.
The content of CaO is more than 0.1%.CaO is required in order to appropriateness maintains the thermal coefficient of expansion of glass Composition.The content of CaO is preferably more than 2%, more preferably more than 3%.The content of CaO is less than 15%. If the content of CaO is more than 15%, the tendency towards devitrification of glass increases, and productivity is deteriorated.The content of CaO Preferably less than 14%, more preferably less than 13%.
SrO can as needed be contained, its content is below 10%.By containing SrO, glass can be adjusted At a high temperature of melting and thermal coefficient of expansion.If the content of SrO is more than 10%, the density of glass increases Greatly, the weight increase of glass.In the case of containing SrO, preferably more than 1%, more preferably more than 1.5%. The content of SrO is more preferably less than 7%, further preferred less than 5%.
BaO can as needed be contained, its content is below 10%.By containing BaO, glass can be adjusted At a high temperature of melting and thermal coefficient of expansion.On the other hand, if containing BaO, the density of glass increases Greatly, so the weight of glass easily becomes big.If additionally, containing BaO, glass becomes fragile, so crackle Cracking load (Japanese：Network ラ ッ Network イ ニ シ エ ー シ ョ ン ロ ー De) step-down, easily sustain damage. Therefore, the content of BaO is less than 7%, preferably less than 5%, more preferably less than 3%.
Alkali metal oxide, i.e. Li2O、Na2O、K2Total (Li of the content of O2O+Na2O+K2O) for 1% with On.If Li2O+Na2O+K2O less than 1%, then in order to maintain glass at a high temperature of melting and appropriateness Thermal coefficient of expansion, needs a large amount of addition alkaline-earth metals oxide, i.e. MgO, CaO, SrO and BaO, its As a result, the tendency towards devitrification increase of glass, productivity are deteriorated.Li2O+Na2O+K2O is preferably more than 3%, More preferably more than 5%, further preferred more than 8%, particularly preferred more than 10%.Li2O+Na2O+K2O is excellent Elect less than 25% as.If it exceeds 25%, it is likely that the temperature difference of DEFORMATION POINTS and yield point diminishes, residual Residue stress diminishes.Li2O+Na2O+K2O is preferably less than 25%, more preferably less than 20%.
Na2The content of O is more than 8%.Na2Even if O be glass density it is relatively low, can also increase thermal expansion system Several compositions, therefore contain Na in glass composition to adjust the purpose of thermal coefficient of expansion2O。Na2O's contains Amount is preferably more than 9%, more preferably more than 10%.Na2The content of O is less than 20%.If Na2O's More than 20%, then because the temperature difference of DEFORMATION POINTS and yield point diminishes, enhancement stress diminishes content, Er Qiere The coefficient of expansion becomes too much.Na2The content of O is preferably less than 17%, more preferably less than 15%.
K can as needed be contained2O, its content is preferably more than 0.1%.K2The content of O is more than 0.1% In the case of, it is able to maintain that the thermal coefficient of expansion of the melting at a high temperature of glass and appropriateness.K2The content of O More preferably more than 0.5%, particularly preferred more than 1%.K2The content of O is less than 4%.If K2O's contains More than 4%, then the density increase of glass, the weight of glass increases amount.K2The content of O be preferably 3.5% with Under, more preferably less than 3%.
The present invention air-cooled reinforcing glass be preferably substantially made up of mentioned component, it is also possible to as needed and In the limit of technological thought for not violating the present invention, containing total other compositions less than 10%.As Other compositions, can enumerate such as ZrO2、Y2O3、CeO2, MnO, CoO etc..In addition it is also possible to contain PbO Deng, but preferably it is substantially free of these compositions.In addition, being substantially free of expression less than 0.01%.
Additionally, as fining agent during glass melting, can suitably contain SO3, chloride, fluoride, halogen Element, SnO2、Sb2O3、As2O3Deng.Further, in order to adjust tone, it is also possible to containing Ni, Cr, V, Se, Au, Ag, Cd etc..Processed glass is preferably substantially free of As, Sb, Pb.Because these compositions have Toxicity, so in order to prevent the impact to environment, these compositions are not contained in preferred glass.In addition, substantially 0.01% is less than without representing.
Even if the air-cooled reinforcing glass of the present invention is in the feelings for making the thin glass that thickness is below 2.5mm Under condition, could be used that common air-cooled intensifying device effectively gives residual stress, it is possible to glass is light Quantify.From from the viewpoint of lightweight, preferred thickness is below 2.4mm, more preferably below 2.3mm, is entered Preferred below the 2.0mm of one step, below 1.5mm, below 1.3mm.But, should from remnants are effectively given From the viewpoint of power, preferably its thickness of slab is more than 0.5mm, more preferably more than 0.7mm.
The air-cooled reinforcing glass of the present invention can be by glass plates such as float glass process, fusion method, glass tube down-drawing and roll-in methods Any one method in manufacturing process is manufacturing.If using float glass process, easily producing large-area glass plate, And easily reduce thickness deviation, it is advantageous to.
Even if the air-cooled reinforcing glass of the present invention is in the feelings for making the thin glass that thickness is below 2.5mm Under condition, could be used that common air-cooled intensifying device effectively gives residual stress.Thickness is being made for 2.5mm In the case of following thin glass, the surface compression stress value of the glass preferably after air-cooled reinforcing is 110MPa More than, more preferably more than 122MPa, further preferred more than 130MPa.
In the case where the thin glass that thickness is below 2.0mm is made, the glass preferably after air-cooled reinforcing Surface compression stress value is more than 70MPa, more preferably more than 78MPa, further preferred more than 85MPa.
In the case where the thin glass that thickness is below 1.5mm is made, the glass preferably after air-cooled reinforcing Surface compression stress value is more than 60MPa, more preferably more than 65MPa, further preferred more than 70MPa.
The air-quench toughened glass of the present invention is that the air-cooled reinforcing to the present invention carries out air-cooled reinforcing with glass and obtains Air-quench toughened glass.
The thickness of the air-quench toughened glass of the present invention is different according to purposes, but according to above-mentioned wind of the invention The feature of cold reinforcing glass, the thickness preferably with below 2.5mm.
The surface compression stress value of the air-quench toughened glass of the present invention is different with the thickness of air-quench toughened glass, In the case where thickness is below 2.5mm, preferred surface compression stress value is more than 110MPa, more preferably More than 122MPa, further preferred more than 130MPa.In the case where thickness is made for below 2.0mm, Preferred surface compression stress value be more than 70MPa, more preferably more than 78MPa, further preferred 85MPa with On.In the case where thickness is made for below 1.5mm, preferred surface compression stress value is more than 60MPa, More preferably more than 65MPa, further preferred more than 70MPa.
The air-quench toughened glass of the present invention is preferred for that the various uses of strengthens glass can be used.Specifically, It is preferred for mobile applications, building occupancy.Additionally, preferably as the light panel of solar module Or backplate is used.
As solar module backplate use in the case of, if the transparency of air-quench toughened glass Height, then it can be seen that wiring etc., design variation.In order that design is good, air-quench toughened glass Transmission of visible light (D65 light sources) Tv_D65 is preferably less than 82% specified in ISO-9050 (2003), more It is preferred that less than 80%, further preferred less than 77%.
Embodiment
The present invention is further illustrated by the following examples.
To form the glass that the condition of the glass composition shown in table 1, appropriate selective oxidation thing etc. are usually used Raw material, in feeding the mixture into platinum alloy crucible, and puts into 1600 DEG C of electric resistor heating type electric furnace, fusing 3 Hour, after carrying out deaeration, homogenizing, in pouring mold materials into, with about 30 DEG C higher than vitrification point of temperature After degree is kept for more than 1 hour, room temperature is annealed to 0.3～1 DEG C per minute of cooling velocity, has made enforcement The glass specimen of example 1～5, the tabular of comparative example 1～6.
For the glass specimen of gained, according to the graphs of the glass specimen using spectrophotometric determination, Fe-Redox is calculated using following formula (1).
Fe-Redox (%)=- loge(T1000nm/91.4)/(Fe2O3Amount × t × 20.79) × 100 ... (1)。
Wherein,
T1000nmIt is that (Perkinelmer Inc. (Perkin Elmer societies) makes, Lambda using spectrophotometer 950) transmissivity (%) at the wavelength 1000nm for determining；
T is the thickness (cm) of glass specimen；
Fe2O3Amount is tried to achieve by fluorescent X-ray measure with Fe2O3Content (the %=of the full iron of conversion meter Mass percent).
Above-mentioned Fe-Redox is adopted and calculated according to the spectrum curve of the glass specimen using spectrophotometric determination The method for going out, its value can be considered equal to same glass in Fe2O3The Fe of conversion meter2+Content with Fe2O3 The ratio of all iron content of conversion meter.
Then, according to JIS R 3103-3:2001 standard, by glass specimen diameter 5mm, length are made The cylindric sample of 20mm, with dilatometer (Brooker AXS companies (Block ル カ ー エ イ エ ッ Network ス エ ス societies) system, TMA4000SA) thermal expansion is determined with the loading condition of 5 DEG C/min of programming rate, 10g, Calculate vitrification point (Tg).
Additionally, according to JIS R 1618:2002 standard, for processed glass, with vitrification point Determine and similarly use dilatometer (Brooker AXS company systems, TMA4000SA), with 5 DEG C/min of liter Warm velocity determination thermal expansion, mean thermal expansion coefficients α when calculating 50～350 DEG C50～350And high warm Coefficient of expansion αmax。
Additionally, using transmission of visible light (for Tv_D65, spectrophotometer (Perkinelmer Inc.'s system, Lambda 950) it is measured.
Further, for embodiment 1～5, the glass specimen of comparative example 1～6, in order to evaluate air-cooled reinforcing Operational ease, the surface residual stress after the cold reinforcing of immunosorbent assay shown below.
Glass specimen is cut into the size of 550mm × 550mm, and implements chamfer machining.In air-cooled reinforcing In process, using common roller the air-cooled strengthening device of formula is carried.Fig. 1 is the setting of the air-cooled strengthening device There is the top view at the position of cooling nozzle, left side illustrates the end face at the position for being provided with the cooling nozzle in figure Shape.As shown in figure 1, multiple cooling nozzles 20,30,40 are arranged in the different mode of height. Nozzle 20 is configured in the way of the processed surface of glass plate that is vertically processed.The diameter of nozzle 20 For 3.1mm, the spacing between nozzle 20 is 24mm.Nozzle 30,40 is inclining towards processed glass plate The mode of processed surface is configured.The diameter of nozzle 30,40 is respectively 3.9mm, spacing between nozzle 30, Spacing between nozzle 40 is respectively 24mm.Relative to nozzle 30, with the spacing of immediate nozzle 20 and The spacing of immediate nozzle 40 is respectively 8mm.The distance of nozzle 20 and the processed surface of processed glass plate For 10mm.The temperature of the air supplied from nozzle 20,30,40 as cooling medium is 60 DEG C, blast (spray Loophole blast) it is 18～19kPa, from the state that processed glass plate is heated to 630～635 DEG C, to quilt The processed surface injection of glass plate is processed as the air of cooling medium, is cooled down.Should using glass surface Power meter (folding former make institute (Zhe Yuan System make institute) FSM-7000H processed) air-quench toughened glass that thus makes of measure Surface compression stress value.By the surface compression stress value of each sample divided by comparative example 5 surface compression stress value, Using the value of gained as apparent surface's compression stress value.
[table 1]
Fe3+Content is with Fe2O3Conversion is calculated as 0.8 mass % less than 2.2 mass %, Fe2+Content With Fe2O3Conversion is calculated as below 0.45 mass %, the value of Fe-Redox be 20% below example 1～ The high-temperature heat expansion factor alpha of 5 glassmaxFor 410 × 10-7/ DEG C more than, the glass after air-cooled reinforcing Apparent surface's compression stress value is more than 1.1.Without Fe2O3Comparative example 1,2 glass and Fe3+ Content is with Fe2O3Comparative example 3 of value of the meter less than 0.8 mass %, Fe-Redox that convert more than 20%～ The high-temperature heat expansion factor alpha of 6 glassmaxLess than 410 × 10-7/ DEG C, the phase of the glass after air-cooled reinforcing 1.1 are less than to surface compression stress value.
Symbol description
20th, 30,40 nozzle

Claims (9)

1. air-cooled reinforcing glass, wherein, Fe3+Content is with Fe2O3Conversion is calculated as more than 0.8 mass % And less than 2.2 mass %, Fe2+Content is with Fe2O3Conversion is calculated as below 0.45 mass %, Fe-Redox Value be less than 20%, the mean thermal expansion coefficients α at 50～350 DEG C50～350For 75 × 10-7/ DEG C with It is upper and 110 × 10-7/ DEG C below, vitrification point be more than 500 DEG C and less than 600 DEG C, vitrifying temperature Maximum α of the thermal coefficient of expansion between degree and yield pointmaxFor 410 × 10-7/ DEG C more than.
2. air-cooled reinforcing glass as claimed in claim 1, it is characterised in that with oxide benchmark Quality % represent, comprising：
3. air-quench toughened glass, it is to enter sector-style to the air-cooled reinforcing glass described in claim 1 or 2 Air-quench toughened glass obtained by cold reinforcing.
4. air-quench toughened glass as claimed in claim 3, it is characterised in that surface compression stress value is More than 60MPa.
5. the air-quench toughened glass as described in claim 3 or 4, it is characterised in that with 2.5mm with Under thickness.
6. the air-quench toughened glass as any one of claim 3～5, it is characterised in that for vapour Automobile-used way.
7. the air-quench toughened glass as any one of claim 3～5, it is characterised in that for building Build purposes.
8. the air-quench toughened glass as any one of claim 3～5, it is characterised in that for too Positive energy battery module.
9. the air-quench toughened glass as any one of claim 3～5, it is characterised in that for too The backplate of positive energy battery module, and transmission of visible light (the D65 light of ISO-9050 (2003) regulations Source) Tv_D65 be less than 82%.
CN201610082301.2A 2015-11-10 2016-02-05 Glass for air-quench tempering and air-quenched tempered glass Pending CN106673422A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113135656A (en) * 2021-05-27 2021-07-20 常州亚玛顿股份有限公司 anti-PID glass for solar cell and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113135656A (en) * 2021-05-27 2021-07-20 常州亚玛顿股份有限公司 anti-PID glass for solar cell and preparation method thereof

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