CN104944749A - Float process for producing a float glass pane and a float glass pane - Google Patents

Float process for producing a float glass pane and a float glass pane Download PDF

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Publication number
CN104944749A
CN104944749A CN201510129120.6A CN201510129120A CN104944749A CN 104944749 A CN104944749 A CN 104944749A CN 201510129120 A CN201510129120 A CN 201510129120A CN 104944749 A CN104944749 A CN 104944749A
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Prior art keywords
glass
temperature
glass ribbon
float
annealing furnace
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CN201510129120.6A
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Chinese (zh)
Inventor
安德烈斯·兰格斯多弗
阿明·沃格
格哈德·劳特恩施拉格
约亨·奥克珀
鲁迪格·迪特里希
沃尔夫冈·瓦拉特
彼得·托马斯
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Schott AG
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Schott AG
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • C03B18/20—Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
    • C03B18/22—Controlling or regulating the temperature of the atmosphere above the float tank
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C03B25/04—Annealing glass products in a continuous way
    • C03B25/06—Annealing glass products in a continuous way with horizontal displacement of the glass products
    • C03B25/08—Annealing glass products in a continuous way with horizontal displacement of the glass products of glass sheets
    • 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
    • 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
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to a float glass pane, and a float process for producing a float glass pane in a drawing section with a float bath and a cooling furnace, whereby a molten glass continuously onto a molten metal, and in a pulling direction to form a glass ribbon having a thickness D with one of the metal melt facing tin side and one of the metal melt facing away from the upper side is pulled out, wherein the glass ribbon along the float bath is transported further cooled from the molten metal is lifted and through the cooling furnace, wherein the glass ribbon has two edge portions along its longitudinal edges which, starting from the longitudinal edges in the direction of the mid-band extending and between which a payload is placed wherein the glass ribbon at the top; a temperature Ttop and on the tin side has a temperature Tbottom, wherein the bottom temperature in the lehr Tboden and the ceiling temperature in the lehr is TDecke, characterized in that in a portion A of the pull line, in which the temperature of the upper side Ttop of Tg + 20 K to Tg - 20 K falls, at any point x within the useful range of the glass ribbon the temperature of the upper side Ttop is greater than the temperature of the tin bath Tbottom.

Description

For the manufacture of floating process and the float glass plate of float glass plate
Technical field
The present invention relates to a kind of floating process for the manufacture of float glass plate, and a kind of float glass plate.
Background technology
Based on its high mechanical strength and be less than the low plate thickness of 1 millimeter, the alumina silicate glass plate of chemicosolidifying had been used as such as the glass cover-plate of the indicating meter of the mobile terminal device of particularly notebook computer and smart mobile phone in recent years.Except other drawing process, especially consider that floating process known in those skilled in the art produces alumina silicate glass plate.But when using floating process, can be observed after chemical tempering, alumina silicate glass plate has bending or arc, and those skilled in the art are also known as warpage.This warpage is owing to the following fact: floating process is asymmetric drawing process, and float glass plate to be called as the side of molten tin bath side different with the upside of the relative of float glass plate, and under identical tempered condition, present different tempering degree, which results in warpage.
According to DE 3 607 404, such as can by the surface of sheet glass being carried out before chemical tempering grind and the formation of warpage is avoided in polishing, but this is unusual time and effort consuming.
Similarly, have and changed ion-exchange and the technological method being designed to make the layer occurred without warpage for float glass plate provides in chemical drawing process before chemical tempering.This technical scheme also unusual time and effort consuming, and what only can not adversely affect subsequent processing steps at applied layer is in particular cases feasible.
WO 13146438 discloses a kind of sheet glass, and the sodium content wherein on side is specially set as 0.2-1.2 % by weight lower than opposite side, is intended to the tendency reducing float glass plate warpage in chemical drawing process thus equally.Shortcoming be two surfaces of sheet glass chemically significantly different each other, have problems being further processed in the process for the glass cover-plate of indicating meter thus.In the technological process of process further, also must guarantee the correct orientation of sheet glass particularly, this means that process involves more work further.
Summary of the invention
The object of this invention is to provide a kind of technique based on the floating process for the manufacture of chemically highly temperable float glass plate, it is intended to according to the few of warpage of the float glass plate of this manufacture technics, avoids extra treatment step, such as coating or lapped face after chemical temper simultaneously.The present invention also aims to provide a kind of corresponding chemically highly temperable sheet glass.Float glass plate is also intended to relative to the few of asymmetry of the chemical composition of both sides.
Described object is realized by independent claim.Preferred embodiment is present in dependent claims.
According to of the present invention for the manufacture of in the floating process of float glass plate, in the drawing zone with float tank and annealing furnace, melten glass is fed into molten metal continuously and is elongated to be formed the glass ribbon of thickness D at draw direction, it has the upside of molten tin bath side towards molten metal and molten metal dorsad, and wherein, glass ribbon cools along float tank, peel off from molten metal, and be conveyed through annealing furnace further, wherein, glass ribbon has temperature T on upside topand on molten tin bath side, there is temperature T bottom, wherein, glass ribbon is along its longitudinal axis having two borderline regions, and the direction of described borderline region from longitudinal edge to the centre of band extends and be furnished with useful region in-between, and wherein, is T in the temperature at the bottom place of annealing furnace floorand be T in the temperature at the top place of annealing furnace ceiling.Feature according to floating process of the present invention is, at the temperature T of the upside of drawing zone topfor T g+ 20K is to T gin the part A of-20K, the temperature difference △ T at each position x place in the useful region of glass ribbon glass=T top-T bottomfor being greater than 0K.
The present inventor finds, and the warpage after the uneven cooling of glass ribbon causes chemical temper significantly reduces, as long as relating separately to the glass transition temp T of same position x of glass ribbon g, temperature T topand T bottomin neighbouring temperature range, the temperature of the upside of glass ribbon is higher than the molten tin bath side of glass ribbon.In this case, T grepresent that those skilled in the art are according to the known glass transition temp of ISO 7884-8.The glass ribbon of drawing zone is in glass transition temp T gunder corresponding part A be usually located in annealing furnace.
On the other hand, according to prior art, when in annealing furnace during cooled glass band, be on its whole cross section at the position x of drawing zone by glass ribbon to be cooled as possible and keep constant temp as far as possible, described temperature reduces in the stretching direction lentamente.Therefore attempt the heating be arranged in such a way in annealing furnace, make perpendicular to the temperature in the cross section of draw direction, to there is the least possible ununiformity at glass ribbon.Particularly, according to prior art, in the position of annealing furnace, the temperature T on the upside of glass ribbon topthe temperature T of the molten tin bath side of glass ribbon should be equivalent to bottom.This is normally by the temperature T at bottom place equal in annealing furnace floorwith the temperature T at top place ceilingrealize.
But according to the present invention, glass ribbon is cooled by this way, makes the temperature T in the part A of drawing zone topbe greater than T bottom, wherein at the upside temperature T of drawing zone topfrom T g+ 20K is reduced to T gin the part A of-20K.Have been found that along with temperature difference △ T glass=T top-T bottomincrease, warpage after chemical tempering reduces.Although as temperature difference △ T after chemical tempering glasswhen=0, the upside of glass ribbon is tending towards forming convex upper, but after chemical tempering, the convex curvature of upside can along with temperature difference △ T glassincrease and reduce, and upside even can finally have recessed curvature.
Control to be here unknown to the butt formula really that works of the warpage after chemical tempering according to asymmetrical temperature according to the present invention.Be not limited to any particular theory, infer that the asymmetrical temperature of upside and molten tin bath side controls the systematical difference created in the glass structure affecting potassium and/or sodium ion diffusibility, make to exchange less ion in the upside of float glass plate in chemical temper subsequently.
The feature of usual floating process is, melten glass is fed into molten metal, pulls out to form glass ribbon and cools down.Floating process according to the present invention is consistent with the floating process of the standard for the manufacture of soda-lime glass plate in basic, but has the typical volume production amount in 10-50 ton/sky on more on a small scale.Molten tin is preferably used as molten metal.Such as by remaining in a small amount of resistates of the tin in top layer very thin on the float tank side of plate, float glass plate floating process can prepared identifies from the sheet glass prepared by other drawing process, and therefore the Theil indices of the float tank side of float glass plate is always than the centre of plate or the higher of upside.
The melten glass being fed to molten metal is generally melting aluminum silicate glass.With commercially available soda-lime glass and low Al 2o 3borosilicate glass, such as SCHOTT AG brand compare, the difference of alumina silicate glass is very good chemical temperability, is therefore preferred for this invention.Glass such as can have the component in following compositional range or the specific components according to table 1.
Table 1
The scope [% by weight] of component Component [% by weight]
SiO 2 40-70 61
Al 2O 3 5-20 17
B 2O 3 0-10 0
Na 2O 8-20 12
K 2O 0-5 4
MgO 0-10 4
CaO 0-2 0
ZrO 2 0-5 1.3
Other 0-5 0.7
The downstream that the drawing zone originating in float tank is positioned at float tank usually in the stretching direction comprises at least one molten tin bath case, annealing furnace and the wherein glass ribbon region that is cut and processes further.In the end of molten metal, glass ribbon peels off from melt and such as transmitted further by roller.The region that glass ribbon crosses on the first roller is wherein commonly called molten tin bath case.Molten tin bath case is separated from float tank by least one separator usually, and is separated similarly by the annealing furnace of at least one separator from downstream.
Glass ribbon has two fringe regions along its longitudinal edge, and it extends from described longitudinal edge to the direction of the centre of being with, and is furnished with useful region in-between.In edge region, glass ribbon contacts with the apex roller for transporting glass ribbon in the stretching direction usually.Apex roller is also for the width of arranged transversely glass ribbon.The fringe region of glass ribbon is also referred to as fringing, and it has larger thickness usually, at least has larger thickness along outward flange.The useful region of glass ribbon is included in the region of the glass ribbon between fringe region, and glass ribbon has uniform thickness wherein.According to the present invention, between the upside of glass ribbon and molten tin bath side, set the temperature difference.But in the fringe region that the upside of glass ribbon and molten tin bath side encounter one another, the temperature difference can be less, or there is not the temperature difference.Therefore each position at least in the useful region of glass ribbon or in the useful region of glass ribbon, instead of edge region, set according to the temperature difference of the present invention.
The temperature T of glass ribbon topand T bottomand their poor △ T glassdepend on the position in draw direction.The temperature T of glass ribbon topand T bottomusually also there is slight dependence to transverse to draw direction, but these temperature difference are very little, and usually negligible.Temperature difference △ T glassshould preferably by measure glass ribbon by the coordinate x in draw direction and the T of position that defines transverse to the coordinate z of draw direction topand T bottomand obtain difference to measure.Temperature T topand T bottompreferably be present in the temperature of the upper side and lower side in the middle part of glass ribbon.
In molten tin bath case, the temperature T of glass ribbon topcan momently at T gbelow.The temperature T of upside topfor from T g+ 20K is reduced to T gtherefore the part of-20K or the starting point of part also can be arranged in molten tin bath case.But the temperature of the ingress of annealing furnace is usually above T g+ 20K, therefore the temperature T of upside topfor T g+ 20K is to T gat least one part of-20K is arranged in annealing furnace.Therefore a lot of part in drawing zone can also be had, the temperature T on the upside of it topfor T g+ 20K is to T g-20K.Drawing zone according to the temperature T of the temperature on the upside of the present invention higher than molten tin bath side bottompart A, be preferably from the part at draw direction end, wherein the temperature T of upside topfor T g+ 20K is to T g-20K, therefore do not carry out in the downstream of this part A any glass ribbon to T gfurther heating.
In the preferred embodiment of floating process, the temperature difference △ T at each position x place in part A in the useful region of glass ribbon glass=T top-T bottomfor at least 0.25K, be preferably at least 0.5K, more preferably at least 1K and particularly preferably at least 1.5K.Temperature difference △ T glasspreferred value relatively low compared with the absolute value of temperature.But, should it is contemplated that, in order to realize such Low Temperature Difference, glass ribbon must stand great asymmetric temperature distribution or great Heated asymmetrically, because glass ribbon preferably only has little thickness D, therefore the temperature difference of upside and molten tin bath side balances very fast.Only have by a large amount of surveying works, could by T topand T bottomdirect measuring result reliably determine temperature difference △ T glass, because such as can the surface temperature T that determines of high temperature measurement when measuring topand T bottomtime, very likely there is temperature difference △ T glassthe error of the order of magnitude.Temperature difference △ T glasstherefore preferably indirectly by the temperature T in annealing furnace ceilingand T floordetermine.
By the temperature T in annealing furnace ceilingand T floorthe temperature of the glass ribbon produced can such as be determined by two-dimentional FEM simulation.Temperature field in annealing furnace is described by following equation in this case:
ρ · c p · ν z · ( δT / δx ) = ▿ ( λ · ▿ T ) ,
Wherein, ρ=2490kg/m 3, c p=900J/ (kgK), λ=1.22W/ (mK).
Wherein ρ is density, c pfor specific heat capacity, ν zfor rate of extension, λ is the thermal conductivity of glass and x is the volume coordinate in the draw direction of glass ribbon.Also can suppose that the heat exchange between glass and its surrounding environment is carried out by thermal conduction with by surface emissivity, cause the final condition of following formula:
α·(T U-T)+σ·ε·(T U 4-T 4)+λ·δT/δy＝0，
Wherein, α=7W/ (m 2k), ε=0.8.
At this, T urepresent envrionment temperature, it is equivalent to the temperature T in annealing furnace ceilingor T floor, σ represents Si Difen-Boltzmann constant, and α represents the heat transfer coefficient at glass-air interface place, and ε represents emittance, and y represents perpendicular to draw direction and the volume coordinate perpendicular to glass ribbon.
Generally speaking, be the sheet glass of about 0.55 millimeter for thickness, FEM simulation there is provided herein, the temperature difference △ T in annealing furnace lehr=T ceiling-T floorfor the temperature difference △ T in glass ribbon glass=T top-T bottom15-30 doubly.For the ribbon thickness of 0.5 millimeter and 0.62 millimeter, analog calculation allows to provide approximate following formula:
△ T glass=-1.9+0.0223T ceiling– 0.0190T floor, thickness D=0.5mm
△ T glass=-2.7+0.0275T ceiling– 0.0228T floor, thickness D=0.62mm
In the preferred embodiment of floating process, at the temperature difference △ T at each position x place in the useful region of glass ribbon in part A lehr=T ceiling-T floorfor at least 15K, preferably at least 30K, more preferably at least 50K and particularly preferably at least 75K.Asymmetric temperature control table in annealing furnace is shown in glass ribbon the preferred possibility setting up asymmetric temperature profile.Annealing furnace for glass ribbon has the part that many front and back are arranged usually, in each several part hot spots to be disposed on glass ribbon and under.In each several part, upper and lower hot spots can control separately usually, so can arrange asymmetric temperature profile.The actual temperature profile occurred in annealing furnace can depend on other factors certainly, and not necessarily consistent with the temperature profile of specifying.
Temperature T can be measured with thermostatted ceiling, described thermostatted is arranged in the minimum potential range of distance glass ribbon and the distance enough apart from hot spots.Therefore T ceilingfor in annealing furnace above glass ribbon the temperature of distance of about 10 to 100 millimeters, instead of the temperature at such as annealing furnace top.Self-evident, temperature T ceilingdepend on the position along drawing zone.Preferably with the thermocouple measuring temperature T of the distance of 30 to 60 millimeters of upside being arranged in glass ribbon along draw direction ceiling.Same equipment is correspondingly applicable to temperature T floor, described temperature T floortherefore be the temperature of the distance of below the glass ribbon in annealing furnace about 10 to 100 millimeters, and preferably by being arranged in multiple thermocouple measurements of the distance of 30 to 60 millimeters of molten tin bath side of glass ribbon along draw direction.
With temperature difference △ T glass=T top-T bottomcompare, temperature T ceilingand T floorand △ T thus lehr, be well suited for measured and be measured as prior art the standard in annealing furnace that provides, the homogeneity large as far as possible of the temperature in annealing furnace can be arranged.
In the preferred embodiment of floating process, △ T glassthe ratio of/D is at least 0.5K/mm, preferably at least 1K/mm, more preferably at least 2K/mm, particularly preferably at least 3K/mm.When cool as prior art the thickness that provides be greater than the plate glass of 2mm time, usually the less temperature difference between the upper side and lower side can not be got rid of, because the sheet glass of larger thickness has larger thermal insulation effect and be conducive to the temperature difference between the upper side and lower side.For less plate thickness, the preferred temperature difference is but very large.
In the preferred embodiment of floating process, △ T lehrthe ratio of/D is at least 30K/mm, preferably at least 60K/mm, more preferably at least 100K/mm, particularly preferably at least 150K/mm.When cool as prior art the thickness that provides be greater than the plate glass of 2mm time, usually can not get rid of the temperature difference of 10K or more, because the sheet glass of larger thickness has larger thermal insulation effect and be conducive to the temperature T at top place ceilingwith the temperature T at bottom place floorbetween the temperature difference.But for less plate thickness, the preferred temperature difference is but very large.
In the preferred embodiment of floating process, melten glass has the aluminium sesquioxide component of at least 5 % by weight, preferably at least 10 % by weight.When such glass, chemical temperability is high especially.
In the preferred embodiment of floating process, float glass plate can be tempered to the tempering layer depth DoL of bearing stress CS and at least 30 micron of at least 600 MPas by elevated chemical.Such as can use equipment FSM6000 stress-mensuration CS and DoL optically of Luceo company.Particularly preferably, float glass plate can at KNO in 4 hours 3with the T of 200K in melt gtemperature is tempered to the tempering layer depth DoL of bearing stress CS and at least 30 micron of at least 600 MPas.
In the preferred embodiment of floating process, the thickness D of glass ribbon in useful region is 2.0 millimeters or following, preferably 1.0 millimeters or following, and particularly preferably 0.3 millimeter to 0.7mm.Thickness D should be understood to the thickness of the glass ribbon referred in the useful region of glass ribbon herein.Such as can carry out measuring at the middle part of glass ribbon and the plate thickness approximated needed for float glass plate.Certainly, glass ribbon such as can have larger thickness at fringing (selvedges) place in varied situations.The sheet glass of less thickness like this can be produced particularly well by floating process, can chemical tempering and have low weight.
In the preferred embodiment of floating process, at the temperature T of the upside of drawing zone topfrom T g+ 50K is reduced to T gin the B1 part of+20K, or the temperature T in upside topfrom T g-20K is reduced to T gin the B2 part of-50K, the temperature difference △ T at each position x place in the useful region of glass ribbon glassfor at least 0.25K, preferably at least 0.5K, more preferably at least 1.0K and particularly preferably at least 1.5K.Therefore, the asymmetric temperature on the upside of sheet glass and molten tin bath side controls, and does not preferably just extend in part A, but from by draw direction part A upstream, or to continue in the downstream of part A.Result can improve the effect reducing warpage properties further.
In the preferred embodiment of floating process, the temperature difference △ T at each position x place in B1 or B2 part in the useful region of glass ribbon lehrfor at least 15K, preferably at least 30K and particularly preferably at least 50K.Result can improve the effect reducing warpage properties further.
In the preferred embodiment of floating process, be in any C part of at least 2 meters, preferred at least 5 meters in the length of annealing furnace, the temperature difference △ T at each position x place in the useful region of glass ribbon lehrfor at least 15K, preferably at least 30K and particularly preferably at least 50K.
In the preferred embodiment of floating process, in annealing furnace, glass ribbon stands thermal output P from below belowand stand thermal output P from top above, be in the D part of at least 2 meters, preferred at least 5 meters in the length of annealing furnace, P below/ P aboveratio for being less than 0.5, be preferably less than 0.3, be particularly preferably less than 0.1.In order to realize the uniform temperature profile of the glass ribbon in annealing furnace, in the common cooling process that such as prior art provides, glass ribbon from above and below equally stand same thermal output.On the other hand, in the preferred method of operation of annealing furnace according to the present invention, in D part, glass ribbon stands higher thermal output from top; Particularly preferably, below hot spots even can be fully closed.D part is preferably equivalent to part A in this case, but it also can comprise B1 and/or B2 part or extend on the first half or whole annealing furnace.
In another preferred embodiment of floating process, in annealing furnace, glass ribbon is from top by heat source, and the heat that thermal source transmits is preferably in the first half of glass ribbon, absorbed in the upper layer of 50 microns at the most.Do not transmitted if directly absorbed the thin surface layer of glass ribbon from the heat energy of top supply, the temperature difference △ T in glass ribbon glass=T top-T bottomcan effectively be increased especially.This is not the situation of the blackbody radiation of T ~ 600K and the high radiation assembly at 2-4 micron place usually, because alumina silicate glass is not opaque in this wavelength region.On the other hand, if be greater than 4 microns by hot gas flow or wavelength, be preferably greater than the IR radiation of 10 microns, such as carbon dioxide laser, convectively carry out the heating of top, heat directly inputs on the surface of glass ribbon.Its heat transmitted preferably in the first half of glass ribbon, be absorbed thermal source in the upper layer of 50 microns at the most particularly preferably in thickness, the thermal source of only top in annealing furnace can be represented, otherwise the thermal source provided in addition except the thermal source of routine.
In the preferred embodiment of floating process, cooled glass band from below in annealing furnace, the temperature difference △ T thus in glass ribbon glass=T top-T bottomcan especially effectively improve equally.Such as, downside can with the air-flow of bottom or the water-bath cooling that can be arranged on annealing furnace.Air-flow may must be preheated, so that it is not too large for making cooling export.Cooling especially uniformly on large surface-area is can be implemented in water-bath.
Theme of the present invention is also a kind of float glass plate, the standard warpage W after its chemical tempering sfor being less than 300 microns, being preferably less than 200 microns, being particularly preferably less than 100 microns, and the pre-warping before the chemical tempering of wherein said plate is for being less than+20 microns, is preferably less than 0 micron, is particularly preferably less than-20 microns.
In this case, float glass plate is a kind of plate prepared in floating process, and the process on any removal surface is not stood in molten tin bath side, such as grinding, polishing or etching.The aluminium sesquioxide component of float glass is at least 5 % by weight.
Float glass plate preferably chemically highly can be tempered to the bearing stress CS (Compressive Stress) of at least 600 MPas and be tempered to the tempering layer depth DoL (Depth of Layer) of at least 30 microns, particularly preferably, float glass plate can at T in 4 hours gat KNO at the temperature of-200K 3in salt-melting, chemistry is tempered to the bearing stress CS (Compressive Stress) of at least 600 MPas and is tempered to the tempering layer depth DoL (Depth of Layer) of at least 30 microns.
Preferably have according to float glass plate of the present invention and be less than 1.5mm, be preferably less than 1.0mm, be particularly preferably less than the typical thickness of 0.6 millimeter.
" the standard warpage W after chemical tempering s" or be called for short " standard warpage W s" describe the build-in attribute of untempered float glass plate warpage after chemical tempering, standard warpage W sbe equivalent to the float glass plate with predetermined plate size, the length I of 217 millimeters 0, the width b of 130 millimeters 0, the predetermined plate thickness D of 0.70 millimeter 0, the warpage had after predetermined chemical temper.Unless expressly stated, otherwise the warp value of specifying in this manual relates in principle is Annealed Strip, do not relate to non-Annealed Strip.Warp value before tempering is also referred to as pre-warping in this manual." the standard warpage W after chemical tempering s" be therefore also called " standard warpage W in this manual for short s", and refer to the build-in attribute of non-returning fire plate.
For the standard warpage W after chemical tempering smensuration, plate thickness D 0the float glass plate being preferably 0.70 millimeter is cut into preferred length I 0be 217 millimeters and preferred width b 0be the plate of 130 millimeters, but and without undergoing any further process, as clean or grinding or polished finish.Do not remove sulfur-bearing coating, but have been found that this is to standard warpage W yet simpact negligible.The chemical tempering of plate is carried out, by plate at T according to standard chemical temper gin saltpetre melt, carry out the time period of hardening more than 4 hours at the temperature of-200K, described saltpetre melt comprises the KNO of >99.9% before tempering 3.Upside and the molten tin bath side of float glass plate have identical temperature-time profiles thus, and the asymmetry in the chemical tempering of upside and molten tin bath side can not be caused by temper.After standard chemical temper, bearing stress CS is generally at least 800 MPas and tempering layer depth DoL for being at least 30 microns.From salt-melting, remove plate subsequently and clean.Subsequently, measure warpage according to DIN 50441-5:1998-05, it has positive sign in principle.According to the annotation in DIN 50441-5:1998-05, the definition of the term " warpage " in DIN 50441-5:1998-05 is equivalent to the warpage defined in ASTM F 1390-92.With regard to amount, standard warpage W sbe equivalent to the warpage according to DIN50441-5:1998-05.But, in addition, if the upside of float glass plate represents the convex side after chemical tempering, standard warpage W sbe assigned with positive sign, if the molten tin bath side of float glass plate represents convex side, standard warpage W sbe assigned with negative sign.Therefore, with compared with the warpage of DIN 50441-5:1998-05, consider the orientation of curvature relative to the orientation of float glass plate in floating process when standard warpage.
For other plate thickness of float glass plate, the standard warpage W after chemical tempering scan be measured approx by the warpage W recorded in the mode corresponding to described method, and be converted to for standard warpage W based on following formula spredetermined plate thickness D 0:
W s=W (D/D 0) 2, wherein D 0=0.70mm.
Similarly, for the float glass plate of other board size with length l and width b, the standard warpage W after chemical tempering scan measure approx in the mode corresponding to described method, and be converted to for standard warpage W based on following formula spredetermined plate size:
W S＝W·[(b 2+l 2)/(b 0 2+l 0 2)] 1/2。
But the size of plate should not depart from standard size too much, because these are approximate mathematical formulas.The width of plate is that b, length l and thickness D should be respectively relative to standard size b 0, l 0and D 050% to 200%.
Even before chemical tempering, float glass plate can have warpage, and it is called as pre-warping in this manual.Based on the above method, according to DIN 50441-5:1998-05, be of a size of 217 millimeters × 130 millimeters, be equivalent to cornerwise plate of about 10 inches measures pre-warping.When the geometrical shape of different samples, the conversion of the geometrical shape of on-gauge plate can be proceeded to.With standard warpage W sthe just identical mode of situation in, if the upside of float glass plate represents the convex side after chemical tempering, standard warpage W sbe assigned with positive sign, if the molten tin bath side of float glass plate represents convex side, standard warpage W sbe assigned with negative sign.Therefore, with compared with the warpage of DIN 50441-5:1998-05, consider the orientation of curvature relative to the orientation of float glass plate in floating process when pre-warping.
Normally positive according to the pre-warping of the float glass plate of prior art manufacture, that is the upside of float glass plate has slight convex curvature, and floating trough side has slight recessed curvature.When according to float glass plate of the present invention, curvature accurately orientation the other way around, also just state upside and have recessed curvature and downside has convex curvature, pre-warping is assigned with negative sign thus.
The pre-warping of float glass plate is preferably less than 20 microns, is preferably less than 0 micron, is particularly preferably less than-20 microns.
In the preferred embodiment of float glass plate, the Na of the upside of the float glass plate after standard chemical tempering 2o content Na 2o topwith the Na of molten tin bath side 2o content Na 2o bottompoor △ Na 2o=Na 2o top-Na 2o bottomfor being greater than-0.2 % by weight and being less than 0.2 % by weight.The present inventor has realized that, the present invention can provide a kind of special float glass plate by following true difference: the chemical composition of the upside of float glass plate is only slightly different from the chemical composition of molten tin bath side, and it has the standard warpage W after low-down chemical tempering simultaneously s.Therefore, the standard warpage W after chemical tempering is achieved slow-down value, the Na of the upside of the float glass plate after chemical tempering 2o content Na 2o topwith the Na of molten tin bath side 2o content Na 2o bottompoor △ Na 2o=Na 2o top-Na 2o bottomfor being greater than-0.2 % by weight and being less than 0.2 % by weight.Therefore the float glass plate chemical constitution of both sides while that warpage being inclined to also after having low-down chemical tempering to very low asymmetry can be advantageously provided.There is no need further process in processes, to distinguish float tank side and the upside of float glass plate, the problem of this means is greatly simplified.
Such as can measure Na by x-ray fluorescence analysis method of masurement with Bruker S8Tiger measuring apparatus under the electric current of the acceleration voltage of 20 kilovolts and 50 milliamperes 2o concentration.Sulfur-bearing coating should be removed before carrying out the measurements.
Those skilled in the art know various clear identification float glass plate itself and distinguish the molten tin bath side of float glass plate and the feasible method of upside.Such as, molten tin bath side by identifying by ultraviolet radiation on the basis of fluorescence, or can measure the Theil indices on surface.Molten tin bath side has the Theil indices higher than the upside of float glass plate in principle.
In the preferred embodiment of float glass plate, the Na of the upside of untempered float glass plate 2o content Na 2o topwith the Na of molten tin bath side 2o content Na 2o bottompoor △ Na 2o=Na 2o top-Na 2o bottomfor being greater than-0.2 % by weight and being less than 0.2 % by weight.Float glass plate before the present inventor has realized that chemical tempering has the asymmetry of the chemical constitution of low-down upside and float tank side equally.Untempered state is interpreted as the state referring to the stress on surface to be the degree of depth (DoL) of 300 MPas and tempering layer be at the most 15 microns at the most in this case.Na before chemistry tempering 2the poor △ Na of O concentration 2o tends to be in the level than higher after tempering.
Float glass plate is prepared preferably through method according to the present invention.
Below in elucidated on basis the present invention of exemplary embodiment.
There is the SiO of 61 % by weight 2, 17 % by weight Al 2o 3, 12% B 2o 3, 12% Na 2o, 4% K 2o, the MgO of 4%, the ZrO of 1.3% 2with refining agent SnO 2the melten glass of component be fed into molten tin bath and the glass ribbon that to be elongated to be formed thickness be 0.57 millimeter and width is about 2500 millimeters.The T of glass git is 616 DEG C.Rate of extension is 200-250 m/h, and turnout is about 25 tons/day.In addition, in order to avoid cut, in the molten tin bath side of the section start glass ribbon of annealing furnace band with the SO of 50 ls/h (liter per hours) 2with the N of 250 ls/h 2be exposed to and comprise SO 2air-flow.
Glass ribbon is with roller cooling in conventional annealing kiln, and the annealing furnace with roller has the part S of a lot of front and back setting n, wherein by an electric heating element glass ribbon by the thermal output P stood respectively from top n, abovethermal output P from below n, below.An electric heating element is conventional design in this case, and launches the thermal-radiating thermal radiation being about as much as the black matrix of this temperature.Major part quantity of radiant energy is launched in the near infrared range that wavelength is 1-4 micron.Sillico aluminate glass this radiation of transmission at least in part, therefore thermal radiation is not absorbed at thin upper layer and can be realized the only relatively little temperature difference in glass ribbon.Conventional an electric heating element does not represent preferred for carrying out the thermal source according to technique of the present invention.
At each part S nsection start and end, in the region intermediate of glass ribbon, measure the temperature T above glass ribbon with thermopair ceilingwith the temperature T below glass ribbon floor.Carry out the various thermal treatments of the glass ribbon according to table 2.In the downstream of annealing furnace, glass ribbon is cut into the float glass plate of large format and is of a size of the float glass plate of the small breadth of 217 millimeters × 130 millimeters for measuring warpage.Float glass plate did not carry out any further process before chemical temper, as cleaned or grinding or polished finish.
Before chemical tempering, float glass plate has slight warpage, and it is hereinafter referred to as pre-warping.Be of a size of 217 millimeters × 130 millimeters according to DIN 50441-5:1998-05, be equivalent to cornerwise plate of about 10 inches measures pre-warping based on the above method.With standard warpage W sthe just identical mode of situation in, if the upside of float glass plate represents convex side, pre-warping is assigned with positive sign, if the molten tin bath side of float glass plate represents convex side, pre-warping is assigned with negative sign.Therefore, compared with the definition of the warpage according to DIN 50441-5:1998-05, consider the orientation of curvature relative to the orientation of float glass plate in floating process when pre-warping.
At 416 DEG C, the time period of chemical tempering more than 4 hours of plate is carried out, that is T in the saltpetre of 100% gfollowing 200K.For all samples, the bearing stress CS after chemical tempering is in the scope of 850 MPa-950 MPas; Tempering layer depth DoL is 30 microns to 45 microns.With equipment FSM6000 stress in a usual manner-mensuration CS and DoL optically of Luceo company.
Be of a size of 217 millimeters × 130 millimeters according to DIN 50441-5:1998-05, be equivalent to the warpage after cornerwise plate of about 10 inches measures tempering.Because plate has some other thickness, if needed, the standard warpage W after chemical tempering scalculated by measured warpage and plate thickness D.
In table 2, temperature in the various piece of annealing furnace and thermal output and measured warpage and pre-warping value and standard warpage W is organized in table form s:
Table 2:
Title A V1 V2
Warpage, observed value (260mm x 156mm, 12 ") μm 419 1023 799
Standard warpage W s(D 0:0.7mm,10″) μm 231 853 443
Pre-warping μm -50 24 67
Stress CS MPa 876 910 887
Ribbon thickness mm 0.57 0.70 0.57
Float tank turnout t/d 25 23 22
The total width of glass ribbon mm 2500 2650 2390
Rate of extension m/h 237 210 224
Pyrometer, the middle part of 1 part ℃ 658 620 660
The temperature T of 1 part section start ceiling ℃ 659 618 652
The temperature T of 1 part section start floor ℃ 635 613 648
The Δ T of 1 part section start lehr K 24 5 4
The Δ T of 1 part section start glass(calculating) K 0.76 0.18 0.17
The temperature T at 1 portion distal end place ceiling ℃ 645 611 611
The temperature T at 1 portion distal end place floor ℃ 622 602 592
The Δ T of portion distal end lehr 23 9 19
The Δ T of portion distal end glass(calculating) K 0.74 0.17 0.62
The thermal output on 1 part top, P 1,above kW 144.4 43 24
The thermal output of 1 section lower, P 1,below kW 0 43 24
The ratio P of part 1,below/P 1,above ％ 100 0 0
Δ TNa before chemistry tempering 2O wt％ -0.1±0.1 n.a. -0.1±0.1
Δ TNa after chemistry tempering 2O wt％ -0.1to 0 n.a. -0.1to 0
Example V1 is the comparative example according to prior art, and it has and almost cools symmetrically.In 1 part of annealing furnace, thickness be 0.7 millimeter glass ribbon from above and below stand the thermal output of 43 kilowatts in each case.Temperature T above glass ribbon ceilingbeing 618 DEG C at section start, is 611 DEG C in the end of 1 part; Temperature T below glass ribbon floorbeing 613 DEG C at section start, is 602 DEG C in the end of 1 part.Temperature difference △ T lehrbe 5K at section start and be 9K in the end of 1 part.Be in the glass ribbon of 0.7 millimeter at thickness, this creates the temperature difference △ T of 0.18K at section start glassand the temperature difference △ T of 0.17K is created in the end of 1 part glass.Sheet glass has the pre-warping of 24 microns, and the very high standard warpage of 853 microns.
Example V2 is also comparative example, and it has slight asymmetric cooling, but it is not also equivalent to according to cooling of the present invention.In 1 part of annealing furnace, thickness be 0.57 millimeter glass ribbon from above and below stand the thermal output of 24 kilowatts in each case.Temperature T above glass ribbon ceilingbeing 652 DEG C at section start, is 611 DEG C in the end of 1 part; Temperature T below glass ribbon floorbeing 648 DEG C at section start, is 592 DEG C in the end of 1 part.Temperature difference △ T lehrtherefore be 5K and be 19K in the end of 1 part at section start.Although from above and below symmetrical heating, the temperature difference △ T in 1 part increased lehrbe caused by the very large Heated asymmetrically of 2 parts in annealing furnace, it has the effect of reviewing in 1 part.This creates the temperature difference △ T of the 0.17K at section start in glass ribbon glassand the temperature difference △ T of 0.62K in the end of 1 part glass.Sheet glass has the pre-warping of 67 microns and the warpage after the very high chemical tempering of 799 microns, but it greatly reduces compared with example A, result in the standard warpage W after the chemical tempering of 443 microns s.Measure according to x-ray fluorescence analysis, at the Na of chemical tempering front upper side and float tank side 2the difference of O concentration in the scope of-0.1 ± 0.1 % by weight, and reduces after tempering further, falls in the scope of-0.1 % by weight to 0.0 % by weight.About Na 2o concentration, therefore float glass plate has extraordinary symmetry.
Example A is according to example of the present invention, and it has very large cooling asymmetrically.In 1 part of annealing furnace, thickness is that the glass ribbon of 0.57 millimeter stands the thermal output of 144.4 kilowatts and stands the thermal output of 0 kilowatt from below from top, and namely in 1 part, downside heating is closed.Temperature T above glass ribbon ceilingbeing 659 DEG C at section start, is 645 DEG C in the end of 1 part; Temperature T below glass ribbon floorbeing 635 DEG C at section start, is 622 DEG C at the place of last portion of 1 part.Temperature difference △ T lehrtherefore be 24K and be 23K in the end of 1 part at section start.This creates the temperature difference △ T of the 0.76K at section start in glass ribbon glassand the temperature difference △ T of 0.74K in the end of 1 part glass.Sheet glass has the warpage after the chemical tempering significantly reduced of the pre-warping of-50 microns and 419 microns, result in the standard warpage W after the chemical tempering of 231 microns s.It should be noted that when example A, obtain the pre-warping with contrary sign of-50 microns, it is contrary with the warpage after chemical tempering.
But compared with example V2, the reduction of warpage can not owing to the formation of pre-warping with contrary sign, because pre-warping only changes 117 microns, from 67 microns to-50 microns, and warpage reduces 380 microns, from 799 microns to 419 microns.The change of the warpage after chemistry tempering exceedes 3 times of the change of pre-warping.The reduction of the warpage of 380 microns of maximum 1/3rd can owing to the change of pre-warping.
Measure according to x-ray fluorescence analysis, at the Na of chemical tempering front upper side and float tank side 2the difference of O concentration is in the scope of-0.1 ± 0.1 % by weight and reduce further after tempering, afterwards in the scope of-0.1 % by weight to 0.0 % by weight.Usually almost Na can not be detected by x-ray fluorescence analysis 2the deviation little like this of O concentration, the measuring error therefore enumerated has been Na 2the order of magnitude of O concentration difference.About Na 2o concentration, therefore float glass plate has extraordinary symmetry.Therefore distinguish according to sheet glass of the present invention by the following fact: in upside and molten tin bath side, there is chemically closely similar composition, there is difference substantially that inevitably caused by floating process, such as, comprise the upper layer of tin.But float glass plate has almost identical Na on both sides 2o concentration, and no matter upside or molten tin bath side, in production process subsequently its can process further, such as coating.The small Na of molten tin bath side 2it may be the SO of scuffing in order to avoid being caused by transport roller by molten tin bath side that O leaches 2coating causes.Before chemical tempering and after chemical tempering, by the Na of the upside of float glass plate 2o concentration Na 2o topwith the Na of molten tin bath side 2the poor △ Na of O concentration 2o, distinguishes float glass plate, and described difference is for being greater than-0.2 % by weight and being less than+0.2 % by weight.
Accompanying drawing explanation
Fig. 1: the cross sectional representation of part drawing zone.
Fig. 2: the floor map of part drawing zone.
Fig. 3: the schematic diagram of the temperature of the upside above the drawing zone with A, B1 and B2 part.
Fig. 4: according to the schematic diagram of float glass plate of the present invention.
Fig. 5: the temperature difference △ T in glass ribbon glasswith the function of the top of annealing furnace and the temperature at bottom place.
Embodiment
Diagrammatically illustrate the cross section of the relative section being suitable for the float glass equipment carried out according to method of the present invention in FIG.Drawing zone (9) comprises the end with molten metal (13) of float tank (10), molten tin bath case (11) and annealing furnace (12) at draw direction (8), the glass ribbon (14) in described molten tin bath case (11) with molten tin bath side (15) and upside (16) above runs at the first transport roller (17) after leaving molten metal (13), and in described annealing furnace (12), glass ribbon (14) is cooled to low-stress state.Annealing furnace (12) has the part (12a, 12b) of arranging before and after some, and wherein glass ribbon (14) stands thermal output P by top an electric heating element (31a, 31b) from top n, above, and stand thermal output P from below by bottom an electric heating element (32a, 32b) n, below.An electric heating element (31,32) is conventional design in this case, and launches the thermal-radiating thermal radiation being about as much as black matrix at the temperature of annealing furnace and launching.Major part quantity of radiant energy is launch in the near infrared range that wavelength is 1-4 micron in this case.In addition, by means of supply pipe (34), molten tin bath side (15) can be exposed to and comprise SO in annealing furnace (12) 2air-flow, to form protective membrane.
In fig. 2, the orthographic plan of the part drawing zone shown in Fig. 1 is diagrammatically illustrated.Can find out in plan view, an electric heating element (31,32) extends respectively on the whole width of glass ribbon (14), therefore achieves uniform temperature on the width of glass ribbon (14).
In figure 3, the temperature profile along drawing zone schematically shows A, B1 and B2 part limited by the region of drawing zone, the temperature T wherein on the upside of glass ribbon toppass and glass transition temp T grelevant specified range.In practice, temperature profile is not must be uniform, and can have local or interim Schwellenwert in the region of molten tin bath case especially.Therefore shown temperature profile should be understood to be only example.
Fig. 4 shows according to sheet glass of the present invention (1), and it has the molten tin bath side (15) and relative upside (16) that contact with molten metal (13) during floating process.Sheet glass preferably has sulfur-bearing coating (2) on molten tin bath side (15).
In Figure 5, the temperature difference △ T calculated in the glass ribbon that thickness D is 0.5 millimeter glassbe shown as the function in the top of annealing furnace and the temperature of bottom obtained from analog calculation.By the temperature T at the bottom place of 605 DEG C floor, the temperature T at top place of 680 DEG C ceilingwith the temperature difference △ T of 75K lehr, such as, obtain the temperature difference △ T of only 2.5K glass.
Reference numerals list
1 float glass plate
2 sulfur-bearing coatings
8 draw directions
9 drawing zones
10 float tanks
11 molten tin bath casees
12 annealing furnaces
12a annealing furnace, 1 part
12b annealing furnace, 2 parts
13 molten metals
14 glass ribbons
The molten tin bath side of 15 glass ribbons/sheet glass
The upside of 16 glass ribbons/sheet glass
17 transport rollers
30 synthesis gas atmosphere
The annealing furnace heating of 31a top, 1 part
The annealing furnace heating of 31b top, 2 parts
Annealing furnace heating bottom 32a, 1 part
Annealing furnace heating bottom 32b, 2 parts
34 SO 2supply pipe

Claims (17)

1. the floating process for manufacture float glass plate (1) in the drawing zone (9) with float tank (10) and annealing furnace (12), wherein melten glass is fed into molten metal (13) continuously and in draw direction (8), is elongated to be formed the glass ribbon (14) of thickness D, described glass ribbon (14) has the upside (16) of molten tin bath side (15) towards described molten metal (13) and described molten metal (13) dorsad, wherein, described glass ribbon (14) cools along described float tank (10), peel off from described molten metal (13), and be conveyed through described annealing furnace (12) further, wherein, described glass ribbon (14) is along its longitudinal axis having two borderline regions, the direction of described borderline region from longitudinal edge to the centre of band extends and is furnished with useful region in-between, wherein, described glass ribbon (14) has temperature T on described upside (16) topand on described molten tin bath side (15), there is temperature T bottom, wherein, be T in the temperature at the bottom place of described annealing furnace floorand be T in the temperature at the top place of described annealing furnace ceiling, it is characterized in that, at the temperature T of the described upside (16) of described drawing zone topfrom T g+ 20K is reduced to T gin the part A of-20K, the temperature difference △ T at each position x place in the described useful region of described glass ribbon (14) glass=T top-T bottomfor being greater than 0K.
2. floating process according to claim 1, is characterized in that, the temperature difference △ T at each position x place in described part A in the described useful region of described glass ribbon (14) glass=T top-T bottomfor at least 0.25K, be preferably at least 0.5K, more preferably at least 1K and particularly preferably at least 1.5K.
3. floating process according to claim 1 and 2, is characterized in that, the temperature difference △ T at each position x place in described part A in the useful region of described glass ribbon (14) lehr=T ceiling-T floorfor at least 15K, be preferably at least 30K, more preferably at least 50K and particularly preferably at least 75K.
4. the floating process according to any one of claim 1-3, is characterized in that, △ T glassthe ratio of/D is at least 0.5K/mm, preferably at least 1K/mm, more preferably at least 2K/mm, particularly preferably at least 3K/mm.
5. the floating process according to any one of claim 1-4, is characterized in that, △ T lehrthe ratio of/D is at least 30K/mm, preferably at least 60K/mm, more preferably at least 100K/mm, particularly preferably at least 150K/mm.
6. the floating process according to any one of claim 1-5, is characterized in that, described melten glass has the aluminium sesquioxide component of at least 5 % by weight, preferably at least 10 % by weight.
7. the floating process according to any one of claim 1-6, is characterized in that, described float glass plate (1) chemically highly can be tempered to the tempering layer depth DoL of bearing stress CS and at least 30 micron of at least 600 MPas.
8. the floating process according to any one of claim 1-7, is characterized in that, the thickness D of described glass ribbon (14) in useful region is 2.0 millimeters or following, preferably 1.0 millimeters or following, particularly preferably between 0.3 millimeter and 0.7 millimeter.
9. the floating process according to any one of claim 1-8, is characterized in that, at the temperature T of the described upside of described drawing zone topfrom T g+ 50K is reduced to T gin the B1 part of+20K, or the temperature T in described upside topfrom T g-20K is reduced to T gin the B2 part of-50K, the temperature difference △ T at each position x place in the described useful region of described glass ribbon (14) glassfor at least 0.25K, preferably at least 0.5K, more preferably at least 1K and particularly preferably at least 1.5K, and preferably, the temperature difference △ T at each position x place in described B1 or B2 part in the described useful region of described glass ribbon (14) lehrfor at least 15K, preferably at least 30K and particularly preferably at least 50K.
10. the floating process according to any one of claim 1-9, it is characterized in that, be in any C part of at least 2 meters, preferred at least 5 meters in the length of described annealing furnace (12), the temperature difference △ T at each position x place in the described useful region of described glass ribbon (14) lehrfor at least 15K, preferably at least 30K and particularly preferably at least 50K.
11. floating process according to any one of claim 1-10, it is characterized in that, described in described annealing furnace (12), glass ribbon (14) stands thermal output P from below belowand stand thermal output P from top above, be in the D part of at least 2 meters, preferred at least 5 meters in the length of described annealing furnace (12), P below/ P aboveratio for being less than 0.5, be preferably less than 0.3, be particularly preferably less than 0.1.
12. floating process according to any one of claim 1-11, it is characterized in that, described in described annealing furnace (12), glass ribbon (14) heats from top by thermal source (20), and the heat (21) that described thermal source (20) transmits is preferably in the first half of described glass ribbon (14), absorbed in the upper layer of 50 microns at the most.
13. floating process according to any one of claim 1-12, is characterized in that, cool described glass ribbon (14) in described annealing furnace (12) from below.
14. 1 kinds of float glass plate (1), the standard warpage W after its chemical tempering sfor being less than 300 microns, being preferably less than 200 microns, being particularly preferably less than 100 microns, the pre-warping before the chemical tempering of wherein said plate, for being less than+20 microns, being preferably less than 0 micron, being particularly preferably less than-20 microns.
15. float glass plate according to claim 14 (1), is characterized in that, the Na on the upside of the described float glass plate (1) after chemical tempering 2o concentration Na 2o topwith the Na of molten tin bath side 2the poor △ Na of O concentration 2o=Na 2o top-Na 2o bottomfor being greater than-0.2 % by weight and being less than 0.2 % by weight.
16. 1 kinds of float glass plate (1), is characterized in that, the Na of the upside of untempered described float glass plate (1) 2o content Na 2o topwith the Na of molten tin bath side 2the poor △ Na of O content 2o=Na 2o top-Na 2o bottomfor being greater than-0.2 % by weight and being less than 0.2 % by weight.
17. float glass plate (1) according to any one of claim 14-16, it is prepared by the floating process according to any one of claim 1-13.
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