CN108431726A - Hot-reinforced glass and related system and method - Google Patents

Abstract

The present invention provides a kind of reinforcing glass or glass ceramics sheet material or product and the method and system for manufacturing the reinforcing glass or glass ceramics sheet material or product.The method includes cooling down the sheet glass sufficiently long time by contactless heat transfer with the surface compression and center tension of the fixation sheet material.The method generates hot-reinforced glass piece.

Description

Hot-reinforced glass and related system and method

The U.S.Provisional Serial 62/288,851 that the application requires to submit on January 29th, 2016 according to Patent Law Senior interest, and also according to the senior interest of the following patent application of Patent Law requirement, each patent application is by drawing With being hereby incorporated by reference in its entirety：The U.S. Patent Application No. 14/814,232 that on July 30th, 2015 submits；On July 30th, 2015 The U.S. Patent Application No. 14/814,181 of submission；The U.S. Patent Application No. 14/814,274 that on July 30th, 2015 submits； The U.S. Patent Application No. 14/814,293 that on July 30th, 2015 submits；On July 30th, 2015 U.S. Patent Application No. submitted 14/814,303；The U.S. Patent Application No. 14/814,363 that on July 30th, 2015 submits；On July 30th, 2015 U.S. submitted State's patent application serial number 14/814,319；The U.S. Patent Application Serial Number 14/814,335 that on July 30th, 2015 submits.

It is integrally incorporated herein this application involves following patent application and by reference by following patent application：2014 7 The U.S. Provisional Patent Application No. 62/031,856 that the moon is submitted on the 31st；On November 4th, 2014 U.S. Provisional Patent Application submitted Number 62/074,838；The U.S. Provisional Patent Application No. 62/031,856 that on April 14th, 2015 submits；On July 30th, 2015 carries The U.S. Patent Application No. 14/814,232 of friendship；The U.S. Patent Application No. 14/814,181 that on July 30th, 2015 submits；2015 The U.S. Patent Application No. 14/814,274 that on July 30, in submits；The U.S. Patent Application No. 14/ that on July 30th, 2015 submits 814,293；The U.S. Patent Application No. 14/814,303 that on July 30th, 2015 submits；On July 30th, 2015, the U.S. submitted was special Sharp application number 14/814,363；The U.S. Patent Application No. 14/814,319 that on July 30th, 2015 submits；On July 30th, 2015 The U.S. Patent Application No. 14/814,335 of submission；The U.S. Provisional Patent Application No. 62/236 that on October 2nd, 2015 submits, 296；The U.S. Provisional Patent Application No. 62/288,549 that on January 29th, 2016 submits；On January 29th, 2016, the U.S. submitted faced When number of patent application 62/288,566；The U.S. Provisional Patent Application No. 62/288,615 that on January 29th, 2016 submits；2016 The U.S. Provisional Patent Application No. 62/288,695 that January 29 submitted；On January 29th, 2016 U.S. Provisional Patent Application submitted Number 62/288,755.

Technical field

The disclosure relates generally to thermal conditioning (for example, enhancing, tempering, heating etc.) glass, and more particularly to heat enhancing glass Glass and the correlation technique and system for being used to carry out glass (especially to thin glass sheet) hot enhancing.

Background technology

In heat (or " physics ") enhancing of sheet glass, sheet glass is heated to above to the glass transition temperature of glass Then high temperature makes sheet surface be quickly cooled down (" quenching "), while the interior zone of sheet material being made to be cooled down with more slow rate.Inner area Domain is more slowly cooling, because they are isolated by the thickness of glass and rather low thermal conductivity.Differentiation cools down in glass surface area Residual compressive stress is generated in domain, the residual compressive stress is balanced by the tensile residual stresses in center of glass region.

The heat enhancing of glass is different from the Chemical enhancement of glass, by changing near-surface region in the Chemical enhancement In the Chemical composition that (pass through such as ion spread method) of glass generate bearing stress.At some based on ion expansion In scattered method, can by the way that larger ion is changed into the exterior section compared with small ion come reinforcing glass near glass surface, So as on the surface or surface is applied around compression (also referred to as negative tensile stress).Compression is considered as limiting crack initiation And/or it propagates.

The heat enhancing of glass is also different from the glass enhanced by the following method：In the method by combining two types The glass of type enhances or arranges the exterior section of glass.In such method, the glass combination with different heat expansion coefficient The layer of object combines or laminated together when hotter.For example, by the molten glass layers with relatively low thermel expansion coefficient (CTE) Between sandwich the melten glass with higher CTE, when glass cool down, the positive tension in inner glass compresses outer layer, thus again The secondary compression that formed on the surface is to balance positive tensile stress.This bearing stress provides enhancing.

Hot-reinforced glass has the advantage that relative to non-reinforced glass.Compared with non-reinforced glass, the surface of reinforcing glass is pressed Contracting provides the resistance to fracture of bigger.The increase of intensity is usually proportional to the amount of bearing stress.If sheet material is relative to its thickness Spending has enough heat enhancings horizontal, if that sheet material is damaged, then usually it will be divided into fractionlet and have without being divided into The big fragment or elongated chips of sharp edges.As defined by the various standards established, it is divided into sufficiently small fragment or " cuts The glass of block " can be described as safety glass or " complete tempering " glass, or sometimes referred to simply as " tempering " glass.

Because enhancing degree depends on the glass sheet surface during quenching and the temperature difference between center, more thin glass needs Will more high cooldown rate to reach given applied stress.Moreover, more thin glass usually requires higher bearing stress value and center Stress value so as to fracture when realize stripping and slicing at little particle.Therefore, if not can not possibly if, be about 3mm or more in thickness Realize that desired temper level is very challenging in small glass.

All aspects of this disclosure are also generally related to glass or glass with the stress distribution for enhancing its exterior section Ceramics.Glass and glass and ceramic product (such as sheet glass) can be used for being widely applied.The example of such application includes：In window It is used in family, work top, container (for example, food, chemicals)；As display device (for example, tablet computer, honeycomb are electric Words, television set) backboard, foreboard, cover glass etc.；As high temperature substrate or support construction；Or other application.

Invention content

Disclosure part is related to highly reinforcing thin glass sheet and product, and is related under past unconsummated thickness real Method, process and the system of existing surprising sheet glass height heat enhancing.In various embodiments, it is believed that the mistake of the disclosure Journey and method are more than the thickness of glass limitation and rate of heat transfer that conventional convection air heat Enhancement Method is provided, without with liquid Body or solid radiator contact glass.In such system and method, during quenching, glass is only contacted with gas.It is disclosed System and method can be few to realizing heat enhancing in sheet glass thin at least 0.1mm in thickness, including reach " complete tempering " Or stripping and slicing behavior；It (in the embodiment of at least some considerations) and in some embodiments, is provided in thin glass sheet This enhancing, the thin glass sheet also have low roughness and height flat during quenching due to lacking liquid or solid contact Degree.In various embodiments, compared with conventional convection glass tempering system, these advantageous sheet glass material forms are by quenching The significant lower system and method for power requirement provide.

One embodiment of the disclosure is related to the method for hot-reinforced glass material.The method includes providing by glass The product that glass material is formed.The method includes product is heated to the glass transition temperature of glass material or more.The side Method includes that the product of heating is moved in cooling stations.The cooling stations include radiator, and the radiator has in face of heating Product spreader surface and the gas gap that separates the product of spreader surface and heating so that spreader surface is not Contact the product of heating.The method includes the part cooling that will be heated to the temperature less than glass transition temperature so that Bearing stress and center tensile stress are generated in product.By the convection current across the gap, by the way that thermal energy is passed from the product The radiator is delivered to cool down the product, so that being more than the thermal energy of 20% product for leaving the heating across institute It states gap and is received by the radiator.

Another embodiment of the disclosure is related to a kind of system for hot-reinforced glass piece.The system comprises heating It stands, the heating station includes heat being delivered to the heating element of the sheet glass, and sheet glass includes the first main surface, the Thickness between two main surfaces and the first main surface and the second main surface.The system comprises cooling stations, the cooling stations packet Opposite the first spreader surface and the second spreader surface are included, first spreader surface and the second spreader surface are at it Between limit channel so that during cooling, the sheet glass is located in the channel.The system comprises gas bearing, described Gas-pressurized is delivered to the channel so that the sheet glass is supported in the channel, without contacting first by gas bearing With the second spreader surface, and gas bearing limit interval area.The gas bearing will be in gas delivery to channel so that For square metre interval area, into channel total gas mass velocity be more than zero and be less than 2k/gC_p, wherein k is in heat conduction The thermal conductivity of gas in the channel assessed on direction, g are the distance between sheet glass and spreader surface, and C_pIt is in channel The specific heat capacity of gas.

Another embodiment of the disclosure is related to reinforcing glass or glass and ceramic product.The product includes the first main table Face, second main surface opposite with the first main surface and the interior zone between the first main surface and the second main surface. The average thickness that the product includes between the first main surface and the second main surface is less than 2mm.Product includes at least 70 weights Measure at least part of ion concentration and chemical composition of the first main surface and second main surface described in the silica of % It is identical as at least part of ion concentration and chemical composition of the interior zone.First main surface and the second main surface Under compression and interior zone is under tensile stress, and compression is more than 150MPa.The table of first main surface Surface roughness is between 0.2 and 1.5nm R_aBetween roughness.

Another embodiment of the disclosure is related to the method for hot-reinforced glass material.The method includes by glass Material product is heated to the glass transition temperature of glass material or more and supports the system of the heating with gas-pressurized stream Product.The method includes the products of the cooling heating in cooling stations, and the cooling stations include radiator, the heat dissipation Utensil has in face of the spreader surface of the product of the heating and separates the spreader surface and the product of the heating Gas gap.The product of the heating is supported on by the gas-pressurized stream in the gas gap so that described dissipate Hot device surface does not contact the product of the heating.By the part cooling of the heating to less than the glass in the cooling stations Change the temperature of transition temperature so that generating bearing stress in the product.For every square metre of the product of the heating Surface area, the gas-pressurized stream is delivered to by the gas gap with the flow velocity of 50slpm to 50,000slpm.

Another embodiment of the disclosure is related to a kind of system for sheet glass of the heat enhancing with surface area.It is described System includes heating station, and the heating station includes the heating element that heat is delivered to the sheet glass.The system comprises cold But stand, the cooling stations include opposite the first spreader surface and the second spreader surface, first spreader surface and Second spreader surface defines therebetween channel so that during cooling, the sheet glass is located in the channel.The system System includes gas bearing, described in gas-pressurized is delivered to the channel so that the sheet glass is supported on by the gas bearing In channel.For every square metre of surface area of the sheet glass, the gas bearing is with the stream of 50slpm to 50,000slpm The gas-pressurized is delivered to the channel by speed.

Another embodiment of the disclosure is related to reinforcing glass product.The product includes the first main surface and first The second opposite main surface of main surface and the interior zone between the first main surface and the second main surface.First table At least one of face or the second surface have relatively large surface area, i.e., at least 2500mm².First main surface With at least one of second main surface under compression and the interior zone is under tensile stress, and it is described Compression includes the hot tempering stress of at least 100MPa and the 20% chemical tempering stress less than the hot tempering stress.

Other feature and advantage will illustrate in detailed description below, and by describing, in these feature and advantage Part those skilled in the art will be apparent, or also can by put into practice this paper written description and its claim Book and attached embodiment described in figure and recognize the part in these feature and advantage.

It will be appreciated that the two outlined above and described below is exemplary only and is intended to provide for understanding the power The summary or frame for the property and feature that profit requires.

It is further understood and the attached drawing is incorporated in this specification and is constituted the one of this specification including attached drawing with providing Part.The one or more embodiments of description of the drawings and principle and the behaviour for being used to explain various embodiments together with the description Make.

Description of the drawings

Fig. 1 (prior art) is the curve graph for depending on the blower power needed for thickness of glass " complete tempering ".

Fig. 2 (prior art) is to depend on thickness of glass for aging method or machine O and compared with new method or machine N The curve graph of blower power needed for " complete tempering ".

Fig. 3 (prior art) is to be scaled the old curve O of curve graph and Fig. 2 superposed thereon to match Fig. 1 and new The curve graph of curve N.

Fig. 4 is according to the glass or glass and ceramic product of exemplary implementation scheme or the perspective view of sheet material.

Fig. 5 is the diagram partial cross section according to the hot-reinforced glass piece of Fig. 4 of exemplary implementation scheme.

Fig. 6 is the figure according to the estimation tensile stress relative thickness of the glass or glass and ceramic product of exemplary implementation scheme It indicates.

Fig. 7 shows a part for glass or glass and ceramic product according to the fracture of exemplary implementation scheme.

Fig. 8 is the curve graph of the fragmentation every square centimeter depending on the positive tensile stress from experiment.

Fig. 9 is the curve graph that tensile stress magnitude is born depending on the surface of the initial hot zone temperature from experiment, shows reality The threshold value of existing stripping and slicing.

Figure 10 is the fictive temperature obtained for one or more embodiments of method and system through the invention The curve graph of dimensionless surface fictive temperature parameter θ s.

Figure 11 is the curve graph of the bearing stress calculated by simulation for different glass composition, is for shown What the drawability parameter Ψ of various compositions having been proposed that was drawn.

Figure 12 and Figure 13 is two parameter P of the function depending on heat transfer coefficient h₁And P₂Curve graph.

Figure 14 is the song of the glass sheet surface compression (as unit of MPa) depending on sheet thickness t (in millimeters) Line chart, the performance zones for showing one or more embodiments by the system and method for the disclosure newly to open.

Figure 15 be show for the disclosure tempered glass piece selected exemplary implementation scheme draw depend on thickness Compression curve graph.

Figure 16 is the flow chart for showing some aspects according to disclosed method.

Figure 17 is the flow chart for some aspects for showing another method according to the disclosure.

Figure 18 is the curve graph of Fig. 3, is marked with region R and point A, B, A' and B' to show disclosed method and system Allow the region (compared with prior art) of operation.

Figure 19 is another expression of the region R and point A, B, A' and B' of Figure 18, but the minification copy of neighborhood graph 2 It shows (and being positioned relative to ratio).

Figure 20 (prior art) is the curve graph of the required heat transfer coefficient needed for the tempering depending on thickness of glass.

Figure 21 be according to exemplary implementation scheme by conduction rather than the diagram of sheet glass that is cooled down by convection current Section.

Figure 22 is the schematic sectional view according to the conduction enhancing system of exemplary implementation scheme.

Figure 23 is another embodiment according to the system similar with the system of Figure 22 of exemplary implementation scheme Perspective cut-away schematic view.

Figure 24 is the perspective cut-away schematic view according to the alternate embodiment of the insertion feature of Figure 23 of exemplary implementation scheme.

Figure 25 is the perspective according to another alternate embodiment of the insertion feature of Figure 23 of exemplary implementation scheme Sectional view.

Figure 26 is the flow chart for some aspects for showing another method according to exemplary implementation scheme.

Figure 27 is the perspective view according to the building with windowpane of exemplary implementation scheme.

Figure 28 is the perspective view of the display on the work top according to exemplary implementation scheme.

Figure 29 is the decomposition perspective view according to the device including glass or glass and ceramic product of exemplary implementation scheme.

Figure 30 is according to the glass or glass and ceramic product of exemplary implementation scheme or the perspective view of sheet material.

Figure 31 be according to exemplary implementation scheme include the forming of glass or forming and fusing consistent with heat treatment system The block diagram of the system of system.

Figure 32 is the schematic diagram for showing the glass tape being heat-treated in roll-to-roll system according to exemplary implementation scheme.

Specific implementation mode

Applicants have realized that need for hot-reinforced glass method and system and gained heat enhancing glass The heat treatment of glass is improved in terms of glass piece itself.For example, the thinner but sheet glass of high optical quality and including such sheet glass Product can be used for many applications (including portable electronic device, vehicle glass, building glass etc.).The compressibility of glass is very By force, but it is relatively weak in terms of fighting surface tension.By providing compression at sheet surface, (compression is not by exposing Tension at the center on surface balances), the useful intensity of sheet glass dramatically increases.Although however, relative to alternative enhancing Method (for example, Chemical enhancement, enhancing based on lamination), traditional hot glass strengthening is usually less expensive and more rapidly, but for Enhance thin glass (for example, 2-3mm or smaller sheet glass), it is known that traditional hot glass strengthening is not effective.Traditional Hot glass strengthening method is typically considered to be limited to thicker sheet glass, because of the horizontal glass depending on during process for quenching of enhancing The temperature difference generated between piece surface and center；And because of the heat conduction rate limitation of traditional Enhancement Method, due to being usually happened at Relatively uniform cooling on entire thin glass sheet, therefore, it is difficult to realize the notable temperature between thin glass sheet surface and center Difference.

On the other hand, by ion exchange come enhance thin glass may be take and it is troublesome, such as need extend glass The period of chemical bath.Directly different types of glass laminates are such as related to that may need complicated manufacturing method each other Double overflow slot fusion draw.

Therefore, it is necessary to the enhancing caused to glass for various uses (such as in window, work top, device Used in) particular stress distribution glass or glass and ceramic product, the glass or glass and ceramic product by with tradition Method is relatively low compared to resource density and/or more unpainful method is made.Specifically, the method and system shape being discussed herein At the glassware of the stress distribution of the exterior section with reinforcing glass, and then for mitigating cracking and destroying, permit simultaneously Perhaps various other required glass qualities (for example, the transmissivity of geometry, surface quality, visible light, flexibility etc.) are to have Help the use in various glass applications.

Present description provides for using heat enhancing come produce highly reinforcing glass material (and especially height increase Strong thin glass sheet) improved method and system.Method and system solves the various limitations of Conventional glass Enhancement Method, to Allow thickness be less than about 3mm, less than 2mm, less than 1.5mm, less than 1.0mm, less than 0.5mm, less than about 0.25mm and be less than High-caliber enhancing is realized in the sheet glass of about 0.1mm.Specifically, applicant, which develops, provides very high heat conduction rate System and method, even if to form the sufficiently large temperature difference between glass sheet surface and center so as in very thin sheet glass In also provide enhancing or tempering.

The summary of conventional thermal tempering technology and limitation

Conventional commercial method for hot-reinforced glass includes：(or two kinds of technologies are used in radiation energy stove or convection furnace " integrated mode " stove) in sheet glass is heated to predetermined temperature, then typically via by being blown against or along glass surface The convection current of a large amount of surrounding airs is sent to carry out gas cooling (" quenching ").This method for gas cooling is mainly convection current, is thus led to The mass motion (collective motion) of fluid is crossed to be conducted heat (by diffusion and advection) because gas by heat from hot glass sheet It takes away.

In conventional tempering method, certain factors can limit in sheet glass (especially thin glass sheet) and be typically considered to possibility Enhancing amount.Be partially present limitation because the compression amount on finished sheet directly with the sheet surface realized during quenching Temperature difference size between center is related.However, the temperature difference during quenching is bigger, the possibility that glass ruptures during quenching is got over Greatly.For given cooling rate, rupture can be reduced by being quenched since higher initial glass temperature.In addition, more High initial temperature allows generally for tempered glass piece to realize the whole enhancing potentiality provided by high cooldown rate.However, quenching Increasing sheet temperature when beginning also has the shortcomings that its is potential.For example, higher initial glass temperature may cause sheet material because of it Become softer and excessive deformation, to limit the practical achievable temperature difference.

In conventional tempering method, sheet thickness also applies significant limitation to the achievable temperature difference during quenching.For Given cooling rate during quenching, sheet material is thinner, and the temperature difference between surface and center is with regard to smaller.This is because for will in The heart and the thickness of glass of surface thermal insulation are smaller.Therefore, the heat enhancing of thin glass usually requires higher cooling rate (with thicker glass The hot reinforced phase ratio of glass), and therefore remove heat more quickly from glass outer surface and usually require significant energy expenditure, with Just the enhancing for generating the temperature difference between the inside and outside of sheet glass is horizontal.

For example, Fig. 1 shows to be used carrys out " complete tempering " soda-lime glass to blow enough surrounding airs Needed for the air blower of (" SLG ") power (by kilowatt/every square metre of sheet glass area as unit of), depend on millimeter being single The thickness of glass of position, based on the hot Enhancement Method of professional standard developed before 35 years.With thinning, the required work(of used glass Rate is grown exponentially.Therefore, the sheet glass of about 3mm thickness is the commercial glass of most thin complete hot tempering available for many years.

In addition, sheet material is thinner, the possibility of glass deformation is bigger under given pliability (that is, in given viscosity).Cause This, reduced thickness directly reduces the achievable temperature difference, and because the risk of sheet material deformation increases and tends to reduce using more Machine of the high sheet temperature to obtain whole benefits of more high cooldown rate and prevent the glass caused by more high cooldown rate from rupturing Meeting.Therefore, in conventional convection gas glass strengthening method, higher cooling rate is accomplished by the following way：Increase empty Gas velocity reduces air jet orifice to the distance of glass sheet surface, increases the temperature (when beginning to cool) of glass, and appoint Selection of land reduces the temperature of cooling air.

As nearest example, the performance curve of Fig. 2 (prior art) is the glass heat enhancing equipment using the prior art Publication.This improved equipment is continuing with traditional air blowing convective methods to cool down glass, but by least in heating During final stage roller of the systematic substitution of glass for supporting glass during heating is supported using air.It is connect in no roller In the case of touching, glass can be heated to higher temperature (and higher pliability/lower viscosity) before quenching, It is reported that allow the complete tempered glass for producing 2mm thickness.As shown in Fig. 2, compared with using roller (curve O), using empty Under higher temperature of the gas to support glass (curve N) realization, enhance the blower power reported needed for the sheet material of 2 millimeters thicks From 1200kW/m²It is reduced to 400kW/m²。

Although it indicates that the process of the 2mm heavy sheet glass of complete tempering can be produced, such as shown in Fig. 3 (prior art), It scales the old curve O and new curve N of Fig. 2 and is illustrated convection current toughening method by state of the art to match the ratio of Fig. 1 The performance improvement that (shown in Fig. 2) is realized is relatively small and only to the first feed-forward nets of the energy requirement in sheet glass convection current enhancing In progressive change.In figure 3, the old curve O and new curve N of Fig. 2 is scaled the curve graph to match Fig. 1 and is covered in it It is upper that (wherein old curve O is in 240kW/m²Top be truncated in order to check new curve N).From figure 3, it can be seen that when glass is thick When degree is reduced to 2mm from 3mm, the technology indicated by curve N only slightly changes the performance curve of convection gas process for quenching.It is high Operating point (is directed to 2mm glass, blower power 400kW/m²) show and handled by this method compared with needed for thin glass Power still has great increase.Air-flow sharply increases, therefore required power shows, it is difficult to use conventional convection gas Enhancement Method reaches while producing full tempered glass less than the thickness of 2mm (as engineering practice and economic problem). In addition, required very high air-flow it is also possible that thin slice shape distortion.Therefore, in order to realize thickness be less than 2mm glass Complete tempering or in order to be less than the coefficient of thermal expansion of the soda-lime glass using hot tempering in coefficient of thermal expansion (" CTE ") The complete tempering of 2mm is realized in glass, applicant have determined that needing using another toughening method/system.

Also the hot Enhancement Method of substituted type of current commercial convection type gas enhancing has been had attempted to, but each method is right There are certain disadvantages in terms of the enhancing of gas body.Specifically, realizing the typical alternative hot Enhancement Method of more high cooldown rate It usually requires that at least some liquid or solids are contacted with glass surface, rather than is only contacted with gas.This with sheet glass connects Glass surface quality, the uniformity of glass flatness and/or Enhancement Method may be negatively affected by touching.These defects sometimes can be with It is detected by human eye, when especially being watched in reflected light.As described in more detail below, at least in some embodiments, The heat conduction tempering system of the disclosure be reduced or eliminated it is such with contact relevant defect.

Contact enhancing using liquid (in the form of immersing in liquid bath or working fluid and in the form of spraying) Enhance higher cooling rate than convection gas to realize, but has and cause excessive thermal change on sheet material during cooling means The shortcomings that change.In the spraying of immersion or class immersion or flowing of liquid, due to the spontaneous production in liquid bath or liquid flowing Larger thermal change may occur in smaller area for raw convection current.In finer spraying, discontinuous spray droplet Significant thermal change is also generated with the effect of nozzle spray pattern.Excessive thermal change is tended to increase in the heat contacted by liquid Glass is caused to rupture during strong, this can mitigate by limiting cooling rate, but limiting that cooling velocity also reduces can be real Existing gained intensity.In addition, the necessary processing of sheet material (is located or is maintained in liquid bath or liquid flows or liquid spray In) also due to being physically contacted with sheet material and leading to physical stress and excessive thermal change, to also tend to cause during enhancing It ruptures and limits cooling velocity and gained is slight.Finally, some liquid cooling methods (such as pass through oil immersion and various spraying skills The high cooldown rate of art quenches) glass surface can be changed in this cooling period, thus it requires being moved later from glass sheet surface Except glass material to generate satisfactory finish.

The enhancing of solid contact heat includes that the surface of hot glass is made to be contacted with the colder surface of solids.Enhance as liquid contacts Equally, excessive thermal change may be easy tod produce in quenched period, as seen in liquid contact enhancing.Sheet glass Surface smoothness, any defect of the consistency of hardened face or sheet thickness all can cause the bad of some region of sheet material to connect It touches, and this bad contact may lead to larger thermal change, tends to that glass is made to rupture and such as chankings during processing Material may also lead to undesirable birefringence if surviving.Additionally, so that hot glass sheet is contacted with solid objects can result in Surface defect, chip, check, cracking, crackle, cut etc..With the increase of sheets of sizes, in the whole surface of sheet glass Upper realization good physical contact may also become more and more difficult.Physical contact with the surface of solids can also during quenching machine Sheet material is suppressed to tool, to increase the possibility for destroying sheet material during the method.In addition, the hypervelocity when starting contact Temperature change can cause thin slice processing during rupture, and therefore thin glass substrate contact cooling be commercially can not Capable.

The hot-reinforced glass of applicant and the general introduction of related conductive cooling procedure and method

The disclosure surmounted above-mentioned conventional method so as to according to commercial size efficiently and effectively and uniformly underground heat enhancing it is thin Sheet glass, without generating common various defects in conventional method, for example, not damaging glass surface, not causing birefringence, do not have Have non-uniform enhancing, and/or do not lead to unacceptable rupture etc..One or more embodiment party disclosed herein can be passed through Case produces the relatively thin hot tempering/reinforcing glass piece that can not have previously obtained.The system and method being discussed herein pass through with accurate side Formula provides very high rate of heat transfer to complete this point, wherein carrying out good physical control and soft processing to glass. In specific embodiment, the method and system being discussed herein utilizes small―gap suture gas bearing, application in cooling/quenching part People has determined that the cooling/quenching part allows to handle thin glass sheet in the beginning of cooling with higher relative temperature, to lead Cause higher hot enhancing horizontal.As described below, this small―gap suture gas bearing cooling/quenching part passes through across the gap to scattered The heat transfer of hot device rather than cooled down using the convection current moved based on upper air current and realize very high rate of heat transfer.By by glass Glass is supported in the gas bearing in gap, is realized this high rate of heat transfer and is led, while not making glass and liquid or solid material Material contact.As described below, applicant has also been determined that, at least some embodiments, the method and system shape that is discussed herein At the hot-reinforced glass (especially heat enhancing thin glass) with one or more peculiar properties.

By being had than previously known according to some embodiments of disclosed method and/or the sheet glass of system processing Higher levels of permanent thermotropic stress.In the case of without wishing to be bound by theory, it is believed that realize the thermotropic of level Stress can be due to combination and obtain.Glass has been reduced or eliminated in the high homogeneity of heat transfer in method detailed in this article In physics and undesirable thermal stress, to allow sheet glass with higher rate of heat transfer carry out tempering without rupture.In addition, This method can execute under lower sheet glass viscosity and (begin with higher initial temperature in quenching), while still keep institute The glass flatness and shape needed, this temperature that bigger is provided in cooling means change, to which the heat for increasing realized increases It is strong horizontal.

Hot tempering sheet glass

As described above, applicant has developed the system for being used to form hot-reinforced glass piece (especially thin glass sheet) and Method, and as this section is discussed, the heat enhancing thin glass sheet formed as discussed herein is with one or more The peculiar property and/or combination of properties that previously cannot achieve by conventional thermal tempering method or other toughening methods.

The structure snd size of hot tempering sheet glass

With reference to figure 4 and Fig. 5, shown with high bearing stress and/or high center tension according to exemplary implementation scheme Hot-reinforced glass piece.Fig. 4 shows the perspective view of hot-reinforced glass or glass and ceramic product or sheet material 500, and Fig. 5 is basis The diagram partial cross section of the hot-reinforced glass piece 500 of one or more embodiments.

As shown in figure 4, reinforcing glass or glass and ceramic product 500 (such as sheet material, beam, plate) include the first main surface 510, the second main surface 520 (can be translucent as disclosed herein to the dotted line of the back side of sheet material 500), And the main body 522 extended therebetween.Second main surface 520 on the side opposite with the first main surface 510 of main body 522, So that reinforcing glass or the thickness t of glass ceramics piece 500 are defined as between the first main surface 510 and the second main surface 520 Distance, wherein thickness t are also the size of depth.Reinforcing glass or the width w of glass ceramics piece 500 are defined as the first main surface 510 and second one of main surface 520 the first size orthogonal with thickness t.The length l of reinforcing glass or glass ceramics piece 500 It is defined as second size orthogonal with thickness t and width w of one of the first main surface 510 and the second main surface 520.

In an exemplary embodiment, the thickness t of sheet glass 500 is less than the length l of sheet glass 500.It is exemplary at other In embodiment, the thickness t of sheet glass 500 is less than the width w of sheet glass 500.In other other exemplary implementation schemes, The thickness t of sheet glass 500 is less than both the length l and width w of sheet glass 500.As shown in figure 5, sheet glass 500 is also in the first master At surface 510 and the second main surface 520 and/or nearby with permanent thermotropic compression region 530 and 540, pass through sheet material Permanent thermotropic center tensile stress (i.e. tension) region 550 in central part balances.

Method and system can be used to form the reinforcing glass piece with various thickness range.In various embodiments In, the range of the thickness t of sheet glass 500 is from 0.1mm to 5.7mm or 6.0mm, other than end point values, including 0.2mm, 0.28mm, 0.4mm, 0.5mm, 0.55mm, 0.7mm, 1mm, 1.1mm, 1.5mm, 1.8mm, 2mm and 3.2mm.The embodiment party of consideration Case includes hot-reinforced glass piece 500, and the range of thickness is as follows：From 0.1mm to 20mm, from 0.1mm to 16mm, from 0.1mm to 12mm, from 0.1mm to 8mm, from 0.1mm to 6mm, from 0.1mm to 4mm, from 0.1mm to 3mm, from 0.1mm to 2mm, from 0.1mm To less than 2mm, from 0.1mm to 1.5mm, from 0.1mm to 1mm, from 0.1mm to 0.7mm, from 0.1mm to 0.5mm and from 0.1mm To 0.3mm.

In some embodiments, the use of thickness is 3mm or smaller sheet glass.In some embodiments, glass is thick Degree be about (for example, add deduct 1%) 8mm or smaller, about 6mm or smaller, about 3mm or smaller, about 2.5mm or smaller, about 2mm or Smaller, about 1.8mm or smaller, about 1.6mm or smaller, about 1.4mm or smaller, about 1.2mm or smaller, about 1mm or smaller, about 0.8mm or smaller, about 0.7mm or smaller, about 0.6mm or smaller, about 0.5mm or smaller, about 0.4mm or smaller, about 0.3mm or Smaller or about 0.28mm or smaller.

In some embodiments, hot-reinforced glass piece there is high aspect ratio-that is, length and width and the ratio of thickness compared with Greatly.Because of air of the hot tempering method being discussed herein independent of high pressure or large volume, it is possible to by using begging for herein The gas bearing of opinion and high heat transfer rate system keep various glass piece performances (such as surface roughness peace after tempering Smooth degree).Similarly, the hot tempering method being discussed herein allows heat while keeping expectation or necessary shape to enhance height in length and breadth Than sheet glass (that is, length and sheet glass that the ratio of thickness is higher or the ratio of width and thickness is higher or both).It is specific and Speech, it is about at least 10 that can enhance length with thickness ratio and/or width and thickness ratio (" aspect ratio "):1, at least 20:1、 And it is up to and more than 1000:1 sheet material.In the embodiment of consideration, it is at least 200 that can enhance aspect ratio:1, at least 500:1, at least 1000:1, at least 2000:1, at least 4000:1 sheet material.

According to exemplary implementation scheme, the length l of reinforcing glass or glass ceramics piece 500 is greater than or equal to width w, such as Twice more than width w, five times more than width w, and/or no more than 50 times of width w.In some such embodiments In, the width w of reinforcing glass or glass ceramics piece 500 is greater than or equal to twice of thickness t, all such as larger than thickness t, is more than thickness Five times of t, and/or no more than 50 times of thickness t.

In some embodiments, such as discussed below about the disclosed applications of Figure 27-30, for example, glass or The length l of glass ceramics piece 500 is at least 1cm, such as at least 3cm, at least 5cm, at least 7.5cm, at least 20cm, at least 50cm, and/or it is not more than 50m, such as no more than 10m, no more than 7.5m, no more than 5m.In some such embodiments, glass Glass or the length w of glass ceramics piece 500 are at least 1cm, such as at least 3cm, at least 5cm, at least 7.5cm, at least 20cm, at least 50cm, and/or it is not more than 50m, such as no more than 10m, no more than 7.5m, no more than 5m.With reference to figure 4, glass or glass ceramics In the form of sheet material 500, the thickness t of the sheet material 500 is less than 5 centimetres, such as 2.5cm or smaller, 1cm or smaller, 5mm or more Small, 2.5mm or smaller, 2mm or smaller, 1.7mm or smaller, 1.5mm or smaller, 1.2mm or smaller, or the implementation in consideration Even 1mm or smaller, such as 0.8mm or smaller in scheme；And/or thickness t is at least 10 μm, such as at least 50 μm, at least 100 μm, at least 300 μm.

In the embodiment of other considerations, may be sized to for glass or glass and ceramic product is public with institute herein The difference opened.In the embodiment of consideration, length l, width w and/or the thickness t of glass or glass and ceramic product can be opposite In changing each other, such as more complicated geometry (referring generally to Figure 30), wherein size disclosed herein is at least applicable in In the various aspects of corresponding glass or glass and ceramic product defined above with length l, width w and thickness t.

In some embodiments, at least one of the first surface 510 of sheet glass 500 or second surface 520 have Relatively large surface area.In various embodiments, the area of first surface 510 and/or second surface 520 is at least 100mm², such as at least 900mm², at least 2500mm², at least 5000mm², at least 100cm², at least 900cm², at least 2500cm², at least 5000cm²M, and/or it is not more than 2500m², such as no more than 100m², be not more than 5000cm², be not more than 2500cm², be not more than 1000cm², be not more than 500cm², be not more than 100cm².In this way, glass or glass ceramics piece 500 can have Relatively large surface area；Except through method disclosed herein and system, it is likely difficult to or hot can not enhances, especially together When thickness with the sheet glass being discussed herein, surface quality and/or strain uniformity.In addition, except through disclosed herein Method and system, not against ion exchange or type of glass change, it may be difficult to or stress distribution is cannot achieve, The especially negative tensile stress part of stress distribution (referring generally to Fig. 6).

Hot-reinforced glass piece compression and tensile stress

As indicated above, the hot-reinforced glass piece being discussed herein can have unexpected high bearing stress (for example, In region 530,540 shown in Fig. 5), unexpected high center tensile stress (for example, in region 550 shown in Fig. 5) And/or unique stress distribution (see Fig. 6).In view of sheet glass 500 as discussed herein low thickness and/or other solely In the case of special physical property (for example, low-down roughness, high flat degree, various optical properties, fictive temperature property etc.), This is especially true.

The glass formed by method disclosed herein and system compression (for example, region 530 shown in Fig. 5, In 540) it can change depending on thickness of glass t.In various embodiments, thickness is 3mm or smaller glass (such as glass Glass piece 500) compression (for example, bearing stress) it is as follows：At least 80MPa, at least 100MPa, at least 150MPa, at least 200MPa, at least 250MPa, at least 300MPa, at least 350MPa, at least 400Mpa and/or be not more than 1GPa.In the reality of consideration It applies in scheme, thickness is that the compression of 2mm or smaller glass is as follows：At least 80MPa, at least 100MPa, at least 150MPa, extremely Lack 175MPa, at least 200MPa, at least 250MPa, at least 300MPa, at least 350MPa, at least 400Mpa and/or is not more than 1GPa.In the embodiment of consideration, thickness is that the compression of 1.5mm or smaller glass is as follows：At least 80MPa, at least 100MPa, at least 150MPa, at least 175MPa, at least 200MPa, at least 250MPa, at least 300MPa, at least 350Mpa and/or No more than 1GPa.In the embodiment of consideration, thickness is that the compression of 1mm or smaller glass is as follows：At least 80MPa, extremely Lack 100MPa, at least 150MPa, at least 175MPa, at least 200MPa, at least 250MPa, at least 300MPa and/or is not more than 1GPa.In the embodiment of consideration, thickness is that the compression of 0.5mm or smaller glass is as follows：At least 50MPa, at least 80MPa, at least 100MPa, at least 150MPa, at least 175MPa, at least 200MPa, at least 250MPa and/or be not more than 1GPa.

In some embodiments, pass through method disclosed herein and system (for example, in region 550 shown in Fig. 5) Thermotropic center tension in the glass of formation can be more than 40MPa, be more than 50MPa, be more than 75MPa, be more than 100MPa.At other In embodiment, thermotropic center tension can be less than 300MPa or be less than 400MPa.In some embodiments, thermotropic center Power can be from about 50MPa to about 300MPa, about 60MPa to about 200MPa, about 70MPa to about 150MPa or about 80MPa be to about 140MPa.In some embodiments, hot-reinforced glass piece has higher thinness, is extremely thin.Because this can be passed through The system and method that text discusses apply very high rate of heat transfer, it is possible to be generated in SLG piece of the thickness less than 0.3mm aobvious The fuel factor (for example, center tension of at least 10MPa or even at least 20MPa) of work.It is in fact possible to which heat enhancing is very thin Sheet material (sheet material for being at least as thin as 0.1mm).Herein be described in further detail realized with it is achievable, be considered taking Certainly in the particular thermal stress level of thickness and its dependent variable.

With reference to figure 6, the reinforcing glass of Fig. 4 or the concept stress curve 560 of glass ceramics piece 500 are (in 25 DEG C of room temperature and mark Under quasi- atmospheric pressure) interior section 550 of reinforcing glass or glass ceramics piece 500 under positive tensile stress is shown and at negative Reinforcing glass or glass ceramics piece 500 under stress (for example, positive compression) except interior section 550 and adjacent inside portion Divide 550 part 530,540.It is applicant's understanding that by limit across glass or the cracking of glass ceramics piece 500 beginning and/ Or propagate, negative tensile stress strengthens reinforcing glass or glass ceramics piece 500 at least partly.

It is believed to be specific to the technology of the present invention, as disclosed herein, in given reinforcing glass or glass ceramics piece 500 Relatively large surface area and/or lower thickness in the case of, tensile stress in stress distribution 560 interior section 550 just Tensile stress and sharp turn except interior section 550 and between the negative tensile stress of the part 530,540 of adjacent interior section 550 Become.This transformation drastically is construed as the rate of change (i.e. slope) of tensile stress, can be represented as the size of stress (for example, the difference of the peak value of 100MPa, 200MPa, 250MPa, 300MPa, 400MPa, i.e., positive tensile stress+σ and negative tensile stress-σ It is different) divided by the thickness that changes distance (distance of such as 1mm, such as 500 μm, 250 μm, 100 μm of distance), (it is Distance for quantifying rate of change, can be a part for products thickness, and be not necessarily the size of product geometry). In some such embodiments, the change of tensile stress is not passed through 7000MPa divided by 1mm, such as no more than 5000MPa divided by 1mm. In the embodiment of consideration, the difference of the peak value of positive tensile stress and negative tensile stress is at least 50MPa, such as at least 100MPa, At least 150MPa, at least 200MPa, at least 250MPa, at least 300MPa, at least 400MPa, at least 500Mpa, and/or it is not more than 50GPa.In the embodiment of consideration, it is at least 50MPa that the peak value of glass or glass ceramics piece 500, which bears the size of tensile stress, Such as at least 100MPa, at least 150MPa, at least 200MPa, at least 250MPa, at least 300MPa, at least 400MPa, at least 500MPa.The drastically tensile stress profile changeover generated by the system and method being discussed herein is considered indicating：For given thickness The ability of the negative tensile stress of higher size is realized at glass sheet surface, and/or manufactures more thin glass product to realize higher water The ability of flat negative tensile stress (such as to realize the fragmentation potentiality of stripping and slicing as disclosed herein).Conventional hot tempering method can Such drastically tensile stress curve can be cannot achieve.

According to an exemplary implementation scheme, the high rate that changes of tensile stress is stretched in the thickness direction of stress distribution 560 At least one of lasting above-mentioned magnitude or greater value in exhibition, i.e. at least 2% thickness of sheet glass 500, such as at least 5% Thickness, at least 10% thickness, at least 15% thickness or at least 25% thickness.In the embodiment of consideration, enhancing It in depth extends in reinforcing glass or glass ceramics piece 500 so that change the thickness direction stretching, extension of rate with high tensile stress The depth between 20% and 80% of the thickness apart from first surface is concentrated on, this can for example further discriminate between chemical steel Change.

In the embodiment of at least some considerations, reinforcing glass or glass and ceramic product include it in terms of ion concentration Composition change, the dotted line 562 being conceptually shown as in Fig. 6.More specifically, in such embodiment, reinforcing glass or The composition of glass and ceramic product 500 includes the ion of the exchange or the injection that influence stress distribution 560.In some such embodiment party In case, the ion of exchange or injection does not extend completely through the portion of reinforcing glass or glass and ceramic product 500 under negative tensile stress Divide 530,540, because negative tensile stress is also the result of hot tempering disclosed herein.

Therefore, the curve with ion exchange intensity increased tensile stress distribution 560 is in curve tangent line discontinuous or prominent Become on 564 either side includes discontinuous or mutation 564 in different directions from each other.Mutation 564 is located at portion under negative tensile stress In points 530,540 so that tensile stress is close to being negative on discontinuous or mutation 564 either side.Discontinuous or mutation 564 can be right The portion under tensile stress should be born in the depth of different ions content, however in some such embodiments, in terms of ion concentration Divide 530,540 other parts still there is composition identical with the part 550 under positive tensile stress.

In specific embodiments, wherein reinforcing glass or glass ceramics piece 500 is all by hot tempering and ion exchange Intensity increases (for example, discontinuous 564 in stress distribution as shown in FIG. 6 are discribed), caused by ion exchange or returns Because the relative quantity of the negative tensile stress in ion exchange is relatively low, this is because generated by hot tempering method disclosed herein Very high-caliber negative stretch intensity.For example, in such embodiment, reinforcing glass or such as this paper institutes of glass ceramics piece 500 It states like that by hot tempering, and then after hot tempering, reinforcing glass or glass ceramics piece 500 are by ion exchange come into one Step enhancing.In such embodiment, by ion exchange enhancing caused by or be attributed to ion exchange enhancing be located at by surface The increase of negative tensile stress at 510 and 520 is less than caused by hot tempering or is attributed to 20% (tool of the negative tensile stress of hot tempering It is less than 10%) to body.For example, in specific embodiments, reinforcing glass or glass ceramics piece 500 have positioned at surface 510 Enhance negative tensile stress with the hot of 200MPa at 520, is enhanced by ion exchange enhancing or reinforced, this will be located at surface Total negative tensile stress at 510 and 520 increases to the maximum value of 240MPa, and more specifically increases to the maximum value of 220MPa. As it will be appreciated, in the embodiment wherein by Chemical enhancement to enhance hot tempering, in ion concentration and chemical constituent side Face, composition and internally positioned part of the reinforcing glass product at least one of the first main surface and the second main surface place Composition in at least part of (under tensile stress) is different so that at least some compression are (for example, close to main surface In relatively shallower region) depend on reinforcing glass item compositions change.

In other words, at least some reinforcing glasss or glass and ceramic product 500, ion exchange or implantation are being with or without In the case of, at least part in the part 530,540 of reinforcing glass or glass ceramics piece 500 (its under negative tensile stress simultaneously And except interior section 550 and adjacent interior section 550) composition and interior section 550 at least part (just Under tensile stress) composition it is identical.In such embodiment, at least some negative tensile stress of stress distribution and reinforcing glass or The change of the composition (for example, ionic composition) of glass ceramics piece 500 is unrelated.This structure can be by providing sufficient intensity Chemistry is not had to and/or is less frequently utilized to simplify the composition of reinforcing glass or glass ceramics piece 500 at least to a certain extent Tempering.Further, since discontinuous/change in composition, this structure can reduce the reinforcing glass or glass ceramics piece Stress concentration in 500, so as to reduce the possibility of layering and/or cracking that composition is discontinuously located.

In specific embodiments, reinforcing glass or glass ceramics piece 500 by hot tempering and include it is at least some not By the section of Chemical enhancement (such as being enhanced by ion exchange) or part.In some such embodiments, in negative tensile stress Under part 530,540 at least part of Chemical composition that (for example, ionic composition) and surface 510 and 520 in At least part of Chemical composition that and at least part of Chemical composition that in interior section 550 under positive tensile stress It is identical.In specific embodiments, the whole Chemical composition that in the part 530,540 under negative tensile stress (for example, from Sub-portfolio object) and whole Chemical composition thats and the interior section 550 under positive tensile stress in surface 510 and 520 change It is identical to learn composition.In some such embodiments, as at least some section thickness positions measure, reinforcing glass or The Chemical composition that of glass ceramics piece 500 substantially constant on thickness t.In such embodiment, reinforcing glass or glass pottery The stress distribution (as shown in Figure 6) of tile 500 is hot tempering stress distribution so that is only discussed herein by hot tempering generation each The horizontal compression of kind (for example, negative tensile stress) and positive tensile stress (for example, center tensile stress).

Hot tempering sheet glass ruptures performance

If storing enough energy in tensile stress region 550, glass can be as safe glass when fully being damaged Glass or " stripping and slicing " equally rupture.As used herein, when area is 25cm²Sheet glass when being broken into 40 pieces or more blocks, it is believed that By sheet glass stripping and slicing.In some embodiments, stripping and slicing be used as indicate sheet glass by " complete tempering " observational measurement (that is, For 2mm or thicker glass, wherein sheet glass has at least compression of 65MPa or the edge compression of at least 67MPa). In various embodiments, sheet glass 500 has enough tensile stress in tensile stress region 550 so that one piece of 25cm²Glass Piece 500 is broken into 40 or more pieces.

With reference to figure 7, have as disclosed herein about glass or the glass of the property of glass ceramics piece (such as sheet material 500) Or glass and ceramic product 610 has been broken, such as using centre punch or other instruments and/or generally based on American National Standard Association (ANSI) Z97.1 (impact test) and 1048 standards of ASTM.According to exemplary implementation scheme, glass or glass ceramics system Product 610 be enhanced to fracture when occur stripping and slicing degree, to formed multiple little particle blocks 616 (for example, fragment, Piece).In some embodiments, apply impact with hammer or punch to cause cracking glasses to be surveyed at the fragmentation of sheet of particles wherein In examination, thermotropic stress possessed by glass or glass and ceramic product 610 is enough the 50mm in glass or glass and ceramic product 610 Multiple particulate mass 616 not less than 40 are generated in the region of x50mm.Show the mark of the metallic pin length 614 with about 1cm Quasi- office's drawing pin 612 is for reference.

According to the embodiment of various considerations, although the thinner thickness of reinforcing glass or glass and ceramic product 610, stress Distribution (referring generally to Fig. 6) assigns high fragmentation potentiality to reinforcing glass or glass and ceramic product 610 so that in fracture, enhancing Glass or glass and ceramic product 610 are broken into especially small particulate mass 616, and the particulate mass is in first surface or second surface Any surface on area be less than 90mm², all such as less than 50mm², all such as less than 20mm², all such as less than 10mm², it is all such as less than 5mm², and/or at least 10 μm².In some such embodiments, the fragmentation potentiality of reinforcing glass or glass and ceramic product 610 are So that when reinforcing glass or glass and ceramic product are broken, particulate mass 616 at least 20% (for example, at least 50%, at least 70%, the area of the first surface at least 95%) with one of above-mentioned amount or at least one of second surface.

At least partially due to the technology of the present invention can be used to be answered by disclosed herein in some embodiments Power come the glass manufactured or the extremely thin geometry of glass and ceramic product 610, reinforcing glass or glass and ceramic product 610 Rupture potentiality make in fracture, and reinforcing glass or glass and ceramic product 610 are broken into the particulate mass of special low volume, described The fast volume of grain is less than 50mm³, all such as less than 40mm³, all such as less than 30mm³, all such as less than 25mm³, and/or at least 50 μm³'s Volume.

At least partially due to the technology of the present invention can be used to be answered by disclosed herein in some embodiments Power come the glass manufactured or the king-sized area of glass and ceramic product 610, reinforcing glass or glass and ceramic product 610 it is broken Potentiality so that reinforcing glass or glass and ceramic product 610 are broken at least 100 volumes and are at least 50 μm in fracture³ Grain block 616, such as at least 200, at least 400, at least 1000, at least 4000 volumes are at least 50 μm³Particulate mass 616。

Referring now to Fig. 8 and Fig. 9, experiment is executed on the sheet glass of 1.1mm thickness, the glass for constituting the sheet glass includes By weight at least 70% silica, and/or by weight at least 10% sodium oxide molybdena, and/or by weight at least 7% Calcium oxide, and enhanced using apparatus and methods disclosed herein.As shown in Figure 8, it has been found that glass every square centimeter Size of the quantity of the particulate mass 616 of glass usually with the positive tensile stress at the center of corresponding glass or glass and ceramic product 610 has It closes.Similarly, as shown in figure 9, the ruler based on the glass sheet surface during quenching and the gap between radiator/gas bearing Very little and based on the gas used in gap thermal conductivity also found the broken potentiality of corresponding glass or glass and ceramic product 610 with Below in connection with：The temperature (for example, see Figure 21, Figure 22 and Figure 23) of glass in hot-zone and effectively apply during quenching To glass surface calculating expection heat transfer coefficient (h) (with cal/cm²S DEG C of (metric unit watt/m²° K) it is single Position).

Hot tempering sheet glass fictive temperature

In various embodiments, the hot-reinforced glass piece formed by the system and method being discussed herein is (for example, glass Piece 500) there is high fictive temperature.It will be appreciated that in various embodiments, the high imagination temperature for the glass material being discussed herein Degree is related to the high temper level of sheet glass 500, high center tensile stress and/or high bearing stress.It can be by any suitable Method (including differential scanning calorimetry, brillouin spectroscopy or Raman spectroscopy) determine surface fictive temperature.

According to exemplary implementation scheme, the part of glass or glass ceramics piece 500 (such as in first surface 510 and/or At or near second surface 520) there is extra high fictive temperature, such as at least 500 DEG C, such as at least 600 DEG C or one In a little embodiments even at least 700 DEG C (such as soda-lime glass).According to exemplary implementation scheme, glass or glass ceramics A part (such as at or near first surface 510 and/or second surface 520) for piece 500 is relative to identical Chemical composition that Annealed glass there is extra high fictive temperature, such as at least 10 DEG C or more, at least 30 DEG C or more, at least 50 DEG C or more, extremely It is 70 DEG C or more or even at least 100 DEG C or more few.High fictive temperature may be implemented by presently disclosed inventive technique, this is extremely The fast transition from hot-zone to cooling zone being at least partially due in enhancing system (for example, with reference to Figure 21, Figure 22 and Figure 23).Shen It asks someone to think the increase or related to the increase of glass anti-destructive that high fictive temperature can correspond to glass anti-destructive.

In the certain methods for determining surface fictive temperature, it may be necessary to which breaking glass is caused with mitigating by hot Enhancement Method " tempering stress " so as to rational accuracy measurement fictive temperature.It is well known that being surveyed by Raman spectrum analysis method The feature structure band of amount is deviated relative to fictive temperature and relative to the applied stress in silicate glass in a controlled manner. If tempering stress is known, which can be used for non-destructively measuring the fictive temperature of hot-reinforced glass piece.

General reference Figure 10 shows the determination of the fictive temperature of several exemplary glass products.D.R Tallant, " the The effects of tensile stress on the Raman of T.A.Michalske and W.L.Smith Stress pair two is reported in spectrum of silica glass " J.Non-Cryst.Solids, 106 380-383 (1988) The influence of the Raman spectrum of silica glass.Commercial glass with 65 weight % or higher silica is with substantially phase Same response.Although the stress response reported is to be directed to simple stress, in uniaxial stress state (such as in tempered glass The stress state observed) the case where condition under, σ_xx=σ_yy, it is contemplated that the offset of the peak value is expected by simple stress Twice of offset.1090cm in soda-lime glass and glass 2^-1Neighbouring peak value, which corresponds in quartz glass, to be observed 1050cm^-1Peak value.Stress is to the 1050cm in silica^-1Peak value influence and to SLG and other silicate glasses In the influence of correspondence peak value can pass through equation a) ω (cm^-1)=1054.93-0.00232 σ are expressed as unit of MPa Stress σ function.

Calibration curve is generated according to Raman band position, the letter as SLG and the fictive temperature of another glass (glass 2) Number.The heat treatment of different time is carried out to glass sample, the structural relaxation time that the time ratio is calculated by τ=10* η/G is long 2-3 times, wherein η is viscosity and G is modulus of shearing.After the heat treatment, by glass in water sudden fire so as to by fictive temperature It is frozen in heat treatment temperature.Then, in 200-1800cm^-1In the range of using the laser of 442nm, 10-30s time for exposure and 100% power measures glass under the magnifying power of 50x and 1-2 μm of spot size by micro Raman spectra analytic approach Surface.In this case, 1000-1200cm is matched using computer software (Renishaw WiRE 4.1 editions)^-1Under peak It is worth position.Pass through equation b) ω (cm^-1)=1110.66-0.0282Tf, which gives, to be measured in the SLG of air side 1090cm^-1Raman peak values it is good fit (as fictive temperature Tf (by DEG C as unit of) function).For glass 2, pass through Formula c) ω (cm^-1)=1102.00-0.0231Tf gives good fit.

By using equation a), b) and c) in the relationship established, the fictive temperature of glass can be expressed as to the drawing measured The function of graceful peak position and the correction factor caused by bearing stress.The compression stress ot of 100MPa_cKeep Raman band position inclined It moves, is equivalent to about 15 to 20 degrees Celsius of reduction of fictive temperature.Following formula is suitable for SLG：

Equation suitable for glass 2 is：

In these equatioies, ω is to be directed to 1090cm^-1The measurement peak value wave number of neighbouring peak value, σ_cIt is by any suitable Technology measure bearing stress, to generate by DEG C as unit of fictive temperature stress correct measured value.As with really The demonstration of the relevant increased anti-destructive of fixed fictive temperature, is prepared for four pieces of glass sheet samples, passes through conventional tempering method Soda-lime glass (SLG) piece of two 6mm is prepared as to the bearing stress (CS) of about 70MPa and 110MPa, and is passed through herein The SLG pieces of two 1.1mm are prepared as the CS of roughly the same level by disclosed method and system.Two additional sheet materials conducts pair According to each sheet material has respective thickness.Bear standard Vickers impression in the surface of each test sheet.Apply different level Power, every time it is for 15 seconds, and wait for 24 hours after, check respectively for impression.As shown in Table I, 50% is determined for each sample (par for being defined as occurred cracking is two points for tending to cause in four points of the pressure head of cracking to cracking threshold value Load).

Table I indicates that the Vickers crack initiation threshold value of the SLG handled by conventional convection gas tempering (is reflected in the piece of 6mm In material) it is essentially identical with the Vickers crack initiation threshold value of annealing or the SLG pieces that will be delivered, i.e., between zero Niu Yuyi oxen (N) About one N is risen to less than two Ns.This and surface fictive temperature (T_fsOr Tf_surface) with respect to conventional tempering offer Glass transition temperature (T_g=550 DEG C, for SLG, it is defined as η=10^12-13.3Pool) about 25 DEG C to 35 DEG C of rather moderate on It rises related.In contrast, tempering being carried out by using this method and system, Vickers crack initiation threshold value is increased to greater than 10N, than 10 times are increased by the Vickers anti-destructive of conventional tempering imparting.In the glass embodied, T_fsSubtract T_gBe at least 50 DEG C or At least 75 DEG C or at least 90 DEG C or in the range of from about 75 DEG C to 100 DEG C.Even if including lower level heat enhancing In embodiment, the glass embodied still can for example provide increased resistance (level of such as 5N).In certain considerations In embodiment, the 50% cracking threshold value after Vickers crack initiation test in 15 seconds can be equal to or more than 5N, 10N, 20N Or 30N.

Dimensionless fictive temperature parameter θ below can be used for the hotter Enhancement Method in terms of generated fictive temperature Relative performance.In this case, it is provided in terms of the fictive temperature θ s of surface：

θ s=(T_fs-T_Annealing)l(T_Softening-T_Annealing) (3)

Wherein T_fsIt is surface fictive temperature, T_Annealing(viscosities il=10^13.2Glass temperature under pool) it is annealing point, and T_Softening (viscosities il=10^7.6Pool under glass temperature) be sheet material glass softening point.Figure 10 is the heat depended in two different glass The curve graph of the θ s of the surface fictive temperature of the measurement of the rate of heat transfer h applied during enhancing.As shown in Figure 10, two kinds of different glass The result of glass is relatively closely to superimposed each other.This means that parameter θ provides the fictive temperature for directly comparing different glass Means, to produce they needed for rate of heat transfer h it is related.The vertical range of result under each h corresponds to when quenching starts Initial temperature T₀Value variation.In embodiments, parameter θ s include from about (for example, add deduct 10%) 0.2 to about 0.9, Or 0.21 to 0.09 or 0.22 to 0.09 or 0.23 to 0.09 or 0.24 to 0.09 or 0.25 to 0.09 or 0.30 to 0.09 or 0.40 to 0.09 or 0.5 to 0.9 or 0.51 to 0.9 or 0.52 to 0.9 or 0.53 to 0.9 or 0.54 to 0.9, Or 0.54 to 0.9 or 0.55 to 0.9 or 0.6 to 0.9 or even 0.65 to 0.9.

Hot tempering sheet glass drawability parameter

In various embodiments, the hot-reinforced glass piece formed by the system and method being discussed herein is (for example, glass Piece 500) there is high drawability and/or heat transfer number." the specific thermal stress " of glass is given by：

Wherein α is the elasticity modulus that glass (low-temperature linear) CTE, E is glass material, and μ is the pool of glass material Loose ratio.The value is used to indicate the stress level for giving in bearing temperature gradient and being generated in glass composition.It is also used as The estimator of hot " drawability ".However, compared under high heat transfer rate (such as in about 800W/m²K or more), the high temperature of glass Or " liquidus curve " CTE starts to influence tempering performance.Therefore, under such conditions, based on the CTE value to the variation on viscograph Integral approximation, find drawability parameter Ψ be useful：

Wherein α^S _CTEBe with 1/ DEG C (DEG C^-1) indicate low-temperature linear CTE (be equivalent to glass from 0-300 DEG C of average linear The coefficient of expansion), α^L _CTEBe with 1/ DEG C (DEG C^-1) indicate the linear CTE of high temperature (be equivalent to observation glass transition point with softening The somewhere high temperature plateau value to be occurred between point), E is that (its permission is (immeasurable for the glass modulus that is indicated with GPa (non-MPa) Guiding principle) parameter Ψ value range usually between 0 and 1), T_StrainIt is with DEG C strain point of glass temperature (viscosities il=10 indicated^14.7 Glass temperature under pool), and T_SofteningIt is with DEG C glass softening point (viscosities il=10 indicated^7.6Glass temperature under pool).

For with glass of different nature, the bearing stress of hot Enhancement Method and gained is modeled to determine steel Change parameter Ψ.10^8.2Glass is modeled under the identical initial viscosity of pool and under different heat transfer coefficient.Table in Table II Show the property of various glass and 10^8.2The temperature of each glass under pool and the drawability parameter Ψ of each glass Calculated value.

Table II

Glass	Modulus	CTE is low	CTE high	108.2Pool DEG C	Softening point DEG C	Strain point DEG C	Ψ
								SLG	72	8.8	27.61	705	728	507	0.76
2	73.3	8.53	20.49	813	837	553	0.77
								3	65.5	8.26	26	821	862	549	0.83
4	65	8.69	20.2	864	912	608	0.74
								5	63.9	10.61	22	849	884	557	0.84
6	58.26	3.5	20.2	842	876	557	0.49
								7	73.6	3.6	13.3	929	963	708	0.44
8	81.1	3.86	12.13	968	995	749	0.48

It is in Table II the result shows that the heat enhancing performance of Ψ and glass is proportional.This correlation is further shown in fig. 11 Property, this provides high heat transfer rate (2093W/m²K(0.05cal/s·cm²DEG C) heat transfer coefficient) and the sheet glass of only 1mm it is thick The specific example of degree.As shown, the variation of the gained compression of seven kinds of different glass is with the drawability parameter Ψ's of suggestion Variation is very related.

Hot tempering sheet glass heat transfer coefficient and relationship with bearing stress and middle cardiac stress

In another aspect, it has been found that, for any glass, heat transfer coefficient h any given value (with cal/ cm²- s- DEG C of expressions) under, hyperbolic fit bearing stress (σ can be passed through_cs, as unit of MPa) and (t is relative thickness with mm Unit) (in the range of 0mm to 6mm) curve, wherein P¹And P₂It is the function of h so that：

Or Ψ is substituted into expression formula, stress in compression sigma_csThe curve of (Glass, h, t) is given by：

Constant P in wherein above-mentioned (6) or (7)₁、P₂The individually continuous function of heat transfer number h, is given by：

And

In figure 12 and figure 13, constant P₁、P₂It is plotted as the function of h respectively.Therefore, by expression above (6) Or the P for giving h is used in (7)₁Value and the identical h correspondence P₂, specify corresponding to the obtainable surface pressure at the h The curve of stress (CS), the function as thickness t.

In some embodiments, by the way that simply by the compression predicted under identical conduction divided by 2, class can be used As expression formula transmitted come the center tension (CT) (especially thickness be equal to or less than 6mm) and heat for predicting hot-reinforced glass piece Coefficient (such as 800W/m²K or more).Therefore, it is contemplated that center tension can be given by：

Wherein P_1CTAnd P_2CTIt provides as follows：

And

In some embodiments, for given heat enhancing Physical Examples, h and h_CTHaving the same it can be worth.However, In some embodiments, they can change, and provide independent variable and the variation between them is allowed to allow (describing In performance curve) capture 2:The invalid example of the typical ratios of 1CS/CT.

One or more embodiments of presently disclosed method and system all rates of heat transfer shown in Table III It is worth (h and h_CT) under produce heat enhancing SLG pieces.

Table III

In some embodiments, heat transfer number rate (h and h_CT) can be from about 0.024 to about 0.15, about 0.026 to about 0.10 or about 0.026 to about 0.075cal/scm²·℃。

Figure 14 shows the new opening as unit of MPa that the glass sheet surface depending on thickness t (as unit of mm) is compressed Performance space, by the figure of set point value C (h, the t) Ψ (SLG) of the h of 6-9 from the equations above, wherein Ψ (SLG) corresponds to table The Ψ values of SLG in II.Indicate relatively thin by the maximum stress of the achievable SLG pieces of gaseous exchange tempering labeled as the trace of GC The estimation range of degree, i.e., from 0.02cal/scm²DEG C (or 840W/m²K 0.03cal/scm) is arrived²DEG C or 1250W/ m²K, it is assumed that in the method can be 10^8.2Heating glass viscosity under it is horizontal using these heat transfer coefficients.Pool is equal to or about 704 DEG C, that is, it is higher than the temperature of convection gas method ability.

The example of highest report sheet material CS values based on gaseous exchange toughening method is by marking the triangle for being in legend Shape label is shown.Value 601 indicates the advertised product performance capability of business machine, and value 602 is based in glass processing meeting Verbal report.Indicate that the maximum stress for being estimated as to contact the SLG pieces that tempering is realized by liquid is opposite labeled as the trace of LC The curve of thinness, by 0.0625cal/scm²DEG C (or about 2600W/m²K rate of heat transfer h) is provided, it is also assumed that 10^8.2Pool or It is handled under about 704 DEG C of initial heating glass viscosity.The highest that toughening method is contacted based on liquid reports sheet material CS values Example is by marking the circles mark for being to show in legend.The higher person in two values under 2mm thickness is based on borosilicic acid The tempering of salt sheet glass is reported, and passes through (Ψ_slg)/(Ψ_borosilicate) for figure scale realized stress with into Row scaling is directly relatively.

It is indicated in 0.20cal/s cm labeled as 704 trace²DEG C (or about 8370W/m²K rate of heat transfer) and 704 DEG C initial temperature (i.e. will quenching before) under one or more embodiments by presently disclosed method and system can The stress of realization.Thus the stress level on achievable sheet glass indicates the improvement almost the same with liquid toughening strength level Range, because liquid toughening indicates the gaseous exchange tempering of the prior art.But the trace labeled as 704 is not the upper limit-implementation It is feasible that scheme, which has been illustrated as the value or more, because to small (under the relatively low viscosity of glass) under even higher temperature The good control of the shape and flatness of the enhancing of gap gas bearing heat.It is shown at 730 DEG C (closely labeled as 730 trace Or be higher than glass softening point) SLG sheet material initial temperatures under pass through 0.20cal/scm²DEG C (or about 8370W/m²K biography) Some additional enhancing performances that hot rate is realized.It is achieved in significantly improving and being achieved in sheet glass intensity for compression Significantly improve, especially by high heat transfer rate combination and using by closed gas bearing sheet flatness and The high initial temperature of the good processing and control and realization of shape, and this improvement is particularly significant in 2mm and thickness below.

Figure 15 shows the trace in 2mm and above-mentioned Figure 14 below, but compression is as passing through the one of the disclosure The function for the thickness that the selected example for the tempered glass piece that a or multiple embodiments generate is drawn, it is shown that pass through disclosure reality The existing horizontal extreme combinatorial with thinness of heat enhancing.

Hot tempering sheet glass with low surface roughness and high flat degree

In various embodiments, hot-reinforced glass piece (such as sheet material 500) disclosed herein have high thermal stress and Low formation surface roughness.Process and method disclosed herein can form surface with hot-reinforced glass piece without increasing Surface roughness.For example, before and after the treatments, by atomic force microscope (AFM) to the float glass air side of entrance The glass surface of the fusion forming of surface and entrance is characterized.For the sodium calcium float glass of the 1.1mm of entrance, R_aSurface is thick Rugosity is less than 1nm (0.6-0.7nm), and according to this method, R_aThe obstructed overheat of surface roughness enhances and increases.Similarly, According to the disclosure, the R of the fusion formed glass sheet of 1.1mm is kept by heat enhancing_aSurface roughness is less than 0.3nm (0.2- 0.3).Therefore, at least on 10 μm x10 μm of area, surface roughness of the hot-reinforced glass piece at least first surface is (i.e. R_aRoughness) range be from 0.2nm to 1.5nm, 0.2nm to 0.7nm, 0.2nm to 0.4nm, or even such as 0.2nm is extremely 0.3nm.In an exemplary embodiment, can on 10 μm x10 μm of area measurement surface roughness, or some implementation In scheme, can on 15 μm x15 μm of area measurement surface roughness.

In the embodiment of some considerations, hot-reinforced glass piece disclosed herein is not only with high thermal stress but also with low Formed (for example, not polishing) surface roughness and/or coating surface.Process and method disclosed herein can heat enhancing glass Glass piece, without increase sheet glass it is smooth formed or the surface roughness on delivered surface, and do not damage sensitivity equally Low-emissivity coating or anti-reflection coating or other coatings.Before and after the treatments, by atomic force microscope (AFM) into The glass surface of the fusion forming of the float glass air side surface and entrance that enter is characterized.R_aSurface roughness is less than 1nm (such as 0.6nm to 0.7nm) for enter in the air side of the sodium calcium float glass of 1.1mm and according to the disclosure it is obstructed Overheat enhances and increases.R_aSurface roughness is less than 0.3nm (such as 0.2nm to 0.3nm) for being shaped in the fusion of 1.1mm Enter on glass sheet and enhances also according to the obstructed overheat of the disclosure and increase.Therefore, in the embodiment of consideration, root According to the disclosure, hot-reinforced glass piece has surface roughness within the scope of at least 0.2nm and/or not at least first surface More than the R of 1.5nm (such as no more than 0.7nm, such as no more than 0.4nm or even such as no more than 0.3nm)_aRoughness；Or There is person hot reinforcing sheet, the hot reinforcing sheet to have the coating for the type that can apply before enhancing on it；Or tool The combination for having these low roughness values and coating is from the present invention side being used together with the corresponding sheet glass as starting material What method obtained.In specific embodiments, according to the disclosure, hot-reinforced glass piece is in the first main surface and the second main surface There is low surface roughness discussed above, and in some such implementations on (for example, surface 510 and 520 shown in Fig. 5) In scheme, the first main surface and the second main surface are the non-polished surfaces for having low surface roughness discussed above.Applicant Understanding be that this preservation of surface quality and/or face coat previously needs to use convection gas tempering or may needs Low heat transfer liquid toughening method, this generates limited heat enhancing effect with respect to active procedure and the available total size of method It answers.

In another embodiment, hot-reinforced glass piece described herein has high flat degree.In various embodiments In, the enhancing system that is discussed herein supports glass material using controlled air bearing during transport and heating, and In some embodiments, it can be used for assisting control and/or improve the flatness of sheet glass, so as to cause than previously available Higher flatness, especially for thin and/or highly reinforcing sheet glass.For example, at least piece of 0.6mm can be enhanced Material, while the flatness enhanced after improving.The flatness of the hot-reinforced glass piece embodied herein may include：Along its first table 100 μm of any 50mm length of one of face or second surface or smaller total indicator bounce (TIR), in first surface or the 300 μm or smaller TIR, the 50mm long on one of first surface or second surface in 50mm length on one of two surfaces 200 μm or smaller TIR, 100 μm or TIR or 70 μm or smaller TIR smaller in degree.In an exemplary embodiment, Along any 50mm or smaller profile measurement flatnesses of sheet glass.In the embodiment of consideration, have disclosed herein Flatness of the sheet material of thickness in the 20mm length on one of first surface or second surface is 200 μm or smaller TIR, all If flatness is 100 μm or smaller TIR, flatness is 70 μm or smaller TIR, and flatness is 50 μm or smaller TIR.

According to the embodiment of consideration, the reinforcing glass or glass and ceramic product being discussed herein are (for example, glass shown in Fig. 4 Glass piece 500) there is height dimension consistency so that along the change of its thickness t of the length direction stretching, extension of the 1cm of main body 522 No more than 50 μm, such as no more than 10 μm, no more than 5 μm, no more than 2 μm.Due to it is practical consider (such as coldplate alignment and/ Or the surface irregularity of size may be distorted), as disclosed herein, for given thickness, area and/or negative tensile stress Size, it is not achievable that this dimensional uniformity may be by solid quenching.

According to the embodiment of consideration, the reinforcing glass or glass and ceramic product that are discussed herein have at least one main surface (for example, reinforcing glass or the first surface of glass ceramics piece 500 510 and second surface 520 in Fig. 4), is flat so that The distribution of 1cm along its length is maintained in 50 μm of straight line, such as in 20 μm, 10 μm, 5 μm, 2 μm；And/or along it The distribution of the 1cm of width direction is maintained within 50 μm of straight line, in such as 20 μm, 10 μm, 5 μm, 2 μm.Due to practical consideration (warpage of the glass such as enhanced in these methods due to the convection current of fluid and forces associated or bending), as disclosed herein , for given thickness, area and/or negative tensile stress size, this high flat degree may be by liquid hardening can not be real Existing.

Hot-reinforced glass piece CTE

On the other hand include low thermal coefficient of expansion (CTE) sheet glass of heat enhancing.As discussed above (for example, see equation 7 and 10), hot enhancement effect significantly depends on the CTE for the glass for constituting sheet glass.However, the heat enhancing of low CTE glass can carry For the reinforcing glass composition with favorable property, such as increased chemical resistance of the favorable property, or due to Lower alrali content And it generates preferably compatible with electronic device.CTE is 65,60,55,50,45,40 and even 35x10^-6℃^-1And it is below Sheet glass can have a break pattern (" stripping and slicing ") as safety glass, thickness be less than 4mm, less than 3.5mm, be less than 3mm, it is even less than 2mm.CTE value can be enhanced using method described herein as 40x10^-6℃^-1And glass below. Under same thickness, by locate herein discuss system and method enhancing this low CTE glass can have with by conventional quotient The similar surface compression of SLG pieces of industry (gaseous exchange) method enhancing.In some embodiments, for following thickness Sheet glass：No more than 1cm, no more than 5mm, no more than 3mm, no more than 2mm, no more than 1.5mm, no more than 1mm, be not more than 0.75mm, no more than 0.5mm, no more than 0.3mm, no more than 0.2mm or be not more than 0.1mm, the compression of low CTE glass can be with Including at least 50MPa, at least 100MPa, at least 125MPa, at least 150MPa, at least 200MPa, at least 250MPa, at least 300MPa or at least 400MPa.

According to the disclosure formed sheet glass have a variety of applications, such as electronic device, display and laminate (such as The glass used in vehicle glass side lamp-interlayer-glass laminate) in.The larger and thinner laminated material of intensity can be produced, To mitigate weight and cost-effective, and improve fuel efficiency.It is desirable that heat enhancing fine sheet by clod wash and can be laminated To the relatively heavy sheet glass of formation, to provide any hot forming of the simple and reliable manufacturing method without fine sheet.

The Alpha of hot tempering sheet glass

Table IV below indicates the result (" method source " I is identified as in table) obtained by disclosed method and product Prime factor Alpha, the rough measurement as the heat exchange coefficient obtained in toughening method.Alpha is given by：

Wherein CS is physics compression (as unit of MPa), and t is thickness in millimeters, CTE be with DEG C^-1For list Position coefficient of thermal expansion, and E be with (MPa) be unit glass elasticity, and the unit of output be DEG C/mm.

Table IV

Sample number	Method source	Glass	Thickness (mm)	CS(MPa)	GTE(1/C)	E(MPa)**	Alpha(C/mm)
								1	I	SLG	1.84	156	9.20E-06	68900	129
2	I	SLG	1.84	172	9.20E-06	68900	147
								3	I	SLG	1.07	190	9.20E-06	68900	280

Sample 1 and sample 3 are the repeatable values obtained from disclosed method, and sample 1 uses air as in method Gas and sample 3 uses helium as the gas in method.Sample 2 indicates " champion " value using air in the method, I.e. unreliable so far repetition.The glass sample (sample 1-3) handled by disclosed method is all at 117 DEG C/mm More than Alpha.It is applicant's understanding that as thickness of glass reduces, the slope of Alpha and thickness may have what is reduced inherently to incline To.Alpha possessed by glass disclosed herein is more than 20t+77, and wherein t is the thickness of glass, in some embodiments, As unit of mm.

Heat enhancing system and method

In various embodiments, the method for reinforcing glass piece include by sheet glass (such as sheet glass 500) extremely Few part support is directed to cooling or quenching area, and sheet material is cooled rapidly in the cooling or quenching area, to generate Reinforcing glass piece with the one or more properties being discussed herein.In various embodiments, sheet glass at least partially by It is delivered to flowing or the pressure support of the gas in the gap between glass sheet surface and one or more radiators.In general, When sheet material is moved in cooling zone, the temperature of sheet glass is higher than the transition temperature of glass, and in various embodiments, glass Glass piece is cooling by heat conduction in cooling zone rather than is cooled down by convection current.Conduction is passed by the interaction between adjacent molecule The heat-transferring method of energy is passed, and convection current is to transmit the heat transfer side of energy by the movement of fluid (for example, air, helium etc.) Method, the fluid such as wherein heated are removed from heat source and are substituted by colder fluid.Therefore, this system with conventional based on right The glass strengthening of stream/tempering system is significantly different, the main heat transfer pattern of the cooling period of sheet glass in the conventional system It is convection current.

In some embodiments, the holistic approach for reinforcing glass piece be included in hot-zone heat sheet glass and so The cooled glass sheets in cooling zone afterwards.Transition temperature possessed by sheet glass is that glass viscosity value is η=10¹²-10^13.3The temperature of pool Degree.Glass is fully heated to make sheet glass be higher than transition temperature, then glass is moved in cooling zone.Optionally, glass Glass can be converted to cooling zone by limited proportionality from hot-zone.In cooling zone, glass sheet surface is located near radiator, in glass There are one radiators on the either side of glass piece, wherein between respectively having between a glass surface and the apparent surface of radiator Gap.By multiple apertures in radiator by gas delivery to gap, and in some embodiments, the gas of the delivering Air bearing is formed, the air bearing supports glass so that glass surface is not contacted with radiator between radiator. In cooling zone, sheet glass is cooled down by conducting cooling by convection current, and is sufficiently cooled with fixed or generation sheet material Thermotropic surface compression and thermotropic center tension, provide as discussed herein increased intensity.In various embodiments, By realizing the mainly cooling by conduction with low-down gap size in cooling zone so that sheet glass is close but not Contact the apparent surface of radiator.

Equipment for realizing described method may include the temperature for sheet glass to be heated to transition temperature or more The heating zone of degree and sheet glass for cooling heating are to provide the cooling zone of the sheet glass of enhancing.Equipment can heat It include optional transition region between area and cooling zone.Cooling zone may include radiator, and the radiator, which has, limits gap Pair of opposing surfaces receives the sheet glass of heating in the gap.Cooling zone may include being arranged in the opposite side in the gap On a pair of of gas bearing, be used to sheet glass being supported in gap.Gap may be configured to logical by conduction Convection current is crossed to cool down the sheet glass of heating.In some embodiments, between gas bearing may include for arriving gas delivery Multiple apertures of gap, and air bearing surface serves as radiator, can be by conduction rather than by convection current from the glass of heating Glass piece conduct heat away.

Enhancement Method and equipment (referring generally to Figure 21-25) disclosed herein allow hot tempering form through the invention Reinforcing glass or glass and ceramic product (referring generally to Fig. 4-7 and Figure 27-30).This method allows precipitous tensile stress relatively thick Degree/depth curve (referring generally to Fig. 6), it is especially precipitous in the slope near glass or glass and ceramic product surface, this Make it possible to enhance glass or glass and ceramic product to especially high-caliber for the given thickness near corresponding product surface Negative tensile stress, without being enhanced by ion exchange or lamination different glass.However, in some embodiments, herein Disclosed hot tempering method can be enhanced with ion exchange or is laminated applied to glass-glass.Hot tempering disclosed herein Method makes the especially high-caliber enhancing of realization in large area product (for example, sheet material), and the large area product is for passing through May be excessive for the enhancing of conventional thermal tempering method, such as due to the alignment limitation of contact hardening equipment, conventional convection system Cooling rate limitation, and/or warpage associated with liquid hardening tempering damage.Method disclosed herein uniquely allows High-caliber enhancing in extremely thin sheet material, the fine sheet may mistakes for the enhancing by conventional tempering method It is thin, such as due to thin glass or glass and ceramic product during Enhancement Method rupture or fracture and quench with solid or liquid The susceptibility of the associated contact force of fire, and/or cooling rate limitation due to conventional convection hardening.However, in other considerations Embodiment in, (such as can mutually be tied with unique Enhancement Method disclosed herein by least some solids or liquid hardening Close) manufacture glass or glass and ceramic product disclosed herein.

An embodiment according to disclosed method is shown in the flow chart of Figure 16.Process or method 100 include Step 140, that is, the sheet glass that temperature is higher than sheet glass transition temperature is provided.Process or method 100 further include step 160, i.e., extremely Sheet glass is supported at least partially through gas (passing through gas flowing and pressure).Step 160 includes, in sheet glass by air supporting While, cooling sheet material：1) by conduction rather than by convection current (passing through gas to radiator), and 2) in environment temperature It is enough to generate or fix the thermotropic bearing stress of sheet material and thermotropic center tensile stress under degree.

According to the modification (being depicted as the method 100' in the flow chart of Figure 17) of the embodiment of Figure 16, method can wrap Step 110 is included, i.e., fully heating sheet glass is so that sheet material is higher than the transition temperature of glass.One as cooling step 160 Divide or as its preparation, in the step 120, method 100' further includes providing to have the first spreader surface and the second radiator table The radiator (no matter as single-piece or with separate pieces) in face (referring generally to Figure 21-25), each spreader surface has wherein There is aperture.In step 130A, the method further includes that the first sheet surface is positioned to face the first heat dissipation across the first gap Device surface, and in step 130B, the method further includes that the second sheet surface is positioned to face second across the second gap Spreader surface.Spreader surface may include aperture and/or can be porous.In a step 160, method 100 ' can be with Including by conduction rather than by convection current (passing through gas to corresponding spreader surface) come coldplate, it is sufficient to reinforcing glass (example Such as, fully to generate or fix thermotropic bearing stress and thermotropic center tensile stress in sheet material).Step 160 can be with Including by aperture or porous radiator by gas delivery to the first gap and the second gap, and in some such embodiments In, delivering gas is to be formed in the air bearing that radiator nearby supports sheet glass.In some embodiments, only pass through heat dissipation The aperture of device only delivers gas by one or more holes of porous radiator and aperture.

These and other correlation techniques of the disclosure, as refrigerating mode is dominated rather than convection current, are violated by using conduction The gaseous exchange cooling technology of current dominant.Method described herein is not the heat using solid and gas (glass and air) Exchange, but use solid and solid (glass and radiator) heat exchange, by a small amount of gas (for example, glass surface and It is not physically contacted between radiator) it is reconciled in small―gap suture, to start and complete to generate the cooling of heat enhancing.Although in gas There are some convection current when body (for example, air bearing gas) flows into small―gap suture, but by gas and enter the direct of radiator Across gap conduction is leading refrigerating mode.Applicant have determined that relative to the cooling means based on convection current, the advantage of heat transfer Increase rate of heat transfer.

Because the conduction (or even across gap) of solid and solid allows heat flow more faster than convection current, compared with thin glass sheet Required cooling rate increase is not limited by gas velocity and volume.According to various embodiments, not usually by convection current Can be other purposes selection, control or optimization gas in the case of the constraint that gas flowing and gap size in system apply Body flows and gap size, such as controlling the rigidity of the air cushion in gap, being used to support sheet material, for flattening or with it His mode makes sheet forming, for optimizing heat conduction, being used to keep sheet flatness and/or shape, and/or use during heat enhances In balance sheet material ease of handling and high cooldown rate.For example, in some embodiments, because cooling is not to pass through convection current , so while the low-down gas flow rate of support gas bearing, helium become viable economically in the system of the disclosure Air substitute, and in such embodiment, helium provides the thermal conductivity for being about five times in air.Even if price it is assumed to work as The several times of preceding available rates, helium also become economically feasible alternative solution under the low flow velocity of the system of the disclosure.

In addition, because the disclosure system reduce during cooling the air flowed on the glass sheet volume (relative to Contracurrent system), thus the system and method being discussed herein reduce typically by routine in the tempering system based on convection current needed for High speed, the potential risk of hot thin glass sheet deformation caused by the flowing of high volumes of air.This also allow it is no deformation or most Softer, higher temperature sheet glass is handled in the case of small deformation, to be further improved achievable enhancing degree.It eliminates high Air velocity also mitigate sometimes in the following areas in the problem of seeing：It is (dynamic against upper air current that sheet material is transported to quenching chamber It is mobile) and prevent height from flowing, the adjacent part of cooler air entrance and the cooling stove for heating plate.

It is contacted with conventional liq or solid contact quenching tempering is related in addition, can be mitigated by the use of the conduction of gas Contact damage, warpage, forming of connection etc..It keeps adding by avoiding contact of the solid with solid using gas as middle conductor The surface quality of work product.High conduction rate, which is reconciled, by gas also avoids liquid contact.Some type of liquid hardening can Cause undesirable deformation, the pollution of the spatial variations in tempering and glass surface.These embodiments mainly provide non-contact The cooling of (in addition to gas) but very high speed.In other embodiments, as set forth above, it is possible to be contacted including solid or liquid.

The power consumption of hot tempering system/method

Another advantage of upper air current speed is avoided to be to be used as major glass by using solid-gas-solid conduction The saving for the power and energy that cooling body is realized.The point A and B of Figure 18 and Figure 19 indicate the air bearing of every square metre of sheet glass The high-end estimation (being supplied by compressed air under relatively high flowing) that uses of peak power.The practical low side of compressed air Peak power using may as low as institute's indicating value 1/16.Point A and point B does not include the active cooling of radiator, however, it can be wrapped It includes in some embodiments, especially in the case where machine is in continuous, quasi-continuous or high-frequency operation.

Referring again to Figure 18 and Figure 19, point A' and B' indicate when in view of the active cooling of spreader surface in point A and The peak power level of the conservative estimation of air bearing operation at point B, it is assumed that by heat-machinery (or electricity) efficiency ratio be 7.5 to 1 Active Cooling System (point A ' is declined 2.1 to complete the thermic load of be equivalent in sheet glass temperature 300 DEG C of decline In the time limit of second and for point B ' in 1 second).(these points are approximately corresponding in equipment described herein by practical tempering Sheet glass.)

Although four points in the region R of Figure 18 and Figure 19 show to improve as obtained by disclosed method and system Importance (at least to a certain extent), it should be noted that because power demand is represented quantity, attached Whole incomes may be significantly underestimated in figure.For example, as represented by curve N, the peak power of air blower cannot effectively be beaten It is open and close, it usually needs gate air flue is to stop big fan, the big fan still rotation (but load when not needing air Reduce).It usually can more effectively adapt to the fluid cooling system (such as cooling water factory) being for example easily achieved according to the disclosure Peak power requirements (being indicated by point A' and B'), and effective peak power will be significantly reduced, to only close to complete Just close to A' and B' when continuous operation.Therefore, as shown, tendency is more than peak value energy demand by the difference of total energy demand Difference.In some embodiments, peak power possessed by method described herein is less than 120Kw/m², be less than 100Kw/m²、 Less than 80KW/m²So that heat enhancing thickness is 2mm or smaller sheet glass.

The heat transfer from thin glass sheet during hot tempering

In general, in the system and method for the present invention, the heat transfer from thin glass sheet includes conducted component, to flow point Amount and radial component.It explains in detail as noted above and herein, the hot tempering system of the disclosure is passed by using heat It leads as providing thin glass tempering for quenching the principal organ of thin glass sheet.

It is understanding of the applicant to basic theory below.The those of ordinary skill in glass tempering technology field can be easy to Expect, wherein conduction effect is usually so small that in being typically ignored to be conducive to independent analysis convection current and radiation very much, is ask Whether ask can actually realize the foot of thin glass sheet (such as at 2 millimeters and following) by the conduction via gas (such as air) Enough high cooling rates-and if so, if such rate can be realized under actual gap size.

Heat conduction amount under conditions of embodiment in the method using system described herein can be through being determined by the following.First, Under the background by conducting the hot enhancing of progress in such as disclosure, it is necessary to assess gap on the conduction orientation along hot slope The thermal conductivity of interior gas.High temperature air at or near the surface of the sheet material cooled down, which has, compares Cryogenic air significantly more High thermal conductivity, the room temperature compared with Cryogenic air such as at spreader surface or near it or close to the air of room temperature (the nominal thermal conductivity of (dry) air at room temperature (25 DEG C) is about 0.026W/mK).Using the air assumed on entire gap cold Approximation in two apparent surface's mean temperatures when but starting.In the beginning of cooling, sheet glass can be for instance in 670 DEG C Temperature, and spreader surface can for example start at 30 DEG C.Therefore, the mean temperature of the air in gap will be 350 DEG C, Dry air has the thermal conductivity of about 0.047W/mK at this temperature；It is higher by 75% or more than its thermal conductivity at room temperature and It is sufficiently high so that a large amount of thermal energy is conducted in the gap of the size in system through the invention, as discussed below As, it is assumed that sheet material is finish-machined to surface and the consistency of thickness of reasonable altitudes.

In order to illustrate Q_cond, i.e., by distance be g gap heat transfer rate conducted component (with the gap On the vertical direction in the direction of distance g) (area possessed by the gap is A_g) can be given by：

Wherein k is the thermal conductivity of material (gas) in the gap assessed in heat transfer direction (or opposite direction), T_SIt is The temperature of glass surface, and T_HSIt is the temperature of spreader surface (or being heat source surface in other embodiments).As carried above And, Due Diligence k will need the thermal conductivity for merging the gas along (or opposition) conduction direction of heat flow, because of the heat conduction of gas Rate changes with temperature-but as good approximation, in two surface temperatures Ts and T_HSAverage value under, k can be seen Make the k values of gas in gap.

As unit of heat transfer coefficient (by hot-fluid power/square metre/Kelvin as unit of) reconfigure equation (14) to Go out：

So the effective heat transfer coefficient conducted across gap is the thermal conductivity of medium in gap (being in this case air) (as unit of W/mK) divided by gap length (as unit of rice), to provide the temperature difference as unit of Watt/ square metres/degree Value.Table V indicate merely due to conduction gap size from 10 μm until the air-filled clefts of 200 μm (each step-length be 10 μm) and Helium fills the heat transfer coefficient (k/g) in gap.

Table V

Figure 20 (prior art) show about 35 years before industrial standard curve (being added to the reference line under 2mm), to show The heat transfer coefficient (function as the thickness as unit of mm) needed for complete tempered glass piece under the conditions of certain hypothesis is gone out. As can be seen that about 40 μm of air-filled clefts can allow by conducting come complete tempering 2mm from the comparison of Table V and Figure 20 Thick glass.Although slightly less than 40 microns are fairly small gaps, the flat porous air bearing in conveyer application is logical It often can be down to reliably running under 20 microns of gap.Therefore, for the air supplied by the hole in spreader surface Gap can reach 37 microns.It, can using helium (or hydrogen has similar thermal conductivity) as gas Carry out the glass of complete tempering 2mm thickness with the gap for using about 200 μm.For identical heat transfer coefficient, made using helium or hydrogen Allow about 5 times of big gap sizes for gas.In other words, use helium or hydrogen as gap in gas in the case of, Under identical gap size, gap makes about 5 times of the heat transfer coefficient increase that can be used for quenching.So even if in case of air, Away from nor unpractical, and under the gas of high conductance, gap spacing is relatively easily realized, even for less than 2 The sheet thickness of millimeter is also such.

Except being cooled down except through conduction rather than by convection current (passing through gas), another embodiment includes passing through It conducts rather than is heated (or heating and/or cooling) by convection current (passing through gas).About conduction and convection current relative contribution, It is either directed to heating or cooling, across the convective component Q of the rate of the heat transfer in gap (or multiple gaps)_convIt can be given by following formula Go out：

Wherein m is the mass velocity of gas, and Cp is the specific heat capacity of gas, T_iIt is the gas entrance when gas flows into gap Temperature, and e is the heat between the gas flowed in gap, sheet surface and radiator/heat source surface (" wall " in gap) The validity of exchange.The value of e changes to 1 from 0 (indicating zero surface-gas heat exchange) and (indicates that the temperature on surface is fully achieved in gas Degree).The technical staff of field of heat transfer can calculate the value of e using such as e-NTU methods.

However, in general, if the gap very little between sheet surface and radiator/heat source surface, the value of e Very close it will be equal to 1, it means that gas almost heat-on average, equal to temperature of two surfaces on either side The average value-of degree is before it leaves gap.It is assumed that e=1 (slightly higher to estimate convection current rate of heat transfer), and gas by radiator/ The surface of heat source is supplied to gap, it can be assumed that the initial temperature of gas is identical as the temperature of radiator/heat source surface in gap (T_i=T_HS).Then the rate conducted heat caused by convection current can be reduced to：

It is outside from sheet material under treatment at a temperature of being typically used for the heat enhancing or heat treatment of glass and similar material Radiant heat transfer it is relatively small.In order to mainly by conduct cool down (or heating, it is assumed that carry out the amount of radiation of self-heat power when heated Excessively high) sheet material (for example, sheet material 200 shown in Figure 21), gap (for example, gap 204a shown in Figure 21, In region 204b), therefore require nothing more than：

Q_cond＞ Q_conv (18)

(18) are combined with equation (14) and (17) and give the following conditions：

It will substantially ensure that when being kept in the gap area discussed, mainly (or is added to cool down by conducting Heat) thin slice.Therefore, the mass velocity m of the interval area for every square metre, gas should be less than 2kA_g/gC_pOr 2k/gC_p. In one embodiment, m<B(2kA_g/gC_p), wherein B is the convection current cooling ratio cooling with conduction.As used herein, B is small In one and the normal number more than zero, specifically there is 2/3 or smaller or even 4/5 or 9/10 or smaller value.In general, m It should keep as low as possible, sheet glass is controlled (for example, sheet material 200 shown in Figure 21 is opposite using gas flowing to meet In spreader surface) position of (for example, spreader surface 201b, 202b shown in Figure 21) or the position of heat exchange surface itself Needs.Convection current cool down the ratio cooling with conduction can be from less than 1 to 1x10^-8Any value.In some embodiments, B be less than 0.9,0.8,0.7,0.6,0.5,0.4,0.1,5x10^-2、1x10^-2、5x10^-3、1x10^-3、5x10^-4、1x10^-4、5x10^-5、 1x10^-5、5x10^-6、1x10^-6、5x10^-7、1x10^-7、5x10^-8Or 1x10^-8.In some embodiments, m is minimized, and is met The needs of the sheet locations relative to spreader surface are supported and controlled using gas flowing.In other embodiments, it answers The selection m is to control position of the heat exchange surface relative to sheet material itself.

In various embodiments, compared with the conventional tempering system based on convection current, the disclosure based on the cold of conduction But the mass velocity m essence of the gas in system is lower.As discussed herein, the lower gas flow rate of this essence allows to pass Guiding systems are operated with the power use of substantive reduction.In addition, at least some embodiments, with conventional convection cooling system It compares, the gas stream speed of reduction also results in the more quiet cooling system of essence.In such embodiment, the reduction of noise can To increase behaviour by reducing hearing impaired possibility and even reducing or eliminating operator using the needs of hearing protection The safety of author.In such embodiment, these low gas flowing advantages are realized in the cooling system based on conduction, institute Stating cooling system allows high cooldown rate as described herein and resulting improved tempering and glass performance.

In a particular embodiment, total gas flow rate to the gas bearing channel of the cooling system based on conduction is relatively low , and can be for the minimum gas stream in cooling system inner support glassware particularly in some embodiments Speed (that is, being cooled down for convection current because gas is not delivered).In a particular embodiment, the glass surface for every square metre Product, to gas bearing channel two surfaces of glassware (for example, to) gas flow rate 50 standard liter/mins (slpm) with Between 50,000slpm, and especially for every square metre of glass surface area between 100slpm and 30,000slpm. In some such embodiments, gap length g be greater than or equal to 10 μm and be less than or equal to 500 μm, and be specifically greater than or Equal to 25 μm and it is less than or equal to 300 μm.In a particular embodiment, gas can be air, helium or other suitable gas Body.Compared at least some tempering systems based on convection current, it is applicant's understanding that the air velocity that the system of the disclosure is utilized is small In at least 20% of the representative gases flow velocity at least some conventional tempering systems based on convection current, and can down to 0.1% or less of representative gases flow velocity at least some tempering systems based on convection current.

As an example, and in order to further illustrate the low gas utilized in the cooling system based on conduction being discussed herein Flow velocity, applicant using air and helium as gas bearing gas and various gap lengths and various air velocitys come Test cooling system.Applicant for every square metre glass surface area 3600slpm and 12,000slpm air stream Bearing gas (gap length is 38 μm) is used air as under speed and carrys out cooled glass sheets, this leads to total heat transfer percentage of heat transfer Than being respectively 95% and 92%.Applicant is for every square metre of glass surface area 3600slpm's and 12,000slpm Bearing gas (gap length is 250 μm) is used air as under air velocity and carrys out cooled glass sheets, this leads to the total of heat transfer Heat transfer percents are respectively 76% and 64%.

Applicant is for every square metre of glass surface area under the helium flow velocity of 3600slpm and 12,000slpm Using helium as bearing gas (gap length be 38 μm) come cooled glass sheets, this leads to total heat transfer percents point of heat transfer It Wei 99% and 98%.Applicant for every square metre glass surface area 3600slpm and 12,000slpm helium Using helium as bearing gas (gap length is 250 μm) come cooled glass sheets under flow velocity, this leads to total heat transfer of heat transfer Percentage is respectively 94% and 90%.

In the embodiment of consideration, applicant have determined that, for every square metre of glass surface area, it is discussed herein Conduction cooling zone uses air as bearing gas under the air velocity of 100slpm and 28,700slpm, and (gap length is 25 μ M) it is respectively 98% and 91% by total heat transfer percents of heat transfer are caused.In the embodiment of other considerations, applicant is Through determination, for every square metre of glass surface area, the conduction cooling zone being discussed herein is in 100slpm and 28, the sky of 700slpm Bearing gas (gap length be 300 μm) is used air as under gas velocity will cause total heat transfer percents of heat transfer to be respectively 80% and 44%.

In the embodiment of other considerations, applicant have determined that, for every square metre of glass surface area, beg for herein The conduction cooling zone of opinion uses helium as bearing gas (gap length under the helium flow velocity of 100slpm and 10,000slpm It is 25 μm) by total heat transfer percents of heat transfer are caused it is respectively 100% and 99%.In the embodiment of other considerations, Shen Ask someone it has been determined that glass surface area for every square metre, the conduction cooling zone being discussed herein in 100slpm and 10, Use helium that will lead to total heat transfer of heat transfer as bearing gas (gap length is 300 μm) under the helium flow velocity of 000slpm Percentage is respectively 95% and 89%.In specific embodiments, heat transfer percentage discussed here is based on having 680 DEG C Tg glass material.

As it will be appreciated, being supported on the embodiment party in the air bearing between opposite heat sink surface in glass material piece In case, it will occur from sheet glass both sides to the heat transfer of two spreader surfaces.Therefore, in such embodiment, sheet glass With the first sheet surface and the second sheet surface, and by the way that the first sheet surface (for example, lower surface of sheet glass) is fixed Position is at neighbouring first spreader surface (for example, surface of lower radiator) so that the first gap is located at the first sheet surface and the It is dissipated between one spreader surface and by the way that the second sheet surface (for example, upper surface of sheet glass) is positioned adjacent to second Hot device surface (for example, surface of upper radiator) so that the second gap be located at the second sheet surface and the second spreader surface it Between sheet glass is cooled down.In such embodiment, allow occur from the first sheet surface to the first spreader surface with And from the second sheet surface to the heat conduction of the second spreader surface.In such embodiment, the first gap has between first The length g of gap₁With the first interval area A_g1, and the second gap has the length g across the second gap₂With the second interval area A_g2.In such embodiment, first flowing of the first gas to the first gap is provided, and provide second gas between second Second flowing of gap.As it will be appreciated, similar to described above, first gas has thermal capacitance C_p1With thermal conductivity k₁, and first Flowing is set as mass velocity m₁.In such embodiment, m₁More than zero and it is less than (2k₁A_g1)/(g₁C_p1).In addition, the second gas Body has thermal capacitance C_P2With thermal conductivity k₂, and the second flowing is set as mass velocity m₂.In such embodiment, m₂More than zero And it is less than (2k₂A_g2)/(g₂C_p2).In such embodiment, the first flowing and the second flowing contact sheet glass so that sheet glass It is supported without contacting spreader surface.In this way, in a certain way by conduction rather than by convection current come cooling fin Material is to generate the bearing stress and center tension of sheet material.

Glass strengthening system including high conduction cooling zone

With reference to figure 21, show high conduction glass cooling/quenching station and by conduction rather than cooled down by convection current The diagrammatic section of sheet glass.Between first (master) surface 200a and second (master) surface 200b of hot glass sheet 200 are crossed over accordingly Gap 204a and 204b respectively face the corresponding first surface 201b and the of corresponding first radiator 201a and the second radiator 202a Two surface 202b.As indicated by the arrows, between by first surface 201b and second surface 202b supply gas 230 to supply Gap 204a, 204b and to help to maintain sheet glass placed in the middle or be positioned in other ways between radiator 201a, 202a.Such as arrow Shown in first 240, air or other gases may exit off, to by the edge of radiator 201a, 202a.According to begging for for this paper By the flow velocity of size and gas and gas 230 by selecting gap 204a, 204b will be by conduction rather than by right Stream carrys out cooled glass sheets 200.In a particular embodiment, by radiator 201a and 202a come cooled glass sheets 200, so that More than 20%, more than 30%, more than 40%, be especially more than 50% and be more specifically more than 80% to leave heating product (all Such as sheet glass 200) thermal energy across gap (such as gap 204a and 204b) and by radiator 201a and 202a receive.

In some embodiments, gap 204a, 204b is configured to, with the enough thickness or distance across gap, make Obtain through conduction rather than cooled down by convection current the sheet glass of heating.As it will be appreciated, the size of gap 204a, 204b are usual It is the distance between main glass surface and opposite heat sink surface.

In some embodiments, thickness possessed by gap 204a and 204b can be about (for example, add deduct 1%) 100 μm or bigger are (for example, in following range：About 100 μm to about 200 μm, about 100 μm to about 190 μm, about 100 μm to about 180 μm, about 100 μm to about 170 μm, about 100 μm to about 160 μm, about 100 μm to about 150 μm, about 110 μm to about 200 μm, about 120 μm to about 200 μm, about 130 μm to about 200 μm or about 140 μm to about 200 μm).In other embodiments, gap 204a Can be about 100 μm of (for example, add deduct 1%) or smaller (for example, in following range with thickness possessed by 204b：About 10 μ M to about 100 μm, about 20 μm to about 100 μm, about 30 μm to about 100 μm, about 40 μm to about 100 μm, about 10 μm to about 90 μm, about 10 μm to about 80 μm, about 10 μm to about 70 μm, about 10 μm to about 60 μm or about 10 μm to about 50 μm).

Radiator 201a, 202a can be solid configuration or porous configuration.Suitable material includes but not limited to aluminium, blueness Copper, carbon or graphite, stainless steel etc..The size of radiator can be designed as the size for being enough to handle sheet glass, and can have It imitates and efficiently conducts heat and do not have to significantly change radiator temperature.Be in radiator 201a and/or 202a it is porous, it Can still include additional aperture for making gas flow or hole or flowing or two can be provided using porous structure Person.In some embodiments, radiator further includes that fluid is allowed to flow for controlling the channel of radiator temperature, is being schemed It 23-25 and is described in more detail below.

Very small aperture or hole in radiator face can be made it possible for by eliminating the high gas flow of the prior art 206, as shown in figure 21, to provide gas to gap.In some embodiments, aperture in minimum direction (for example, in round hole Mouthful in the case of be diameter) on be measured when can be less than 2mm, less than 1.5mm, less than 1mm, less than 0.5mm, be less than 0.25mm, or it is less than or equal to 200 μm, 150 μm, 100 μm, 50 μm, 30 μm, 20 μm or 10 μm.In some embodiments, hole Mouthful from 10 μm of about (for example, add deduct 1%) to about 1mm, about 20 μm to about 1mm or about 50 μm to about 1mm.

When being measured from the edge-to-edge in aperture, the interval between adjacent aperture 206 can be from about (for example, add deduct 1%) 10 μm to about 3mm, about 20 μm to about 2mm or about 50 μm to about 1mm.Microstome or hole can be used as independent current limiter, from And high performance gas bearing type dynamics (rigidity and consistency of the height of such as sheet support) is provided with position sheet material and Control gap size, to allow the high uniformity of hot enhancement effect to avoid or reduce stress birfringence.In addition, because can be with Using very small hole or aperture, so the relative quantity of the solid matter at spreader surface of the clearance plane to sheet surface can To be maximized, thus increase conduction hot-fluid.

According to various embodiments because radiator 201a and 202a serve as the gas bearing of support hot glass sheet 200 with And both radiators of hot glass sheet 200 are cooled down basically by conduction, so radiator 201a and 202a have been configured to To this double action.In a particular embodiment, radiator 201a and 202a be configured to have enough thermal masses so as to Heat is received by the conduction from hot glass sheet 200, at the same time can deliver enough gas to support hot glass sheet 200。

In some such embodiments, the amount of radiator 201a and 202a occupied by aperture 206 are relatively small so that For receiving the increase of quantity of material present in the radiator 201a and 202a of heat or maximizing.In a particular embodiment, hole Mouth 206 occupies being less than 10%, being particularly less than 5%, be particularly less than 2% for the surface area of spreader surface 201b and 202b, And more particularly less than 1%.In specific exemplary test system, applicant is cold conduct using radiator But, wherein 1.1% and the 0.5% of the surface area of spreader surface 201b and 202b is occupied by aperture 206.In radiator 201a and In the specific embodiment that 202a is formed by porous material (for example, porous graphite or porous aluminum), hole is very small so that can The surface area of surface 201b and 202b for heat conduction are substantially 100%.It is applicant's understanding that at least some regular air axis It holds design to compare, the ratio essence higher of the surface 201b and 202b of heat conduction is can be used in this system.

According to various embodiments, using such aperture 206 as the unique road for providing gas to gap 204a, 204b Diameter, and desirably using the aperture 206 being located adjacent on the direction vertical with spreader surface 201b, 202b, it is ensured that it is empty Gas bearing type dynamics is optimised, and is not flowed or come from except through neighbouring sheet material 200 by the gas from larger aperture Spreader surface 201b, 202b except source gas flowing damage, or damaged by other excessive lateral flowings Evil.In other embodiments, gas can be provided to gap by other sources (such as other than aperture 206 or hole) 204a、204b.Therefore, all aspects of this disclosure are allowed to be flowed by using low gas and solid-gas-solid conduct to save Power and energy (such as relative to conventional convection toughening method).

Figure 22-25 shows the exemplary implementation scheme of the glass strengthening system 300 according to the disclosure.Figure 22 shows system 300 schematic sectional view, wherein can by the heat from sheet glass by gas conduction to conductive heat spreader come cold But sheet glass.Equipment includes hot-zone 310, cold-zone 330 and transition gas bearing 320.Transition gas bearing 320 is by glassware (for example, sheet glass 400a) is moved from hot-zone 310 or is guided to cold-zone 330, so that not being in contact between glass and bearing Or it is not in contact substantially.Hot-zone 310 has the gas bearing 312 that each free hot-zone pumping chamber 318 supplies, and bearing 312 With the cartridge heater 314 being inserted by bearing 312 in hole, it is used to hot-zone gas bearing 312 being heated to desired Beginning method temperature.Sheet glass (hot-zone) 400a be maintained at it is long enough between hot-zone gas bearing 312 so that its Reach desired precooled temperature (for example, being higher than transition temperature).

In some embodiments, it can mainly be completed by making heat be conducted through thin barrier layer for gases from radiator Sheet material is heated in hot-zone.The conduction used in hot-zone can be similar with cooling means as described herein, still (for example, heat is pushed into sheet glass) on the contrary.

In some embodiments, the gap 316 between hot-zone gas bearing 312 and sheet glass 400a can be relatively Big, about 0.05 " (1.27mm) to 0.125 " (3.175mm) or bigger, because sheet glass 400a can be by relatively slowly It heats and is sufficient to the purpose from hot gas bearing 312 to the heat radiation in sheet glass 400a in ground.In other embodiments In, hot-zone gap size can be as small as 150 microns of every side or per 500 microns of side.In some embodiments, small gap may It is advantageous, because they enable bearing that there is better " rigidity "-so that glass is occupied when glass is in soft state In and the ability that makes it flatten.In some embodiments, the pressure that this method can for example by being provided by gas bearing 312 Come re-form sheet glass-make its flatten-in initial heating step.In some embodiments, top and bottom hot-zone axis Hold to allow to change in a continuous manner gap width, or alternatively, to allow when gap is larger on the actuator By glass bring into hot-zone and then compression clearance to make the glass flatten when glass is still soft.

In the specific embodiment that hot-zone 310 is configured to basically by conduction to heat sheet glass 400a, base is arrived Total gas flow rate in the gap 316 of 310 system of the hot-zone of conduction is relatively low, and can be in some embodiments particularly Minimum gas flow rate for the support glassware in hot-zone 310.In some such embodiments, for every square metre Glass surface area, to gap 316 two surfaces of sheet glass 400a (for example, to) gas flow rate in 50slpm and 50, Between 000slpm, and especially for every square metre of glass surface area between 100slpm and 30,000slpm.One In a little such embodiments, gap length g is greater than or equal to 50 μm and is less than or equal to 1000 μm, and is particularly less than or waits In 700 μm.In a particular embodiment, gas can be air, helium or other suitable gases.In particular embodiment In, the gas for being delivered to hot-zone 310 includes vapor, and in such embodiment, (potentially) is helped using vapor In the relatively low surface viscosity of hot glass surface, so as to cause crack healing.

In the embodiment of consideration, applicant have determined that, for every square metre of glass surface area, it is discussed herein Conduction heating area (all hot-zones 310 as discussed in this article) is made under the air velocity of 100slpm and 28,700slpm using air By total heat transfer percents of heat transfer are caused it is respectively 98% and 91% for bearing gas (gap length is 75 μm).It examines at other In the embodiment of worry, applicant have determined that, for every square metre of glass surface area, the conduction heating area that is discussed herein (all hot-zones 310 as discussed in this article) uses air as bearing gas under the air velocity of 100slpm and 28,700slpm (gap length is 700 μm) is respectively 74% and 27% by total heat transfer percents of heat transfer are caused.

In the embodiment of other considerations, applicant have determined that, for every square metre of glass surface area, beg for herein The conduction heating area (all hot-zones 310 as discussed in this article) of opinion uses helium under the helium flow velocity of 100slpm and 10,000slpm Gas is respectively 96% and 89% by total heat transfer percents of heat transfer are caused as bearing gas (gap length is 75 μm).At it In the embodiment that he considers, applicant have determined that, for every square metre of glass surface area, the conduction heating that is discussed herein Area (all hot-zones 310 as discussed in this article) uses helium as bearing gas under the helium flow velocity of 100slpm and 10,000slpm Body (gap length is 700 μm) is respectively 74% and 46% by total heat transfer percents of heat transfer are caused.In specific embodiment party In case, glass material of the heat transfer percentage based on the Tg with 680 DEG C discussed here.

In hot-zone, gas bearing 312 to the heat conduction of sheet glass 400a from gas bearing 312 by heating sheet glass 400a Such embodiment in, gas bearing 312 is configured to not only support sheet glass 400a but also promotes heat conduction.In specific embodiment In, gas bearing 312 is configured to have enough thermal masses will pass through from hot-zone gas bearing 312 to sheet glass 400a's Conduction carrys out delivery of heat, at the same time can deliver enough gas to support sheet glass 200.In some such embodiments In, the amount of the gas bearing 312 occupied by gas delivery aperture is relatively small so that is used for the hot-zone gas bearing of delivery of heat Quantity of material present in 312 increases or maximizes.In a particular embodiment, gas bearing aperture in hot-zone occupies opposite bearing table The surface area of spherical bearing 312 is less than 10%, is particularly less than 5% and more particularly less than 4%.Specific exemplary In test system, applicant has utilized hot-zone gas bearing 312, wherein the surface area of opposing bearing surfaces bearing 312 3.7% and 0.8% is occupied by gas delivery aperture.In other embodiments, not there is discrete gas delivery aperture, heat Area's gas bearing 312 can be formed by porous bearing material (for example, porous graphite or porous aluminum).In such embodiment, Hole is very small so that can be used for transferring heat to the surface area base of the apparent surface of the hot-zone gas bearing 312 of sheet glass 400a It is 100% in sheet.

Method temperature depends on many factors, including glass composition, thickness of glass, glass property (CTE etc.) and institute Desired enhancing is horizontal.In general, it can be appointing between glass transition temperature and Littleton softening point to start method temperature What is worth, or even higher in some embodiments.For example, for SLG, sheet glass 400a is heated to by system 300 About 640 DEG C of (for example, add deduct 1%) is to the temperature between about 730 DEG C or about 690 DEG C to about 730 DEG C.In some embodiments In, sheet glass 400a is heated to certain temperature by system 300：From 620 DEG C to about 800 DEG C of about (for example, add deduct 1%), about 640 DEG C to about 770 DEG C, about 660 DEG C to about 750 DEG C, about 680 DEG C to about 750 DEG C, about 690 DEG C to about 740 DEG C or about 690 DEG C to about 730℃。

Sheet glass 400a is heated to its desired beginning method temperature (for example, being higher than glass transition temperature), and Then it is moved to cold-zone 330 from hot-zone 310 using any suitable means.In some embodiments, by sheet glass 400a is moved to cold-zone 330 from hot-zone 310 and can be completed by following：Such as entire component is inclined such that effect by (1) Gravity on the glass sheet compels to make it move to cold-zone, and (2) block the air-flow of the leftmost side outlet from hot-zone 310 (in this reality Apply closed side in scheme), thus force the rightmost side outlet from all gas that all gas bearing is sent out from cold-zone to be arranged Go out, to cause fluid force being applied on sheet glass 400a and cause to be moved into cold-zone 330, or (3) by (1) and (2) combination.

Transition bearing pumping chamber 328 can supply gas to transition gas bearing 320.The surface of transition gas bearing 320 The solid material thickness at rear can be it is relatively thin, have low thermal mass and/or low heat conductivity, to allow from hot-zone 310 to The heat transfer of cold-zone 330 is reduced.Transition gas bearing 320 may be used as the thermal break between the areas Liang Ge 310 and 330 or transition, And it can be used for being transitioned into downwards the small―gap suture 336 of cold-zone 330 from the larger gap 316 of hot-zone.In addition, transition gas bearing 320 low thermal mass and/or low heat conductivity limitation heat output and therefore limitation sheet glass 400a are by transition gas bearing The cooling being subjected to when 320.

Once sheet glass (cold-zone) 400b moves into cold-zone 330 and enters in the 330a of channel, then pass through mechanical stop Block or any other suitable blocking mechanism (being illustrated as stopping door 341) prevent it from leaving right-side outlet.Once sheet glass 400b The center of being cooled sufficiently that have been subjected to glass transition (for example, in the case of the SLG of 1mm thickness, to being below about 490 DEG C, Correspond to about 325 DEG C at surface in the example), then stopping door 341 can move, to unlock cold-zone channel 330a, and Then sheet glass 400b can be removed from system 300.If desired, sheet glass 400b can be stayed in cold before the removal Until some temperature close to room temperature in area 330.

As described above, in hot-zone 310, sheet glass 400 is heated to above the temperature of the glass transition temperature of sheet glass Degree.In the embodiment shown in Figure 22, cold-zone 330 includes channel 330a, is used to receive the glass of heating by the 330b that is open Glass piece 400b, transmission sheet glass 400b and the cooled glass sheets 400b in cold-zone.In one or more embodiments, lead to Road 330a includes conveyer system, and the conveyer system may include gas bearing, roller, conveyer belt or be used for physical transportation glass Other devices that glass piece passes through cold-zone.As shown in figure 22, cold-zone 330 includes the gas bearing 332 supplied by pumping chamber 338, institute Pumping chamber 338 and hot-zone pumping chamber 318 and transition pumping chamber 328 is stated to separate.

As shown in figure 22, cold-zone 330 includes one or more radiators 331 of adjacent channel 330a settings.Utilizing two In the case of a radiator, such radiator can be arranged on the opposite side of channel 330a, the faces each other across path clearance 330a It is right.In some embodiments, radiator includes the multiple aperture 331a for the part to form gas bearing 332, and cold-zone The surface of 330 cold air bearing 332 is used as two spreader surfaces.Due to relatively low air velocity in the 330a of channel and logical The reduced size of road gap 330a, thus in cold-zone 330 mainly by since sheet glass, across gap and to solid dissipate Heat transfer in hot device 331 carrys out cooled glass sheets 400b, and sheet glass 400b does not contact spreader surface.

In some embodiments, radiator and/or its surface can be segmented.As described above, in some embodiments In, radiator can be porous, and in such embodiment, and the gas of gas bearing 332 is used for by its delivering Aperture is the hole of porous radiator.Multiple aperture 332b, gas source and path clearance 330a can be in fluid communication.In some implementations In scheme, gas flows through hole mouth 331a to form air cushion, layer or bearing in path clearance 330a.Some embodiments Air cushion prevent sheet glass 400b contact radiator 331 surface.Gas also serves as sheet glass 400b therethrough and passes through conduction It cools down rather than passes through the gas that convection current cools down.

Because cooling is substantially to be occurred by the solid across gap to solid conductive heat, it is possible that needing to solve right Flow the problem of being not present in prevailing cooling.For example, for the big fine sheet of tempering, (1) can quickly introduce sheet material In cold-zone, optionally grasped with quasi-continuous pattern with speed more higher than the speed used in the quenching based on convection current, and/or (2) Make the method, wherein multiple sheet materials are heated and cool down one by one in continuous flow, wherein the sky between the sheet material Between very little, and wherein radiator is therefore actively cooled so that it reaches thermal balance, so that the leading edge and rear of big sheet material With similar thermal history.

In some embodiments, the gas cooling radiator of aperture 331a is flowed through.In some embodiments, hole is flowed through Mouthful gas contribute to since glass, across gap, to the heat conduction in radiator, and also cooling radiator 331.At some In the case of, radiator 331 can be cooled down using individual gas or fluid.For example, radiator 331 may include cold for making But fluid flows through wherein to cool down the channel 334 of radiator 331, as being more fully described relative to Figure 23.Channel 334 can be with It is closed.

Using two radiator (that is, the first radiator and second radiators), one or more can be used A gas source to provide gas to path clearance 330a.Gas source may include mutually the same gas or different gas.Cause This, path clearance 330a may include a kind of gas, the mixture of gas from gas with various source or identical gas source. Example gases include air, nitrogen, carbon dioxide, helium or other inert gases, hydrogen nd various combinations thereof.Exemplary In embodiment, the gas for being delivered to path clearance 330a is vapor.When gas will start conductively cooled glass sheets Before 400b, gas can be described when entering channel 330a by its thermal conductivity.In some cases, possessed by gas Thermal conductivity can be about (for example, add deduct ± 1%) 0.02W/ (mK) or bigger, about 0.025W/ (mK) or bigger, about 0.03W/ (mK) or bigger, about 0.035W/ (mK) or bigger, about 0.04W/ (mK) or bigger, about 0.045W/ (mK) Or bigger, about 0.05W/ (mK) or bigger, about 0.06W/ (mK) or bigger, about 0.07W/ (mK) or bigger, about 0.08W/ (mK) or bigger, about 0.09W/ (mK) or bigger, about 0.1W/ (mK) or bigger, about 0.15W/ (mK) or Bigger or about 0.2W/ (mK) or bigger.

Method described herein and system allow high heat transfer rate, as discussed above, even if the high heat transfer rate exists Also allow to form the temperature difference of enhancing degree in very thin sheet glass.In the case where using air as gas, in sheet glass There are gaps between radiator, and only by conduction, rate of heat transfer may be up to 350,450,550,650,750,1000 and 1200kW/m²Or more.Using helium or hydrogen, 5000kW/m may be implemented²Or more rate of heat transfer. In another embodiment, can fluent material be delivered to path clearance 330a to replace gas.In some such implementations In scheme, the liquid delivered is the liquid for not undergoing phase transition or decomposing at the high-end place for the treatment of temperature, such as fuse salt, melting Metal etc..

The radiator 331 of one or more embodiments can be static, or can be moveable logical to change The thickness of road gap 330a.The orientation of the thickness of sheet glass 400b can be about 0.4 times of the thickness of path clearance 300a to about 0.6 times, the thickness of the path clearance 300a is defined as the apparent surface of radiator 331 (for example, being in the arrangement of Figure 22 The distance between the upper and lower surface of radiator 331).In some cases, path clearance is configured to have enough Thickness so that cool down by conduction rather than by convection current the sheet glass of heating.

In some embodiments, thickness possessed by path clearance can make when sheet glass 400b be transmitted through it is logical The distance between the main surface of road 330a or when in the 330a of channel, sheet glass 400b and spreader surface (for example, beg for above The gap size of opinion) it is about 100 μm of (for example, add deduct 1%) or bigger (for example, in following range：About 100 μm to about 200 μm, about 100 μm to about 190 μm, about 100 μm to about 180 μm, about 100 μm to about 170 μm, about 100 μm to about 160 μm, about 100 μ M to about 150 μm, about 110 μm to about 200 μm, about 120 μm to about 200 μm, about 130 μm to about 200 μm or about 140 μm to about 200μm).In some embodiments, thickness possessed by path clearance can make when sheet glass 400b be transmitted through it is logical When road, the distance between sheet glass and spreader surface (one or more gaps 336) are about 100 μm of (for example, add deduct 1%) Or smaller is (for example, in following range：About 10 μm to about 100 μm, about 20 μm to about 100 μm, about 30 μm to about 100 μm, about 40 μm to about 100 μm, about 10 μm to about 90 μm, about 10 μm to about 80 μm, about 10 μm to about 70 μm, about 10 μm to about 60 μm or about 10 μm to about 50 μm).The overall thickness of path clearance 330a depends on the thickness of sheet glass 400b, but can usually be characterized as being scattered The thickness of the extraordinarily upper glass plate of the 2 of distance between hot device surface and sheet glass.In some embodiments, sheet glass and radiator The distance between or gap 336 may be unequal.In such embodiment, the overall thickness of path clearance 330a can be characterized The thickness of sheet glass is added for the summation of the distance between sheet glass and each spreader surface.

In some cases, the overall thickness of path clearance can be less than about 2500 μm of (for example, add deduct 1%) (for example, In following range：About 120 μm to about 2500 μm, about 150 μm to about 2500 μm, about 200 μm to about 2500 μm, about 300 μm to about 2500 μm, about 400 μm to about 2500 μm, about 500 μm to about 2500 μm, about 600 μm to about 2500 μm, about 700 μm to about 2500 μ M, about 800 μm to about 2500 μm, about 900 μm to about 2500 μm, about 1000 μm to about 2500 μm, about 120 μm to about 2250 μm, about 120 μm to about 2000 μm, about 120 μm to about 1800 μm, about 120 μm to about 1600 μm, about 120 μm to about 1500 μm, about 120 μm To about 1400 μm, about 120 μm to about 1300 μm, about 120 μm to about 1200 μm or about 120 μm to about 1000 μm).At some In the case of, the overall thickness of path clearance can be about 2500 μm or more (for example, in following range：About 2500 μm to about 10, 000 μm, about 2500 μm to about 9,000 μm, about 2500 μm to about 8,000 μm, about 2500 μm to about 7,000 μm, about 2500 μm extremely About 6,000 μm, about 2500 μm to about 5,000 μm, about 2500 μm to about 4,000 μm, about 2750 μm to about 10,000 μm, about 3000 μm to about 10,000 μm, about 3500 μm to about 10,000 μm, about 4000 μm to about 10,000 μm, about 4500 μm to about 10, 000 μm or about 5000 μm to about 10,000 μm).

Aperture 331a in radiator 331 can be positioned so that perpendicular to spreader surface or may be with 20 degree or smaller Angle positioning, such as with the vertical line of spreader surface at a distance of about 15 degree of (for example, add deduct 1%) or smaller, about 10 degree or more Small or about 5 degree or smaller.

In some embodiments, the material at radiator (cold bearing 332) surface rear can be with high heat transfer rate Any suitable material, including metal (for example, stainless steel, copper, aluminium), ceramics, carbon etc..As shown in figure 22, with transition bearing 320 The material at surface rear compare, which can be relatively thick so that radiator can easily receive relatively large amount Thermal energy.In an exemplary embodiment, the material of radiator 331 is stainless steel.

Figure 23 is the section view aperspective cross section of the equipment similar with the equipment of Figure 22, although inverting from right to left, and is also wrapped Include the loading/unloading area 340 on the side of cold-zone 330 of system 300 comprising loading/unloading gas bearing 342 and disposed thereon Sheet glass 400c.Moreover, the equipment of Figure 23 uses close interchannel in hot-zone 310, transition bearing 320 and cold-zone 330 Gap (not shown).

Illustration in Figure 23 shows the alternate embodiment of cold-zone gas bearing 332a, wherein by being supplied in gas bearing It is actively cooled gas bearing 322a, the wherein surface of supply hole supply bearing 322a to the coolant channel 334 between hole 333 In hole.Cooling duct 334 is limited between radiator section 333b, and the radiator section 333b is assembled together with shape At radiator 331 and its in face of the surface of sheet glass 400b.

Cooling duct 334 can be oriented the table very close to radiator 331 in the solid material of gas bearing 332 Face, wherein in radiator/air bearing surface and coolant channel 334 closest to existing solid bearing between marginal surface The region of material has with coolant channel 334 closest to the identical width of marginal surface.Therefore, in some embodiments In, in the solid material of coolant channel 334 and the 331/ gas bearing 332a of radiator between the surface of glass 400b In do not have section reduce region.This is different from typical convection gas cooling equipment, because high gas flow rate is required in gas Significant space is arranged so that air-flow escapes in the intermediate of nozzle array.Using active cooling in the case of, relative near The solid material of glass surface, 331/ gas bearing 332a of radiator subtract in the solid material that gas nozzle designs with section Small region.The region that section reduces is conventionally positioned between the sheet glass in active cooling fluid and processing, so as to for from piece A large amount of heat gas that material returns provide high volume path.

Figure 24 shows another alternate embodiment again of cold-zone gas bearing 332, the cold-zone with the illustration of Figure 23 Gas bearing is similar.In this embodiment, in gas bearing supply member 335 and gas comprising gas bearing supply hole 333 Body forms coolant channel 334 between carrying surface member 337a, this provides the sheet glass in face of the surface of gas bearing 332 400b.Figure 25 is shown and another alternative cold-zone gas bearing 332c, has the structure similar with the embodiment of Figure 24, But there is porous member 339 between bearing board member 337b and sheet glass 400b so that 339 forming face of porous member is to glass The surface of glass piece 400b.

It should be understood that in various embodiments, can use or operate the glass described herein in regard to Figure 16-26 Enhancement Method and system are to form the feature with any glassware embodiment being discussed herein, characteristic, size, physical Any combination of glass or glass and ceramic product (such as sheet glass 500) of matter etc..

Be subjected to hot Enhancement Method as described herein sheet glass can by be subjected to ion exchange be further processed with Further enhance its intensity.In the embodiment of some such considerations, to the surface of hot-reinforced glass as described herein into Row ion exchange can make above-mentioned compression increase at least 20MPa, such as at least 50MPa, such as at least 70MPa, such as at least 80MPa, such as at least 100MPa, such as at least 150MPa, such as at least 200MPa, such as at least 300MPa, such as at least 400MPa, such as at least 500MPa, such as at least 600Mpa and/or be not more than 1GPa.

For thermal conditioning and/or the system and method for heating sheet glass

Other than heat enhances thin glass sheet, method described herein and system can also be used for additional thermal conditioning method. Although specifically discussing cooling herein, the system and method can be used for transferring heat to glass by transmission method In piece.Therefore, the additional embodiment of disclosed method includes the gas by conduction rather than is heated by convection current. This process or method 700 are shown in the flow chart of Figure 26.

Method 700 includes two key steps.First step (step 710) includes providing the system at least one surface Product (such as sheet glass).Second step (step 720) includes that a part for product surface is heated or cooled, and up to and includes product Whole surface.As shown in subdivision 720a, by conduction rather than convection current (passing through the gas of make a return journey heat source or heat sink source) Step 720 is executed, and in subdivision 720b fully executes step 720 to complete to product or product surface part Thermal conditioning, and (450kW/m is at least with high heat transfer rate for the area of part in subdivision 720b²) execute step The conduction of 720 cooling/heating.

For example, product can be thermally regulated-be heated or cooled-it is (more by cooling or heating product surface a part Reach and include the whole surface (part with area) of product), by conduction rather than by convection current, pass through radiator of making a return journey Or heat source gas rather than the conduction is reconciled by the contact of solid to solid, it is sufficient to complete product or product surface portion Point thermal conditioning, and during at least some times being heated or cooled at least 250,450,550,650,750,800, 900,1000,1100,1200,1500,2000,3000,4000 or even 5000 or more Kw/ square metres of rates execute biography It leads.

Other than tempering, the high power delivery rate permission provided by the system and method being discussed herein is all types of Heat treatment is adjusted, and includes edge enhancing, ceramics, glass or the other materials of the heating and cooling, glass during tempering Fire or be sintered etc..Further, since mainly being extracted by conducting or delivery of heat, therefore the heat in processed product is gone through History and heat distribution provide stringent control, while holding surface smoothness and quality.Therefore, in the another aspect of the disclosure, To in processed product thermal history and heat distribution stringent control is provided because mainly extracting or delivering heat by conducting Amount, also holding surface smoothness and quality.Therefore, it is possible to use the system and method for the disclosure, so as in thickness direction and piece Intentionally change the stress distribution for carrying out self-strengthening method in the following manner on direction where material plane：Change gap, change Become radiator/source materials, change radiator/heat source temperature, change admixture of gas-and it is all these can be by piece At the same time material the positioning along sheet path, the positioning across sheet path or may become when moving not only by positioning Change (for most number variable).

Including the device of reinforcing glass piece, product and structure

The reinforcing glass or glass and ceramic product and sheet material being discussed herein are in broad range of product, device, product, structure Have in and has been widely used.

With reference to figure 27, structure 1010 (building, house, vehicles etc.) include in window, wall part (for example, Surface), the glass or glass and ceramic product 1012 of the forms such as separator.It, can reinforcing glass or pottery in expected embodiment Ceramic products 1012, so that glass or ceramic 1012 have negative tensile stress on the surface thereof or nearby, this is by its inside Positive tensile stress is balanced, as disclosed herein.In addition, glass or glass and ceramic product 1012 can have a kind of composition, It passes through with the relatively high dioxide-containing silica (titanium dioxide of such as at least 70 weight % (such as at least 75 weight %) Silicon), it can tolerate chemical substance that may be present and/or corrosion in outdoor environment.

According to exemplary implementation scheme, glass or glass and ceramic product 1012 have the main surface vertical with its thickness (big Body piece 500 shown in Figure 4), wherein relative to glass or glass for other application (for example, lens, battery component etc.) Glass ceramic, main surface have large area (for example, at least 5cm², at least 9cm², at least 15cm², at least 50cm², at least 250cm²).In the embodiment of consideration, when glass or glass and ceramic product 1012 have thickness as disclosed herein, The wavelength that about 300nm to about 800nm is directed to by the total light transmission of glass or glass and ceramic product 1012 is at least about 50% (for example, at least 65%, at least 75%), such as following thickness of the thickness：Less than 5cm, less than 3cm, less than 2cm, be less than 1.75cm, less than 1.5cm, less than 1cm, less than 5mm, less than 3mm, less than 2mm, less than 1.75mm, less than 1.5mm, be less than 1mm, it is less than 0.8mm, is less than 0.6mm, is less than 0.5mm, is less than 0.4mm, is less than 0.2mm, and/or at least 10 microns, such as extremely It is 50 microns few.

The lower thickness of glass or glass and ceramic product 1012 can not damage glass or glass and ceramic product 1012 is being built It builds, automobile or relative to the function in the other application of conventional articles, because of the glass provided by invention disclosed herein method Or the high-caliber intensity of glass and ceramic product 1012.Thin glass or glass and ceramic product 1012 may be in such building, automobiles Or be particularly useful in other application, because glass or glass and ceramic product 1012 can be lighter than this conventional based article, to Reduce corresponding integrally-built weight.As a result can be higher fuel efficiency for automobile.For building, As a result can be firmer or less resource-intensive structure.In the embodiment of other imaginations, glass disclosed herein Or glass and ceramic product can have more by a small margin, the region of larger thickness, transmit less light, and/or can be used for different Using such as about Figure 27-30 those disclosed applications.

With reference to figure 28, surface 1110 includes glass or glass and ceramic product 1112, manufactured as disclosed herein and/or Any combinations with the stress distribution, structure and/or the physical property that are discussed herein, and as work top and/or as aobvious Show a part for device.In some embodiments, about 800nm is directed to by the total transmittance of glass or glass and ceramic product 1012 Infrared wavelength to about 1500nm is at least about 30% (for example, at least 50%), consequently facilitating using surface 1110 as kitchen range. In some embodiments, glass or glass and ceramic product 1112 have following coefficient of thermal expansion (CTE)：About 10x10^-7℃^-1Extremely About 140x10^-7℃^-1, about 20x10^-7℃^-1To about 120x10^-7℃^-1, about 30x10^-7℃^-1To about 100x10^-7℃^-1, about 40x10^-7 ℃^-1To about 100x10^-7℃^-1, about 50x10^-7℃^-1To about 100x10^-7℃^-1Or about 60x10^-7℃^-1To about 120x10^-7℃^-1。 In various embodiments, the method is preferably suited for the glass composition with medium supreme CTE.By being described herein The exemplary glass of method works fine include alkali alumino-silicates, such asGlass, boron aluminium Silicate and soda-lime glass.In some embodiments, CTE possessed by the glass used be more than 40, be more than 50, be more than 60, More than 70, more than 80 or more than 90x10^-7/℃.As disclosed herein, some such CTE are for hot tempering as described herein For may be especially low, wherein the degree of negative tensile stress is not more than 50MPa and/or at least 10MPa.

With reference to figure 29, device 1210 is (for example, handheld computer, tablet computer, portable computer, cellular phone, electricity Depending on machine, display board etc.) include one or more glass or glass and ceramic product 1212,1214,1216, as being disclosed herein Manufacture and/or the arbitrary combination with stress distribution as disclosed herein, structure and/or physical property, and further include electronics Component 1218 and shell 1220.In the embodiment of consideration, shell 1220 can be or including glass as disclosed herein Or glass and ceramic product.In the embodiment of imagination, the substrate 1222 for electronic unit 1218 can be as institute is public herein The glass or glass and ceramic product opened.

In some embodiments, glass or glass and ceramic product 1212,1214 may be used as front plane substrate and backboard lining Bottom, and glass or glass and ceramic product 1216 may be used as the cover glass in device 1210.According to an exemplary embodiment party Case, the glass or glass and ceramic product 1216 of device 1210 are alkali alumina silicate glasses.This composition can allow by such as Hot tempering disclosed herein comes reinforcing glass or glass and ceramic product 1216, and can additionally be increased by ion exchange By force, at its surface or be provided about the negative tensile stress (for example, at least 200MPa, at least 250MPa) of special high level. In other embodiments, glass or glass and ceramic product 1216 may include sodium carbonate, calcium oxide, miemite, titanium dioxide Silicon (for example, at least 70 weight %), aluminium oxide and/or other components；And it can be increased by invention disclosed herein method By force.Glass or glass and ceramic product 1216 can be extremely thin or otherwise construct, such as with as disclosed herein Any size.

Referring now to Figure 30, according to method disclosed herein manufacture and/or with stress distribution as disclosed herein, knot Any combination of glass or glass and ceramic product 1310 of structure and/or physical property have curvature and/or variable cross section dimension D. This based article can have thickness disclosed herein, such as the average value of dimension D or the maximum value of dimension D.Although glass or glass pottery Ceramic products 1310 are illustrated as the sheet material of bending, but can enhance other shapes by method disclosed herein, such as more multiple Miscellaneous shape.In the embodiment of imagination, glass or glass and ceramic product 1310 may be used as the window of automobile (for example, day Window), lens, container or be used for other application.In one embodiment, from sheet material glass-cutting or glass and ceramic product 1310, the sheet material is heat enhancing before being cut.In another embodiment, before the heat treatment from glass material piece Glass-cutting or glass and ceramic product 1310, and hot-reinforced glass or glass ceramics as discussed herein after dicing Product 1310.

In various embodiments, according to method disclosed herein manufacture and/or with disclosed herein any The glass material of the stress distribution of combination, structure and/or physical property can be used to form (such as in many vehicle glass side lamps Use) at least a piece of glass-polymer-interlayer-glass laminated material.The larger and thinner laminated material of intensity can be produced, To mitigate weight and cost-effective, and improve fuel efficiency.It is desirable that heat enhancing fine sheet can by clod wash (referring generally to Figure 30) and it is in turn laminated to the relatively heavy sheet glass to be formed, to provide simple and reliable manufacturing method without fine sheet Any hot forming/molding.

The glass and glass ceramic material of hot-reinforced glass piece

The system and method discussed can be used for thermal conditioning, enhancing and/or the various glass of tempering and/or ceramic material Material.

Method described herein and system can be usually used together with substantially any glass composition, and some embodiment party Case can be used together with glass laminates, glass ceramics and/or ceramics.In various embodiments, the method can be with tool There is the glass composition of high CTE to be used together.In embodiments, the glass bag enhanced by method described herein and system Include alkali aluminosilicate (such as'sGlass), SLG, without sodium or alkali-free glass etc..In some embodiments In, CTE is more than 40x10 possessed by the glass by the method and system enhancing being discussed herein^-7/ DEG C, be more than 50x10^-7/℃、 More than 60x10^-7/ DEG C, be more than 70x10^-7/ DEG C, be more than 80x10^-7/ DEG C or be more than 90x10^-7/℃。

In some applications and embodiment, pass through glass (such as sheet glass for the method and system enhancing being discussed herein 500) there can be the composition for being configured for chemical durability.In some such embodiments, composition includes by weight At least 70% silica of gauge, and/or by weight at least 10% sodium oxide molybdena, and/or by weight at least 7% oxygen Change calcium.Conventional articles with such composition are likely difficult to by chemical tempering to deeper depth, and/or are directed to lower thickness Be likely difficult to (if not can not possibly if) come by conventional method hot tempering to enough size negative surface tensile stress, such as Due to the fragility and power of conventional method.However, in the embodiment of consideration, invention disclosed herein method allows have this The reinforcing glass or glass and ceramic product or sheet material (such as sheet glass 500) of kind composition, wherein bearing tensile stress from first surface Corresponding reinforcing glass or glass are extended to at least one of second surface (for example, surface 510, surface 520 of sheet glass 500) In glass potsherd and reach certain distance, the distance is at least the 10% of reinforcing glass or the thickness of glass ceramics piece, such as Thickness at least 12%, the 15% of thickness, the 18% of thickness, thickness 20%.

In some embodiments, the glass or glass ceramics piece and product enhanced as discussed herein has in glass The one or more coatings being placed on before the enhancing of glass piece heat on glass.The method being discussed herein can be used for produce tool there are one or The reinforcing glass piece of multiple coatings, and in some such embodiments, coating is placed on glass before heat enhances And the influence of the not heated Enhancement Method of coating.The specific coating being advantageously stored on the sheet glass of the disclosure includes that low E is applied Layer, reflectance coating, anti-reflection coating, anti-fingerprint coating, edge filter, pyrolytic coating etc..

According to exemplary implementation scheme, glass discussed in this article or glass ceramics piece or product (such as shown in Figure 29 1214) product 1212 of device 1210 is Boroalumino silicate glasses.In some embodiments, the glass or glass being discussed herein Glass potsherd or product (such as product 1212,1214 of device 1210 shown in Figure 29) are typically non-alkali glass, but still are had There are stress distribution and structure as disclosed herein.This composition to reduce the relaxation degree of glass, to promote transistor with Its coupling.In some embodiments, the sheet glass/product being discussed herein is flexible glass piece.In other embodiments, Sheet glass/product described herein includes the laminates of two or more sheet glass.

In the embodiment of some considerations, pass through glass (such as sheet glass for the method and system enhancing being discussed herein 500) it may include amorphous substrate, crystalline substrates or combinations thereof, such as glass ceramic substrate.By the method that is discussed herein and The glass (such as sheet glass 500) of system enhancing may include alkali alumino-silicates glass, containing alkali borosilicate glass, alkaline aluminium Phosphate glass or alkaline aluminium borosilicate glass.In one or more embodiments, by the method being discussed herein and it is The glass (such as sheet glass 500) of system enhancing may include having with molar percentage in its part without ion exchange (mol%) it is the glass of the composition of unit, the composition includes：About (for example, add deduct 1%) 40mol% is to about SiO within the scope of 80mol%₂, Al within the scope of about 10mol% to about 30mol%₂O₃, about 0mol% to about 10mol% ranges Interior B₂O₃, R within the scope of about 0mol% to about 20mol%₂RO within the scope of O, and/or about 0mol% to about 15mol%. Some consider embodiment in, composition may include it is following either or both：Within the scope of about 0mol% to about 5mol% ZrO₂P within the scope of about 0mol% to about 15mol%₂O₅.In the embodiment of some considerations, TiO₂It may be with about 0mol% to about 2mol% exists.

In the embodiment of some considerations, the combination of reinforcing glass or glass ceramics piece or product for being discussed herein Object can be with 0-2mol% selected from including below group of at least one fining agent come dispensing：Na₂SO₄、NaCl、NaF、NaBr、 K₂SO₄, KCl, KF, KBr and SnO₂.Can also include in following range according to the glass composition of one or more embodiments SnO₂：About 0mol% to about 2mol%, about 0mol% are to about 1mol%, about 0.1mol% to about 2mol%, about 0.1mol% To about 1mol% or about 1mol% to about 2mol%.In some embodiments, reinforcing glass disclosed herein or glass ceramics The glass composition of piece 500 can be substantially free of AS₂O₃And/or Sb₂O₃。

In the embodiment of consideration, the reinforcing glass or glass ceramics piece or product that are discussed herein may include by from The alkali alumino-silicates glass composition or alkaline composition of aluminum boron silicate glass that sub- exchange method further enhances.It is a kind of Exemplary glass compositions include SiO₂、B₂O₃And Na₂O, wherein (SiO₂+B₂O₃) >=66mol% and/or Na₂O >=9mol%. In one embodiment, glass composition includes at least aluminium oxide of 6 weight %.In another embodiment, it is discussed herein Reinforcing glass or glass ceramics piece or product may include the glass composition for having one or more alkaline earth oxides, So that the content of alkaline earth oxide is at least 5 weight %.In some embodiments, suitable glass composition also includes K₂O, at least one of MgO and CaO.In a specific embodiment, the reinforcing glass for being discussed herein or glass pottery The glass composition of tile or product may include the SiO of 61-75mol%₂；The Al of 7-15mol%₂O₃；0-12mol%'s B₂O₃；The Na of 9-21mol%₂O；The K of 0-4mol%₂O；The MgO of 0-7mol%；And/or the CaO of 0-3mol%.

Suitable for reinforcing glass or another of glass ceramics piece or product exemplary glass compositions packet being discussed herein It includes：The SiO of 60-70mol%₂；The Al of 6-14mol%₂O₃；The B of 0-15mol%₂O₃；The Li of 0-15mol%₂O；0-20mol% Na₂O；0-10mol%K₂O；The MgO of 0-8mol%；The CaO of 0-10mol%；The ZrO of 0-5mol%₂；0-1mol%'s SnO₂；The CeO of 0-1mol%₂；Al less than 50ppm₂O₃；And the Sb less than 50ppm₂O₃；Wherein 12mol%≤(Li₂O+ Na₂O+K₂O)≤20mol% and/or 0mol%≤(MgO+CaO)≤10mol%.Suitable for the reinforcing glass or glass being discussed herein Another another exemplary glass compositions of glass potsherd or product include：The SiO of 63.5-66.5mol%₂；8-12mol%'s Al₂O₃；The B of 0-3mol%₂O₃；The Li of 0-5mol%₂O；The Na of 8-18mol%₂O；0-5mol%K₂O；The MgO of 1-7mol%； The CaO of 0-2.5mol%；The ZrO of 0-3mol%₂；The SnO of 0.05-0.25mol%₂；The CeO of 0.05-0.5mol%₂；It is less than The Al of 50ppm₂O₃；And the Sb less than 50ppm₂O₃；Wherein 14mol%≤(Li₂O+Na₂O+K₂O)≤18mol% and/or 2mol%≤(MgO+CaO)≤7mol%.

In the embodiment of specific consideration, the alkali suitable for the reinforcing glass or glass ceramics piece or product that are discussed herein Property alumina silicate glass composition includes：Aluminium oxide, at least one alkali metal, and be more than in some embodiments The SiO of 50mol%₂, at least 58mol%SiO in other embodiments₂, and at least 60mol% in other embodiments SiO₂, wherein ratio (Al₂O₃+B₂O₃)/∑ dressing agent (i.e. the sum of dressing agent) be more than 1, wherein in the ratio component with Mol% is indicated and dressing agent is alkali metal oxide.In a particular embodiment, this glass composition includes 58- The SiO of 72mol%₂；The Al of 9-17mol%₂O₃；The B of 2-12mol%₂O₃；The Na of 8-16mol%₂O；And/or 0-4mol% K₂O, wherein ratio (Al₂O₃+B₂O₃)/∑ dressing agent (i.e. the sum of dressing agent) is more than 1.In yet another embodiment, enhance Glass or glass ceramics piece 500 may include alkali alumino-silicates glass composition comprising：The SiO of 64-68mol%₂；12- The Na of 16mol%₂O；The Al of 8-12mol%₂O₃；The B of 0-3mol%₂O₃；The K of 2-5mol%₂O；The MgO of 4-6mol%；And The CaO of 0-5mol%, wherein：66mol%≤SiO₂+B₂O₃+ CaO≤69mol%；Na₂O+K₂O+B₂O₃+MgO+CaO+SrO> 10mol%；5mol%≤MgO+CaO+SrO≤8mol%；(Na₂O+B₂O₃)-Al₂O₃≤ 2mol%；2mol%≤Na₂O-Al₂O₃ ≤ 6mol%；And 4mol%≤(Na₂O+K₂O)-Al₂O₃≤ 10mol%.In an alternative embodiment, the increasing being discussed herein Strong glass or glass ceramics piece or product may include alkali alumino-silicates glass composition, it includes：2mol%'s or more Al₂O₃And/or ZrO₂Or the Al of 4mol% or more₂O₃And/or ZrO₂。

In the embodiment of consideration, the suitable glasses of reinforcing glass or glass ceramics piece or product for being discussed herein The example of ceramics may include Li₂O-Al₂O₃-SiO₂System (i.e. LAS systems) glass ceramics, MgO-Al₂O₃-SiO₂System is (i.e. MAS systems) glass ceramics, and/or include the glass ceramics of leading crystalline phase, the leading crystalline phase includes β-quartz solid solution, β- Spodumene ss, cordierite and lithium disilicate.The feature of the reinforcing glass or glass ceramics piece or product that are discussed herein can be it Generation type.For example, the reinforcing glass or glass ceramics piece or product that are discussed herein may be characterized as can float forming (that is, logical Cross float glass production process formation), can draw downwards and particularly, fusible forming or can kerve (that is, It is formed by the downward method of such as fusion draw method or slot drawn method).

The reinforcing glass or glass ceramics piece of float forming or the feature of product can be smooth surface and uniform thickness, and And it is made by being placed on melten glass float glass process on molten metal (being usually tin) bed.In illustrative methods, it is supplied to Melten glass or glass ceramics on molten tin bed surface form float glass or glass ceramics band.When glass tape is along molten tin bath stream When dynamic, temperature is gradually reduced, until glass or glass ceramics band are solidified into and can be promoted from tin to the solid glass or glass on roller Glass ceramic.Once leaving molten tin bath, glass or glass and ceramic product can be further cooled and be annealed to reduce internal answer Power.In the case where glass or glass and ceramic product are glass ceramics, pass through the glassware of float glass production process formation Ceramming processes can be subjected to, one or more crystalline phases are generated by the ceramming processes.

The glass or glass and ceramic product of downward uniform thickness of the drawing method production with relatively primitive surface.Because of glass The average bending strength of glass or glass and ceramic product by surface defect amount and size Control, so original with minimal-contact Surface has higher initial strength.(such as change when then this high strength glass or glass and ceramic product be further augmented Learn ground) when, gained intensity can be higher than with the intensity ground with the glass of polished surface or glass and ceramic product.It pulls down The glass or glass and ceramic product of system can be drawn into the thickness less than about 2mm.In addition, the glass or glass ceramics that draw downwards There is product very flat, smooth surface, the surface can be used for its final application without expensive grinding and polishing. In the case that glass or glass and ceramic product are glass ceramics, the glass or glass and ceramic product that are formed by downward drawing method Ceramming processes can be subjected to, one or more crystalline phases are generated by the ceramming processes.

For example, fusion drawing method uses the drawing slot with the channel for receiving molten raw.In channel two On side, the weir in channel is along passage length in open-top.When channel is full of melted material, melten glass overflows weir.Due to Gravity, melten glass flow down the glass-film flowed as two along the outer surface for drawing slot.Draw these appearances of slot It downwards and extends internally so that they are drawing the edge combination below slot.The glass-film of two flowings is at this edge Place is combined to form the glassware individually flowed.The advantages of merging drawing method is, because of two flowed on a passage Glass-film fuses together, so the outer surface of obtained glassware is not contacted with any part of equipment.Therefore, it melts Melt the surface nature of the glassware of drawing is not influenced by this contact.It is glass ceramics in glass or glass and ceramic product In the case of, the glass or glass and ceramic product that are formed by melting method can be subjected to ceramming processes, pass through the ceramic Method generates one or more crystalline phases.

Slot drawn method is different from fusion draw method.In slot drawn method, fused raw material glass is supplied to Draw slot.Draw the nozzle that the bottom of slot has opening groove and extends along slot length.Melten glass is flowed through slit/spray Mouth and as continuous glassware downwards draw and enter annealing region.It is glass ceramics in glass or glass and ceramic product In the case of, the glassware formed by slot drawn method can be subjected to ceramming processes, be produced by the ceramming processes Raw one or more crystalline phases.

In some embodiments, glassware can use such as U.S. Patent number 8,713,972, U.S. Patent number 9, 003,835, the thin rolling side described in U.S. Patent Publication No. 2015/0027169 and U.S. Patent Publication No. 20050099618 Method is formed, and the content of the patent application is incorporated herein by reference in their entirety.More specifically, glass or glass and ceramic product can To be formed in the following manner：Supply the vertical current of melten glass；With a pair of of forming rolls to the melten glass or glass supplied Ceramic stream is formed, and the roller is maintained at about 500 DEG C or higher or about 600 DEG C or higher surface temperature, to form tool There is the molding glass band for being formed by thickness；Roller is sized with a pair to be sized to being formed by glass tape, the roller is protected It holds in about 400 DEG C or lower surface temperature, is less than the expectation thickness and expectation thickness that are formed by thickness to produce to have The glass tape of consistency being sized.The equipment for being used to form glass tape may include：Supply for supplying melten glass The glass feeder of stream；It is maintained at a pair of of forming rolls of about 500 DEG C or higher surface temperature, the forming rolls is close each other Be adjacent to it is spaced apart, to limit the forming of glass gap between forming rolls, wherein the forming of glass gap is vertically located in The lower section of glass feeder makes between forming rolls the supply of melten glass for receiving the supply stream of melten glass Rheology is thin to form the molding glass band with the thickness formed；And it is maintained at the one of about 400 DEG C or lower surface temperature To being sized roller, the roller that is sized is spaced apart closely adjacent one anotherly, is sized to limit glass between being sized roller Gap, wherein glass are sized gap and are vertically located in the lower section of forming rolls for receiving molding glass band and making molding glass With thinning, to generate the glass tape being sized with expectation thickness and expectation thickness consistency.

In some cases, when the viscosity of glass does not allow using melting or slot drawn method, thin roll can be used Method processed.For example, when glass shows the liquidus viscosity less than 100kP, glass or glass can be formed using thin rolling Glass ceramic.Glass or glass and ceramic product can be polished or otherwise be handled by acid to be lacked to remove or reduce surface Sunken influence.

In the embodiment of consideration, composition is with side possessed by the glass or glass ceramics piece or product that are discussed herein Surface and it is different.On the side of glass or glass ceramics piece 500, exemplary composition is：The SiO of 69-75 weight %₂、0- The Al of 1.5 weight %₂O₃, 8-12 weight % CaO, 0-0.1 weight % Cl, 0-500ppm Fe, 0-500ppm K, 0.0- The Na of MgO, 12-15 weight % of 4.5 weight %₂O, the SO of 0-0.5 weight %₃, 0-0.5 weight % SnO₂, 0-0.1 weight Measure the TiO of SrO, 0-0.1 weight % of %₂, 0-0.1 weight % ZnO, and/or 0-0.1 weight % ZrO₂.It is being discussed herein Glass or the other side of glass ceramics piece or product on, exemplary composition is：The SiO of 73.16 weight %₂, 0.076 weight Measure the Al of %₂O₃, the CaO of 9.91 weight %, the Cl of 0.014 weight %, 0.1 weight % Fe₂O₃, 0.029 weight % K₂O、 The Na of the MgO of 2.792 weight %, 13.054 weight %₂O, the SO of 0.174 weight %₃, 0.001 weight % SnO₂, 0.01 weight Measure the SrO of %, the TiO of 0.01 weight %₂, 0.002 weight % ZnO, and/or 0.005 weight % ZrO₂。

In the embodiment of other considerations, the composition of the glass or glass ceramics piece or product that are discussed herein includes The SiO of 55-85 weight %₂, 0-30 weight % Al₂O₃, 0-20 weight % B₂O₃, 0-25 weight % Na₂O, 0-20 weights Measure the K of CaO, 0-20 weight % of %₂O, BaO, 0.002-0.06 weight % of MgO, 5-20 weight % of 0-15 weight % Fe₂O₃And/or the Cr of 0.0001-0.06 weight %₂O₃.In the embodiment of other considerations, the glass or glass that are discussed herein The composition of potsherd or product includes the SiO of 60-72mol%₂, 3.4-8mol% Al₂O₃, 13-16mol% Na₂O、0- The K of 1mol%₂O, the TiO of MgO, 0-0.2mol% of 3.3-6mol%₂, 0.01-0.15mol% Fe₂O₃, 6.5-9mol% CaO, and/or 0.02-0.4mol% SO₃。

Integrated glass formation system

As shown in figure 31, in various embodiments, be discussed herein glass heating and/or tempering system can with it is various Glass melting/formation system binding operation.For example, tempering system and method disclosed herein can be with forming of glass or glass Fusing and manufacturing process consistently operate, so as to cause heat enhancing or the lower cost production of heat-treated glass.For example, sheet glass Or glass continuous band can be received in gas bearing heat treatment system and (be illustrated as system 1000), directly from forming or Person is melted and manufacturing process 1002, and at the same time glass itself is still close or even higher than glass transition temperature.Various In embodiment, system 1000 can be any tempering system being discussed herein.In one embodiment, system 1000 can be with It is system 300 discussed above.In another embodiment, system 1000 can be that gas bearing shown in Figure 21 cools down Arrangement.This consistency treatment can save energy and preferably control the thermal history of glass.In various embodiments, side Method 1002 may include various methods, such as float glass production process, fusion drawing method, slot drawn method, rolling side Method etc..For example, system 1000 can also be integrated into manufacturing process at place in any position, such as either in sheet separation method Before or after.

With reference to figure 32, system and method disclosed herein can be also used at roll-to-roll (or roller arrives other) of glass tape Reason.As shown in figure 32, system 1400 includes the glass supplied from roller 1404 by gas bearing heat treatment system (such as system 300) Glass band 1402, and after the heat treatment, hot tempering glass tape 1402 is stored on roller 1406.(or roller arrives it roll-to-roll He, such as roller to sheet material) heat enhancing is consistently executed during processing can reduce the bending sensibility of glass tape.It is disclosed herein to add But method allows to enhance along the short distance heat of belt path hot and cold, so as to cause the system reduced compared with other hot Enhancement Methods Make space requirement.

Embodiment

As described in detail above, the equipment includes three area-hot-zones, transition region and cold-zone or quenching for equipment setting- Area.Desired spacing is set in gap between the hot bearing in the top and bottom of hot-zone and quenching area (radiator).Setting heat The gas flow rate in area, transition region and quenching area is placed in the middle in air bearing to ensure glass material, sheet material or part.Hot-zone is pre- It is heated to desired T₀, glassware then will be from the T₀Start to quench.In order to ensure uniformly heating, in individual pre- hot charging Set Preheat glass product in (such as batch furnace or continuous oven).In general, sheet glass is preheated before being loaded into hot-zone more than 5 points Clock.For soda-lime glass, preheated at 450 DEG C or so.After warm-up phase, glassware is loaded into hot-zone and is allowed It is balanced, wherein balance is glass in T₀Lower uniform place.T₀It can be determined by desired enhancing/toughening degree, but It generally remains between softening point and glass transition temperature.Reach thickness of the time at least dependent on glass of balance Degree.For example, for about 1.1mm or smaller sheet glass, balanced in about 10 seconds.For the sheet glass of 3mm, at about 10 seconds It is balanced in 30 seconds.For compared with sheet material (being up to about 6mm), equilibration time may be at 60 seconds or so.Once glass is Equilibrate to T₀, the transition region that it just runs through in air bearing shifts and enters cold-zone or quenching area.Glassware is quenching Rapid quenching is extremely less than the temperature of glass transition temperature Tg in area.Depending on desired temper grade and/or when removed It is expected that glass temperature, sheet glass can be kept in quenching area 1 second, 10 seconds or a few minutes or section of longer any time.It is moving Except, optionally allowing to cool down glass before treatment later.

Table VI summarizes following embodiment.

Embodiment 1- by thickness be 5.7mm soda lime glass piece (e.g., including at least titanium dioxide of 70 weight % The calcium oxide of silicon, and/or at least sodium oxide molybdena of 10 weight %, and/or at least 7 weight %) it is preheated 10 minutes at 450 DEG C, it After be transferred into hot-zone, the T in the hot-zone by the sheet glass at 690 DEG C₀It is lower to be kept for 60 seconds.Equilibrating to T₀Later, By the sheet glass be quickly transferred to full of helium gap be 91 μm (wherein gap be the nearest radiator of glass sheet surface figure it Between distance) quenching area, in the quenching area by the sheet glass keep 10 seconds.Resulting product surface compression be- 312MPa, center tension 127MPa, and flatness is 83 μm.

Embodiment 2- preheats the soda lime glass piece that thickness is 5.7mm 10 minutes at 450 DEG C, then by its turn Hot-zone is moved on to, the T in the hot-zone by the sheet glass at 690 DEG C₀It is lower to be kept for 60 seconds.After the equilibration, by the glass Piece is quickly transferred to the quenching area that gap is 91 μm, is kept in the quenching area 10 seconds.Resulting product surface compression For -317MPa, center tension 133MPa, and flatness is about 89.7 μm.

Embodiment 3- preheats the soda lime glass piece that thickness is 1.1mm 10 minutes at 450 DEG C, then by its turn Hot-zone is moved on to, the T in the hot-zone by the sheet glass at 700 DEG C₀It is lower to be kept for 10 seconds.After the equilibration, by the glass Piece is quickly transferred to the quenching area that the gap full of helium is 56 μm, is kept in the quenching area 10 seconds.Gained system The fictive temperature on the surface of product is measured as 661 DEG C, and surface compression is -176MPa, center tension 89MPa, flatness 190 μm, and Vickers cracking threshold value is 10-20N.

Embodiment 4- preheats the soda lime glass piece that thickness is 0.55mm 10 minutes at 450 DEG C, then by it It is transferred to hot-zone, the T in the hot-zone by the sheet glass at 720 DEG C₀It is lower to be kept for 10 seconds.After the equilibration, by the glass Glass piece is quickly transferred to the quenching area that gap is 25 μm, is kept in the quenching area 10 seconds, is passed so as to cause effective Hot rate is 0.184cal/ (cm²-s-℃).Resulting product surface compression is -176MPa, and center tension is 63MPa.This Outside, flatness possessed by gained enhanced article is that about 168 microns (for 710 DEG C of samples of initial temperature) and 125 microns are (right In 720 DEG C of sample of initial temperature).

Thickness is 1.5mm's by embodiment 5-Sheet glass preheats 10 minutes at 550 DEG C, Hot-zone is transferred it to, the T in the hot-zone by the sheet glass at 790 DEG C₀It is lower to be kept for 30 seconds.After the equilibration, The sheet glass is quickly transferred to the quenching area that gap is 226 μm, is kept in the quenching area 10 seconds.Glass system The improvement of the flatness of product is measured as 113 μm (before processing) and 58 μm (after processing).

Embodiment 6- preheats the soda lime glass piece that thickness is 0.7mm 10 minutes at 450 DEG C, then by its turn Hot-zone is moved on to, the T in the hot-zone by the sheet glass at 730 DEG C₀It is lower to be kept for 10 seconds.After the equilibration, by the glass Piece is quickly transferred to the quenching area that the gap full of helium is 31 μm, is kept in the quenching area 10 seconds, to lead It is 0.149cal/ (cm to cause effective rate of heat transfer²-s-℃).Resulting product surface compression is -206MPa, and center tension is 100MPa, and flatness is 82 μm.In fracture, observe that sheet glass " stripping and slicing " (is 2mm or the sheet material of bigger for thickness The standard terminology-i.e. that stripping and slicing uses 5x5 square centimeters of sheet glass is broken into 40 or more pieces), this shows that sheet material is complete Tempering.

Embodiment 7- preheats the Borofloat-33 sheet glass that thickness is 3.3mm 10 minutes at 550 DEG C, then by it It is transferred to hot-zone, the T in the hot-zone by the sheet glass at 800 DEG C₀It is lower to be kept for 30 seconds.After the equilibration, by the glass Glass piece is quickly transferred to the quenching area that gap is 119 μm, is kept in the quenching area 10 seconds.Resulting product it is flat Degree is 120 μm.When the portion fractures, " stripping and slicing " (standard used for the sheet material stripping and slicing of 2mm or bigger for thickness is observed Term-i.e. 5x5 square centimeters of sheet glass is broken into 40 or more pieces), this shows that sheet material is complete tempering.

Embodiment 8- preheats the soda lime glass piece that thickness is 3.2mm 10 minutes at 450 DEG C, then by its turn Hot-zone is moved on to, the T in the hot-zone by the sheet glass at 690 DEG C₀It is lower to be kept for 30 seconds.After the equilibration, by the glass Piece is quickly transferred to the quenching area that gap is 84 μm, is kept in the quenching area 10 seconds.Resulting product surface compression For -218MPa, center tension 105MPa, and flatness is 84 μm.

Embodiment 9- preheats the soda lime glass piece that thickness is 0.3mm 10 minutes at 450 DEG C, then by its turn Hot-zone is moved on to, the T in the hot-zone by the sheet glass at 630 DEG C₀It is lower to be kept for 10 seconds.After the equilibration, by the glass Piece is quickly transferred to the quenching area that gap is 159 μm, is kept in the quenching area 10 seconds.Resulting product has and can lead to The membrane stress that grey field polarimetry is observed is crossed, this shows that glass has been incorporated with thermal stress.

Thickness is 0.1mm's by embodiment 10-Sheet glass preheats 10 points at 550 DEG C Clock transfers it to hot-zone, the T in the hot-zone by the sheet glass at 820 DEG C₀It is lower to be kept for 10 seconds.In balance Afterwards, the sheet glass is quickly transferred to the quenching area that gap is 141 μm, is kept in the quenching area 10 seconds, from And effective rate of heat transfer is caused to be 0.033cal/ (cm²-s-℃).In fracture, resulting product is shown and residual stress glass Consistent behavior.

Embodiment 11- preheats the soda lime glass piece that thickness is 1.1mm 10 minutes at 450 DEG C, then by it It is transferred to hot-zone, the T in the hot-zone by the sheet glass at 700 DEG C₀It is lower to be kept for 10 seconds.After the equilibration, by the glass Glass piece is quickly transferred to the quenching area that gap is 65 μm, is kept in the quenching area 10 seconds, is passed so as to cause effective Hot rate is 0.07cal/ (cm²-s-℃).The fictive temperature on the surface of resulting product is measured as 657 DEG C, and surface compression is- 201MPa, center tension 98MPa, flatness are 158 μm, and Vickers cracking threshold value is 10-20N.

Thickness is 1.1mm's by embodiment 12-Sheet glass preheats 10 points at 550 DEG C Clock transfers it to hot-zone, the T in the hot-zone by the sheet glass at 810 DEG C₀It is lower to be kept for 10 seconds.In balance Afterwards, the sheet glass is quickly transferred to the quenching area that gap is 86 μm, is kept in the quenching area 10 seconds, to It is 0.058cal/ (cm to lead to effective rate of heat transfer²-s-℃).The fictive temperature on the surface of resulting product is measured as 711 DEG C, Surface compression is -201MPa, center tension 67MPa, and Vickers cracking threshold value is 20-30N.

Thickness is 1.1mm's by embodiment 13-Sheet glass preheats 10 points at 550 DEG C Clock transfers it to hot-zone, the T in the hot-zone by the sheet glass at 800 DEG C₀It is lower to be kept for 10 seconds.In balance Afterwards, the sheet glass is quickly transferred to the quenching area that gap is 91 μm, is kept in the quenching area 10 seconds.Gained The fictive temperature on the surface of product is measured as 747 DEG C, and surface compression is -138MPa, center tension 53MPa, and flatness is 66 μm, and Vickers cracking threshold value is 20-30N.

Table VI

The glass that additional embodiment-helium and about 90 microns gap 204a, 204b (Figure 21) processing thickness are 5.7mm Glass piece (including at least silica of 70 weight % and/or at least oxygen of the sodium oxide molybdena of 10 weight % and/or at least 7 weight % Change calcium).Glass is heated to about 690 DEG C of initial temperature and is quickly cooled down.The enhanced article of gained has about on the surface thereof The negative tensile stress of 300MPa and center have about 121MPa positive tensile stress.Moreover, the flatness of the enhanced article of gained About 106.9 microns.

Additional embodiment-is in using one of invention disclosed herein technology experiment, with helium and about 160 microns Gap 204a, 204b (Figure 21) handle sheet glass that thickness is 1.1mm (including at least silica of 70 weight % and/or extremely The sodium oxide molybdena of few 10 weight % and/or the calcium oxide of at least 7 weight %).Glass is heated to about 680 DEG C of initial temperature and fast Quickly cooling is but.The enhanced article of gained on the surface thereof the negative tensile stress with about 112MPa and at center with about 54MPa's Positive tensile stress.Before enhancing, sheet glass has about 96 microns of flatness, but obtained enhanced article is micro- with about 60 The flatness of rice.Therefore, Enhancement Method also makes the glass of enhancing or glass and ceramic product flatten.

By reading the whole instruction and the appended claims, other aspects and advantage will be evident.

As shown in each exemplary implementation scheme, the construction and arrangement of glass and glass ceramics are merely illustrative. Although some embodiments are only described in detail in the disclosure, taught away from the novelty of theme described herein in not essence Many modifications are possible (for example, the size of various elements, size, structure, shape and ratio in the case of content and advantage Example, the value of parameter, installation arrangement, the use of material, the variation of color, orientation).Show that some elements being one of the forming can be with It is made of multiple parts or element, the position of element can be that opposite or other modes change, and resolution element or position The characteristic or quantity set can also be altered or varied.According to alternate embodiment, any method, logical algorithm or method and step Sequence or sequence can be changed or resequence.In the design of each exemplary implementation scheme, operating conditions and arrangement It can also carry out other to replace, modification, change and omit, without departing from the range of the technology of the present invention.

Claims (20)

1. a kind of method for hot-reinforced glass material comprising：

The product of glass material is heated to above to the glass transition temperature of the glass material；

The product of the heating is supported with gas-pressurized stream；And

The product of the cooling heating in cooling stations, the cooling stations include the radiator with the product in face of the heating The radiator on surface and the gas gap for separating the product of the spreader surface and the heating, wherein the heating Product is supported on by the gas-pressurized stream in the gas gap, so that the spreader surface does not contact described add The product of heat；

The product of the wherein described heating is cooled to below the temperature of the glass transition temperature in the cooling stations, so that It obtains and generates bearing stress in the product；

The wherein described gas-pressurized stream is between the surface area 50slpm and 50,000slpm of the product of heating described in every square metre Flow velocity be delivered to the gas gap.

2. the method as described in claim 1, wherein the flow velocity of the gas-pressurized is low so that by by across institute It states the conduction of gas gap and thermal energy is transmitted to the radiator from the product of the heating to cool down the product of the heating, from And it is more than that 20% thermal energy of the product for leaving the heating connects across the gas gap and by the radiator to make It receives.

3. the method as described in claim 1, wherein the flow velocity of the gas-pressurized is low so that by by across institute It states the conduction of gas gap and thermal energy is transmitted to the radiator from the product of the heating to cool down the product of the heating, from And it is more than that 50% thermal energy of the product for leaving the heating connects across the gas gap and by the radiator to make It receives.

4. the method as described in claim 1, wherein the gas gap is dissipated in the outer surface of the product of the heating with described There is average length, the average length is small so that by by the conduction across the gas gap between hot device surface Thermal energy is transmitted to the radiator to cool down the product from the product of the heating, so that being more than 20% to leave institute The thermal energy for stating the product of heating is received across the gas gap and by the radiator, wherein the institute of the gas gap Average length is stated more than or equal to 10 μm and is less than or equal to 500 μm.

5. method as claimed in claim 4, wherein the average length of the gas gap be greater than or equal to 25 μm and Less than or equal to 300 μm.

6. the method as described in claim 1, wherein the gas-pressurized is air, and the flow velocity of the forced air More than or equal to the product of heating described in every square metre surface area 100slpm and be less than 30,000slpm.

7. the method as described in claim 1, wherein the gas-pressurized is helium, and the flow velocity of the pressurized helium More than or equal to the product of heating described in every square metre surface area 100slpm and be less than 10,000slpm.

8. the method as described in claim 1, wherein the product of the glass material is to be supplied to the cooling from the first spool The glass tape stood, and the product of the glass material is stored in after cooling on the second spool.

9. the method as described in claim 1, wherein the product of the glass material carry out fusing and with the cooling stations one Cause at least one of ground forming.

10. the method as described in claim 1, wherein the glass material is one kind in annealed glass and glass ceramics.

11. a kind of system for sheet glass of the heat enhancing with surface area, the system comprises：

Heating station comprising heat is delivered to the heating element of the sheet glass；

Cooling stations comprising opposite the first spreader surface and the second spreader surface, first spreader surface and institute It states the second spreader surface and defines therebetween channel so that during cooling, the sheet glass is located in the channel；And

Gas-pressurized is delivered to the channel so that the sheet glass is supported in the channel by gas bearing；

The wherein described gas bearing is between the surface area 50slpm and 50,000slpm of sheet glass described in every square metre The gas-pressurized is delivered to the channel by flow velocity.

12. system as claimed in claim 11, wherein the gas bearing passes through in first spreader surface and described The aperture formed in second spreader surface delivers the gas-pressurized, wherein the aperture has total orifice area, wherein institute State total orifice area is less than the total surface area of first spreader surface and second spreader surface 10%.

13. system as claimed in claim 11, wherein the gas bearing passes through in first spreader surface and described The aperture formed in second spreader surface delivers the gas-pressurized, wherein the aperture has total orifice area, wherein institute State total orifice area is less than the total surface area of first spreader surface and second spreader surface 5%.

14. system as claimed in claim 11, wherein the gas bearing passes through in first spreader surface and described The aperture formed in second spreader surface delivers the gas-pressurized, wherein the aperture has total orifice area, wherein institute State total orifice area is less than the total surface area of first spreader surface and second spreader surface 1%.

15. system as claimed in claim 11, wherein the heating station limits heating channel, and the system also includes add Gas-pressurized is delivered to the heating channel so that the sheet glass quilt by heat stations gas bearing, the heating station gas bearing It is supported in the heating channel, wherein heating station gas bearing is with the surface area 50slpm of sheet glass described in every square metre Gas-pressurized is delivered to the heating channel by the flow velocity between 50,000slpm.

16. system as claimed in claim 15, wherein the heating channel is in the outer surface of the sheet glass and the heating Has average length between gas bearing of standing, the average length is greater than or equal to 50 μm and is less than or equal to 1000 μm.

17. system as claimed in claim 15, wherein the heating station includes at least one heating element for generating heat, institute State the channel that heat is delivered to the heating station.

18. a kind of reinforcing glass product comprising：

First main surface；

Second main surface, it is opposite facing with first main surface；

Interior zone, between first main surface and second main surface；And

At least one of the wherein described first surface or the second surface have relatively large surface area, i.e., at least 2500mm²；

At least one of wherein described first main surface and second main surface are under compression and the inner area Domain is under tensile stress；

The wherein described compression includes the hot tempering stress of at least 100MPa and 20% chemistry less than the hot tempering stress Tempering stress.

19. reinforcing glass product as claimed in claim 18 is answered wherein the compression includes at least hot tempering of 500MPa Power and 10% chemical tempering stress less than the hot tempering stress.

20. reinforcing glass product as claimed in claim 18, wherein in terms of ion concentration and chemical composition, the enhancing glass Glass product is in part of the reinforcing glass product under the compression except the interior zone and adjacent institute State the composition and at least one of the interior zone under the tensile stress at least part of the part of interior zone Composition in part is identical so that the change of at least some compositions independently of the reinforcing glass product of the compression Change, wherein in terms of ion concentration and chemical composition, the reinforcing glass product is in first main surface and second master At least one of surface place composition be in the tensile stress under the interior zone at least part in it is described Composition is different so that the variation of at least some compositions depending on the reinforcing glass product of the compression.