WO2007032961A2 - Verre d'aluminosilicate de lithium renforce chimiquement ayant une resistance elevee efficace pour resister a la fracturation sous l'effet de la flexion imposee par l'impact de projectiles a vitesse elevee - Google Patents

Verre d'aluminosilicate de lithium renforce chimiquement ayant une resistance elevee efficace pour resister a la fracturation sous l'effet de la flexion imposee par l'impact de projectiles a vitesse elevee Download PDF

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Publication number
WO2007032961A2
WO2007032961A2 PCT/US2006/034552 US2006034552W WO2007032961A2 WO 2007032961 A2 WO2007032961 A2 WO 2007032961A2 US 2006034552 W US2006034552 W US 2006034552W WO 2007032961 A2 WO2007032961 A2 WO 2007032961A2
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Prior art keywords
glass
salt bath
compression
microns
salt
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PCT/US2006/034552
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English (en)
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WO2007032961A3 (fr
Inventor
Arun K. Varshneya
Ian M. Spinelli
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Saxon Glass Technologies, Inc.
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Priority claimed from US11/468,470 external-priority patent/US8304078B2/en
Application filed by Saxon Glass Technologies, Inc. filed Critical Saxon Glass Technologies, Inc.
Publication of WO2007032961A2 publication Critical patent/WO2007032961A2/fr
Publication of WO2007032961A3 publication Critical patent/WO2007032961A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions

Definitions

  • the present invention relates to the field of chemically strengthened lithium aluminosilicate glass.
  • Glasses generally break because tension acting on a surface flaw exceeds the engineering strength of the glass.
  • glass products can be effectively strengthened if compression is introduced into the surface.
  • the strengthening depends to a great extent on the flaw condition of the glass, which, in turn, depends upon how the glass has been handled through product manufacturing as well as subsequent user-handling stages.
  • One practical means of glass strengthening is to immerse the product in a bath of molten alkali salt at a temperature well below the transition temperature of the glass.
  • Recommended molten salt is potassium nitrate for a sodium ion-containing glass and sodium nitrate for a lithium ion-containing glass.
  • the basic principle is to use salt bath alkali ions that are larger than those in the glass.
  • MOR modulus of rupture
  • ASTM standard C158-84 One way to perform the MOR test is to load rectangular or circular cross-sectional beams in a 3-point or 4 point-mode.
  • the rectangular beam tests in particular, tend to be edge condition-dependent and, hence, flaws on the sawed/ground edge are invariably the origin of the fracture.
  • the MOR test is desensitized to edge conditions by performing concentric "ball-on-ring” or “ring-on-ring” (also called “concentric ring”) tests; see ASTM F-394.
  • the performance of chemically strengthened glass products depends not only on the magnitude of the surface compression introduced but also on the "case depth,” which is the depth of the compression below the surface (depth at which the decreasing compression magnitude essentially reaches zero stress, changing over to a tension at larger depths).
  • the ASTM standard C1422-99 thus classifies chemically strengthened flat glass products based on (i) the magnitude of surface compression and (ii) the magnitude of case depth. For protection against impacting projectiles, both should be as large as possible. Unfortunately, the ion exchange process, being atomic diffusion dependent, is extremely sluggish.
  • ion exchange-strengthened glass is aircraft windshield manufactured in the USA by PPG, Incorporated. With roughly 400 MPa (about 58,000 psi) of surface compression and a case depth of about 300 microns, such glass, when assembled as a multilayer laminate with polymers such as polyvinyl butyrate and polycarbonate, is designed to protect the aircraft from flying birds. In a quality control test such windshields exhibited full containment after impacting a 4-Lb standardized thawed chicken (or equivalents 4-Lb gel mass) flying from a gas- pressurized cannon at 400 knots.
  • Aircraif WiridShielcf is a typical example of a high security application for multilayered glass and polymer laminate.
  • the laminates are constructed to be thick enough such that the outboard plies of a tough polymer act to absorb the energy of an impacting projectile and the glass plies provide the resistance to flexure due to their high elastic moduli. After most of the energy of the projectile is absorbed by the "sacrificial" outer plies, the inboard plies of glass prevent the penetration due to their high resistance to fracture.
  • the thickness of the composite not only provides energy absorption but also reduced flexure which, in turn, results in lesser tension on the convexed surface, hence, lesser probability of glass fracture.
  • the higher thicknesses of such composites can add greatly to the overall weight of the assembly which, in turn, may be detrimental to the performance of, say, a vehicle equipped with such glass laminate.
  • the use of extremely high strength glass plies inboard reduces the need for high glass ply thickness, hence, forms a significantly superior design.
  • glasses are often only heat-strengthened or fully tempered (“Kind-HS” or “Kind-FT” of ASTM C1048-97b) and laminated.
  • Kind-HS heat-strengthened or fully tempered
  • the thermal tempering process which takes only a few minutes to introduce surface compression, creates a case depth from each side that is roughly 1/5* of the glass thickness, thus about 1.2mm deep for an approximately 6mm thick conventional glass window.
  • the thermally tempered glasses are limited to achieving no more than about 100 MPa surface compression, which is rarely adequate for protection against high velocity flying debris in a Category 4 or stronger hurricane. Further, because the thermal tempering process necessarily raises the temperature of the glass to well above the glass transition temperature during the manufacturing process, some optical distortion of the glass due to viscous flow is unavoidable. Use of such windows in critical applications such as military armored vehicles, hence, is not recommended. Additionally, the high we'ight 1 of glass wificfoWs 1 In buildings designed to withstand hurricanes could present structural limitations.
  • soda- lime-silicate glasses which generally form the basis of most architectural and windshield applications, can only be strengthened to a depth of a few microns using immersion in potassium nitrate bath. Use of higher temperatures relaxes the beneficial compression and the use of lower bath temperatures requires days of immersion substantially increasing the costs of manufacturing.
  • a publication by Nordberg et.al. from Corning Glass Works discusses the strengthening of a 9 mol% lithium oxide-containing aluminosilicate glass immersed in a molten sodium nitrate salt bath at about 400 0 C for 4 hours.
  • tumble-abraded strengths increased from about 35 Kpsi (1000 psi) to as much as 100 Kpsi. Case depths obtained were 0.010 inch (about 250 microns) to 0.020 inch (about 500 microns).
  • Garfinkel and King J. Amer. Ceram. Soc, vol 53, p.686, 1970 disclose strengthening a 5.15 wt% lithium oxide-containing aluminosilicate glass immersed in sodium nitrate salt bath at 404 °C for 4 hours to achieve a case depth of about 210 microns and an MOR of about 97 Kpsi.
  • U.S. Patent 3,790,430 by Mochel describes the chemical strengthening of an 18 mol% lithium oxide-containing aluminosilicate glass immersed in a molten sodium nitrate salt bath at about 400 °C for 4 hours. Strengths of 106,000 psi were claimed to have been achieved. However, no measurements of case depth were reported.
  • Patent 3,357,876 by Rinehart and assigned to Pittsburgh Plate Glass Company discusses strengthening lithia-soda-alumina-phosphorus pentoxide- silica glasses containing 1 to 25 wt% phosphorus pentoxide, by immersion in salt baths containing sodium nitrate or potassium nitrate and in serially conducted exchange experiments where each successive treatment is conducted using an alkali metal which is larger in ionic size than that employed in the prior experiment.
  • This patent disclosure requires phosphorus pentoxide (P 2 O 5 ) and Na 2 ⁇ in the base glass.
  • This patent discloses using a mixed salt bath having a ratio of potassium nitrate salt to sodium nitrate salt in a range of 2:1 to 50:1.
  • the patent discloses that the stress profiles of the lithia-soda-alumina-phosphorus pentoxide-silica glasses obtained by immersion in an 8:1 potassium nitrate to sodium nitrate bath at 875°F (468°C) for 60 minutes show surface compression of about 96 Kpsi dropping steeply to about 35,000 at a depth of 20 microns and subsequently falling to zero around 220 microns depth (Example III, paragraph 6; Figure 3).
  • U.S. Patent 3,410,673 by Marusak and assigned to Corning Glass Works discloses a method of chemically strengthening lithium aluminosilicate glass containing lithium and sodium ions.
  • the glass may be subjected to immersion in multiple salt baths, for example, immersion in a bath of sodium salt, followed by immersion in a potassium salt bath.
  • the purpose indicated is to first exchange lithium in th f b ' gl' ⁇ ss 1 ' b ⁇ TddiufWfrorri 1 the bath and, subsequently, lithium and/or sodium ions in the surface of glass by potassium ions from the bath.
  • the patent also discloses using a salt bath comprising a 50:50 mixture of sodium and potassium salt to strengthen a glass which originally contained both lithium and sodium.
  • glasses having 59-63% SiO 2 , 10-13% Na 2 O, 4 -5.5% Li 2 O, 15-23% AI 2 O 3 and 2 to 5% ZrO 2 .
  • Rinehart's glass composition avoided using B 2 O 3 and P 2 O 5 in view of their volatility but employed a high amount of Na 2 O.
  • Rinehart chemically strengthened the glass by immersion in pure sodium nitrate bath at 705 0 F for 22 hours (or 75O 0 F for 4 hours).
  • An MOR of about 45 kpsi with a case depth of about 190 microns were reported.
  • a published U.S. patent application 20050090377 by Shelestak et al., assigned to PPG Industries Inc. discloses using high strain point lithium aluminosilicate glasses and a sodium salt bath or predominantly sodium, mixed Na/ K salt bath, in an attempt to achieve deeper surface compression and higher MOR.
  • the authors disclose lithium aluminosilicate glasses having a composition comprising (in weight %): Li 2 O in a range of 3 to 9%, Na 2 O + K 2 O in an amount of less than 3.5% and AI 2 O 3 in an amount ranging from 7% to 30%.
  • the molten salt bath disclosed in the '377 patent application preferably uses at least 50% sodium salt (generally sodium nitrate) and, in particular 100% sodium salt, to enable sodium exchange.
  • This reference discloses case depths of, for example, 11.5 to 17.4 mils (about 300 to 450 microns).
  • U.S. Patent 6,814,453 by Miwa and Kanai and assigned to Nippon Electric Glass Co. Ltd. describes strengthening high annealing point lithium aluminosilicate glass in a bath of potassium nitrate at 500 0 C for about 6 hours to develop a strengthened substrate to prevent projector lamp fragments from flying forward after sudden failure.
  • the depth of compression stated is only about 20 to 30 microns.
  • the Miwa et. al. patent essentially confirms the results of Sandia National Laboratories, that exchange of lithium ion in glass for potassium ion from a salt bath is a very slow process.
  • Figure 1 shows modulus of rupture (MOR) of a chemically strengthened glass as a function of ion exchange treatment and time.
  • MOR modulus of rupture
  • Figure 2 shows compressive stress profiles in an unbroken plate of the inventive aluminosilicate glass as a function of ion exchange treatment for various salt baths wherein circle and triangle datapoints correspond to use of the indicated mixed sodium and potassium salt bath used in the invention whereas the diamond and square comparative datapoints correspond to use of a sodium salt bath followed by a potassium salt bath;
  • Figure 3 shows Weibull plots of the strengths of the inventive lithium aluminosilicate silicate glass as a function of ion exchange at 475 0 C for 24 hours in a sodium nitrate and potassium nitrate mixed salt bath.
  • the inset shows the molar ratio of sodium to potassium in the mixed salt bath.
  • Figure 4 shows compressive stress profiles in an unbroken plate of the inventive lithium aluminosilicate glass as a function of ion exchange treatment for various salt baths.
  • the inset shows the molar ratio of sodium salt to potassium salt in the mixed salt bath.
  • the present invention features chemically strengthened lithium aluminosilicate glass of a composition that provides the glass with a high strain point, which achieves unexpectedly high surface compression, deep compression case depth and high strength effective to resist fracture upon flexing from impact of high velocity projectiles.
  • the inventive glass is characterized by a surface compression of at least 100,000 psi and a compression case depth of at least 600 microns and, in particular, of at least 1000 microns.
  • the glass can exhibit a strength at 50 microns below a surface of the glass that is at least 30,000 psi.
  • the compression level is 30,000 psi, hence, a tensile stress higher than 30,000 psi would be needed to cause fracture.
  • the term "annealing point” is the temperature at which stresses in a glass at a viscosity of 10 13 poise are relieved in 15 minutes.
  • case depth is defined herein as a distance measured from a surface of a glass article to a position in the interior of the article at which there is zero stress in the glass article.
  • the surface of the glass can be any surface that is exposed to the molten salts of the ion exchange bath.
  • the present invention uses a molten salt bath having a balanced mix such that both exchanges (sodium for lithium deep inside the glass and potassium for lithium in the surface) occur concurrently.
  • conventional salt baths having high sodium salt concentration there is little potassium-lithium exchange.
  • the inventors have recognized the advantage of using elevated temperature of the bath of 450 0 C and higher to increase the mobility of potassium ions, which requires the glass to have a s ⁇ iffi ' cfe ⁇ y ; "h ⁇ h ' atl ⁇ lall ⁇ g "point such that viscous relaxation of stresses does not occur significantly.
  • the inventors have further recognized the need for high amounts of potassium in the mixed bath to encourage potassium for lithium exchange in the surface. This results in glass having high strength adapted for use under the extreme condition of resisting fracture upon flexing from impact of high velocity projectiles.
  • the present invention can strengthen commercially available flat glass.
  • Glass that may be chemically strengthened according to the present invention has a composition comprising (in weight %): Li 2 O in an amount ranging from 3 to 9%, Na 2 O + K 2 O in an amount less than about 3.5%, and AI 2 O 3 in an amount ranging from 7 to 30%.
  • Na 2 O + K 2 O in the glass ranges from O to 3%
  • AI 2 O 3 ranges from 18 - 28%.
  • the inventive glass has a composition consisting essentially of: Li 2 O in an amount ranging from 3 to 9%, Na 2 O + K 2 O in an amount less than about 3.5%, AI 2 O 3 in an amount ranging from 7 to 30%, up to about 4% each of ZrO 2 , TiO 2 ⁇ MgO, ZnO and other similar constituents totaling no more than 10%, with the balance being SiO 2 and unavoidable impurities.
  • the inventive composition does not add B 2 O 3 or P 2 Os and these compounds are not present in amounts greater than 0.05 wt% or other than what is considered an impurity or tramp ingredient.
  • Additional compositions of glasses that may be suitable for strengthening in accordance with the present invention are those disclosed in published U.S. patent application 20050090377 by Shelestak et al., incorporated herein by reference, which have an annealing point of at least 58O 0 C.
  • Exemplary glass that is suitable for being strengthened in the method of the present invention is a pre-cerammed glass manufactured by Nippon Electric Glass (NEG) of Japan.
  • This glass (shown in column 2) and other suitable glasses have the compositions shown in Table 1 below, and may be treated by the salt bath temperatures and immersion times shown in Table 1.
  • the Treatments indicated in Table 1 specify the type of salt bath, and temperature, time of immersion of the glass therein.
  • the Properties reported in Table 1 specify the case depth and surface compression of the glass, respectively.
  • Other glasses that may be suitable for being strengthened by the method of the present invention are ROBAX® glass by Schott Inc. having the composition shown in Table 1 (but using the inventive mixed salt bath, temperature and period of immersion) and HERCUVIT® pre-cerammed glass by PPG, Inc.
  • Glass that is suitable for being treated to effect high strength and deep compression case depths according to the present invention has a composition that provides it with an annealing point of 580 0 C or higher. This allows chemical strengthening to be carried out using a molten mixed salt bath having a temperature of 450 0 C or higher and, in particular, 475 0 C or higher. Although the glass can be preheated, neither the salt bath temperature nor the glass temperature should be close to the glass annealing point temperature or exceed a temperature that is about 25°C less than the glass annealing point temperature.
  • the lithium aluminosilicate glass has a high transition temperature (Tg) of, for example, about 620-630 0 C.
  • the present invention advantageously uses a high concentration of potassium salt in the dual salt bath.
  • a ratio of moles of sodium salt to moles of potassium salt in the salt bath ranges from 1:10 to 1:2 and, in particular, is about 1:4.
  • the amount of sodium salt in the total salt of the molten mixed salt bath is well below 50 mol%.
  • the composition of the salt bath comprises sodium salt in an amount ranging from 10 mol% to 40 mol%, with the balance being potassium salt and unavoidable impurities.
  • the salt bath has a composition consisting essentially of sodium salt in an amount ranging from 20 mol% to 40 mol%, with the balance being potassium salt, unavoidable impurities and optional scavengers therefor.
  • An exemplary composition of the salt bath that is advantageously used in the present invention is about 20 mol% sodium salt, about 80 mol% potassium salt and unavoidable impurities.
  • One way of preparing the salt bath is to weigh the salts dry in the indicated amounts, mix the salts, place the salts in the vessel that will contain the bath and turn on the electricity to the bath to melt the salt mixture and heat the bath to the specified temperature.
  • the molten salt bath contains molten salt and no other solvents.
  • the salt bath has no water, besides trace amounts of structure bound water.
  • the composition of the salt bath is maintained over time, such as by periodically changing out the salt.
  • Other salts of sodium and potassium may be used instead of nitrate salts. That is, other anions such as chlorides, sulfates, phosphates and the like can be used instead of nitrates, and may be preferred when bath temperatures are high in order to reduce salt volatilization.
  • Unavoidable impurities build up in the molten salt bath over time. As a result of the continuing exit of lithium and other ions contained in the parent glass structure from the glass, the ions build up in the bath. The amount of lithium oxide in the bath is maintained below 1 mol%, preferably below 0.1 mol%.
  • other potential impurities include aluminum, boron, calcium, magnesium, barium, zinc, titanium and zirconium.
  • Potential impurities from the steel of the vessel that contains the bath include iron, chromium and nickel. Initially, “scavengers” or “getters” such as sodium and potassium silicate powders or flakes are used to absorb some of the impurities.
  • the scavenging effect is reduced and the bath is dumped and replaced with uncontaminated salt.
  • the salts have varying impurities that should be minimized as much as commercially possible. Salts of extremely high purity may be most advantageous in the present invention. Commercially obtained salt may need to be purified to a suitable level determined by one skilled in the art in view of this disclosure, such as by scavenging, before the bath is used.
  • the scavengers are left in the bath, or the bath can first be treated by a bag containing the scavengers and the bag is subsequently removed.
  • the present invention advantageously enables high speed strengthening. Compared to conventional immersion lasting often 10 days, maybe more, the invention can achieve very high strength in as little as 4 hours of immersion and very high strength such as for security glass (bullet-resistant applications) in as little as a day of ⁇ i ⁇ f ⁇ tfet ⁇ i ⁇ W H Refer*t(r l&Ble -i above for exemplary durations of immersion and resulting surface compression and case depth for the glass compositions provided.
  • the invention features a chemically strengthened glass with greater than 100,000 psi (about 690 MPa) surface compression and in particular, not less than 30,000 psi compression at 50 micron depth from the surface and a total case depth of at least 600 microns (about 24 mils).
  • Fig. 2 shows a stress profile plot for 4 specimens of the NEG's column 2 "mother” glass (see Table 1) prior to ceramming.
  • the square and diamond comparative datapoints are for sequential exchange at 450 °C first with NaNO 3 and then at 475 0 C with KNO 3 . This sequential exchange is not part of the present invention.
  • the circle and triangle datapoints are for concurrent sodium and potassium salt exchange at 475 0 C that embody our invention.
  • FIG. 3 Shown in Figure 3 are Weibull fracture probability plots for glass ion exchange- strengthened in mixtures of sodium nitrate (NaNO 3 ) and potassium nitrate (KNO 3 ) salts where the ratio of salt has been varied from 0 to 30 mol% (4.25 to 26.5 weight%) and compared with data obtained with unstrengthened and unstrengthened-plus-abraded specimens.
  • the plots show the superiority of the 20 mol% sodium nitrate salt mixture over others.
  • the chemically strengthened glasses have narrower strength distributions compared to the unstrengthened glass.
  • glass strength distributions For product specifications, one prefers glass strength distributions to be narrow.
  • the slope of the curves yields Weibull modulus. Whereas the Weibull modulus values for the unstrengthened glasses were around 4.5, the strengthened glasses had Weibull modulus values ranging between 9 and 18.
  • Figure 4 shows stress profiles for 5, 10 and 20 mol% sodium nitrate (balance potassium nitrate) baths. Again, the higher stresses achieved with ion exchange in the 20 mol% sodium nitrate bath are evident. NEG's column 2 "mother” glass shown in Table 1 was used for all specimens.
  • the surface compression and case depth for the glass treated according to the invention correspond to a glass level 5F, which is an extreme high strength limit recognized to 1 CIaIe.
  • glass treated according to the present invention may exhibit a maximum compression value that is not exactly on the surface. While not wanting to be bound by theory, such treated glass may advantageously possess a maximum compression value that is a few microns below the surface (disclosed in U.S. patent 6,516,634 by Green et al.).
  • the strengthened glass of the present invention advantageously exhibits a relatively high compression value at about 50 microns below the surface compared to the Saunders patent publication.
  • Glass transparencies for high-security applications such as, bullet and blast-resistant glass
  • glass for armored defense vehicles such as, bullet and blast-resistant glass
  • windows for government buildings and monuments such as, private vehicles, train and aircraft transparencies, and hurricane and earthquake-resistant windows.
  • Lower security need applications such as bank teller windows, display cases, and ATM touch panels may also benefit from our invention.

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

Abstract

La présente invention concerne un verre d'aluminosilicate de lithium renforcé chimiquement qui se caractérise par une compression de surface d'au moins 100000 psi et une profondeur de cémentation de compression d'au moins 600 microns. Le verre peut également se caractériser par une compression à 50 microns en-dessous d'une surface du verre, qui vaut au moins 30000 psi. L'invention a également pour objet un procédé pour produire ce verre, comprenant la mise à disposition d'un verre d'aluminosilicate de lithium dont la composition comprend (en % en poids) Li2O en une quantité de 3 à 9 %, Na2O + K2O en une quantité inférieure ou égale à 3 %, et AI2O3 en une quantité de 7 à 30 %. La composition confère au verre une température de recuit d'au moins 580 °C. L'invention fait intervenir un bain mixte de sels de potassium et de sodium comprenant une quantité prédominante de sel de potassium. Le rapport entre les moles de sel de sodium et les moles de sel de potassium dans le bain de sels mixte, peut valoir de 1:10 à 1:2. La température du bain de sels est maintenue sur une plage de valeurs de 450 °C à la température de recuit du verre. Le verre est immergé dans le bain de sels pendant une durée de 2 à 96 heures. Le verre de l'invention a une résistance élevée efficace pour résister à la fracturation sous l'effet de la flexion imposée par l'impact de projectiles à vitesse élevée, et comprend: un verre résistant aux balles, un verre résistant aux explosions, un verre pour véhicule de défense blindés, des fenêtres pour bâtiments gouvernementaux, des fenêtres pour monuments, des vitres véhicules, des éléments transparents de train, des éléments transparents d'aéronef, des fenêtres résistant aux ouragans, des fenêtres résistant aux tremblements de terre, des vitres de guichet de banque, des vitrines, et des panneaux tactiles de guichets bancaires automatiques.
PCT/US2006/034552 2005-09-12 2006-09-05 Verre d'aluminosilicate de lithium renforce chimiquement ayant une resistance elevee efficace pour resister a la fracturation sous l'effet de la flexion imposee par l'impact de projectiles a vitesse elevee WO2007032961A2 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US71620905P 2005-09-12 2005-09-12
US60/716,209 2005-09-12
US38256706A 2006-05-10 2006-05-10
US11/382,567 2006-05-10
USPCT/US2006/18769 2006-05-16
US2006018769 2006-05-16
US11/468,470 2006-08-30
US11/468,470 US8304078B2 (en) 2005-09-12 2006-08-30 Chemically strengthened lithium aluminosilicate glass having high strength effective to resist fracture upon flexing

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WO2007032961A3 WO2007032961A3 (fr) 2009-06-18

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EP2771195A1 (fr) * 2011-10-25 2014-09-03 Corning Incorporated Procédé et appareil pour former une surface inscriptible et effaçable sur un objet
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WO2020009957A1 (fr) * 2018-07-02 2020-01-09 Corning Incorporated Articles à base de verre à profils de contrainte améliorés
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CN103097319B (zh) * 2010-09-13 2016-10-12 法国圣-戈班玻璃公司 玻璃片
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US11312657B2 (en) 2018-07-02 2022-04-26 Corning Incorporated Glass-based articles with improved stress profiles
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CN113284241B (zh) * 2021-03-11 2022-03-15 广东锡源爆破科技股份有限公司 一种堆形为Weibull分布的爆堆表面岩块三维模拟方法

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