EP4493526A1 - Low-melting glass compositions, articles, and methods of making the same - Google Patents
Low-melting glass compositions, articles, and methods of making the sameInfo
- Publication number
- EP4493526A1 EP4493526A1 EP23771314.4A EP23771314A EP4493526A1 EP 4493526 A1 EP4493526 A1 EP 4493526A1 EP 23771314 A EP23771314 A EP 23771314A EP 4493526 A1 EP4493526 A1 EP 4493526A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mol
- glass composition
- article
- glass
- exhibits
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- 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
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0092—Compositions for glass with special properties for glass with improved high visible transmittance, e.g. extra-clear glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
Definitions
- Glass is commonly used for commodity applications and technological applications related to the automotive industry, electronic industry, spectroscopy, and the like. Often glass articles are also exposed to various atmospheres, and to ensure the article's durability in the long term, glass compositions need to be designed to withstand such environments.
- glass articles such as container glasses, flat glasses for windows, automotive windshields, laser host materials, fibers, tubing, and the like, are employed in both commodity applications such as bottles, vases, art and craft glass objects, architectural windows, automotive windshields, and the like as well as technological applications such as glass tubing, glass fibers, laser host materials, and the like, often endure the environmental attack of moisture and can lose their initial properties as a result.
- the present invention is directed to a glass composition
- a glass composition comprising: about 25 to about 55 mol% of P 2 O 5 ; about 5 to about 45 mol% of SiO 2 ; about 5 to about 22 mol% of Al 2 O 3 ; about 5 to about 30 mol% of ZnO; greater than 0 to about 20 mol% a total amount of Na 2 O, K 2 O, and/or Li 2 O; about 2 to about 8 mol% of CaO, and/or about 2 to about 8 mol% of MgO.
- the glass composition disclosed herein exhibits a melting point of less than about 1,400 °C.
- the glass composition disclosed herein can comprise Fe 2 O 3 in an amount up to about 10 mole%.
- an article comprising a glass composition comprising about 25 to about 55 mol% of P 2 O 5 ; about 5 to about 45 mol% of SiO 2 ; about 5 to about 22 mol% of Al 2 O 3 ; about 5 to about 30 mol% of ZnO; greater than 0 to about 20 mol% a total amount of Na 2 O, K 2 O, and/or Li 2 O; about 2 to about 8 mol% of CaO, and/or about 2 to about 8 mol% of MgO.
- the articles disclosed herein can comprise foodware, tableware, cookware, flat glass, windows, windshields, hollowware, jars, art and craft glass objects, laser host materials, optical fibers, hollow fibers, tubing fibers, lab-usable containers, or any combination thereof.
- Also disclosed herein are methods comprising: a) providing: about 25 to about 55 mol% of P 2 O 5 ; about 5 to about 45 mol% of SiO 2 ; about 5 to about 22 mol% of A l 2O 3 ; about 5 to about 30 mol% of ZnO; greater than 0 to about 20 mol % a total amount of Na 2 O, K 2 O, and/or Li 2 O; about 2 to about 8 mol% of CaO, and/or about 2 to about 8 mol % of MgO; b) forming a homogeneous mixture; c) melting the mixture at a temperature of about 1,000 °C to about 1,300 °C; and cooling the composition to form any of the disclosed herein glass compositions.
- Figures 2A-2D show the relaxation behavior of an exemplary glass composition according to one aspect.
- DETAILED DESCRIPTION [16] The present invention can be understood more readily by reference to the following detailed description, examples, drawings, and claims, and their previous and following description. However, before the present articles, systems, and/or methods are disclosed and described, it is to be understood that this invention is not limited to the specific or exemplary aspects of articles, systems, and/or methods disclosed unless otherwise specified, as such can, of course, vary.
- range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, a description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, 6 and any whole and partial increments therebetween. This applies regardless of the breadth of the range.
- composition is intended to encompass a product comprising the specified ingredients in the specified amounts, as well as any product which results, directly or indirectly, from a combination of the specified ingredients in the specified amounts.
- glass composition refers to a glass that was melted to form a defined composition but before it was formed into a specific glass article. It is further understood that the glass composition as used herein is not the same as batch ingredients that were introduced into the mix before forming the glass. In some aspects, the batch ingredients used to form the composition can comprise elements that the glass composition is substantially free of.
- a weight percent (wt.%) of a component is based on the total weight of the formulation or composition in which the component is included.
- concentration of constituent components e.g., SiO 2 , Al 2 O 3 , B2O3, CuO, NiO, and the like
- mol% mole percent
- the term "substantially” means that the subsequently described event or circumstance completely occurs or that the subsequently described event or circumstance generally, typically, or approximately occurs.
- the term “substantially” can, in some aspects, refer to at least about 80 %, at least about 85 %, at least about 90 %, at least about 91 %, at least about 92 %, at least about 93 %, at least about 94 %, at least about 95 %, at least about 96 %, at least about 97 %, at least about 98 %, at least about 99 %, or about 100 % of the stated property, component, composition, or other condition for which substantially is used to characterize or otherwise quantify an amount.
- the term “substantially free,” when used in the context of a composition or component of a composition that is substantially absent, is intended to indicate that the recited component is not intentionally batched and added to the composition but can be present as an impurity along with other components being added to the composition.
- the term “substantially free” is intended to refer to trace amounts that can be present in the batched components, for example, it can be present in an amount that is less than about 1 % by weight, e.g., less than about 0.5 % by weight, less than about 0.1 % by weight, less than about 0.05 % by weight, or less than about 0.01 % by weight of the stated material, based on the total weight of the composition.
- the term “substantially,” in, for example, the context “substantially identical” or “substantially similar,” refers to a method or a system, or a component that is at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, or about 100% by similar to the method, system, or the component it is compared to.
- the compositions disclosed herein are commonly expressed as oxides, however, it is understood that the specific elements can be present in an ionic state.
- a glass transition temperature or Tg can be used interchangeably and is defined as the inflection point of a differential scanning calorimetry (DSC) curve during the second heating, where the cooling and heating of the sample occurs at a rate of 10 °C/min and is plotted as Heat Flow in mW vs. Temperature in °C.
- melting point refers to a temperature at which the batch materials fully melt to obtain a homogeneous liquid. By glass industry convention, the melting point occurs at a liquid viscosity of around 10-20 Pa ⁇ s.
- COMPOSITIONS [38] is a glass composition comprising: about 25 to about 55 mol% of P 2 O 5 ; about 5 to about 45 mol% of SiO 2 ; about 5 to about 22 mol% of Al 2 O 3 ; about 5 to about 30 mol% of ZnO; greater than 0 to about 20 mol% a total amount of Na 2 O, K 2 O, and/or Li 2 O; about 2 to about 8 mol% of CaO, and/or about 2 to about 8 mol% of MgO.
- the glass composition can also comprise about 25 mol% to about 55 mole% of P 2 O 5 , including exemplary values of about 26 mol%, about 27 mol%, about 28 mol%, about 29 mol%, about 30 mol%, about 31 mol%, about 32 mol%, about 33 mol%, about 34 mol%, about 35 mol%, about 36 mol%, about 37 mol%, about 38 mol%, about 39 mol%, about 40 mol%, about 41 mol%, about 42 mol%, about 43 mol%, about 44 mol%, about 45 mol%, about 46 mol%, about 47 mol%, about 48 mol%, and about 49 mol%.
- the glass composition can comprise about 5 to about 45 mol% of SiO 2 , including exemplary values of about 6 mol%, about 7 mol%, about 8 mol%, about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol%, about 13 mol%, about 14 mol%, about 15 mol%, about 16 mol%, about 17 mol%, about 18 mol%, about 19 mol%, about 20 mol%, about 21 mol%, about 22 mol%, about 23 mol%, about 24 mol%, about 25 mol%, about 26 mol%, about 27 mol%, about 28 mol%, about 29 mol%, about 30 mol%, about 31 mol%, about 32 mol%, about 33 mol%, about 34 mol%, about 35 mol%, about 36 mol%, about 37 mol%, about 38 mol%, about 39 mol%, about 40 mol%, about 41 mol%, about 42 mol%, about
- the glass composition can comprise about 5 to about 22 mol% of Al 2 O 3 , including exemplary values of about 6 mol%, about 7 mol%, about 8 mol%, about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol%, about 13 mol%, about 14 mol%, about 15 mol%, about 16 mol%, about 17 mol%, about 18 mol%, about 19 mol%, about 20 mol%, and about 21 mol%.
- the glass composition can comprise about 5 to about 30 mol% of ZnO, including exemplary values of about 6 mol%, about 7 mol%, about 8 mol%, about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol%, about 13 mol%, about 14 mol%, about 15 mol%, about 16 mol%, about 17 mol%, about 18 mol%, about 19 mol%, about 20 mol%, about 21 mol%, about 22 mol%, about 23 mol%, about 24 mol%, about 25 mol%, about 26 mol%, about 27 mol%, about 28 mol%, and about 29 mol%.
- the glass composition comprises greater than 0 to about 20 mol % a total amount of Na 2 O, K 2 O, and/or Li 2 O, including exemplary values of about 0.01 mol%, about 0.05 mol%, about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, 6 mol%, about 7 mol%, about 8 mol%, about 9 mol%, about 10 mol%, about 11 mol%, about 12 mol%, about 13 mol%, about 14 mol%, about 15 mol%, 16 mol%, about 17 mol%, about 18 mol%, and about 19 mol%.
- the glass composition can comprise Na 2 O, K 2 O, and Li 2 O, such that the total amount of Na 2 O, K 2 O, and Li 2 O falls within the disclosed above ranges.
- the glass composition disclosed herein can also comprise about 2 to about 8 mol % of MgO, including exemplary values of about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, and about 7 mol%.
- the glass composition can comprise both CaO and MgO. While in other aspects, the glass composition can comprise either CaO or MgO in any of the disclosed above amounts. [47] In still further aspects, the glass composition disclosed herein is comparable in its characteristics and properties with the conventional soda-lime silicate glass while exhibiting superior melting properties. It is understood that the compositions of conventional soda-lime silicate glass are known.
- the soda-lime silicate glasses comprise about 70-75 wt% of SiO 2 , about 12-17 wt% of Na 2 O, about 7-12 wt% of CaO, greater than 0 to about 2.5 wt % of Al 2 O 3 , greater than 0 to about 1.0 wt % of K 2 O, greater than 0 to about 5 wt % of MgO, greater than 0 to about 0.15 wt % of Fe 2 O 3 , 0 to about 0.5 wt % of TiO2, and in some instances 0 to about 0.5 wt % of SO3.
- the melting point of the soda-lime silicate glass is known to be in a range of about 1,400 to about 1,450 °C.
- the glass composition disclosed herein exhibits a melting point of at least about 50 °C, at least about 100 °C, at least about 150 °C, at least about 200 °C, at least about 250 °C, or at least about 300 °C less than the melting point of a conventional soda-lime silicate glass composition.
- the glass composition disclosed herein exhibits a melting point of less than about 1,400 °C, less than about 1,350 °C, less than about 1,300 °C, less than about 1,250 °C, less than about 1,200 °C, less than about 1,150 °C, or less than about 1,000 °C.
- the thermal properties disclosed above are determined by the disclosed composition.
- the specific composition of phosphate is determined due to the need to maintain a significant percentage of Q 3 bonded tetrahedra in the network to lower the melt temperature while simultaneously allowing for both silicate and alumina Q 4 bonded tetrahedra contributions to increase the chemical durability of the disclosed composition.
- the glass composition having the disclosed range of phosphates allows for achieving the disclosed low melting point while maintaining sufficient chemical durability.
- the disclosed range for silicates also was observed to allow sufficient chemical durability without the need for high melting temperatures. It is understood that sufficient chemical durability can be determined by the specific application. It is further understood that the actual durability can be dependent on the exact glass composition and the specific conditions it is exposed. For example and without limitations, the condition can include the type of solvent the glass is present in, the solvent’s pH, the presence of corrosive elements, temperature, and the like. The durability can be tailored to the specific application.
- the glass compositions used to create artistic artifacts will have different sufficient chemical durability as compared to the articles used as tableware or cookware or labware.
- the disclosed amount of alumina was found to be sufficient to maintain the melt conditions and needed Q 4 bonded tetrahedra for sufficient chemical durability.
- the presence of alumina in the disclosed ranges can also impart additional mechanical stability to the glass.
- the disclosed amount of ZnO can also help increase the chemical durability of the glass composition without altering the electronic configuration of the glass and without substantially imparting coloration of the glass.
- the disclosed herein glass compositions can further comprise iron oxides.
- the glass composition can comprise up to about 10 mol% of Fe 2 O 3 , including exemplary amounts of about 0.01 mol%, about 0.05 mol%, about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 1.5 mol%, about 2 mol%, about 2.5 mol%, about 3 mol%, about 3.5 mol%, about 4 mol%, about 4.5 mol%, about 5 mol%, about 5.5 mol%, about 6 mol%, about 6.5 mol%, about 7 mol%, about 7.5 mol%, about 8 mol%, about 8.5 mol%, about 9 mol%, and about 9.5 mol%.
- the glass composition can be substantially color free.
- a specific color of glass composition can be determined spectroscopically.
- such a composition when the glass composition is substantially color free, such a composition exhibits an absorption coefficient average over the visible range of about 400 to about 800 nm, including the wavelength of about 450 nm, about 500 nm, about 550 nm, about 600 nm, about 650 nm, about 700 nm, and about 750 nm, of less than or equal to about 0.49 cm -1 , including exemplary values of less than or equal to about 0.45 cm -1 , less than or equal to about 0.4 cm -1 , less than or equal to about 0.35 cm -1 , less than or equal to about 0.3 cm -1 , less than or equal to about 0.25 cm -1 , and less than or equal to about 0.2 cm -1 .
- such a composition when the glass composition is substantially color-free, such a composition exhibits a percent transmittance greater than about 80%, greater than about 85%, greater than about 90%, greater than about 95%, or even greater than about 99% over a wavelength range of about 400 nm to about 800 nm, including wavelength about 450 nm, about 500 nm, about 550 nm, about 600 nm, about 650 nm, about 700 nm, and about 750 nm.
- composition when Fe 2 O 3 is present in amount of about 0.5 to about 5 mol%, including exemplary amounts of about 0.6 mol%, about 0.6 mol%, about 0.8 mol%, about 0.9 mol%, about 1 mol%, about 1.5 mol%, about 2 mol%, about 2.5 mol%, about 3 mol%, about 3.5 mol%, about 4 mol%, and about 4.5 mol%, such a composition can be translucent grey.
- the composition can also comprise other valencies of iron oxides, for example, FeO or a combination of Fe 2 O 3 and FeO.
- the specific ratio can be determined based on the desired color. In yet other aspects, the ratio can also be affected by the potential presence of other ions, such as, for example and without limitations, alkali ions or other intermediates.
- the composition can also comprise multiple valences of Mn, Cr, and/or Ni to achieve the desired color of the glass.
- iron oxides are often present in the batch products used to form the disclosed glass compositions.
- the disclosed glass compositions are either substantially color free or show edge-on- color grey.
- the glass composition when the amount of ion oxides is higher than about 0.5 mol%, the glass composition takes on a translucent grey color.
- the glass composition when the glass composition comprises up to about 10 mole% of iron oxide, such a composition becomes black.
- the black composition can be defined by color coordinates, such as L* being from 20.0 to 40.0, a* being from -1.0 to 1.0, and b* being from -5.0 to 2.0.
- the glass composition disclosed herein can comprise additional transitional metals in various concentrations.
- additional transitional metals can be present as salts or oxides.
- the composition can further comprise one more transitional metal oxides comprising oxides of copper, nickel, cobalt, chromium, silver, tin, or any combination thereof. It is understood that any known valencies of such transitional metals can be present in the composition.
- the one or more transition metal oxides are present in an amount up to about 2 mol %, including exemplary values of about 0.01 mol%, about 0.05 mol%, about 0.1 mol%, about 0.15 mol%, about 0.2 mol%, about 0.25 mol%, about 0.3 mol%, about 0.35 mol%, about 0.4 mol%, about 0.45 mol%, about 0.5 mol%, about 0.55 mol%, about 0.6 mol%, about 0.65 mol%, about 0.7 mol%, about 0.75 mol%, about 0.8 mol%, about 0.85 mol%, about 0.9 mol%, about 0.95 mol%, about 1.0 mol%, about 1.05 mol%, about 1.1 mol%, about 1.15 mol%, about 1.2 mol%, about 1.25 mol%, about 1.3 mol%, about 1.35 mol%, about 1.4 mol%, about 1.45 mol%, about 1.5 mol%, about 1.55 mol
- such a glass composition when the one or more transition metal ions are present, such a glass composition can obtain a specific color as desired.
- the glass composition as described herein can be translucent.
- such exemplary and unlimited glass composition can exhibit a percent transmittance less than about 85%, less than about 80%, less than about 75%, less than about 70%, less than about 65%, less than about 60%, less than about 55%, or less than about 50% over a wavelength range of about 400 nm to about 800 nm, including the wavelengths of about 450 nm, about 500nm, about 550 nm, about 600 nm, about 650 nm, about 700 nm, and about 750 nm.
- the glass composition can exhibit photochromicity.
- the glass composition disclosed herein can comprise one or more rare-earth metal compounds. Again, without wishing to be bound by any theory, it is assumed that the inclusion of rare-earth metals can further provide photoluminescence properties to the disclosed herein glass compositions. Such properties in certain aspects can be leveraged to produce laser host materials if desired.
- the glass composition is photoluminescent.
- the one or more rare earth metal ions are present in an amount up to about 10 mol%, including exemplary values of about 0.01 mol%, about 0.05 mol%, about 0.1 mol%, about 0.5 mol%, about 1 mol%, about 1.5 mol%, about 2 mol%, about 2.5 mol%, about 3 mol%, about 3.5 mol%, about 4 mol%, about 4.5 mol%, about 5 mol%, about 5.5 mol%, about 6 mol%, about 6.5 mol%, about 7 mol%, about 7.5 mol%, about 8 mol%, about 8.5 mol%, about 9 mol%, and about 9.5 mol%.
- the disclosed herein glass composition exhibits a difference between the crystallization temperature and the glass transition temperature greater than about 100 °C when measured at room temperature and ambient pressure. It is understood that such property shows resistance to crystallization and, therefore, would allow the formation of various articles by any known in the art methods, such as, for example, and without limitation, down drawing (by either a slot draw or fusion draw process), fiber-drawing, float processing, or thin rolling the glass, and the like.
- the methods can comprise shaping the glass to any desired shape. Various shaping methods can also be used, such as casting, molding, pressing, rolling, floating, and the like.
- the articles disclosed herein can be formed by a float/flat glass press process, a press-and-blow process, a blow-and-blow process, or any combination thereof.
- the methods can also comprise glassblowing, hot casting, flameworking, kiln casting, and/or kiln forming. It is further understood that other low temperature glass-making methods can also be utilized. For example, and without limitations, glass wheel forming methods are also contemplated.
- the disclosed herein glass compositions are substantially free of carbonates. It is understood, however, that the batch material used to form the disclosed herein glass compositions can contain some amounts of carbonates.
- the glass composition disclosed herein exhibits a linear temperature expansion coefficient greater than about 80 x 10 -7 K -1 , greater than about 90 x 10 -7 K -1 , greater than about 100 x 10 -7 K -1 , greater than about 110 x 10 -7 K -1 , greater than about 120 x 10 -7 K -1 , greater than about 130 x 10 -7 K -1 , greater than or equal to about 140 x 10 -7 K -1 .
- methods of machine forming of the disclosed herein glass compositions would need to be adjusted for lower temperature working range and reduced radiative heat flux loss, but at a potentially significant CTE. In some aspects, additional cooling could be needed during the glass transition.
- the Vickers hardness of the disclosed herein glasses is dependent on the applied load.
- the disclosed herein glass compositions can exhibit Vickers hardness substantially equal to or less than Vickers hardness of a conventional soda-lime glass composition.
- any of the disclosed herein glass compositions can exhibit a crack resistance greater than a crack resistance of a conventional soda- lime glass composition.
- Crack resistance is defined as the force at which 50% of the corners of a Vickers indent are expected to have cracks and can be thought of as the resistance of a material to crack initiation. It is a particularly important mechanical property for glasses, as it can be used to characterize the glass's damage resistance.
- the glass compositions disclosed herein can exhibit a crack resistance greater than about 0.1 kgf, greater than about 0.2 kgf, greater than about 0.3 kgf, greater than about 0.4 kgf, greater than about 0.5 kgf, greater than about 0.6 kgf, greater than about 0.7 kgf, greater than about 0.8 kgf, greater than about 0.9 kgf, or even greater than about 1.0 kgf.
- any of the disclosed above compositions comprising any of the disclosed above compositions.
- articles comprising a glass composition comprising about 25 to about 55 mol% of P 2 O 5 ; about 5 to about 45 mol% of SiO 2 ; about 5 to about 22 mol% of Al 2 O 3 ; about 5 to about 30 mol% of ZnO; greater than 0 to about 20 mol% a total amount of Na 2 O, K 2 O, and/or Li 2 O; about 2 to about 8 mol% of CaO, and/or about 2 to about 8 mol% of MgO.
- any of the disclosed above additional elements can be present in the glass compositions used to form the disclosed herein articles.
- the articles can be transparent or translucent depending on the desired applications.
- the articles can also be photoluminescent. It is further understood that other ions and elements can also affect the translucency of the article.
- the translucence can be obtained by any of the disclosed above additives, including but not limited to, for example, by the addition of tin oxides.
- the articles can comprise any known in the art articles that require the disclosed herein mechanical, chemical, and optical properties.
- the articles disclosed herein can comprise a hollowware, tableware, container, plate, sheet (including sheets prepared via the float process), cookware, powder, fiber, cones, spheres, blades, or any combination thereof.
- the articles can comprise foodware, tableware, cookware, flat glass, windows, windshields, hollowware, jars, art and craft glass objects, laser host materials, optical fibers, hollow fibers, tubing fibers, lab-usable containers, or any combination thereof.
- the articles can be formed to both satisfy technological demands (high chemical resistance and durability, mechanical strength combined with low melting point, and the like) and artistic expression and aesthetic appearances.
- the color of the articles can be controlled by changing the amount of iron oxide and/or amounts of one or more other transitional oxides to form the desired articles.
- articles having darker colors can be formed.
- the articles can comprise colored bottles (wine bottles, beer bottles, etc.), colored pharmaceutical vials/ampoules (to protect light-sensitive medicines), sunglass lenses, art or craft objects, and the like.
- the articles disclosed herein can be formed by any process.
- the articles can be formed by a float or flat press process, a press-and-blow process, a fiber-drawing process, a blow-and-blow process, or any combination thereof.
- articles can also be used in a variety of electronic devices or portable computing devices, light diffusers, automotive, appliances, medical industry, food industry, and even architectural applications.
- the articles disclosed herein can have any known in the art shape or configuration.
- a method comprising: a) providing: about 25 to about 55 mol% of P 2 O 5 ; about 5 to about 45 mol% of SiO 2 ; about 5 to about 22 mol% of Al 2 O 3 ; about 5 to about 30 mol% of ZnO; greater than 0 to about 20 mol % a total amount of Na 2 O, K 2 O, and/or Li 2 O; about 2 to about 8 mol% of CaO, and/or about 2 to about 8 mol % of MgO; b) forming a homogeneous mixture; c) melting the mixture at a temperature of about 1,000 °C to about 1,300 °C; and cooling the composition to form a glass composition.
- the glass composition is any of the disclosed above glass compositions.
- the mixture can be melted at a temperature of about 1,000 °C to about 1,300 °C, including exemplary values of about 1,050 °C, about 1,100 °C, about 1,150 °C, about 1,200 °C, and about 1,250 o C.
- any of the disclosed above components and elements can also be present in the mixture prior to the melt.
- the plurality of nanoparticles can be formed during the melting and cooling process and present in the cooled article.
- the methods can further comprise forming any of the disclosed above articles.
- the glass compositions can exhibit any of the disclosed above characteristics and properties. In such exemplary aspects, these compositions can be transparent, translucent, or opaque depending on the specific percentage of each component and have any of the disclosed above color characteristics. [88] In still further aspects, the methods of forming the disclosed herein glass compositions exhibit at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50% reduction in CO2 emission as compared to a reference method of making a conventional soda-lime glass composition. It is understood that such reduction in CO2 can be explained by lower melting points of the composition and by the substantial absence of carbonates in the composition itself.
- the methods disclosed herein can require at least about 30% less, at least about 35% less, at least about 40% less, at least about 45% less, or at least about 50% less btu as compared to a reference method of making a conventional soda-lime glass composition.
- the methods disclosed herein require at least about 50%, at least about 55%, at least about 60%, at least about 65%, or at least about 70% of the power required for soda-lime silicate glass manufacture.
- the methods disclosed herein comprise a step of forming a glass article.
- any known in the art methods of forming or shaping an article can be utilized.
- the methods of forming a glass article disclosed herein can comprise down drawing (by either a slot draw or fusion draw process), fiber-drawing, float processing, or thin rolling of the glass.
- the methods can comprise shaping the glass to any desired shape.
- Various shaping methods can also be used, such as casting, molding, pressing, rolling, drawing, floating, and the like.
- the articles disclosed herein can be formed by a float/flat glass press process, a press-and- blow process, a blow-and-blow process, or any combination thereof.
- the methods can also comprise glassblowing, hot casting, flameworking, kiln casting, and/or kiln forming. It is further understood that other low temperature glass-making methods can also be utilized. For example, and without limitations, glass wheel forming methods are also contemplated.
- EXAMPLE 1 [93] Table 1 shows the comparative properties of the exemplary article formed according to the disclosure in one aspect and the soda-lime silicate article.
- EXAMPLE 2 [94] Tables 2 and 3 show exemplary and unlimiting glass compositions as formed according to this disclosure. [95] Table 1. Comparison of properties of the articles formed from the soda-lime silicate reference composition and the exemplary composition disclosed herein in one aspect (Glass No.1 in Table 2, 5, and 6). 0 0 0 0 0 0 0 0 0 ) % 0 l 0 o 0 m ( .
- Table 4 shows glass compositions according to some aspects of the disclosure and a reference soda-lime silicate glass composition as disclosed in Ashby, M.F. Material profiles. In Materials and the Environment, 2 nd ed.; Elsevier, 2013, pp.459-595, in mol.% Table 4. Composition of various glasses according to some aspects of the disclosure and a soda-lime silicate composition for comparison (mol%).
- Table 5 exhibits the glass transition temperature (Tg) of the exemplary glass composition that was annealed at 700 K for one hour according to one aspect of the disclosure at four evenly distributed and slow heating rates (the values were calculated by using TransitionPy software).
- Tg glass transition temperature
- FIG.1 shows the absorption spectrum of the glass composition according to one aspect in the wavelength range of 300-850 nm. Table 5. Glass Transition Temperature as a function of heating rate (Glass 1 from Table 2)
- Table 6 shows the thermal properties of Glass 1 measured via DSC at a heating rate of 10 K. min and subsequently analyzed using Transition Py software. The values are compared to soda-lime silicate glass found in Mancini, M., Sendova, M., and Mauro, J. C.
- FIGS.2A-2D show the relaxation behavior of the glass composition according to one aspect.
- glass was melted at 1.5xTg, quenched at 10 °C/min to room temperature, and then reheated to 0.9xTg and held for one hour to allow relaxation.
- Stretching parameter beta evolution is shown in Fig.2A.
- Fig.2B shows the viscosity evolution, while relaxation time evolution is shown in Fig.2C.
- Fig.2D shows the thermal history of the simulation.
- EXAMPLE 4 [101] Various glass compositions were evaluated to measure their linear temperature expansion coefficient (CTE), and the results are shown in Table 7. Table 7.
- CTE linear temperature expansion coefficient
- ASPECTS [108] A glass composition comprising: about 25 to about 55 mol% of P 2 O 5 ; about 5 to about 45 mol% of SiO 2 ; about 5 to about 22 mol% of Al 2 O 3 ; about 5 to about 30 mol% of ZnO; greater than 0 to about 20 mol% a total amount of Na 2 O, K 2 O, and/or Li 2 O; about 2 to about 8 mol% of CaO, and/or about 2 to about 8 mol% of MgO.
- Aspect 2 The glass composition of Aspect 1, wherein the glass composition exhibits a melting point of at least about 150 °C less than the melting point of a conventional soda-lime silicate glass composition.
- Aspect 3 The glass composition of Aspect 1 or 2, wherein the glass composition exhibits a melting point of at least about 250 °C less than the melting point of a conventional soda-lime silicate glass composition.
- Aspect 4 The glass composition of any one of Aspects 1-3, wherein the glass composition exhibits a melting point of less than about 1,400 °C.
- Aspect 5 The glass composition of any one of Aspects 1-4, further comprising Fe 2 O 3 in an amount up to about 10 mole%.
- Aspect 6 The glass composition of Aspect 5, wherein when Fe 2 O 3 is present up to about 0.5 mol%, the glass composition is substantially color-free.
- Aspect 7 The glass composition of Aspect 6, wherein the composition exhibits an absorption coefficient average over the visible range of about 400 to about 800 nm less than or equal to about 0.49 cm -1 .
- Aspect 8 The glass composition of Aspect 6 or 7, wherein the glass composition exhibits a percent transmittance greater than about 80% over a wavelength range of about 400 nm to about 800 nm.
- Aspect 9 The glass composition of Aspect 5, wherein when Fe 2 O 3 is present in an amount of about 0.5 mol% to about 5 mol%, the glass composition is translucent grey.
- Aspect 10 The glass composition of any one of Aspects 1-5, further comprising one or more transitional metal oxides comprising oxides of copper, nickel, cobalt, chromium, silver, tin, or any combination thereof.
- Aspect 11 The glass composition of Aspect 10, wherein the one or more transition metal oxides are present in an amount up to about 2 mol %.
- Aspect 12 The glass composition of Aspect 11, wherein the glass composition is translucent.
- Aspect 13 The glass composition of Aspect 11 or 12, wherein the glass composition exhibits a percent transmittance less than about 85% over a wavelength range of about 400 nm to about 800 nm.
- Aspect 14 The glass composition of any one of Aspects 10-13, wherein the glass composition comprises a plurality of nanoparticles.
- Aspect 15 The glass composition of any one of Aspects 1-14, wherein the glass composition comprises one or more rare earth metal ions.
- Aspect 16 The glass composition of Aspect 15, wherein the one or more rare earth metal ions are present in an amount up to about 10 mol%.
- Aspect 17 The glass composition of Aspect 15 or 16, wherein the glass composition is photoluminescent.
- Aspect 18 The glass composition of any one of Aspects 1-17, wherein the composition exhibits a difference between the crystallization temperature and the glass transition temperature greater than about 100 °C when measured at room temperature and ambient pressure.
- Aspect 19 The glass composition of any one of Aspects 1-18, wherein the glass composition is substantially free of carbonates.
- Aspect 20 The glass composition of any one of Aspects 1-19, wherein the glass composition exhibits a linear temperature expansion coefficient greater than about 100 x 10 -7 K -1 .
- Aspect 21 The glass composition of any one of Aspects 1-20, wherein the glass composition exhibits a crack resistance greater than about 0.1 kgf.
- Aspect 22 The glass composition of any one of Aspects 1-21, wherein the glass composition exhibits a crack resistance greater than about 0.3 kgf.
- Aspect 23 The glass composition of any one of Aspects 1-22, wherein the glass composition exhibits a crack resistance greater than about 0.6 kgf.
- Aspect 24 The glass composition of any one of Aspects 1-23, wherein the glass composition exhibits a crack resistance greater than about 1.0 kgf.
- Aspect 25 An article comprising the glass composition of any one of Aspects 1-24.
- Aspect 26 The article of Aspect 25, comprising foodware, tableware, cookware, flat glass, windows, windshields, hollowware, jars, art and craft glass objects, laser host materials, optical fibers, hollow fibers, lab-usable containers, or any combination thereof.
- a glass article comprising a glass composition comprising about 25 to about 55 mol% of P 2 O 5 ; about 5 to about 45 mol% of SiO 2 ; about 5 to about 22 mol% of Al 2 O 3 ; about 5 to about 30 mol% of ZnO; greater than 0 to about 20 mol % a total amount of Na 2 O, K 2 O, and/or Li 2 O; about 2 to about 8 mol% of CaO, and/or about 2 to about 8 mol % of MgO.
- Aspect 28 The article of Aspect 27, wherein the glass composition exhibits a melting point of at least about 150 °C less than the melting point of a conventional soda-lime silicate glass composition.
- Aspect 40 The article of any one of Aspects 36-39, wherein the glass composition comprises a plurality of nanoparticles.
- Aspect 41 The article of any one of Aspects 27-40, wherein the glass composition comprises one or more rare earth metal ions.
- Aspect 42 The article of Aspect 41, wherein the one or more rare earth metal ions are present in an amount up to about 10 mol%.
- Aspect 43 The article of any one of Aspects 41 or 42, wherein the article exhibits photoluminescence.
- a method comprising: a) providing: about 25 to about 55 mol% of P 2 O 5 ; about 5 to about 45 mol% of SiO 2 ; about 5 to about 22 mol% of Al 2 O 3 ; about 5 to about 30 mol% of ZnO; greater than 0 to about 20 mol % a total amount of Na 2 O, K 2 O, and/or Li 2 O; about 2 to about 8 mol% of CaO, and/or about 2 to about 8 mol % of MgO; b) forming a homogeneous mixture; c) melting the mixture at a temperature of about 1,000 °C to about 1,300 °C; and cooling the composition to form the glass composition of any one of Aspects 1-26.
- Aspect 53 The method of Aspect 52, wherein the method further comprises forming an article comprising the glass composition.
- Aspect 54 The method of any one of Aspects 52 or 53, wherein the method exhibits at least about 25% reduction in CO2 emission as compared to a reference method of making a conventional soda-lime glass composition.
- Aspect 55 The method of any one of Aspects 52-54, wherein the method comprising requiring at least about btu as compared to a reference method of making a conventional soda-lime glass composition.
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Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202263319975P | 2022-03-15 | 2022-03-15 | |
| PCT/US2023/015177 WO2023177659A1 (en) | 2022-03-15 | 2023-03-14 | Low-melting glass compositions, articles, and methods of making the same |
Publications (2)
| Publication Number | Publication Date |
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| EP4493526A1 true EP4493526A1 (en) | 2025-01-22 |
| EP4493526A4 EP4493526A4 (en) | 2026-03-18 |
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| EP23771314.4A Pending EP4493526A4 (en) | 2022-03-15 | 2023-03-14 | LOW-METING GLASS COMPOSITIONS, ARTICLES AND METHOD FOR THEM TO BE MADE |
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| EP (1) | EP4493526A4 (en) |
| JP (1) | JP2025509826A (en) |
| KR (1) | KR20240164516A (en) |
| CN (1) | CN118973972A (en) |
| AU (1) | AU2023234349A1 (en) |
| WO (1) | WO2023177659A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP4524117A1 (en) * | 2023-09-12 | 2025-03-19 | The Penn State Research Foundation | Low-melting glass compositions, articles, and methods of making the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5021366A (en) * | 1990-10-19 | 1991-06-04 | Corning Incorporated | Fluorine-free phosphate glasses |
| US5668066A (en) * | 1995-07-24 | 1997-09-16 | Hoya Corporation | Near infrared absorption filter glass |
| ATE369829T1 (en) * | 2003-12-22 | 2007-09-15 | 3M Espe Ag | GLASS FILLING MATERIAL AND PROCESS FOR PRODUCTION |
| CN101117271B (en) * | 2007-07-25 | 2010-12-15 | 中国科学院上海光学精密机械研究所 | Ytterbium-bismuth co-doped phosphate-based optical glass and method of making the same |
| JP5601319B2 (en) * | 2009-05-13 | 2014-10-08 | 旭硝子株式会社 | Cover glass for solid-state image sensor package |
| CN102190439A (en) * | 2010-03-16 | 2011-09-21 | 李胜春 | Blue phosphate glass used for high-power tube, and preparation method thereof |
-
2023
- 2023-03-14 AU AU2023234349A patent/AU2023234349A1/en active Pending
- 2023-03-14 JP JP2024555338A patent/JP2025509826A/en active Pending
- 2023-03-14 EP EP23771314.4A patent/EP4493526A4/en active Pending
- 2023-03-14 CN CN202380028261.1A patent/CN118973972A/en active Pending
- 2023-03-14 WO PCT/US2023/015177 patent/WO2023177659A1/en not_active Ceased
- 2023-03-14 KR KR1020247030899A patent/KR20240164516A/en active Pending
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| WO2023177659A1 (en) | 2023-09-21 |
| EP4493526A4 (en) | 2026-03-18 |
| AU2023234349A1 (en) | 2024-10-24 |
| CN118973972A (en) | 2024-11-15 |
| KR20240164516A (en) | 2024-11-19 |
| JP2025509826A (en) | 2025-04-11 |
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