CN112079565B - Glass composition, gradient index glass and manufacturing method thereof - Google Patents

Glass composition, gradient index glass and manufacturing method thereof Download PDF

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CN112079565B
CN112079565B CN202011022331.7A CN202011022331A CN112079565B CN 112079565 B CN112079565 B CN 112079565B CN 202011022331 A CN202011022331 A CN 202011022331A CN 112079565 B CN112079565 B CN 112079565B
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glass
expressed
composition
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glass composition
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CN112079565A (en
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马赫
毛露路
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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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
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • 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
    • C03C21/005—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 introduce in the glass such metals or metallic ions as Ag, Cu
    • 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
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium

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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)

Abstract

The invention provides a glass composition, the components of which are expressed by mole percent, and cations of which contain: si4+：30～56％；Al3+：18～25％；B3+：2～10％；Li++Na++K++Rb++Ag+: 20 to 35% of (B)3++Al3+)/(Li++Na++K++Rb++Ag+) 1.0 to 1.3, and the glass composition does not contain Tl+. Through reasonable component design, the glass composition obtained by the invention does not contain thallium, has a large ion diffusion coefficient, and is suitable for manufacturing gradient refractive index glass.

Description

Glass composition, gradient index glass and manufacturing method thereof
Technical Field
The present invention relates to a glass composition, and more particularly to a glass composition suitable for producing a gradient index glass, and a gradient index glass and a method for producing the same.
Background
A Gradient index (GRIN) lens is an optical element used to alter the trajectory of light. The gradient index lens is generally in the shape of a cylinder, a quadrangular prism, a hexagonal prism, a rectangular parallelepiped, or the like. Gradient index lenses generally act in the optical path as convex lenses, but can also be used as concave lenses, the ability to change the trajectory of the light being achieved by a specific continuous change in internal refractive index. The GRIN lens has the advantages of extremely small focal length, large light-receiving angle and easy and accurate assembly, and is mainly applied to optical fiber optical systems, compact optical systems and the like.
Gradient index lenses are generally manufactured by ion exchange methods, which require that the glass constituting the gradient index lens contain a certain proportion of alkali metal components, since alkali metals are external to the glass network and are easily ion-exchanged with the outside. Prior art patents US4495298, US4495299, CN107572776A, etc. disclose gradient index glasses containing a thallium (Tl) component. However, the glass containing thallium component has huge biological toxicity, so that the glass cannot be applied to the fields of medical treatment, neuroscience and the like, and the environmental pollution in the smelting and recovery processes is also large.
In order to solve the problems of toxicity and environmental hazard of the gradient refractive index lens glass, two technical means are available at present. The first means is to apply a coating to a glass preform made of gradient index glass or a gradient index lens, as disclosed in Neurosci Bull.2019,35(3):419-424, which has the effect of preventing the cell topography around the endoscopic lens from shrinking and neurite reduction by coating the surface of the gradient index lens containing thallium. However, in practice the film is susceptible to scratching and corrosion resulting in failure and this approach does not eliminate the environmental hazards of glass melting. The second means is to adopt a certain content of sodium element to replace thallium element in the glass and obtain the gradient refractive index by a silver-sodium ion exchange method, but the ion diffusion coefficient in the method is small, and the problems of long time consumption of silver-sodium ion exchange and the like cannot be overcome.
Disclosure of Invention
The invention aims to provide a glass composition which has a large ion diffusion coefficient, is suitable for ion exchange to manufacture gradient refractive index glass and does not contain thallium.
The invention also provides a gradient index glass without thallium.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) a glass composition having components, expressed in mole percent, cations comprising: si4+：30～56％；Al3+：18～25％；B3+：2～10％；Li++Na++K++Rb++Ag+: 20 to 35% of (B)3++Al3+)/(Li++Na++K++Rb++Ag+) 1.0 to 1.3, and the glass composition does not contain Tl+。
(2) The glass composition according to (1), whose components are expressed in mole percent, the cations further comprising: zn2+: 0 to 5 percent; and/or Mg2+: 0 to 5 percent; and/or Ca2+: 0 to 5 percent; and/or Sr2+: 0 to 5 percent; and/or Ba2+: 0 to 5 percent; and/or Zr4+：0～3％。
(3) Glass composition having components expressed in mole percent, the cations being represented bySi4+：30～56％；Al3+：18～25％；B3+：2～10％；Li++Na++K++Rb++Ag+：20～35％；Zn2+：0～5％；Mg2+：0～5％；Ca2+：0～5％；Sr2+：0～5％；Ba2+：0～5％；Zr4+: 0 to 3% of a component (B)3++Al3+)/(Li++Na++K++Rb++Ag+) 1.0 to 1.3.
(4) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: si4+: 37-44%; and/or Al3+: 20-25%; and/or B3+: 4-8%; and/or Li++Na++K++Rb++Ag+: 27 to 33 percent; and/or Zn2+: 0.2 to 5%, preferably Zn2+: 1-2.5%; and/or Mg2+: 0-2%; and/or Ca2+: 0-2%; and/or Sr2+: 0-2%; and/or Ba2+: 0-2%; and/or Zr4+：0～1％。
(5) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: (B)3++Al3+)/(Li++Na++K++Rb++Ag+) 1.05 to 1.2.
(6) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: b is3+/(B3++Al3+) 0.1 to 0.35, preferably B3+/(B3++Al3+) 0.15 to 0.3.
(7) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: zn2+/(Al3++B3++Si4+) 0.003 to 0.08, preferably Zn2+/(Al3++B3++Si4+) 0.01 to 0.03.
(8) The glass composition according to any one of (1) to (3), whose components are expressed in mol%, wherein: na (Na)+：1832% by weight, preferably Na+: 25-32%; and/or Li+: 0 to 5%, preferably Li+: 0 to 3 percent; and/or K+: 0 to 10%, preferably K+: 0 to 5 percent; and/or Rb+: 0 to 5%, preferably Rb+: 0 to 2; and/or Ag+: 0 to 2.5%, preferably Ag+: 0 to 1.5%, more preferably Ag+：0～0.5％。
(9) The glass composition according to any one of (1) to (3), wherein the components do not contain Mg2+(ii) a And/or does not contain Ca2 +(ii) a And/or does not contain Sr2+(ii) a And/or do not contain Ba2+(ii) a And/or does not contain Zr4+(ii) a And/or does not contain Rb+(ii) a And/or does not contain Pb2 +(ii) a And/or does not contain Cd2+(ii) a And/or does not contain Ti4+(ii) a And/or does not contain As3+(ii) a And/or do not contain Sb3+(ii) a And/or does not contain Ce4 +(ii) a And/or does not contain Sn4+。
(10) The glass composition according to any one of (1) to (3), wherein the glass composition has the following composition in terms of mole percent, and the anion contains: o is2-: 99 to 100%, preferably O2-: 99.5 to 99.95 percent; and/or Cl-+F-: 0 to 1%, preferably Cl-+F-：0.05～0.5％。
(11) The glass composition according to any one of (1) to (3), wherein the glass composition has a refractive index nd1.48 to 1.51; and/or Abbe number vd46 to 60, preferably 48 to 58; and/or light transmission lambda70Is 350nm or less.
(12) The glass composition according to any one of (1) to (3), wherein the glass composition has a light transmittance λ after a sufficient ion exchange for one timeAfter 70-full exchange420nm or less, preferably 410nm or less, more preferably 400nm or less; and/or the difference Deltan between the refractive index of the glass composition after the first sufficient ion exchange and the refractive index of the glass composition is 0.08-0.15, preferably 0.1-0.14.
(13) A gradient index glass produced by using the glass composition according to any one of (1) to (12).
(14) Gradient index glass having a composition, expressed in mole percent, with cations comprising: si4+：30～56％；Al3 +：18～25％；B3+：2～10％；Li++Na++K++Rb++Ag+: 20 to 35% of (B)3++Al3+)/(Li++Na++K++Rb++Ag+) Is 1.0 to 1.3, and the gradient refractive index glass does not contain Tl+。
(15) The gradient index glass according to (14), whose composition is expressed in mole percent, the cations further contain: zn2+: 0 to 5 percent; and/or Mg2+: 0 to 5 percent; and/or Ca2+: 0 to 5 percent; and/or Sr2+: 0 to 5 percent; and/or Ba2+: 0 to 5 percent; and/or Zr4+：0～3％。
(16) Gradient index glasses having a composition expressed in mole percent with cations of Si4+：30～56％；Al3+：18～25％；B3+：2～10％；Li++Na++K++Rb++Ag+：20～35％；Zn2+：0～5％；Mg2+：0～5％；Ca2+：0～5％；Sr2+：0～5％；Ba2+：0～5％；Zr4+: 0 to 3% of a component (B)3++Al3+)/(Li++Na++K++Rb++Ag+) 1.0 to 1.3.
(17) The gradient refractive index glass according to any one of (14) to (16), which has the following components in mol%: si4+: 37-44%; and/or Al3+: 20-25%; and/or B3+: 4-8%; and/or Li++Na++K++Rb++Ag+: 27 to 33 percent; and/or Zn2+: 0.2 to 5%, preferably Zn2+: 1-2.5%; and/or Mg2+: 0-2%; and/or Ca2+: 0-2%; and/or Sr2+: 0-2%; and/or Ba2+: 0-2%; and/or Zr4+：0～1％。
(18) The gradient refractive index glass according to any one of (14) to (16), which has the following components in mol%: (B)3++Al3+)/(Li++Na++K++Rb++Ag+) 1.05 to 1.2.
(19) The gradient refractive index glass according to any one of (14) to (16), which has the following components in mol%: b is3+/(B3++Al3+) 0.1 to 0.35, preferably B3+/(B3++Al3+) 0.15 to 0.3.
(20) The gradient refractive index glass according to any one of (14) to (16), which has the following components in mol%: zn2+/(Al3++B3++Si4+) 0.003 to 0.08, preferably Zn2+/(Al3++B3++Si4+) 0.01 to 0.03.
(21) The gradient refractive index glass as described in any of (14) to (16), which does not contain Mg in its composition2+(ii) a And/or does not contain Ca2+(ii) a And/or does not contain Sr2+(ii) a And/or do not contain Ba2+(ii) a And/or does not contain Zr4+(ii) a And/or does not contain Rb+(ii) a And/or does not contain Pb2+(ii) a And/or does not contain Cd2+(ii) a And/or does not contain Ti4+(ii) a And/or does not contain As3+(ii) a And/or do not contain Sb3+(ii) a And/or does not contain Ce4+(ii) a And/or does not contain Sn4+。
(22) The gradient refractive index glass according to any one of (14) to (16), which has the following composition in mol%, and contains, as an anion: o is2-: 99 to 100%, preferably O2-: 99.5 to 99.95 percent; and/or Cl-+F-: 0 to 1%, preferably Cl-+F-：0.05～0.5％。
(23) A glass preform made of the glass composition according to any one of (1) to (12); or a glass having a gradient refractive index according to any one of (13) to (22).
(24) An optical element produced from the glass composition according to any one of (1) to (12); or the glass is made of the gradient refractive index glass of any one of (13) to (22); or using the glass preform of (23).
(25) An optical device comprising the glass composition according to any one of (1) to (12); and/or a glass composition comprising the gradient refractive index glass according to any one of (13) to (22); and/or an optical element comprising the same as (24).
(26) A method of manufacturing a gradient index glass, the method comprising the steps of: forming the glass composition according to any one of (1) to (12), and forming a gradient index glass from the glass composition by an ion exchange process, or forming a gradient index glass from the glass composition by an ion exchange process after manufacturing the glass composition into a glass molded body.
(27) The method for producing a gradient refractive index glass according to (26), wherein the ion exchange process comprises immersing the glass composition or the glass shaped body in a single salt bath, or immersing the glass composition or the glass shaped body in a plurality of salt baths having the same or different compositions.
(28) The method for producing a gradient refractive index glass as described in (26), wherein the ion exchange process comprises treating a glass composition or a glass shaped body by a two-step ion exchange method, and the molten salt for the first step of ion exchange is composed of two or more compounds in a certain ratio, at least one of the compounds containing Ag+The second step of ion exchange is carried out by mixing two or more compounds in a certain proportion, wherein at least one compound contains Na+。
(29) The method for producing a glass having a graded refractive index according to item (28), wherein the temperature of the first step ion exchange is 300 to 400 ℃, preferably 320 to 370 ℃, the time of the first step ion exchange is 600 hours or less, preferably 500 hours or less, more preferably 400 hours or less, the temperature of the second step ion exchange is 250 to 450 ℃, preferably 300 to 380 ℃, and the time of the second step ion exchange is 2 to 16 hours.
The invention has the beneficial effects that: through reasonable component design, the glass composition obtained by the invention does not contain thallium, has a large ion diffusion coefficient, and is suitable for manufacturing gradient refractive index glass.
Detailed Description
The glass composition of the present invention and the gradient refractive index glass of the present invention are described in detail below, but the present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this. In the following, the glass composition of the present invention is sometimes referred to simply as glass, and the glass composition is ion-exchanged to obtain a graded-index glass.
[ glass composition ]
The ranges of the respective components (ingredients) constituting the glass composition of the present invention are explained below. In the present specification, the content, total amount of each component is expressed in terms of ionic mole percent (mol%), that is, the content, total amount of each cationic component is the percentage of the total mole of the cationic component and all cationic components, if not specifically stated; the content, combined content, of the anionic component is the percentage of the total moles of the anionic component to all anionic components.
Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
It should be noted that the ion valences of the components described below are representative values used for convenience, and are not different from other ion valences, and it is within the scope of the present application that the ion valences of the components in the glass may be other than the representative values.
< cationic component >
Si4+Is a component of a network former of glass, and has the effects of maintaining the stability of glass and the forming viscosity of molten glass and improving the chemical stability. If Si4+Too high a content of (b) results in the glass being refractory and the light-gathering ability of the gradient index glass being reduced. Accordingly, the present inventionSi4+The content of (b) is in the range of 30 to 56%, preferably 37 to 44%.
Al3+Is a network former component of the glass, can improve the chemical stability of the glass and can obviously improve the ion diffusion coefficient of the glass. But Al3+Too much content causes difficulty in glass melting. Therefore, Al in the present invention3+The content of (b) is in the range of 18 to 25%, preferably 20 to 25%.
B3+Is a component of a network former of glass, can improve the melting property of glass raw materials, and can remarkably reduce the high-temperature viscosity of molten glass. But B3+The ion diffusion coefficient of the glass is significantly reduced. Thus, in the present invention B3+The content of (b) is 2 to 10%, preferably 4 to 8%.
Through a great deal of experimental research by the inventor, the inventor finds that in some embodiments of the invention, if B3+/(B3++Al3+) Below 0.1, the high-temperature viscosity of the glass liquid is too high, which causes the difficulty of clarification of the glass to be increased, the bubble degree grade of the glass to be reduced and the internal quality to be deteriorated; if B is3+/(B3++Al3+) Above 0.35, the ion diffusion coefficient of the glass decreases. Therefore, in the present invention, B is preferred3+/(B3++Al3+) 0.1 to 0.35, and more preferably B3+/(B3++Al3+) 0.15 to 0.3.
Na+Is a glass network external component and has an ionic radius of Ag+And is close to that, the component mainly participating in ion exchange in the glass. Increase Na+Content of Na in the graded index glass to enhance the refractive power of the graded index glass+It also has the effects of improving the meltability of glass and reducing the softening temperature of glass. However, Na+Too high a content results in excessive strain on the glass during ion exchange, and the glass is easily broken during ion exchange, and Na+Too high a content also reduces the chemical stability of the glass, which is not good for the glass to resist the attack of molten salts in ion exchange. Thus, Na+The content of (b) is in the range of 18 to 32%, preferably 25 to 32%.
Li+、K+Is glassThe glass network exosome component can also participate in ion exchange. Li+The glass melting aid has strong fluxing action and can obviously reduce the melting temperature of glass; but Li+Too high an amount of incorporation may reduce the devitrification resistance of the glass. Thus, Li+The content of (b) is in the range of 0 to 5%, preferably 0 to 3%. K+Has the effect of reducing the strain to which the glass is subjected during ion exchange, but K+Too high a content tends to cause devitrification of the glass. Thus, K+The content of (b) is in the range of 0 to 10%, preferably 0 to 5%.
Rb+Is a component of the external body of the glass network and can also participate in ion exchange, but the raw materials of the glass network are expensive, which is not beneficial to obtaining low-cost glass. Thus, Rb in the present invention+In the range of 0 to 5%, preferably 0 to 2%, more preferably not containing Rb+。
Ag+Is a glass network external component, and contains Ag in the glass composition+Can reduce the loss of silver-containing raw materials in the ion exchange process, reduce the production cost and reduce the harmful volatilization in the ion exchange process. But Ag+The solubility in molten glass is limited, and when the content is high, the melting time of the glass can be prolonged, and the energy loss is increased. Thus, Ag in the present invention+The content of (b) is in the range of 0 to 2.5%, preferably 0 to 1.5%, more preferably 0 to 0.5%.
Li+、Na+、K+、Rb+、Ag+Total content of (2) Li++Na++K++Rb++Ag+Directly related to the refractive power of the graded index glass designed according to the present invention. If Li++Na++K++Rb++Ag+If the refractive index is too small, the refractive power of the graded-index glass formed after ion exchange is weak, resulting in problems such as too long glass element size and small numerical aperture. But if Li++Na++K++Rb++Ag+Too large, too large gas rate of powder, difficult control of glass melting process and reduced chemical stability of glass. Therefore, Li is preferable in the present invention++Na++K++Rb++Ag+20 to 35 percentMore preferably 27 to 33%.
Al3+And B3+Having consumption of monovalent metal cation component (e.g. Li)+、Na+、K+、Rb+、Ag+) The non-bridging oxygen in the glass is preferably completely consumed by the effect of the introduced non-bridging oxygen, otherwise the glass is easily colored after ion exchange. If Al3+、B3 +If the amount is excessive, the ion diffusion coefficient of the glass is lowered. Therefore, in the present invention, it is preferable to control (B)3++Al3+)/(Li++Na++K++Rb++Ag+) 1.0 to 1.3, and more preferably (B)3++Al3+)/(Li++Na++K++Rb++Ag+) 1.05 to 1.2.
Zn2+The glass network intermediate component has the effects of reducing the melting temperature of glass and the devitrification tendency of the glass when the content is lower, and does not have obvious influence on the ion diffusion coefficient of the glass. But if Zn2+In excess of 5%, tends to devitrify the glass and to cause a decrease in the ion diffusion coefficient of the glass. Thus, Zn in the present invention2+The content of (b) is in the range of 0 to 5%, preferably 0.2 to 5%, more preferably 1 to 2.5%.
The inventors have discovered, through extensive research, that in some embodiments, by increasing Zn2+Content of (C) and Al3+、B3+、Si4+Total content of Al3++B3++Si4+Ratio Zn between2+/(Al3++B3++Si4+) It has obvious effect on the glass to resist the aggregation of Ag after ion exchange. However, if Zn2+/(Al3++B3++Si4+) Too large, the glass has an increased tendency to devitrify. Therefore, Zn is preferred in the present invention2+/(Al3++B3++Si4+) 0.003 to 0.08, more preferably Zn2+/(Al3++B3++Si4+) 0.01 to 0.03.
Mg2+、Ca2+、Sr2+And Ba2+With alkaline earth metal component in alkali metal componentUnder the condition of higher content, the glass can also be used as a network intermediate component of the glass, and has the effect of reducing the melting temperature of the glass within a certain content range. But contains Mg2+、Ca2+、Sr2+And Ba2+The tendency of the glass to devitrify increases. Therefore, Mg in the present invention2+The content of (B) is in the range of 0 to 5%, preferably 0 to 2%, more preferably not containing Mg2+；Ca2+The content of (B) is in the range of 0 to 5%, preferably 0 to 2%, more preferably not containing Ca2+；Sr2+In the range of 0 to 5%, preferably 0 to 2%, more preferably containing no Sr2+；Ba2+The content of (B) is in the range of 0 to 5%, preferably 0 to 2%, more preferably not containing Ba2+。
Zr4+The chemical stability of the glass can be improved, and the ion diffusion coefficient of the glass can be increased. However, in the glass of the present invention, Zr4+Has a very low solubility and a high Zr content4+Have a tendency to cause devitrification of the glass. Thus, Zr4+The content of (B) is in the range of 0 to 3%, preferably 0 to 1%, more preferably no Zr4+。
Tl+、Pb2+、Cd2+Has strong biological toxicity and is not beneficial to environmental protection, so the glass of the invention preferably does not contain Tl+And/or does not contain Pb2+And/or does not contain Cd2+。
Ti4+The ion diffusion coefficient of the glass can be increased, and in some embodiments, a certain amount of Ti can be included4+. But Ti4+Having a variable valence (i.e. Ti)3+) In ion exchange, redox reactions can occur leading to glass staining. Therefore, the glass of the present invention preferably does not contain Ti4+。
In some embodiments, a certain amount of As may be contained3+、Sb3+、Ce4+、Sn4+Used as a clarifying agent. But As3+、Sb3+、Ce4+、Sn4+Having variable valency (i.e. As)5+、Sb5+、Ce3+、Sn2+) In ion exchange can take placeThe redox reaction causes the glass to be colored. Therefore, the glass of the present invention preferably does not contain As3+And/or do not contain Sb3+And/or does not contain Ce4+And/or does not contain Sn4+。
< anionic Components >
The glass composition of the present invention is an oxide glass, and therefore the anionic component is mainly O2-The content range is 99-100%, preferably 99.5-99.95%.
The glass also contains anion Cl-、F-One or two of them. Cl-、F-Can be used as a clarifying agent, and can be violently volatilized in the high-temperature smelting process, so that small bubbles in the molten glass grow and float upwards, and the molten glass is promoted to roll, thereby achieving the clarifying effect. Cl-、F-The introduced amount is too small, and a good clarification effect cannot be achieved; when the introduced amount is too large, the light transmittance of the glass is reduced, and the ultraviolet absorption limit is shifted to the right. Thus, Cl in the glass-+F-The content of (b) is in the range of 0 to 1%, preferably 0.05 to 0.5%.
"0%" or "not containing" as used herein means that the component is not intentionally added to the glass of the present invention as a raw material; however, it is also within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the glass, and may be present in small or trace amounts in the final glass.
[ method for producing glass composition ]
Carbonate, nitrate, sulfate, hydroxide, oxide, fluoride, chloride, etc. are used as raw materials or cullet raw materials, and after being sufficiently and uniformly mixed, the raw materials are supplied into a melting vessel (such as a platinum crucible, a platinum alloy crucible, a quartz crucible, etc.), and then heated and melted. After the above glass raw materials are completely melted, the temperature of the molten glass is raised and fining is performed. Homogenizing the clarified molten glass by stirring with a stirrer, or continuously supplying the homogenized molten glass to a glass outflow pipeline for outflow, and rapidly cooling and solidifying the molten glass in a glass mold to obtain a glass composition; or pouring the mixture into a mold with a specific shape from a melting container, and carrying out processes of quenching, solidification and annealing to obtain the glass composition. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.
[ gradient refractive index glass and method for producing the same ]
Carrying out ion exchange on the glass composition by an ion exchange process to form gradient refractive index glass; or the glass composition is made into a glass forming body through various processes, and then ion exchange is carried out through an ion exchange process to form the glass with the gradient refractive index. The glass shaped bodies made from the glass compositions described above include, but are not limited to, glass preforms having a diameter, and the processes include, but are not limited to, cold working, wire drawing, or other processes known in the art.
The glass composition of the present invention can be used to produce a shaped body such as a glass preform by a method such as grinding or polishing, but the production of a glass shaped body is not limited to these methods. The glass composition of the present invention can be produced into glass shaped articles having various shapes by a method such as hot bending or press molding at a certain temperature, but the production of the glass shaped articles is not limited to these methods.
The glass shaped body includes, but is not limited to, a cylinder, a quadrangular prism, a hexagonal prism, a rectangular parallelepiped, or the like. The glass composition of the invention can also be directly manufactured into the shapes of a cylinder, a quadrangular prism, a hexagonal prism, a cuboid and the like during smelting and molding. The glass compositions or gradient index glasses of the present invention can have any thickness/diameter dimensional range that is reasonably useful.
The ion exchange process according to the present invention means that when the glass composition or the glass shaped body is immersed in a molten salt having a predetermined composition, monovalent metal cations (for example, Li) in the glass composition or the glass shaped body+、Na+、K+、Rb+、Cs+、Ag+Etc.) to other monovalent metal cations near the glass composition or glass shaped body.
The ion exchange process of the present invention is carried out by immersing the glass composition or glass shaped body in a single salt bath or immersing the glass composition or glass shaped body in a plurality of salt baths having the same or different compositions. When ion exchange is performed in multiple salt baths of different compositions, there may be washing and/or annealing steps between immersions.
In some embodiments of the invention, the glass composition or glass shaped body can be treated by a two-step ion exchange process to obtain a graded index glass.
The molten salt in the first step of ion exchange of the two-step ion exchange method of the invention is composed of two or more compounds according to a certain proportion, wherein at least one compound contains Ag+(ii) a The temperature range of the first step of ion exchange is 300-400 ℃, and preferably 320-370 ℃. The time for the first ion exchange step should be such that sufficient ion exchange of the glass composition or glass shaped body is achieved, with shorter times being preferred. In the present invention, a product obtained by subjecting a glass composition or a glass shaped body to the first step of sufficient ion exchange is referred to as a "glass product intermediate".
Immersing the intermediate glass product obtained after the first step of ion exchange in molten salt for the second step of ion exchange, wherein a washing and/or annealing step can be carried out before the second step of ion exchange. The molten salt for the second step of ion exchange is composed of two or more compounds in a certain proportion, wherein at least one compound contains Na+. The temperature range of the ion exchange in the second step is 250-450 ℃, and preferably 300-380 ℃. The time range of the ion exchange in the second step is 2-16 hours.
After the two steps of ion exchange, the glass with the gradient refractive index can be obtained.
In some embodiments, after the above two ion exchange steps, further ion exchange and/or heat treatment steps can be performed to optimize the refractive index profile of the graded index glass.
In the present invention, the term "sufficient ion exchange" means that the exchange of the component to be exchanged with the component to be exchanged in the glass has been substantially completed. It was determined whether the glass achieved sufficient ion exchange according to the following method: processing the sample to be measured into a hexahedron with the thickness of 2.0 +/-0.1 mm, the length of 20 +/-5 mm and the width of 20 +/-5 mm, and carrying out ion exchange on the hexahedron by adopting the ion exchange method for different time. The hexahedral sample after ion exchange is machined to expose the cross section, and the surface roughness of the cross section is smoothed to a sufficiently small state. And measuring the composition distribution of the section by adopting an energy spectrum method, and if the component proportion at the position which is vertically 0.05mm away from the surface of the glass is different from the component proportion at the position which is vertically 1.00mm away from the surface by less than 1 mol%, determining that the glass is subjected to sufficient ion exchange. The minimum time required for sufficient ion exchange was determined by ion exchange experiments of different durations. The minimum time required to determine sufficient ion exchange is within a range of error of 20 hours.
In some embodiments, the time for achieving sufficient ion exchange in the first step of ion exchange of the glass composition or glass shaped body of the present invention is 600 hours or less, preferably 500 hours or less, and more preferably 400 hours or less, and the ion diffusion coefficient of the glass composition of the present invention is large.
The properties of the glass composition and the intermediate for glass products of the present invention will be described below.
< refractive index and Abbe number >
In the present invention, the term "n" is usedd"denotes the refractive index of the glass composition, expressed as" vd"denotes the Abbe number, n, of the glass compositiondV and vdThe test was carried out according to the method specified in GB/T7962.1-2010.
In some embodiments, the refractive index (n) of the glass compositions of the present inventiond) Is 1.48 to 1.51.
In some embodiments, the abbe number (v) of the glass compositions of the present inventiond) 46 to 60, preferably 48 to 58.
< light transmittance >
In the present invention, the term "lambda" is used70"indicates the wavelength at which the glass composition has a transmittance of 70%; by using "lambdaAfter 70-full exchange"indicates the wavelength corresponding to the transmittance of the glass product intermediate of 70%.
“λ70"and" lambdaAfter 70-full exchange"test as follows: spectral transmittance obtained from incident light in a direction perpendicular to the ground surface using a sample having surfaces parallel to each other ground to a thickness of 2.0 ± 0.1 mm. The spectral transmission also includes reflection loss of light on the sample surface. The polishing means that the surface roughness is smoothed to be sufficiently small with respect to the wavelength in the measurement wavelength range. Lambda [ alpha ]70And λAfter 70-full exchangeThe error range of the measurement is. + -. 5 nm.
In some embodiments, the optical transmission (λ) of the glass compositions of the present invention70) Is 350nm or less.
In some embodiments, the optical transmission (λ) of the inventive glass article intermediateAfter 70-full exchange) 420nm or less, preferably 410nm or less, and more preferably 400nm or less.
< difference in refractive index >
In the present invention, the symbol "Δ n" represents a refractive index difference, which is a refractive index (n) of a glass product intermediated after full exchange) Refractive index (n) of glass composition of the present inventiond) The difference between them. If Δ n is too low, the gradient index glass cannot achieve sufficient light convergence, and if Δ n is too high, the chemical stability of the gradient index glass is not easily maintained.
Δ n was tested as follows: the refractive index (n) of the glass composition was measured according to GB/T7962.1-2010d) And refractive index (n) of the intermediate of the glass articled after full exchange)，Δn＝nd after full exchange-nd。
In some embodiments, Δ n of the present invention ranges from 0.08 to 0.15, preferably from 0.1 to 0.14.
Glass preform and optical element
The glass preform can be produced from the glass composition or the gradient index glass by means of, for example, grinding, drawing, or press molding such as hot press molding or precision press molding. That is, the glass composition or the graded-index glass may be subjected to mechanical processing such as grinding or polishing to produce a glass preform, or may be subjected to a hot drawing process using a drawing furnace or the like to produce a glass preform, or the glass composition or the graded-index glass may be subjected to a preform for press molding, followed by reheat press molding of the preform and then grinding to produce a glass preform, or the glass composition or the graded-index glass may be subjected to precision press molding of the preform thus produced. It should be noted that the means for producing the glass preform is not limited to the above means.
As described above, the glass composition or the gradient index glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the glass composition or the gradient index glass of the present invention, and use the preform for reheat press molding, precision press molding, or the like to produce optical elements such as lenses, prisms, or the like.
The glass preform and the optical element of the present invention are each formed of the above-described glass composition or gradient index glass of the present invention. The glass preform of the present invention has excellent characteristics of a glass composition or a gradient-index glass; the optical element of the present invention has excellent characteristics of a glass composition or a gradient index glass, and can provide various optical elements such as lenses and prisms having high optical values.
In some embodiments, the gradient index lens can be obtained by cutting the gradient index glass into a specific length, processing an inclination angle on the surface of the gradient index glass by a cold working method, and polishing.
Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, a plano-concave lens, and a cylindrical lens, each of which has a flat, spherical, or aspherical lens surface.
[ optical instruments ]
The optical element formed by the glass material or the gradient-index glass can be used for manufacturing optical instruments such as optical fiber couplers, imaging equipment (camera shooting/photographing), display equipment, monitoring equipment, vehicle-mounted equipment and the like.
Examples
< glass composition examples >
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In this example, glass compositions having compositions shown in tables 1 to 4 were obtained by the above-mentioned methods for producing glass compositions, and characteristics of each glass composition were measured by the test methods described in the present invention, and the measurement results are shown in tables 1 to 4. Glass compositions having compositions shown in examples 1 to 4 of the present invention were subjected to sufficient ion exchange by a method for producing gradient index glasses to obtain intermediate products of glass products, and their characteristics were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 4, where the "time for sufficient ion exchange" described in the tables means the first step ion exchange time and ensures that the glass compositions achieve sufficient ion exchange.
TABLE 1
Figure BDA0002701034780000141
Figure BDA0002701034780000151
TABLE 2
Figure BDA0002701034780000152
Figure BDA0002701034780000161
TABLE 3
Figure BDA0002701034780000162
Figure BDA0002701034780000171
TABLE 4
Figure BDA0002701034780000172
Figure BDA0002701034780000181
< glass preform example >
Various lenses such as cylindrical lenses, concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses and plano-concave lenses, and preforms such as prisms were produced by using the glass compositions or gradient index glasses obtained in examples 1 to 21, for example, by polishing or by compression molding such as hot press molding or precision press molding.
< optical element example >
The preforms obtained from the above glass preform examples were annealed to reduce the internal stress of the glass and to fine-tune the refractive index so that the optical properties such as refractive index reached the desired values.
Next, each preform is ground and polished to produce various lenses such as a cylindrical lens, a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, and prisms. The surface of the resulting optical element may be coated with an antireflection film.
< optical Instrument example >
The optical element obtained by the above-described optical element embodiment is used for, for example, imaging devices, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automobile field, photolithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for image pickup devices and apparatuses in the vehicle-mounted field, by forming an optical component or an optical assembly by using one or more optical elements through optical design.

Claims (60)

1. Glass composition, characterized in that its components, expressed in molar percentages, have a cation comprising: si4+：30～49.37%；Al3+：18～25%；B3+：2～10%；Li++Na++K++Rb++Ag+: 25.44 to 35% of (B)3++Al3+)/(Li++Na++K++Rb++Ag+) 1.0 to 1.3, and the glass composition does not contain Tl+。
2. The glass composition according to claim 1, wherein the constituents thereof, expressed in mole percent, the cations further comprise: zn2+: 0 to 5 percent; and/or Mg2+: 0 to 5 percent; and/or Ca2+: 0 to 5 percent; and/or Sr2+: 0 to 5 percent; and/or Ba2+: 0 to 5 percent; and/or Zr4+：0～3%。
3. Glass composition, characterized in that its components are expressed in mole percentage, the cations being represented by Si4+：30～56%；Al3+：18～25%；B3+：2～10%；Li++Na++K++Rb++Ag+：20～35%；Zn2+：0～5%；Mg2+：0～5%；Ca2+：0～5%；Sr2+：0～5%；Ba2+：0～5%；Zr4+: 0 to 3% of a component (B)3++Al3+)/(Li++Na++K++Rb++Ag+) Is 1.0 to 1.23.
4. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: si4+: 37-44%; and/or Al3+: 20-25%; and/or B3+: 4-8%; and/or Li++Na++K++Rb++Ag+：27～33%; and/or Zn2+: 0.2-5%; and/or Mg2+: 0-2%; and/or Ca2+: 0-2%; and/or Sr2+: 0-2%; and/or Ba2+: 0-2%; and/or Zr4+：0～1%。
5. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: zn2+：1～2.5%。
6. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: li++Na++K++Rb++Ag+：25.44～33%。
7. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: li++Na++K++Rb++Ag+：26.08～33%。
8. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: li++Na++K++Rb++Ag+：27～32.00%。
9. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: li++Na++K++Rb++Ag+：28.00～31.85%。
10. Glass composition according to claim 1 or 2, characterized in that its components are expressed in mole percentages, in which: (B)3++Al3+)/(Li++Na++K++Rb++Ag+) Is 1.0 to 1.23.
11. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: (B)3++Al3+)/(Li++Na++K++Rb++Ag+) 1.05 to 1.2.
12. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: b is3+/(B3++Al3+) 0.1 to 0.35.
13. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: b is3+/(B3++Al3+) 0.15 to 0.3.
14. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: b is3+/(B3++Al3+) 0.20 to 0.3.
15. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: b is3+/(B3++Al3+) 0.20 to 0.27.
16. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: zn2+/(Al3++B3++Si4+) 0.003 to 0.08.
17. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: zn2+/(Al3++B3++Si4+) 0.006 to 0.046.
18. A method according to any one of claims 1 to 3Glass composition, characterized in that its components are expressed in mole percentages, in which: zn2+/(Al3++B3++Si4+) 0.01 to 0.03.
19. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: na (Na)+: 18-32%; and/or Li+: 0 to 5 percent; and/or K+: 0 to 10 percent; and/or Rb+: 0 to 5 percent; and/or Ag+：0～2.5%。
20. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: na (Na)+: 25-32%; and/or Li+: 0 to 3 percent; and/or K+: 0 to 5 percent; and/or Rb+: 0 to 2; and/or Ag+：0～1.5%。
21. A glass composition according to any one of claims 1 to 3, characterized in that its components, expressed in mole percentages, are: ag+：0～0.5%。
22. A glass composition according to any one of claims 1 to 3, characterised in that the components do not contain Mg2+(ii) a And/or does not contain Ca2+(ii) a And/or does not contain Sr2+(ii) a And/or do not contain Ba2+(ii) a And/or does not contain Zr4+(ii) a And/or does not contain Rb+(ii) a And/or does not contain Pb2+(ii) a And/or does not contain Cd2+(ii) a And/or does not contain Ti4+(ii) a And/or does not contain As3+(ii) a And/or do not contain Sb3+(ii) a And/or does not contain Ce4+(ii) a And/or does not contain Sn4+。
23. A glass composition according to any one of claims 1 to 3, characterized in that the composition comprises, in mole percent, anions comprising: o is2-: 99-100%; and/or Cl-+F-：0～1%。
24. A glass composition according to any one of claims 1 to 3, characterized in that the composition comprises, in mole percent, anions comprising: o is2-: 99.5 to 99.95 percent; and/or Cl-+F-：0.05～0.5%。
25. The glass composition according to any of claims 1 to 3, wherein the glass composition has a refractive index nd1.48 to 1.51; and/or Abbe number vd46 to 60; and/or light transmission lambda70Is 350nm or less.
26. The glass composition according to any of claims 1 to 3, wherein the glass composition has a refractive index nd1.48 to 1.51; and/or Abbe number vdIs 48 to 58.
27. The glass composition of any of claims 1-3, wherein the glass composition has a light transmittance λ after a sufficient ion exchange for one timeAfter 70-full exchangeIs 420nm or less; and/or the difference Deltan between the refractive index of the glass composition after the first sufficient ion exchange and the refractive index of the glass composition is 0.08-0.15.
28. The glass composition of any of claims 1-3, wherein the glass composition has a light transmittance λ after a sufficient ion exchange for one timeAfter 70-full exchangeIs 410nm or less; and/or the difference Deltan between the refractive index of the glass composition after the first sufficient ion exchange and the refractive index of the glass composition is 0.1-0.14.
29. The glass composition of any of claims 1-3, wherein the glass composition has a light transmittance λ after a sufficient ion exchange for one timeAfter 70-full exchangeIs 400nm or less.
30. A gradient index glass made from the glass composition of any of claims 1 to 29.
31. Gradient index glass, characterized in that its composition, expressed in mole percentages, has a cation comprising: si4+：30～49.37%；Al3+：18～25%；B3+：2～10%；Li++Na++K++Rb++Ag+: 25.44 to 35% of (B)3++Al3+)/(Li++Na++K++Rb++Ag+) Is 1.0 to 1.3, and the gradient refractive index glass does not contain Tl+。
32. A gradient index glass according to claim 31, having a composition, expressed in mole percent, wherein the cations further comprise: zn2+: 0 to 5 percent; and/or Mg2+: 0 to 5 percent; and/or Ca2+: 0 to 5 percent; and/or Sr2+: 0 to 5 percent; and/or Ba2 +: 0 to 5 percent; and/or Zr4+：0～3%。
33. Gradient index glass, characterized in that its composition is expressed in mole percentage, the cations being represented by Si4+：30～56%；Al3+：18～25%；B3+：2～10%；Li++Na++K++Rb++Ag+：20～35%；Zn2+：0～5%；Mg2+：0～5%；Ca2+：0～5%；Sr2+：0～5%；Ba2+：0～5%；Zr4+: 0 to 3% of a component (B)3++Al3+)/(Li++Na++K++Rb++Ag+) Is 1.0 to 1.23.
34. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent, wherein: si4+: 37-44%; and/or Al3+：20～25Percent; and/or B3+: 4-8%; and/or Li++Na++K++Rb++Ag+: 27 to 33 percent; and/or Zn2+: 0.2-5%; and/or Mg2+: 0-2%; and/or Ca2+: 0-2%; and/or Sr2+: 0-2%; and/or Ba2+: 0-2%; and/or Zr4+：0～1%。
35. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent, wherein: zn2+：1～2.5%。
36. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent wherein: li++Na++K++Rb++Ag+：25.44～33%。
37. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent wherein: li++Na++K++Rb++Ag+：26.08～33%。
38. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent wherein: li++Na++K++Rb++Ag+：27～32.00%。
39. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent wherein: li++Na++K++Rb++Ag+：28.00～31.85%。
40. A gradient index glass according to claim 31 or 32, having a composition expressed in mole percent, wherein: (B)3++Al3+)/(Li++Na++K++Rb++Ag+) Is 1.0 to 1.23.
41. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent wherein: (B)3++Al3+)/(Li++Na++K++Rb++Ag+) 1.05 to 1.2.
42. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent wherein: b is3+/(B3++Al3+) 0.1 to 0.35.
43. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent wherein: b is3+/(B3++Al3+) 0.15 to 0.3.
44. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent wherein: b is3+/(B3++Al3+) 0.20 to 0.3.
45. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent wherein: b is3+/(B3++Al3+) 0.20 to 0.27.
46. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent wherein: zn2+/(Al3++B3++Si4+) 0.003 to 0.08.
47. A graded index glass as claimed in any one of claims 31 to 33, wherein the components are in molar proportionExpressed in mole percent, wherein: zn2+/(Al3++B3++Si4+) 0.006 to 0.046.
48. A gradient index glass as claimed in any one of claims 31 to 33, having a composition expressed in mole percent wherein: zn2+/(Al3++B3++Si4+) 0.01 to 0.03.
49. The graded-index glass of any one of claims 31 to 33, wherein the composition does not contain Mg2 +(ii) a And/or does not contain Ca2+(ii) a And/or does not contain Sr2+(ii) a And/or do not contain Ba2+(ii) a And/or does not contain Zr4+(ii) a And/or does not contain Rb+(ii) a And/or does not contain Pb2+(ii) a And/or does not contain Cd2+(ii) a And/or does not contain Ti4+(ii) a And/or does not contain As3+(ii) a And/or do not contain Sb3 +(ii) a And/or does not contain Ce4+(ii) a And/or does not contain Sn4+。
50. A gradient index glass according to any of claims 31 to 33, having a composition in terms of mole percent, the anion comprising: o is2-: 99-100%; and/or Cl-+F-：0～1%。
51. A gradient index glass according to any of claims 31 to 33, having a composition in terms of mole percent, the anion comprising: o is2-: 99.5 to 99.95 percent; and/or Cl-+F-：0.05～0.5%。
52. A glass preform characterized by being made from the glass composition according to any one of claims 1 to 29; or a graded index glass as claimed in any one of claims 30 to 51.
53. An optical element produced by using the glass composition according to any one of claims 1 to 29; or a graded index glass according to any one of claims 30 to 51; or using a glass preform according to claim 52.
54. An optical device comprising the glass composition according to any one of claims 1 to 29; and/or a glass comprising a graded index glass according to any one of claims 30 to 51; and/or comprising an optical element according to claim 53.
55. A method for producing a gradient index glass, comprising the steps of: forming a glass composition according to any one of claims 1 to 29, forming a gradient index glass from the glass composition by an ion exchange process, or forming a gradient index glass from the glass composition by an ion exchange process after forming a glass shaped body from the glass composition.
56. The method of claim 55, wherein the ion exchange process is carried out by immersing the glass composition or glass shaped body in a single salt bath or immersing the glass composition or glass shaped body in multiple salt baths of the same or different compositions.
57. A method for producing a graded-index glass as claimed in claim 55, wherein the ion-exchange process comprises treating the glass composition or the glass shaped body by a two-step ion-exchange method, and the molten salt for the first step of ion-exchange is composed of two or more compounds in a certain ratio, at least one of the compounds containing Ag+The second step of ion exchange is carried out by mixing two or more compounds in a certain proportion, wherein at least one compound contains Na+。
58. The method according to claim 57, wherein the temperature of the first step ion exchange is 300 to 400 ℃, the time of the first step ion exchange is 600 hours or less, the temperature of the second step ion exchange is 250 to 450 ℃, and the time of the second step ion exchange is 2 to 16 hours.
59. The method according to claim 57, wherein the temperature of the first step ion exchange is 320 to 370 ℃ and the time of the first step ion exchange is 500 hours or less, the temperature of the second step ion exchange is 300 to 380 ℃ and the time of the second step ion exchange is 2 to 16 hours.
60. The method according to claim 57, wherein the temperature of the first step ion exchange is 320 to 370 ℃ and the time of the first step ion exchange is 400 hours or less, the temperature of the second step ion exchange is 300 to 380 ℃ and the time of the second step ion exchange is 2 to 16 hours.
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