Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • 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
  • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
  • C03C21/008—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in solid phase, e.g. using pastes, powders
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
  • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/083—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
  • C03C3/089—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

Definitions

• the present invention relates to the field of optical glasses. More specifically, it relates to glass substrates comprising at least one gradient-refractive index unit obtained by ion exchange.
• the production of glass substrates comprising one or more refractive index gradient units integrated into the glass has been the subject of numerous developments, the purpose of which is in particular to increase miniaturization and to better control the optical performances.
• the glass substrates comprising such units are generally obtained by a process combining an ion exchange (for obtaining the refractive index gradient) and photolithography (for producing a mask on the surface of the glass in the form of motifs).
• Ion exchange has been used for many years to produce refractive index gradient patterns in glass articles. This is a technique based on the ability of some ions of different polarizabilities, particularly alkaline ions, to be able to exchange with one another and thus form an ionic pattern.
• the ion exchange is carried out by treating the glass in a bath of molten salts of said ions at an elevated temperature, generally between 200 and 550 ° C., for a time sufficient to obtain the desired level of exchange.
• An electric field can be applied to accelerate the ion exchange rate.
• thallium is the most widespread ion for the implementation of ion exchange on glass.
• the ion exchange with silver ions makes it possible to reach a level of refractive index comparable to that obtained with thallium, avoiding the associated risks of toxicity. Nevertheless, it is found that the sodium-calcium silicate glasses develop during the ion exchange an intense yellow coloration caused by the appearance of colloids resulting from the reduction of Ag + ions in Ag °, even when the amount of money is low. Such staining is not acceptable for optical glasses. Many solutions have been developed to overcome these disadvantages.
• these solutions consisted in providing specific glass compositions suitable for ion exchange treatment, in particular alkaline silicate glass compositions (US-A-3,873,408 and US-A-4,952,037) and borosilicate type (US-A-3,880,630, US-A-4,952,037, US-A 5,958,810, US-A-6,066,273, US-A-2001/0003724, US-A-2003/0161048). and US-A-2005/0137075).
• alkaline silicate glass compositions US-A-3,873,408 and US-A-4,952,03
• borosilicate type US-A-3,880,630, US-A-4,952,037, US-A 5,958,810, US-A-6,066,273, US-A-2001/0003724, US-A-2003/0161048.
• the object of the present invention is to provide a glass substrate capable of undergoing a treatment for exchanging the alkaline ions of the glass with silver ions from an external source which allows the formation of at least one ionic unit, said pattern ionic having a gradient of refractive index and an acceptable depth while having a yellow color as low as possible.
• the invention aims to obtain a glass substrate comprising at least one ionic unit having a refractive index variation with respect to the glass located outside the pattern greater than or equal to 0.03, a depth greater than or equal to 100 microns and a light transmittance at 410 nm (TL410) greater than or equal to 60%.
• Said specific glass composition described hereinafter is that of the front substrate the ion exchange and it corresponds to the composition of the glass located outside the silver pattern (s) after the ion exchange treatment.
• the substrate consists of a glass having the following composition, in weight percent: SiO 2 67.0 - 73.0%, preferably 70.0 - 72.0%
• Total iron (expressed as Fe 2 O 3 ) 0 - 0.03%, preferably 0.005 - 0.01% Redox (FeO / total iron) 0.02 - 0.4, preferably 0.02 - 0.2
• the glass substrate according to this embodiment has, after the ion exchange with silver, at the level of the pattern or units, a variation of the refractive index greater than or equal to 0.05, preferably greater than or equal to 0 08.
• the refractive index is identical over the entire thickness of the glass where the ion exchange has occurred.
• the substrate consists of a glass having the following composition, in percentage by mass:
• MgO 0 - 5% preferably 1.0 - 3.0%
• BaO 0 - 5% preferably 0 - 1, 0% TiO 2 0 - 5%, preferably 0 - 3.0%
• Total iron (expressed as Fe 2 O 3 ) 0 - 0.1%, preferably 0 - 0.08%
• the sum of the Li 2 O, Na 2 O and K 2 O contents varies from 3 to 10%.
• a total content of these oxides of less than 6% makes it possible to obtain a substrate having a low coefficient of thermal expansion 06 25 - 300 , in particular between 40 and 60 ⁇ 10 -7 K -1 , whereas a content greater than 6% has the effect of increasing the variation of the refractive index beyond 0.06.
• the glass substrate according to this second embodiment has, after the silver ion exchange, a coefficient of thermal expansion OC 25 - 300 of less than 60 ⁇ 10 -7 K -1 , preferably of between 30 and 45 ⁇ 10 6 ⁇ 7 K "1 .
• the substrate consists of a glass having the following composition, in percentage by mass:
• Total iron (expressed as Fe 2 O 3 ) 0 - 0.1%, preferably 0 - 0.08%
• the glass substrate according to this third embodiment has, after the silver ion exchange, a coefficient of thermal expansion OC 25 - 300 of less than 60 ⁇ 10 -7 K -1 , preferably of between 30 and 45 ⁇ 10 5 ⁇ 7 K "1 .
• the glass substrate according to the invention has, at the level of the ionic unit (s), a light transmission coefficient TL410 greater than or equal to 80%, which corresponds to a weak yellow coloration.
• the substrate according to the invention has an exchange depth of greater than or equal to 200 ⁇ m.
• the method of manufacturing the glass substrate comprising one or more ionic units is also an object of the present invention.
• This process comprises the steps of: a) contacting the glass substrate with an external source of silver ions b) subjecting the assembly to a temperature ranging from 200 to 400 ° C., preferably 250 to 350 ° C., in the presence of an electric field for a time sufficient to at least partially replace the alkaline ions with silver ions, c) optionally, subjecting the substrate to a heat treatment to diffuse the silver ions laterally into the glass.
• the external source of silver ions may be a bath of one or more known molten silver salts, for example a chloride or a nitrate.
• the silver ion source is applied to one side of the substrate in a pattern or pattern network of predefined shape.
• the pattern can be obtained through the silver ion source, which then has a geometry to provide the desired pattern, or by forming on the surface of the glass a diffusion mask capable of withstanding the ion exchange treatment and having appropriate openings to obtain the shape of the pattern.
• the mask may be, for example, a mechanical mask made according to known lithography and / or etching techniques, for example a dielectric, conductive or resin mask, or an ionic mask having a pattern complementary to the desired pattern (s) (s). ) formed by diffusion from an ionic species having a lower mobility than the mobility of the silver ions.
• the face opposite to the first face of the substrate in contact with the silver ions is brought into contact with a bath of molten salts of a second ionic species which allows the diffusion of the alkaline ions coming from the glass, for example a sodium nitrate and or potassium nitrate.
• a mixture of equal parts of sodium nitrate and potassium nitrate is used.
• the external source of silver ions may also consist of a solid layer based on metallic silver (Ag °) or ionic (Ag + ) deposited on one side of the substrate according to the desired pattern or pattern of patterns.
• the deposition of the solid layer can be carried out by known methods, for example by screen printing a paste based on metallic silver or a paste comprising a silver salt, in particular a chloride, a nitrate or a sulphate of silver, and a polymer, by cathodic sputtering of metallic silver or by depositing a solution comprising a silver salt, especially a silver chloride, nitrate or sulphate, and a polymer, followed by a treatment to evaporate the liquid phase.
• the single silver pattern has a sufficient dimension or the silver patterns form a continuous network
• said pattern or said network acts as an electrode and can thus be connected directly to the voltage generator so that the exchange Ionic ion can occur in the next step b).
• This electrode may be solid or perforated and may have a shape and a variable dimension adapted to the pattern (s) to silver.
• the face of the substrate opposite to the coated face of the silver pattern or units is provided with an electrode capable of accepting the alkaline ions extracted from the glass during the exchange.
• step b) an electric field is applied between the baths or the electrodes in contact respectively with the first and second faces of the substrate, which makes it possible to increase the diffusion rate of the silver ions in the glass and thus to reduce the ion exchange time.
• the electric field can vary to a large extent depending on the conductivity of the glass substrate used and its thickness, for example from 0.1 to 1000 V / mm glass thickness, preferably 1 to 200 V / mm.
• step b) aims to reroute the ions in the ionic pattern in a plane parallel to the first face of the substrate.
• This treatment is carried out under the known temperature conditions, for example 300 to 400 ° C.
• the glass substrate according to the invention can be used in particular to form index gradient lenses.
• the following examples illustrate the invention without limiting it.
• a substrate is formed from the glass composition comprising the constituents below, in the following contents expressed in percentages by weight:
• the substrate is a square 5 cm square and 2.1 mm thick.
• the substrate is subjected to an ion exchange treatment in the device shown in Figure 1a (cross section) and 1b (longitudinal section along the axis AA).
• the device comprises the substrate 1 provided with two compartments 2 and 3, forming reservoirs, applied facing one another.
• the compartments 2 and 3 are attached to the substrate by means of an adhesive 4 which also acts as a seal with respect to the contents of the reservoir.
• the compartments 2 and 3 are each provided with a platinum electrode 5 and 6 connected to a voltage generator 9.
• the compartment 2 contains a bath 7 of AgNO 3 and the compartment 3 is filled with a mixture KNO 3: NaNO 3 (1: 1; mass: mass).
• the ion exchange is carried out at a temperature of 300 ° C. for 4 hours by applying an electric field of 38.1 V / mm of glass thickness.
• a substrate is formed under the conditions of Example 1 modified in that the glass composition has the composition given below, in weight percent, in that the substrate has a thickness equal to 3.9 mm and in that the applied electric field is equal to 2 V / mm of glass thickness.
• the substrate has the following properties:
• a substrate is formed under the conditions of Example 1 modified in that the glass composition has the composition given below, in mass percentage, in that the substrate has a thickness equal to 2 mm, in that the field applied electric is equal to 100 V / mm glass thickness and in that the duration of the ion exchange is equal to 6 hours.
• the substrate has the following properties
• a substrate is formed under the conditions of Example 1 modified in that the glass composition has the composition given below, in weight percent: SiO 2 71, 1%
• the substrate has the following properties:
• a substrate is formed under the conditions of Example 1 modified in that the glass composition has the composition given below, in mass percentage, in that the thickness of the glass is equal to 4 mm, the applied electric field is equal to 75 V / mm glass thickness and the duration of the ion exchange is 19 hours.
• the substrate has the following properties:
• the glass compositions of Examples 1, 2 and 3 according to the invention make it possible to have a variation of the refractive index of at least 0.038 over a depth of at least 140 ⁇ m without a significant reduction in the transmission. light measured at 410 nm, that is to say without the appearance of an undesirable yellow coloring.
• Comparative Example 1 shows a high yellowness level resulting in a low TL410 value of 34.5%
• Comparative Example 2 shows a small change in refractive index of 0.015. .
• Substrates are formed under the conditions of Example 1 having the composition given in Table 1, expressed as a percentage by mass.
• Example 4 and 5 are in accordance with the invention and Example 6 is a comparative example with a high total iron content.
• the substrates have a thickness of 2 mm.
• Example 7 AND 8 Substrates are formed under the conditions of Example 1 having the composition given in Table 2, expressed as a percentage by weight.
• the substrates have a thickness of 2 mm.
• a substrate is formed under the conditions of Example 1 modified in that the glass composition has the composition given below, in weight percentage, in that the substrate has a thickness equal to 2 mm, in that the applied electric field is equal to 60 V / mm glass thickness and in that the duration of the ion exchange is equal to 5 hours.
• the substrate has the following properties:

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

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• 2007
  • 2007-09-03 FR FR0757327A patent/FR2920426B1/fr not_active Expired - Fee Related
• 2008
  • 2008-09-03 KR KR1020107004663A patent/KR20100063051A/ko not_active Application Discontinuation
  • 2008-09-03 EP EP08835257A patent/EP2197803A1/fr not_active Withdrawn
  • 2008-09-03 WO PCT/FR2008/051567 patent/WO2009044037A1/fr active Application Filing
  • 2008-09-03 CN CN200880105431A patent/CN101795986A/zh active Pending
  • 2008-09-03 JP JP2010522427A patent/JP2010537924A/ja active Pending
  • 2008-09-03 US US12/675,864 patent/US20100179044A1/en not_active Abandoned

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