WO2014070869A1 - Methods to texture opaque, colored and translucent materials - Google Patents
Methods to texture opaque, colored and translucent materials Download PDFInfo
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- WO2014070869A1 WO2014070869A1 PCT/US2013/067472 US2013067472W WO2014070869A1 WO 2014070869 A1 WO2014070869 A1 WO 2014070869A1 US 2013067472 W US2013067472 W US 2013067472W WO 2014070869 A1 WO2014070869 A1 WO 2014070869A1
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- WIPO (PCT)
- Prior art keywords
- glass
- chemical etching
- etching solution
- ceramic article
- damaged surface
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/22—Removing surface-material, e.g. by engraving, by etching
- B44C1/227—Removing surface-material, e.g. by engraving, by etching by etching
-
- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
-
- 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
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133502—Antiglare, refractive index matching layers
Definitions
- the present disclosure relates to methods of modifying a glass-ceramic article, and more particularly, relates to methods of modifying a non-damaged surface of a glass-ceramic article by applying a chemical etching solution thereto.
- glass ceramics in electronic devices is becoming increasingly popular.
- the use of glass and glass ceramics in electronic devices provides optical properties and surface textures which significantly influence the functionality, touch feeling, and appearance of such devices.
- the surface appearance e.g., gloss value, surface roughness, and antiglare properties
- AR anti-reflection
- AG anti-glare
- AR coatings reduce the refractive index difference between the surface of the glass ceramic and the ambient environment.
- AG treatment through roughening of the surface of the glass ceramic, causes the reflection to be scattered into different direction.
- AR coatings are more expensive than AG treatment.
- AR coatings are generally smooth, which does not change the tactile response from un-treated surfaces.
- Surface glare of glass ceramics may also be reduced by roughening of such surfaces, which may be achieved by the following methods: 1) coating; 2) sand blasting; and 3) chemically etching the surface of the glass ceramic.
- the surface is coated with organic or non-organic droplets or particles. While such coatings can provide scattering properties, they are not normally very durable to scratch.
- surfaces of glass ceramics are first treated by physically damaging of the surfaces (e.g., sand blasting), followed by chemically etching the surfaces with HF. Physically damaging the surfaces is employed to generate a rough and/or damaged glass ceramic surface, and chemically etching is employed to polish and strengthen the rough and/or damaged glass ceramic surface.
- the combined processes may produce a glass ceramic surface with gloss values of from 30% to 90%, and with roughness (i.e. Ra) from 0.1 to 20 ⁇ .
- a method of modifying a non-damaged surface of a glass-ceramic article includes providing a glass-ceramic article having a non- damaged surface and an initial gloss value, applying a chemical etching solution to the non- damaged surface of the glass-ceramic article for an etching time of about 5 s to less than 15 min, and removing the chemical etching solution.
- the chemical etching solution is formed by mixing hydrofluoric acid and an inorganic fluoride salt.
- the chemical etching solution modifies the non-damaged surface such that from about 0.01 ⁇ to about 20 ⁇ of a depth of the glass-ceramic article is removed.
- the chemical etching solution modifies the non-damaged surface of the glass-ceramic article to form a roughened surface having a reduced gloss value and a target roughness value.
- the chemical etching solution is subsequently removed from the roughened surface.
- a method of modifying a non-damaged surface of a glass- ceramic article having a major amorphous phase includes providing a glass-ceramic article having a non-damaged surface and an initial gloss value, applying a chemical etching solution to the non-damaged surface of the glass-ceramic article for an etching time of about 5 s to less than 15 min, and removing the chemical etching solution from the roughened surface.
- the chemical etching solution is formed by mixing hydrofluoric acid and an ammonium fluoride salt.
- the chemical etching solution modifies the non- damaged surface such that from about 0.01 ⁇ to about 20 ⁇ of a depth of the glass- ceramic article is removed.
- the chemical etching solution also modifies the non-damaged surface of the glass-ceramic article to form a roughened surface having a reduced gloss value of from about 1% to about 30% at 60° and a target roughness value of from about 150 RMS (nm) to about 800 RMS (nm).
- a method of modifying a non-damaged surface of a glass- ceramic article having a major crystalline phase includes providing a glass-ceramic article having a non-damaged surface and an initial gloss value, applying a chemical etching solution to the non-damaged surface of the glass-ceramic article for an etching time of about 5 s to less than 15 min, and removing the chemical etching solution from the roughened surface.
- the chemical etching solution includes hydrofluoric acid.
- the chemical etching solution modifies the non-damaged surface such that from about 0.01 ⁇ to about 20 ⁇ of a depth of the glass-ceramic article is removed.
- the chemical etching solution also modifies the non-damaged surface of the glass-ceramic article to form a roughened surface having a reduced gloss value and a target roughness value.
- FIG. 1 is a perspective view of a curtain coating applicator for applying an acid film to a surface of a glass-ceramic substrate;
- FIG. 2 is a graph of depth of removal ( ⁇ ) for a glass-ceramic substrate with major crystalline phase with respect to gloss value (%) at 60°;
- FIG. 3 is an image of a glass-ceramic substrate with a major crystalline phase varying gloss values (%) at 60° achieved by one-step etching;
- FIG. 4 is a graph of etching time (min) for a glass-ceramic substrate with a major crystalline phase with respect to gloss value (%) at 60° achieved by one-step etching with chemical etching solutions having varying concentrations of HF (1.5 M, 1 M, and 0.5 M) and
- FIG. 5 is a contour plot of gloss values (%) at 60° for glass-ceramic substrates with a major crystalline phase achieved by one-step etching with chemical etching solutions having varying concentrations of HF (%) and NH 4 F (%);
- FIG. 6 is a graph of etching time (min) for a glass-ceramic substrate having a major amorphous phase with respect to gloss value (%) at 60° achieved by one-step etching with chemical etching solutions having varying concentrations of Ammonium Bifluoride (10%, 15%) and Propylene Glycol (10%);
- FIG. 7 is a contour plot of gloss values (%>) at 60° for glass-ceramic substrates with a major amorphous phase achieved by one-step etching with chemical etching solutions having varying concentrations of HF (%) and N3 ⁇ 4F (%);
- FIG. 8 is graph of gloss values (%>) at 60° for glass-ceramic substrates with a major amorphous phase achieved by one-step etching with chemical etching solutions with respect to depth of removal (nm,);
- FIG. 9 is a graph of roughness rms (nm) for glass-ceramic substrates with a major amorphous phase achieved by one-step etching with chemical etching solutions with respect to gloss value (%) at 60°.
- Embodiments of the present disclosure relate to methods of modifying a non-damaged surface of a glass-ceramic article.
- the method includes providing a glass-ceramic article having a non-damaged surface and an initial gloss value, applying a chemical etching solution to the non-damaged surface of the glass-ceramic article for an etching time of about 5 s to less than 15 min to form a roughened surface, and removing the chemical etching solution from the roughened surface.
- a glass-ceramic is a material having at least one crystalline phase thermally developed in a substantially uniform pattern throughout at least a portion of a glass precursor.
- glass-ceramics also have an amorphous phase. Glass-ceramics find application in a variety of areas, including the fabrication of articles employed in the preparation and serving of food and also in electronic devices.
- Glass-ceramic materials are generally produced by: 1) melting a mixture of raw materials, generally including a nucleating agent, to produce a glass; 2) forming an article from the glass and cooling the glass below its transformation range; and 3) crystallizing (i.e., "ceramming") the glass article by an appropriate treatment.
- Glass-ceramics provide an array of materials possessing a variety of properties such as zero porosity, high strength, translucency, toughness, opacity, pigmentation, and opalescence. Such properties may be provided by choice of base glass composition and control of the heat treatment and crystallization of the base glass.
- suitable glass-ceramic articles include those formed from the following glass-ceramic systems: 1) Li 2 0-Al 2 03-Si0 2 System (i.e., LAS- System); 2) MgO-Al 2 0 3 -Si0 2 System (i.e., MAS-System); and 3) ZnO-Al 2 0 3 -Si0 2 System (i.e., ZAS-System).
- suitable transparent, translucent, or opaque glass-ceramic articles include LAS-System glass-ceramic articles, i.e. lithium alumino silicate glass-ceramic articles.
- the LAS-System may generally provide highly crystallized glass-ceramics which include a predominant crystalline phase of: 1) a transparent beta-quartz solid solution; or 2) an opaque beta-spodumene solution (dependent upon the ceramming temperature).
- the appearance of such LAS-System glass-ceramics may be varied by varying ceramming conditions, e.g., heat treatment.
- transparent, translucent, or opaque glass-ceramics (which may be water-white, translucent, opaque, white, or variously colored) may be achieved. More particularly, as set forth in U.S. Pat. No. 5,491,115, transparent glass-ceramics in the LAS-System may be achieved by ceramming precursor glass at a relatively low temperature which does not normally exceed about 900 °C. Moreover, ceramming the same glass at a higher temperature of about 1150 °C may produce an opaque beta-spodumene crystalline phase. At such a high temperature, small beta-quartz crystals may convert to beta-spodumene crystals and grow in size, thereby rendering the product opaque.
- the translucent or opaque silicate crystal-containing glass- ceramics include, in weight percent on an oxide basis, 40-80% Si0 2 , 2-30% A1 2 0 3 , 2-30% A1 2 0 3 , 2-10% Li 2 0, 0-8% Ti0 2 , 0-3% ZrO, 0-2% Sn0 2 , 0-7% Br0 3 , 0-4% MgO, 0-12% ZnO, 0-8% BaO, 0-3% CaO, 0-6% SrO, 0-4% K 2 0, up to 2% Na 2 0, 0-1.0% Sb 2 0 3 , 0-0.25% Ag, 0-0.25% CeC 2 , the combination of Li 2 + Na 2 0/Al 2 0 3 + B 2 0 3 in amount of greater than 0.8 mol %, and the combination of Ti0 2 + Zr0 2 + Sn0 2 in an amount of at least 3.0 mol %.
- Such silicate crystal-containing glass-ceramics may be generally formed by: a) melting a batch for, and down drawing a glass article having a composition including, in weight percent on an oxide basis, of 40-80% Si0 2 , 2-30% A1 2 0 3 , 5-30% Na 2 0, 0-8% Ti0 2 , 0-12% ZrO, 0- 2% Sn0 2 , 0-7% B 2 0 3 , 0-4% MgO, 0-6% ZnO, 0-8% BaO, 0-3% CaO, 0-6% SrO, 0-4% K 2 0, 0-2% Li 2 0, 0-1.0% Sb 2 0 3 , 0-0.25% Ag, 0-0.25% Ce0 2 , the combination of Na 2 0/Al 2 0 3 + B 2 0 3 in an amount of greater than 0.8 mol %, and the combination of Ti0 2 + Zr0 2 + Sn0 2 in an amount of at least 3.0 mol %; b) ion exchanging the glass article
- an opaque glass- ceramic article glass-ceramic article having a predominant spodumene crystalline phase and a minor rutile crystalline phase is disclosed.
- Such opaque glass-ceramic articles may be formed from a precursor glass from the basic Si0 2 -Al 2 0 3 -Na 2 0 system. More particularly, a simple sodium alumino silicate glass with the following batched composition, in weight percent, may be produced: 58.8% Si0 2 , 21.5% A1 2 0 3 , 13.6% Na 2 0, 0.3% Sn0 2 , and 4.3% Ti0 2 .
- This glass may be batched, mixed, and melted in a platinum crucible at 1650 °C and thereafter annealed at 650 °C. This glass may then be cut, polished, and placed in a molten salt bath of a composition having 75 wt. % Li 2 S0 4 and 25 wt. % Na 2 S0 4 and held for two hours at a temperature of 800 °C. This time and temperature may be sufficient to allow Li + and Na + ion exchange and to allow internal nucleation and crystallization to occur over the whole thickness of the glass, i.e., ion-exchange and ceramming may occur simultaneously in the molten salt bath.
- the resultant glass-ceramic article may be a white glass-ceramic exhibiting a glossy skin. Additionally, such white glass-ceramic articles may include lithium aluminosilicate as the predominant crystalline phase. More particularly, such white glass- ceramic articles may include beta-spodumene as the predominant crystalline phase, rutile as the minor crystalline phase, and amorphous phases.
- suitable glass-ceramic articles include MAS-System glass- ceramic articles, i.e., magnesium aluminum silicate glass-ceramic articles.
- the MAS-System may generally provide glass-ceramic articles having a predominant crystalline phase of cordierite.
- Such glass-ceramic articles may also include minor crystalline phases of: 1) an acicular crystalline phase such as titanates, including e.g., magnesium titanates, aluminum titanates and combinations thereof; and/or 2) ceramic compounds capable of lamellar twinning, including e.g., enstatite, and/or anorthite.
- such glass-ceramic articles may include from 50-80 volume % cordierite, from 8-20 volume % of an acicular minor phase, and up to 20 volume % of ceramic compounds capable of lamellar twinning.
- the glass-ceramic article may be formed from a composition having, in weight %, 35-50% Si02, 10-35% A1203, 10-25% MgO, 7-20% Ti02, up to 5% CaO, and up to 10% SrO, and up to 5% F, where CaO + SrO is at least 0.5%.
- suitable glass-ceramic articles include ZAS-System glass- ceramic articles, i.e., zinc oxide alumino silicate glass-ceramic articles.
- the ZAS-System may generally provide transparent glass-ceramic articles exhibiting a predominant crystalline phase of hexagonal ZnO crystals.
- such glass-ceramic articles may include at least 15%, by weight, of hexagonal ZnO crystals.
- such glass-ceramic articles may include a total crystallinity ranging from 15-35% of ZnO crystals.
- the glass-ceramic article may be formed from a composition including, in weight percent, 25-50%) Si0 2 , 0-26% A1 2 0 3 , 15- 45% ZnO, 0-25% K 2 0, 0-10% Na 2 0, 0-32% Ga 2 0 3 , K 2 0 + Na 2 0 >10%, and A1 2 0 3 + Ga 2 0 3 > 10%.
- the glass-ceramic article is transparent, translucent, or opaque. In one particular embodiment, the glass-ceramic article is white. In another particular embodiment, the glass-ceramic article is black. In other embodiments, the glass-ceramic article is a lithium alumino silicate glass-ceramic article, a magnesium aluminum silicate glass-ceramic article, or a zinc oxide alumino silicate glass-ceramic article.
- the glass-ceramic article has a major crystalline phase.
- major crystalline phase refers to a glass-ceramic having greater than or equal to 30% by volume crystallinity. In one particular embodiment, the glass-ceramic article has about 90% by volume crystallinity. Alternatively, in other embodiments, the glass-ceramic article has a major amorphous phase. As used herein, the terms “major amorphous phase” or “major glass phase” are used interchangeably to refer to a glass-ceramic having less than 30% by volume crystallinity. In one particular embodiment, the glass- ceramic article has about 95% by volume amorphous phase.
- the glass-ceramic article has a non-damaged surface.
- the glass-ceramic article may also include two or more non-damaged surfaces.
- the terms "non-damaged surface” and “non-damaged surfaces” refer to a surface or surfaces of a glass-ceramic article which have not been subject to physical damage (e.g., sand blasting). Such physical damage to a surface or surfaces of a glass-ceramic article decreases the strength of the glass-ceramic article. Accordingly, glass-ceramic articles which have been subject to physical damage exhibit a reduction in strength relative to those glass- ceramic articles which have not been subject to physical damage.
- the glass-ceramic article has not been subject to physical damage. In further embodiments, the glass-ceramic article exhibits no reduction in strength. More particularly, in some embodiments, formation of the roughened surface on the glass-ceramic article having a reduced gloss value and a target roughness value preserves and/or improves surface strength of the glass-ceramic article.
- the glass-ceramic article has an initial gloss value.
- common gloss and “gloss” refer to the measurement of specular reflectance calibrated to a standard (such as, for example, a certified black glass standard), such as in accordance with ASTM procedure D523, the contents of which are incorporated herein by reference in their entirety. Common gloss measurements are typically performed at incident light angles of 20°, 60°, and 85°, with the most commonly used gloss measurement being performed at 60°.
- the term “initial gloss value” refers to a gloss value which is taken prior to treatment with a chemical etching solution.
- the initial gloss value may be from about 80% to about 100%, or from about 85% to about 95%, or about 90% at 60°.
- Embodiments of applying a chemical etching solution to the non-damaged surface of the glass-ceramic article are disclosed.
- the uniqueness of glass-ceramics in having both a crystalline phase and an amorphous phase allows for differential etching and/or differential modification of the respective phases with chemical etchants, e.g., chemical etching solutions.
- Differential etching refers to the ability of the crystalline phase and the amorphous phase of glass-ceramic articles to be etched and/or modified at different rates by the same chemical etchants and/or chemical etching solutions.
- the chemical etching solution is formed by mixing hydrofluoric acid (i.e., HF) and an inorganic fluoride salt (i.e., an inorganic cation, X + and F " ).
- the chemical etching solution may include from about 0.2% (w/w) to about 10%> (w/w) hydrofluoric acid, or from about 0.5%> (w/w) to about 6%) (w/w) hydrofluoric acid, or alternatively from about 1% (w/w) to about 5% (w/w) hydrofluoric acid, or alternatively from about 3% (w/w) to about 4% (w/w) hydrofluoric acid.
- the chemical etching solution may include hydrofluoric acid having a concentration of from about 0.5 M to about 1.5 M, or from about 0.75 M to about 1 M, or about 1 M.
- the chemical etching solution may include from about 1% (w/w) to about 30% (w/w) inorganic fluoride salt, or from about 10% (w/w) to about 25% (w/w) inorganic fluoride salt, or alternatively from about 15% (w/w) to about 20%) (w/w) inorganic fluoride salt.
- suitable inorganic fluoride salts include ammonium fluoride (i.e., NH 4 F), ammonium bifluoride (i.e., NH 4 F HF and hereinafter "ABF"), buffered hydrofluoric acid (hereinafter "BHF"), sodium fluoride (i.e., NaF), sodium bifluoride (i.e., NaHF 2 ), potassium fluoride (i.e., KF), potassium bifluoride (i.e., KHF 2 ), and combinations thereof.
- ammonium fluoride i.e., NH 4 F
- ammonium bifluoride i.e., NH 4 F HF and hereinafter "ABF”
- BHF buffered hydrofluoric acid
- sodium fluoride i.e., NaF
- sodium bifluoride i.e., NaHF 2
- potassium fluoride i.e., KF
- potassium bifluoride i.e., KHF 2
- etching behavior may be similar to that of glass articles. Accordingly, a chemical etching mask may be necessary to achieve differential etching and/or differential modification of non-damaged surfaces of glass-ceramic articles having a major amorphous phase.
- Such chemical etching masks may be generated in situ by applying suitable chemical etching solutions to a non-damaged surface of the glass-ceramic article having a major amorphous phase.
- the chemical etching solution is formed by mixing hydrofluoric acid and an inorganic fluoride salt. Such chemical etching solution is as previously described.
- the chemical etching solution is formed by mixing a mineral acid and an inorganic fluoride salt.
- the mineral acid may be employed in the absence of hydrofluoric acid to generate hydrofluoric acid and an active etching species and will be described in greater detail in a later section.
- the inorganic fluoride salt is as previously described.
- etching solutions to a non-damaged surface of the glass-ceramic article having a major amorphous phase may result in the generation of an in situ mask, wherein crystals are formed on the non-damaged surface.
- the in situ mask or crystals may be formed upon dissolution of a portion of the glass-ceramic article by the chemical etching solution.
- the chemical etching solution is formed by mixing hydrofluoric acid and an inorganic fluoride salt
- dissolution of the glass-ceramic article results in the formation of the anions SiF 6 2" and A1F 6 3 ⁇ , formed between fluoride ions from the chemical etching solution and elements dissolved thereby from the glass-ceramic material.
- Such anions may then combine with cations from the chemical etching solution, i.e., inorganic cations X + of the inorganic fluoride salt.
- inorganic cations X + with the formed anions SiF 6 2" and A1F 6 3" results in the formation of crystals on the non-damaged surface of the glass-ceramic article.
- differential etching may proceed automatically upon application of an appropriate chemical etching solution.
- Chemical etching solutions which are suitable for differentially etching glass-ceramic articles having a major amorphous phase are also suitable for differentially etching glass-ceramic articles having a major crystalline phase.
- suitable chemical etching solutions for such glass-ceramic articles having a major crystalline phase include those as previously described with regard to glass-ceramic articles having a major amorphous phase and also include additional chemical etching solutions.
- a chemical etching solution suitable for differential etching a glass- ceramic article having a major crystalline phase includes hydrofluoric acid without the addition of an inorganic fluoride salt. This is in contrast to suitable chemical etching solutions for glass-ceramic articles having a major amorphous phase, wherein the chemical etching solution is formed by mixing hydrofluoric acid and an inorganic fluoride salt.
- chemical etching solutions suitable for differential etching of a glass-ceramic article having a major crystalline phase consist essentially of hydrofluoric acid.
- Such chemical etching solutions are capable of modifying a non-damaged surface of the glass-ceramic article having a major crystalline phase to form a roughened surface having a reduced gloss value and a target roughness value.
- the chemical etching solutions for glass-ceramic articles having a major crystalline phase or a major amorphous phase may further include a mineral acid.
- the chemical etching solution may be formed by mixing a mineral acid with hydrofluoric acid and optionally an inorganic fluoride salt, as previously described.
- the use of mineral acids in chemical etching solutions may aid the chemical etching solution in achieving a high or medium gloss value.
- the pH of the chemical etching solution may alter the formation, growth, and/or attachment of crystals to the non-damaged surface.
- the pH of such a chemical etching solution is lowered due to the addition of a mineral acid, while crystals may form, grow, and/or attach to the glass-ceramic article, such crystals may be loosely tied to the non-roughened surface thereof and may not grow as deep as they would without the addition of mineral acid to the chemical etching solution. Accordingly, the addition of such mineral acids may alter the attachment of the crystals to the surface.
- a mineral acid may accelerate the etching rate.
- suitable mineral acids for use with the chemical etching solutions described herein include hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, hydrobromic acid, perchloric acid, and combinations thereof.
- additional mineral acids known to those of skill in the art are also contemplated for use as described herein although not explicitly described.
- the chemical etching solution may include such mineral acids having a concentration of from about 0.5 M to about 6 M, or from about 0.5 M to about 5 M, or from about 1 M to about 4 M, or from about 1.5 M to about 3 M, or from about 0.5 M to about 1 M, or from about 1 M to 2 M, or about 1 M.
- the chemical etching solutions for glass-ceramic articles having a major crystalline phase or a major amorphous phase may also further include a wetting agent.
- the chemical etching solution may be formed by mixing a wetting agent with hydrofluoric acid and optionally an inorganic fluoride salt, as previously described.
- the chemical etching solution may be formed by mixing a wetting agent with an inorganic fluoride salt and a mineral acid, as previously described.
- the wetting agent improves etching uniformity of the chemical etching solutions.
- Suitable wetting agents for use with the chemical etching solutions described herein include glycols (e.g., propylene glycol), glycerols (e.g., glycerol), alcohols (e.g., isopropyl alcohol), surfactants, acids (e.g., acetic acid), and combinations thereof.
- glycols e.g., propylene glycol
- glycerols e.g., glycerol
- alcohols e.g., isopropyl alcohol
- surfactants e.g., acetic acid
- acids e.g., acetic acid
- additional wetting agents known to those of skill in the art are also contemplated for use as described herein although not explicitly described.
- the chemical etching solution may include from about 5% (w/w) to about 25% (w/w) of a wetting agent, or alternatively from about 10% (w/w) to about 20%) (w/w) of a wetting
- the chemical etching solutions for glass-ceramic articles having a major crystalline phase or a major amorphous phase may also further include a thickening agent to increase the viscosity of the chemical etching solution.
- the chemical etching solution may be formed by mixing a thickening agent with hydrofluoric acid and optionally an inorganic fluoride salt, as previously described.
- the chemical etching solution may be formed by mixing a thickening agent with an inorganic fluoride salt and a mineral acid, as previously described.
- the addition of thickening agents to chemical etching solutions functions to: 1) increase the viscosity of the chemical etching solution; 2) improve the handling of the chemical etching solution; 3) improve the ease of application of the chemical etching solution to the glass-ceramic article; 4) increase the safety of applying the chemical etching solution to the glass-ceramic article; and 5) improve the etching uniformity of the chemical etching solutions.
- thickening agents for use with the chemical etching solutions described herein include polysaccharides (e.g., Xanthan gum and starch), polymers derived from cellulose (e.g., hydroxyethyl cellulose, ethyl cellulose, and methyl cellulose), polyethylene oxide polymers (e.g., polyethylene glycol), polyacrylamide, and combinations thereof.
- polysaccharides e.g., Xanthan gum and starch
- polymers derived from cellulose e.g., hydroxyethyl cellulose, ethyl cellulose, and methyl cellulose
- polyethylene oxide polymers e.g., polyethylene glycol
- polyacrylamide e.g., polyacrylamide
- the chemical etching solution may include from about 0.05%) (w/w) to about 5% (w/w) of a thickening agent, or alternatively from about 0.5%) (w/w) to about 2% (w/w) of a thickening agent, or about 1% (w/w) of a thickening agent.
- the chemical etching solutions for glass-ceramic articles having a major crystalline phase or a major amorphous phase may also further include an inert component.
- the chemical etching solution may be formed by mixing an inert component with hydrofluoric acid and optionally an inorganic fluoride salt, as previously described.
- the chemical etching solution may be formed by mixing an inert component with an inorganic fluoride salt and a mineral acid, as previously described.
- a chemical etching solution includes a thickening agent
- addition of a thickening agent to a chemical etching solution aids in the generation of a gel, paste, and/or cream.
- the inert component functions to aid in controlling the etching rate.
- Suitable examples of inert components include organic and inorganic inert components.
- suitable organic inert components include organic acids such as acetic acid, benzoic acid, citric acid, malonic acid, oxalic acid, and combinations thereof.
- suitable inorganic inert components include barium sulfate.
- additional inert components known to those of skill in the art are also contemplated for use as described herein although not explicitly described.
- the chemical etching solution may include from about 1% (w/w) to about 20% (w/w) of an inert component, or alternatively from about 5% (w/w) to about 15% (w/w) of an inert component, or about 10%> (w/w) of an inert component.
- the chemical etching solution is applied to the non-damaged surface of the glass-ceramic article.
- Suitable examples of methods for applying the chemical etching solution to the non-damaged surface of the glass-ceramic article include spraying, curtain-coating, screen-printing, dip-coating, spin-coating, applying with a roller, rod-coating, roll-coating, and similar methods, and combinations thereof.
- the chemical etching solution is applied to the non-damaged surface of the glass-ceramic article by dip-coating, i.e., immersing, the glass-ceramic article in the chemical etching solution.
- chemical etching solutions having increased viscosity e.g., chemical etching solutions which include a thickening agent and/or an inert component
- application of such chemical etching solutions may be performed by curtain-coating.
- such chemical etching solutions may be applied to the non-damaged surface of the glass-ceramic article by curtain-coating with a curtain coating applicator 100, such as is shown in FIG. 1.
- a curtain coating applicator 100 such as is shown in FIG. 1.
- Such applicator includes an acid gel, paste, and/or cream reservoir 102, pressurized air inlet 104, and acid gel, paste, and/or cream inlet 106 for receiving acid gel, paste, and/or cream within the reservoir 102.
- the acid gel, paste, and/or cream 110 may correspond to the chemical etching solutions having increased viscosity as previously described.
- the acid gel, paste, and/or cream is applied through an opening 108 in the acid gel, paste, and/or cream reservoir 102 onto the non-damaged surface 122 of the glass-ceramic article 120 as the acid gel, paste, and/or cream reservoir 102 moves in a direction A.
- a mixture of hydrofluoric acid and a mineral acid may be applied to a non-damaged surface of the glass-ceramic article to pre-etch and/or clean the non-damaged surface prior to application of the chemical etching solution described herein.
- the mineral acid is as described herein.
- the chemical etching solution is applied to the non-damaged surface of the glass-ceramic article after pre-etch and/or cleaning treatment of the non-damaged surface.
- a mixture of hydrofluoric acid and a mineral acid is applied to the non-damaged surface of a glass-ceramic article prior to application and/or formation of a chemical etching mask on the glass-ceramic article having a major amorphous phase.
- a mixture of hydrofluoric acid and a mineral acid may be applied to the roughened surface of the glass-ceramic article to fine-tune and/or optimize the morphology thereof.
- the mineral acid is as described herein.
- the chemical etching solution is applied to the non-damaged surface of the glass-ceramic article before fine-tuning and/or optimization of the roughened surface.
- the chemical etching solution is applied to the non-damaged surface of the glass-ceramic article after the glass-ceramic article has been subjected to ion exchange. In other embodiments, the chemical etching solution is applied to the non- damaged surface of the glass-ceramic article before the glass-ceramic article has been subjected to ion exchange.
- the chemical etching solution may be applied to the non-damaged surface of the glass-ceramic article for an etching time of about 5 s to less than 15 min.
- the chemical etching solution may be applied to the non-damaged surface of the glass-ceramic article for an etching time of about 15 s to about 8 min, 1 min to about 8 min, or from about 1 min to about 4 min, or from about 4 min to about 8 min, or from about 2 min to about 8 min, or from about 2 min to about 6 min, or from about 1 min to about 4 min.
- the chemical etching solution may be applied to the non-damaged surface of the glass- ceramic article for an etching time of less than about 10 min.
- the chemical etching solution may be applied to the non-damaged surface of the glass-ceramic article for an etching time of less than 5 min.
- the chemical etching solution may modify and/or etch the non-damaged surface of the glass-ceramic article such that from about 0.01 ⁇ to about 20 ⁇ of a depth of the glass- ceramic article is removed (i.e., depth of removal).
- the chemical etching solution may modify the non-damaged surface of the glass-ceramic article such that from about 0.1 ⁇ to about 10 ⁇ , or from about 0.1 ⁇ to about 2 ⁇ , or from about 0.25 ⁇ to about 1 ⁇ , or from about 0.25 ⁇ ⁇ about 0.75 ⁇ , or from about 0.5 ⁇ ⁇ about 0.75 ⁇ of the depth of the glass-ceramic article is removed.
- the chemical etching solution may also modify and/or etch the non-damaged surface of the glass-ceramic article to form a roughened surface having a reduced gloss value.
- reduced gloss value refers to a measurement of specular reflectance which is calibrated to a standard, such as in accordance with ASTM procedure D523, and which is less than an initial gloss value of respective specular reflectance.
- the reduced gloss value may be from about 0.04% to about 75%o, or from about 0.1 % to about 75%, or from 0.1 % to about 50%>, or from about 0.1%) to about 40%), or from about 0.1 % to about 30%, or from about 1% to about 30%, or from about 10% to about 40%, or from about 20% to about 50% at 60°.
- the chemical etching solution may also modify and/or etch the non-damaged surface of the glass-ceramic article to form a roughened surface having a target roughness value.
- target roughness value refers to a measure of texture of a surface which is quantified by vertical deviations of the surface from its standard.
- the target roughness value may be from about 10 RMS (nm) to about 1000 RMS (nm), or from about 10 RMS (nm) to about 800 RMS (nm), or from about 25 RMS (nm) to about 800 RMS (nm), or from about 150 RMS (nm) to about 800 RMS (nm), or from about 25 RMS (nm) to about 600 RMS (nm), or from about 50 RMS (nm) to about 700 RMS (nm), or from about 100 RMS (nm) to about 600 RMS (nm), or from about 150 RMS (nm) to about 200 RMS (nm), or from about 200 RMS (nm) to about 400 RMS (nm), or from about 300 RMS (nm) to about 350 RMS (nm).
- the roughened surface has a target roughness value of from about 25 rms (nm) to about 800 rms (nm).
- the reduced gloss value and the target roughness value may be directly related to the depth of the surface being removed (i.e., depth of removal).
- depth of removal the ability to control the depth of removal (hereinafter "DOR") may result in specific reduced gloss values and/or specific target roughness values.
- DOR depth of removal
- a higher DOR may result in a lower reduced gloss value and a higher target roughness value.
- parameters to be considered in controlling DOR and the resulting reduced gloss values and/or target roughness values include: 1) chemical etching solution type and concentration thereof; 2) etching time; 3) temperature; and 4) agitation.
- agitation such as ultrasound, vertical agitation, and gas bubbling refresh the surface of the glass-ceramic article part during etching which may influence the etch rate and the uniformity of the post-etch surface.
- chemical etching solutions suitable for glass-ceramic articles having a major crystalline phase or a major amorphous phase include chemical etching solutions formed by mixing hydrofluoric acid, ammonium fluoride, and a mineral acid.
- the chemical etching solution includes from about 0.5% (w/w) to about 6%) (w/w) hydrofluoric acid, from about 10%> (w/w) to about 25% (w/w) ammonium fluoride, and from about 0.5 M to about 1 M sulfuric acid.
- Additional examples of particular chemical etching solutions suitable for glass-ceramic articles having a major crystalline phase or a major amorphous phase include chemical etching solutions wherein BHF functions as a mixture of hydrofluoric acid and an inorganic fluoride salt.
- the chemical etching solution includes from about 5% (w/w) to about 30% (w/w) ammonium fluoride and from about 1% (w/w) to about 6% (w/w) hydrofluoric acid.
- chemical etching solutions suitable for glass-ceramic articles having a major crystalline phase or a major amorphous phase include chemical etching solutions wherein ABF functions as a mixture of hydrofluoric acid and an inorganic fluoride salt.
- the chemical etching solution includes from about 5% (w/w) to about 25% (w/w), or alternatively from about 10% (w/w) to about 20% (w/w) of ABF.
- the chemical etching solution includes from about 5% (w/w) to about 25% (w/w) of ABF and from about 5% (w/w) to about 25% (w/w) of a wetting agent.
- Such chemical etching solutions may be applied to the non- damaged surface of the glass-ceramic article for an etching time of from about 1 min to about 4 min to modify the non-damaged surface of the glass-ceramic article to form a roughened surface having a reduced gloss value of from about 0.1% to about 30% at 60°.
- the chemical etching solution includes from about 5% (w/w) to about 25% (w/w) ABF and from about 5% (w/w) to about 25% (w/w) propylene glycol.
- Still another example of particular chemical etching solutions suitable for glass- ceramic articles having a major crystalline phase or a major amorphous phase include chemical etching solutions formed by mixing from about 0.2% to about 10% (w/w) hydrofluoric acid and from about 1% to about 30% (w/w) ammonium fluoride.
- Such chemical etching solutions may modify the non-damaged surface of the glass-ceramic article to form a roughened surface having a reduced gloss value of from about 1% to about 30% at 60° and a target roughness value of from about 10 RMS (nm) to about 800 RMS (nm) such that from about 0.1 ⁇ to about 2 ⁇ of the depth of the glass-ceramic article is removed.
- Examples of particular chemical etching solutions suitable for glass-ceramic articles having a major amorphous phase include chemical etching solutions formed by mixing hydrofluoric acid and an ammonium fluoride salt.
- Such chemical etching solutions may modify the non-damaged surface of the glass-ceramic article to form a roughened surface having a reduced gloss value of from about 1% to about 30% at 60° and a target roughness value of from about 150 RMS (nm) to about 800 RMS (nm) such that from about 0.1 ⁇ to about 20 ⁇ of the depth of the glass-ceramic article is removed.
- Examples of particular chemical etching solutions suitable for glass-ceramic articles having a major crystalline phase include chemical etching solutions formed by mixing hydrofluoric acid and sulfuric acid. Such chemical etching solutions may be applied to the non-damaged surface of the glass-ceramic article for an etching time of from about 5 sec to less than about 15 min such that from about 0.1 ⁇ to about 20 ⁇ of the depth of the glass- ceramic article is removed.
- the chemical etching solution includes from about 0.5% (w/w) to about 6%> (w/w) hydrofluoric acid and from about 0.5 M to about 1 M sulfuric acid.
- Such chemical etching solutions may be applied to the non- damaged surface of the glass-ceramic article to form a roughened surface having a reduced gloss value of from about 1% to about 30% at 60° and a target roughness value of from about 10 RMS (nm) to about 800 RMS (nm) such that from about 0.1 ⁇ to about 2 ⁇ of the depth of the glass-ceramic article is removed.
- the chemical etchant is removed from the roughened surface of the glass-ceramic article at the conclusion of the etching time.
- a suitable example of a method for removing the chemical etching solution from the roughened surface is rinsing the roughened surface with deionized water. Deionized water functions to stop the modification of the non-damaged surface and/or the etching reaction.
- a second chemical etching solution may be applied to the roughened surface of the glass- ceramic article. Suitable examples of a second chemical etching solution include mineral acids, as stated above.
- Such second chemical etching solution may not include hydrofluoric acid, as such acid may continue to modify and/or etch the roughened surface of the glass- ceramic article, continuing to reduce the surface roughness.
- the second chemical etching solution may be removed from the roughened surface by rinsing the roughened surface with deionized water.
- a glass-ceramic article formed by the methods described herein is disclosed.
- the glass-ceramic article may be opaque, colored, or translucent.
- Such white glass-ceramic article was as previously described with regard to a simple sodium alumino silicate glass with the following batched composition, in weight percent: 58.8% Si0 2 , 21.5% A1 2 0 3 , 13.6% Na 2 0, 0.3% Sn0 2 , and 4.3% Ti0 2 .
- Gloss values were determined, such as in accordance with ASTM procedure D523.
- DOR was determined via: (1) protecting (i.e., taping) about half of the non-damaged surface of the glass-ceramic article with plastic tape (3M, St. Paul MN); (2) dipping the glass-ceramic article into the etching solution for a period of 1 - 16 minutes as described above; (3) removing the plastic tape (wherein the protected half of the non-damaged surface of the glass-ceramic article is thicker than the unprotected half); and (4) measuring the DOR (i.e., step height) with a Surfcom 2000 SD (Carl Zeiss Industrial Metrology, LLC, Maple Grove, MN).
- Surfcom 2000 SD Carl Zeiss Industrial Metrology, LLC, Maple Grove, MN
- gloss values at 60° were influenced and/or controlled by the chemical makeup of the chemical etching solution and by the concentration thereof. More specifically, gloss values at 60° increased as the concentration of hydrofluoric acid decreased and the concentration of ammonium increased. In the range of hydrofluoric acid concentrations of from 1% to 6% by weight and ammonium concentrations of 5% to 30%) by weight, the gloss values at 60° were precisely controlled from 70%> to 10%>. Such results demonstrate the feasibility of controlling gloss values at 60° using chemical etching solutions having buffered hydrofluoric acid.
- the white glass-ceramic articles were etched by buffered hydrofluoric acid. More particularly, the gloss value at 60° was controllable.
- the white glass-ceramic articles were etched by hydrofluoric acid and sulfuric acid, hydrofluoric acid. More particularly, the gloss value at 60° was controllable.
- Such black glass-ceramic article was Corning® Gorilla® Glass (Corning Incorporated) with color additive to obtain the black color. After applying the chemical etching solution for the appropriate etching time, the black glass-ceramic articles were soaked in sulfuric acid (1 M) for about 5 min to remove crystals formed in the previous steps. Gloss values at 60° were determined, such as in accordance with ASTM procedure D523.
- Gloss values were determined, such as in accordance with ASTM procedure D523.
- DOR was determined via: (1) protecting (i.e., taping) about half of the non-damaged surface of the glass-ceramic article with plastic tape (3M, St. Paul MN); (2) dipping the glass-ceramic article into the etching solution for a period of 1 - 16 minutes as described above; (3) removing the plastic tape (wherein the protected half of the non-damaged surface of the glass-ceramic article is thicker than the unprotected half); and (4) measuring the DOR (i.e., step height) with a Surfcom 2000 SD (Carl Zeiss Industrial Metrology, LLC).
- Surfcom 2000 SD Carl Zeiss Industrial Metrology, LLC
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Abstract
Description
Claims
Priority Applications (5)
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KR1020157014023A KR101921788B1 (en) | 2012-11-02 | 2013-10-30 | Methods to texture opaque, colored and translucent materials |
CN201380069519.9A CN105164078B (en) | 2012-11-02 | 2013-10-30 | Texturing is opaque, coloured and trnaslucent materials method |
US14/438,755 US10040718B2 (en) | 2012-11-02 | 2013-10-30 | Methods to texture opaque, colored and translucent materials |
EP13789664.3A EP2914558B1 (en) | 2012-11-02 | 2013-10-30 | Methods to texture opaque, colored and translucent materials |
JP2015540745A JP6462579B2 (en) | 2012-11-02 | 2013-10-30 | Method for texturing opaque, colored and translucent materials |
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EP (1) | EP2914558B1 (en) |
JP (1) | JP6462579B2 (en) |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5491115A (en) | 1994-07-18 | 1996-02-13 | Corning Incorporated | Colored glass-ceramics and method |
US20030170459A1 (en) * | 2002-03-05 | 2003-09-11 | Zuel Company, Inc. | Anti-reflective glass surface with improved cleanability |
US6936555B2 (en) | 2002-12-31 | 2005-08-30 | Corning Incorporated | Glass ceramics based on ZnO |
US7465687B2 (en) | 2006-05-31 | 2008-12-16 | Corning Incorporated | Tough cordierite glass-ceramics |
US20110317257A1 (en) * | 2009-03-17 | 2011-12-29 | Juan Luis Rendon Granados | Glass Products with Anti-Reflection Properties and Methods for the Production and Use Thereof |
US20120134025A1 (en) * | 2010-11-30 | 2012-05-31 | Shandon Dee Hart | Anti-glare glass sheet having compressive stress equipoise and methods thereof |
WO2012075068A2 (en) | 2010-11-30 | 2012-06-07 | Corning Incorporated | Fusion formed and ion exchanged glass-ceramics |
US20130136909A1 (en) | 2011-11-30 | 2013-05-30 | John Christopher Mauro | Colored alkali aluminosilicate glass articles |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4074992A (en) | 1964-05-05 | 1978-02-21 | Corning Glass Works | Sodium ion-exchange on surface of beta-spodumene |
US3616098A (en) * | 1968-03-18 | 1971-10-26 | Dearborn Glass Co | Method of producing glare-reducing glass surface |
US3812689A (en) | 1972-05-26 | 1974-05-28 | Corning Glass Works | Method of making glass-ceramic articles |
US4683168A (en) | 1985-01-10 | 1987-07-28 | Corning Glass Works | Method of producing a composite body |
DE3789932T2 (en) | 1986-10-09 | 1995-02-09 | Asahi Glass Co Ltd | Glass substrate for a magnetic disk and process for its manufacture. |
JPH07101507B2 (en) * | 1986-10-09 | 1995-11-01 | 旭硝子株式会社 | Magnetic disk substrate and manufacturing method |
US4977110A (en) | 1990-01-12 | 1990-12-11 | Corning Incorporated | Beige-tinted glass-ceramics |
US5176961A (en) | 1991-10-07 | 1993-01-05 | Corning Incorporated | Colored, textured glass-ceramic articles |
US6183892B1 (en) * | 1997-09-19 | 2001-02-06 | Mitsubishi Chemical Corporation | Magnetic recording medium substrate and magnetic recording medium |
JPH11154319A (en) * | 1997-09-19 | 1999-06-08 | Mitsubishi Chemical Corp | Substrate for magnetic recording medium, magnetic recording medium and its production |
JPH11120554A (en) * | 1997-10-14 | 1999-04-30 | Mitsubishi Chemical Corp | Production of substrate for magnetic recording medium |
US6337029B1 (en) | 1999-01-21 | 2002-01-08 | Xim Products | Method and composition for etching glass ceramic and porcelain surfaces |
AU4251001A (en) * | 2000-04-28 | 2001-11-12 | Merck Patent Gmbh | Etching pastes for inorganic surfaces |
JP4520075B2 (en) * | 2001-06-25 | 2010-08-04 | 博 三輪 | Surface processing of glass products with sandblasting |
JP2003229048A (en) * | 2002-02-01 | 2003-08-15 | Nishiyama Stainless Chem Kk | Manufacturing method for pdp glass substrate and pdp |
US7091141B2 (en) | 2003-04-01 | 2006-08-15 | Corning Incorporated | Lamp reflector substrate, glass, glass-ceramic materials and process for making the same |
JP2007170754A (en) | 2005-12-22 | 2007-07-05 | Nippon Electric Glass Co Ltd | Top plate for cooker and its manufacturing method |
US20070270299A1 (en) * | 2006-05-17 | 2007-11-22 | 3M Innovative Properties Company | Glass-ceramics and methods of making same |
JP4978886B2 (en) | 2006-06-14 | 2012-07-18 | 日本電気硝子株式会社 | Phosphor composite material and phosphor composite member |
US8062732B2 (en) | 2007-05-22 | 2011-11-22 | Corning Incorporated | Glass article having improved edge |
JP2009149468A (en) | 2007-12-20 | 2009-07-09 | Nippon Electric Glass Co Ltd | Manufacturing method of crystallized glass substrate, and crystallized glass substrate |
US8771532B2 (en) | 2009-03-31 | 2014-07-08 | Corning Incorporated | Glass having anti-glare surface and method of making |
US8598771B2 (en) * | 2009-09-15 | 2013-12-03 | Corning Incorporated | Glass and display having anti-glare properties |
US8992786B2 (en) | 2010-04-30 | 2015-03-31 | Corning Incorporated | Anti-glare surface and method of making |
US9017566B2 (en) | 2010-04-30 | 2015-04-28 | Corning Incorporated | Anti-glare surface treatment method and articles thereof |
US9085484B2 (en) | 2010-04-30 | 2015-07-21 | Corning Incorporated | Anti-glare surface treatment method and articles thereof |
-
2013
- 2013-10-30 CN CN201380069519.9A patent/CN105164078B/en active Active
- 2013-10-30 CN CN201810923174.3A patent/CN108947264B/en active Active
- 2013-10-30 JP JP2015540745A patent/JP6462579B2/en not_active Expired - Fee Related
- 2013-10-30 EP EP13789664.3A patent/EP2914558B1/en active Active
- 2013-10-30 KR KR1020157014023A patent/KR101921788B1/en active IP Right Grant
- 2013-10-30 US US14/438,755 patent/US10040718B2/en active Active
- 2013-10-30 WO PCT/US2013/067472 patent/WO2014070869A1/en active Application Filing
- 2013-11-01 TW TW102139820A patent/TWI626225B/en not_active IP Right Cessation
-
2018
- 2018-08-03 US US16/054,090 patent/US20180339937A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5491115A (en) | 1994-07-18 | 1996-02-13 | Corning Incorporated | Colored glass-ceramics and method |
US20030170459A1 (en) * | 2002-03-05 | 2003-09-11 | Zuel Company, Inc. | Anti-reflective glass surface with improved cleanability |
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Also Published As
Publication number | Publication date |
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JP2016501810A (en) | 2016-01-21 |
EP2914558A1 (en) | 2015-09-09 |
CN105164078B (en) | 2018-09-04 |
TW201431810A (en) | 2014-08-16 |
US10040718B2 (en) | 2018-08-07 |
CN105164078A (en) | 2015-12-16 |
KR20150082362A (en) | 2015-07-15 |
JP6462579B2 (en) | 2019-01-30 |
US20150299034A1 (en) | 2015-10-22 |
EP2914558B1 (en) | 2020-04-15 |
CN108947264B (en) | 2021-03-30 |
CN108947264A (en) | 2018-12-07 |
KR101921788B1 (en) | 2018-11-23 |
US20180339937A1 (en) | 2018-11-29 |
TWI626225B (en) | 2018-06-11 |
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