Barrier film for hydrogen coloration in glass

Glass manufacturing – Processes – With chemically reactive treatment of glass preform

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Details

65 3011, 65 321, 65 324, 65 601, 65 602, 65 604, 65157, 4271262, 4271263, 427165, C03C 1500, C03C 1700, C03C 2502, C03B 3700

Patent

active

061582468

DESCRIPTION:

BRIEF SUMMARY
BACKGROUND OF THE INVENTION

Hydrogen firing at elevated temperatures to change the color of glasses whose compositions contain reducible ions is well known. A notable commercial application of that technique is found in the Corning Incorporated eyewear product lines marketed under the SERENGETI.RTM. and CPF.RTM. trademarks. Another example of the effect of hydrogen firing on color is the formation of a black color on glass, used for STEUBEN.RTM. ware or on certain glazed dinnerware products. The color changes induced are attributed to the reduction of a portion of the silver and lead ions, respectively, in the glass to the atomic state.
It is known that a chemical reaction proceeds very fast relative to hydrogen diffusion which leads to the condition of a sharp boundary between the reduced region near the surface, and the unreduced region below the surface. Coloration derives from the reduced layer. Accordingly, it is the object of the present invention to provide a method of forming coloration in desired areas near a glass surface using a barrier film.


SUMMARY OF THE INVENTION

The inventive method would enable the forming of color and color gradients or the generation of designs on the surface of the glass article. The patterns could be of a decorative nature or they could be functional. An example of the latter would be diffraction gratings.
In one aspect, the invention relates to a method of forming color patterns or designs on the surface of a glass article by (1) depositing a hydrogen-blocking film on at least one surface of the glass; (2) forming a layer of photoresist over the hydrogen-blocking film; (3) exposing the glass article to light through a mask which contains a desired pattern or design; (4) developing the photoresist and removing the exposed photoresist to reveal the underlying hydrogen-blocking layer; (5) removing the now exposed hydrogen-blocking layer to reveal the underlying glass; (6) removing the unexposed photoresist to reveal the remaining underlying hydrogen-blocking layer; and (7) subjecting the glass article to hydrogen treatment at appropriate temperature for a duration of time to produce the desired coloration.
In another aspect, the invention relates to a method of forming a color or optical density gradient or designs by depositing a hydrogen-blocking layer having a variable thickness (or thickness gradient), and repeating steps (2) to (7) above, to form a glass having a color or optical density gradient.
In still another aspect, the invention relates to a method of forming coloration in glass by: material on the surface of said portion of the glass, the material being capable of retarding or blocking a reducing gas such as hydrogen; reduce the reducible phase therein; and glass having a color pattern or design.
As used herein:
"reducing atmosphere" refers to a gaseous atmosphere in which the chemical potential of oxygen is very low. Examples of reducing gases include hydrogen, hydrazine vapor, cracked ammonia, deuterium and forming gas (i.e., a mixture of hydrogen and an inert gas, for example, H.sub.2 /He and H.sub.2 /N.sub.2).


BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph comparing the spectra of (1) a photochromic glass with those of (2) the same glass having 2500 A chromium film after hydrogen treatment at 400.degree. C. for 25 minutes, and (3) the photochromic glass after the same hydrogen treatment, but without the chromium layer,
FIG. 2a is a graph of the optical density of a 2 .mu.m thick reduced layer on glass versus the wavelength; and
FIG. 2b is a graph of optical density versus wavelength for the chromium-protected regions of the glass of FIG. 2 after hydrogen treatment at 400.degree. C. after 16 hours.


DETAILED DESCRIPTION OF THE INVENTION

According to the inventive method, a layer of material capable of blocking a reducing gas is formed on a glass surface, followed by treatment in a reducing atmosphere. For ease of discussion, the layer of material will be referred to herein as "hydrogen-blocking layer" even though it is understood that in add

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patent: 4240836 (1980-12-01), Borrelli et al.
patent: 4259406 (1981-03-01), Borrelli
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patent: 4304584 (1981-12-01), Borrelli et al.
patent: 4407891 (1983-10-01), Ernsberger
patent: 4760307 (1988-07-01), Howorth
patent: 4854957 (1989-08-01), Borrelli et al.
patent: 4989960 (1991-02-01), Thomas

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