Process for removing hydrogen and carbon impurities from glasses by adding a tellurium halide

• US 5,779,757 A
• Filed: 06/26/1996
• Issued: 07/14/1998
• Est. Priority Date: 06/26/1996
• Status: Expired due to Term

• Current Assignee: the united states of america as represented by the secretary of the navy
• Original Assignee: the united states of america as represented by the secretary of the navy
• Inventors: Nguyen, Vinh Q., Aggarwal, Ishwar D., Sanghera, Jasbinder S.
• Primary Examiner(s): HOFFMANN, JOHN M
• Application Number:
  US08/670,910
• Time in Patent Office: 748 Days
• Field of Search: 65/389, 65/DIG. 15, 65/435, 423/508, 423/509, 423/561.1, 423/511, 501/40
• US Class Current: 65/389
• CPC Class Codes: C03B 2201/86 Chalcogenide glasses, i.e. S, Se or Te glasses
• CPC Class Codes: C03B 2201/88 Chalcohalide glasses, i.e. containing one or more of S, Se, Te and one or more of F, Cl, Br, I
• CPC Class Codes: C03B 37/01265 starting entirely or partially from molten glass, e.g. by dipping a preform in a melt
• CPC Class Codes: C03B 37/01268 by casting
• CPC Class Codes: C03B 5/225 Refining C03B5/18 takes precedence ; Refining agents C03C1/004
• CPC Class Codes: C03B 5/2252 under reduced pressure, e.g. with vacuum refiners
• CPC Class Codes: C03C 1/00 Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
• CPC Class Codes: C03C 1/004 Refining agents refining C03B5/225
• CPC Class Codes: C03C 3/321 Chalcogenide glasses, e.g. containing S, Se, Te
• CPC Class Codes: C03C 3/323 containing halogen, e.g. chalcohalide glasses
• CPC Class Codes: Y10S 65/15 Nonoxygen containing chalogenides

Abstract

Hydrogen and/or carbon impurities are removed from chalcogenide or chalcoide glasses by the addition of a halide, such as TeCl₄, to the batch composition. During melting of the batch composition, the metal halide reacts with the hydrogen and/or carbon impurities to form a hydrogen halide and/or carbon tetrahalide gas and a metal which becomes incorporated into the chalcogen-based glass. Useful halides include halides of sulfur, selenium, tellurium, polonium, or halides of a metal (such as aluminum, magnesium, zirconium, or a mixture thereof) that forms a stable oxide. Mixed metal halides may also be used. The glass melt is then distilled, outgassed, homogenized, fined, and annealed. An apparatus specially designed for making a fiber preform by the above process is also described. An annealed preform made by this method may be drawn into a low-loss fiber in the 2 μm to 12 μm range.

Claims

1. A method comprising the steps of:

adding tellurium halide to a batch composition, thereby forming a halide-containing batch composition, said batch composition contains hydrogen impurities;

heating said halide-containing batch composition to melt said batch composition thus forming a glass melt, and to react said tellurium halide with said hydrogen impurities to form HCl;

distilling said glass melt to form a distillate essentially free of particulate matter; and

outgassing said distillate.

2. The method of claim 1, wherein the concentration of said tellurium halide in said halide-containing batch composition is about 10 ppm-1000 ppm.

3. The method of claim 2, wherein the concentration of said tellurium halide in said halide-containing batch composition is about 10 ppm-100 ppm.

4. The method of claim 1, further comprising the step of cooling said distillate to form a solid glass and annealing said solid glass.

5. The method of claim 4, further comprising the step of drawing said annealed glass into a fiber.

6. The method of claim 1, wherein said tellurium halide is TeCl_n where n is 2, 3, or 4.

7. The method of claim 6, wherein said tellurium halide is TeCl₄.

8. The method of claim 1, wherein said distillate is selected from the group consisting of AsSe glasses, AsS glasses, AsGeSe, GeAsSeTe glasses, GeS glasses, GeSe glasses, AsSSe glasses, GeSSe glasses, GeAsSe glasses GeSbSe glasses, GeAsGaS(In,Se), AsSX glasses where X is a halogen or a mixture of halogens, AsTeX glasses where X is a halogen or mixture of halogens, AsSeX glasses where X is a halogen or mixture of halogens, GeSX glasses, where X is a halogen or mixture of halogens, and GeAsSeTeX glasses where X is a halogen or mixture of halogens.

9. The method of claim 1, further including the step of estimating the amount of hydrogen impurities in said batch composition and wherein the amount of said tellurium halide added to said batch composition provides at least about 1 molar equivalent halogen for one molar equivalent of hydrogen impurities in said batch composition based upon said estimate.

10. The method of claim 1, wherein said tellurium halide is reacted with said hydrogen impurities for from about 7 hrs-14 hrs.

11. A method of forming a glass, comprising the steps of:

providing an apparatus comprising;

a reaction chamber having first and second opposing end surfaces and a longitudinal central axis extending therebetween;

a tailpipe in fluid contact with and extending longitudinally outward from said first opposing end surface of said reaction chamber, wherein said tailpipe forms an airtight connection with said first opposing end surface of said reaction chamber; and

a tube having a first portion, the entirety of which extends within said reaction chamber, said tube having a second portion extending longitudinally from said second opposing end surface of said reaction chamber and terminating external to said reaction chamber, each end of said tube being closed, said tube defining at least one opening along a circumferential surface of said first portion of said tube, and said tube forming an airtight connection with said second opposing end surface of said reaction chamber;

placing a chalcogenide or chalcohalide batch composition within said reaction chamber, said batch composition containing hydrogen impurities;

adding tellurium halide to said batch composition, thereby forming a halide-containing batch composition;

applying vacuum pressure to said apparatus;

sealing said apparatus under said vacuum pressure;

positioning said apparatus within a two-zone furnace so that said longitudinal axis of said reaction chamber is essentially oriented horizontally, said reaction chamber rests entirely within a first zone of said furnace, and said second portion of said tube rests entirely within a second zone of said furnace;

heating said halide-containing batch composition within said first zone of said horizontally oriented reaction chamber to melt said batch composition to form a glass melt and to react said tellurium halide with said hydrogen impurities to form HCl, while said second zone is at a temperature sufficiently higher than the temperature of said first zone to essentially prevent condensation of any glass or components of said glass melt into said second portion of said tube during said heating;

tilting said reaction chamber so that said second opposing end surface is higher than said first opposing end surface;

distilling said glass melt from said reaction chamber into said second portion of said tube while said second zone of said furnace is at a temperature below the temperature of said glass melt in said reaction chamber, so that said glass melt condenses in said second portion of said tube to form a distillate essentially free of particulate matter;

outgassing said distillate while the temperature of the second zone is at a temperature above the softening point of said distillate, and said first zone is at a temperature high enough to essentially prevent condensation of said distillate into said reaction chamber during said outgassing;

cooling said distillate to form a solid glass; and

annealing said solid glass.

12. The method of claim 11, further including the step of estimating the concentration of hydrogen impurities in said batch composition and wherein the amount of said tellurium halide added to said batch composition provides at least about 1 molar equivalent halogen for one molar equivalent of hydrogen impurities in said batch composition based upon said estimate.

13. The method of claim 11, further comprising the step of drawing said annealed glass into a fiber.

14. The method of claim 11, wherein said tellurium halide is TeCl_n where n is 2, 3, or 4.

15. A method comprising the steps of:

adding tellurium halide to a batch composition, thereby forming a halide-containing batch composition, wherein said batch composition contains carbon impurities;

heating said halide-containing batch composition to melt said batch composition thus forming a glass melt, and to react said tellurium halide with said carbon impurities to form CCl₄ ;

distilling said glass melt to form a distillate essentially free of particulate matter; and

outgassing said distillate.

16. A method comprising the steps of:

adding tellurium halide to a batch composition, thereby forming a halide-containing batch composition, said batch composition containing carbon impurities and hydrogen impurities;

wherein heating said halide-contains batch composition to melt said batch composition, thus forming a glass melt, and to react said tellurium halide with said carbon impurities and said hydrogen impurities to form CCl₄ and HCl, respectively;

distilling said glass melt to form a distillate essentially free of particulate matter; and

outgassing said distillate.