US4680048A — Method of preparing doped silica glass

Claim 1

Independent Claim 82 words

A method of preparing a doped silica glass article, comprising: hydrolyzing silicon alkoxide; adding ultrafine particle silica to the hydrolyzed solution to obtain a sol solution; adjusting the pH of the sol solution to a pre-determined value of less than about 7.0; placing the sol solution into a container; gelling the sol solution to a wet gel; drying the wet gel to a dry gel; sintering the dry gel to yield the doped silica glass article; and including at least one dopant.

Claim 2

Independent Claim 82 words

A method of preparing a doped silica glass article, comprising: hydrolyzing silicon alkoxide; adding ultrafine particle silica to the hydrolyzed solution to obtain a sol solution; adjusting the pH of the sol solution to a pre-determined value of less than about 7.0; placing the sol solution into a container; gelling the sol solution to a wet gel; drying the wet gel to a dry gel; sintering the dry gel to yield the doped silica glass article; and including at least one dopant.

Claim 3

Dependent Claim 78 words

The method of claim 1, wherein the dopant is selected from the group consisting of metal alkoxide having the formula M(OR) x wherein M is a metal, R is an alkyl group having less than 20 carbon atoms and x is an integer equal to the valence of the metal, metal oxide having the formula MO y wherein M is a metal and y is an integer equal to one-half the valence of the metal, and pure metal.

Claim 4

Dependent Claim 11 words

The method of claim 2, wherein the dopant is metal alkoxide.

Claim 5

Dependent Claim 12 words

The method of claim 3, wherein the metal alkoxide is germanium tetraalkoxide.

Claim 6

Dependent Claim 16 words

The method of claim 1, wherein the dopant is doped in the form of metal oxide.

Claim 7

Dependent Claim 13 words

The method of claim 1, wherein the dopant is doped in gaseous form.

Claim 8

Dependent Claim 17 words

The method of claim 2, wherein the dopant is metal oxide in the form of fine particles.

Claim 9

Dependent Claim 17 words

The method of claim 1, wherein the container is a cylindrical container formed of a hydrophobic material.

Claim 10

Independent Claim 115 words

A method of preparing a cylindrical doped silica glass article, comprising: hydrolyzing silicon alkoxide; adding ultrafine particle silica to the hydrolyzed solution to obtain a sol solution; adjusting the pH of the sol solution to a pre-determined value of less than about 7.0; placing the sol solution into a hydrophobic cylindrical container; gelling the sol solution to a wet gel; drying the wet gel to a dry gel; sintering the dry gel to yield the doped silica glass article; and including at least one metal alkoxide dopant having the formula M(OR) x , wherein R is an alkyl group, M is a metal and x is an integer equal to the valence of the metal.

Claim 11

Independent Claim 115 words

A method of preparing a cylindrical doped silica glass article, comprising: hydrolyzing silicon alkoxide; adding ultrafine particle silica to the hydrolyzed solution to obtain a sol solution; adjusting the pH of the sol solution to a pre-determined value of less than about 7.0; placing the sol solution into a hydrophobic cylindrical container; gelling the sol solution to a wet gel; drying the wet gel to a dry gel; sintering the dry gel to yield the doped silica glass article; and including at least one metal alkoxide dopant having the formula M(OR) x , wherein R is an alkyl group, M is a metal and x is an integer equal to the valence of the metal.

Claim 12

Dependent Claim 16 words

The method of claim 1 or 9, wherein the dopant is added to the hydrolyzed solution.

Claim 13

Dependent Claim 16 words

The method of claim 1 or 9, wherein the dopant is added to the sol solution.

Claim 14

Dependent Claim 15 words

The method of claim 1 or 9, wherein the dopant is added to the gel.

Claim 15

Dependent Claim 17 words

The method of claim 1 or 9 wherein the dopant is added to the glass during sintering.

Claim 16

Dependent Claim 18 words

The method of claim 1 or 9, wherein the dopant is added in the form of fine particles.

Claim 17

Dependent Claim 22 words

The method of claim 1 or 9, wherein the alkyl group in the metal alkoxide includes from 1 to 20 carbon atoms.

Claim 18

Dependent Claim 39 words

The method of claim 1 or 9, wherein the metal in the metal alkoxide is selected from the group consisting of Li, Na, K, Cs, B, Al, Ga, Ge, N, P, F, Zr, Ti, Ta, Tl, Tb and Ag.

Claim 19

Dependent Claim 20 words

The method of claim 9, wherein the metal alkoxide is germanium tetraalkoxide represented by the general formula Ge(OR) 4 .

Claim 20

Dependent Claim 24 words

The method of claim 17, wherein the germanium tetra alkoxide is selected from the group consisting of germanium tetramethoxide, germanium tetraethoxide and germanium tetrapropoxide.

Claim 21

Dependent Claim 12 words

The method of claim 9, wherein the silicon alkoxide is silicon methoxide.

Claim 22

Dependent Claim 12 words

The method of claim 9, wherein the silicon alkoxide is silicon ethoxide.

Claim 23

Dependent Claim 20 words

The method of claim 9, wherein the metal alkoxide is germanium tetraethoxide represented by the general formula Ge(OEt) 4 .

Claim 24

Dependent Claim 56 words

The method of claim 9, wherein the hydrolyzed solution is prepared by: partially hydrolyzing silicon alkoxide with water at a molar ratio between about 1 and 3 with respect to the silicon alkoxide at a temperature less than about 20° C.; adding an effective amount of metal alkoxide; and hydrolyzing alkoxide groups remaining in the solution.

Claim 25

Dependent Claim 81 words

The method of claim 9, wherein the hydrolyzed solution is prepared by: adding water to a solution of silicon alkoxide and alcohol at a volume ratio of more than about 20% with respect to the silicon alkoxide, the water being used in an amount of between about 1 and 3 moles with respect to the molar amount of silicon alkoxide; adding an effective amount of metal alkoxide to the hydrolyzed silicon alkoxide solution; and hydrolyzing alkoxide groups remaining in the solution.

Claim 26

Dependent Claim 26 words

The method of claim 9, wherein the ultrafine particle silica is ammosil prepared by hydrolyzing a silicon alkoxide with ammonia water or ammonia gas and water.

Claim 27

Dependent Claim 20 words

The method of claim 24, wherein the mean particle diameter of the ammosil is between about 0.01 and 1.0 um.

Claim 28

Dependent Claim 24 words

The method of claim 24, wherein the ammosil is uniformly dispersed in the ammosil containing sol solution by ultrasonic vibration, centrifugal separation, or both.

Claim 29

Dependent Claim 37 words

The method of claim 9, wherein the sol solution is prepared by adding a solution containing fine particle silica in the form of ammosil having a predetermined pH value to the sol solution in a predetermined ratio.

Claim 30

Dependent Claim 20 words

The method of claim 9, wherein the pH of the sol solution is adjusted to between about 3 and 6.

Claim 31

Dependent Claim 51 words

The method of claim 9, wherein the pH of the sol solution is adjusted by adding a base selected from the group consisting of ammonia, ammonia gas, an aqueous solution of ammonia, triethylamine, an aqueous solution of triethylamine, pyridine, an aqueous solution of pyridine, aniline and an aqueous solution of aniline.

Claim 32

Dependent Claim 35 words

The method of claim 9, wherein the temperature and the pH of the sol solution are adjusted so that gelation of the sol is complete in a period of between about 3 and 100 minutes.

Claim 33

Dependent Claim 43 words

The method of claim 9, wherein the composition of the sol solution is adjusted so that the volume of said transparent glass obtained by drying and sintering the wet gel is between about 5 and 15% of the volume of the wet gel.

Claim 34

Dependent Claim 39 words

The method of claim 9, wherein during drying of the wet gel, both ends of the cylindrical container are covered with lids, each lid having openings amounting to less than about 15% of the surface area of the lid.

Claim 35

Dependent Claim 44 words

The method of claim 9, wherein during drying of the wet gel, the wet gel is removed from the hydrophobic cylindrical container and placed into a second container having openings amounting to less than about 15% of the surface area of the second container.

Claim 36

Dependent Claim 56 words

The method of claim 9, wherein the wet gel is dried at a temperature between about 0° and 100° C. and heated to a temperature between about 20° and 120° C. at a heating rate less than about 120° C. per hour, at which temperature the gel is dried to a dry gel by contraction drying.

Claim 37

Dependent Claim 86 words

The method of claim 9, wherein the sintering step includes the steps of: removing absorbed water by heating the gel to a first selected temperature; removing carbon by heating the gel to a second selected temperature; removing hydroxide groups by heating the gel to a third selected temperature; removing hydrochloride or fluoride and making the gel nonporous by heating the gel to a fourth and then to a fifth selected temperature; and converting the gel by heating to a sixth selected temperature to a transparent glass.

Claim 38

Dependent Claim 56 words

The method of claim 35, wherein absorbed water is removed by at least one step of heating the gel to a first selected temperature between about 20° and 400° C. at a heating rate less than about 400° C. per hour and maintaining the gel at the first selected temperature for at least about one hour.

Claim 39

Dependent Claim 56 words

The method of claim 35, wherein carbon is removed by at least one step of heating the gel to a second selected temperature between about 400° and 1200° C. at a heating rate between about 30° and 400° C. per hour and maintaining the gel at the second selected temperature for at least about one hour.

Claim 40

Dependent Claim 101 words

The method of claim 35, wherein hydroxide group is removed by at least one step of heating the gel to a third selected temperature between about 700° and 1200° C. while a carrier gas selected from the group consisting of He, Ne, Ar, N 2 , O 2 and a hydroxide group removing agent selected from the group of consisting of Cl 2 , SOCl, SF 6 , CF 4 , C 2 F 6 and C 3 F 8 flow through the sintering oven at a flowing amount ratio between about 1 and 40% with respect to the carrier gas.

Claim 41

Dependent Claim 99 words

The method of claim 38, wherein after removing hydroxide groups, chloride or fluoride is removed by at least one step of flowing a carrier gas selected from the group consisting of He, Ne, Ar and N 2 and oxygen through the sintering oven at a flowing ratio between about 1 and 100% with respect to the carrier gas at a fourth selected temperature between about 700° and 1200° C. and the gel is made non-porous by heating the gel to a fifth selected temperature between about 1000° and 1500° C. while pure He only flows through the sintering oven.

Claim 42

Dependent Claim 47 words

The method of claim 39, wherein the gel is converted to a transparent glass by heating the gel to a sixth selected temperature between about 1000° and 1600° C. and maintaining the gel at the sixth selected temperature for a period of time to effect the conversion.

Claim 43

Dependent Claim 18 words

The method of claim 38, wherein the heating rate is between about 0.5° and 1000° C. per minute.

Claim 44

Dependent Claim 18 words

The method of claim 39, wherein the heating rate is between about 0.5° and 1000° C. per minute.

Claim 45

Dependent Claim 18 words

The method of claim 40, wherein the heating rate is between about 0.5° and 1000° C. per minute.

Claim 46

Dependent Claim 119 words

In a method of preparing a doped cylindrical silica glass article, by adding ultrafine particle silica into a hydrolyzed solution of silicon alkoxide, adjusting the pH of the sol solution to a value of less than about 7.0, gelling the sol solution to a wet gel, drying the wet gel to a dry gel, and sintering the dry gel to a silica glass, the improvement which comprises adding an effective amount of a metal alkoxide dopant having the general formula M(OR) x , wherein M is the metal, R is an alkyl group and x is an integer representing the valence of the metal to the article to alter the refractive index of the glass to a desired value.

Claim 47

Dependent Claim 119 words

In a method of preparing a doped cylindrical silica glass article, by adding ultrafine particle silica into a hydrolyzed solution of silicon alkoxide, adjusting the pH of the sol solution to a value of less than about 7.0, gelling the sol solution to a wet gel, drying the wet gel to a dry gel, and sintering the dry gel to a silica glass, the improvement which comprises adding an effective amount of a metal alkoxide dopant having the general formula M(OR) x , wherein M is the metal, R is an alkyl group and x is an integer representing the valence of the metal to the article to alter the refractive index of the glass to a desired value.

Claim 48

Dependent Claim 18 words

The method of claim 44, wherein the silicon alkoxide is silicon ethoxide and the dopant is germanium tetraethoxide.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1990-07-13	1991-01-12	1991-07-14	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1994-07-13	1995-01-12	1995-07-14	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1998-07-13	1999-01-12	1999-07-14	$7700.00	Window Closed / Lapsed

Method of preparing doped silica glass

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