US 4,902,650 AGrant
Gradient-Index Glass
Issue Date:1990-02-20
•5 Claims
•3 Drawing Sheets
Abstract
A sol-gel method for making gradient-index glass and a novel composition therefor, comprising at least a ternary system of metal alkoxides.
Metadata
Assignee
- The University of Rochester
Inventors
- J. Brian Caldwell
- Duncan T. Moore
Application Information
Application Number:US 2195038
Filing Date:1988-07-15
Priority Date:1987-06-09
Art Unit:118
Classifications
IPC:
C03C 400C03C 3076C03C 3083C03C 3089
Field of Search:
50112;55;65;66;67;68;900
Patent Drawings (3 sheets)
Description
Drawings Detailed Description and Examples
These and other objects and advantages of this invention will become more apparent from the following detailed description which makes reference to the following figures in which:
FIG. 1 is a plot of delta-n versus radius of a radial gradient element with its central axis at 0.00 radius
FIG. 2 is a plot of temperature versus time for the sintering cycle; and
FIG. 3 is a interferogram of a plane-faced disc element, cut and polished, using a Mach-Zehnder interferometer and an argon-ion laser operating at a wavelength of 0.5145 microns.
An alkoxide of silicon, diluted with alcohol, is partially hydrolyzed by adding a small amount of slightly acidic water to form a mixture. After the partial hydrolysis, at least two different metal alkoxides are added to the mixture. The first of the alkoxides act as index modifiers (or dopants) and are selected from the group consisting of titanium and zirconium. The second of the alkoxides act as gel modifiers and are selected from the group consisting of boron, aluminum and germanium. The resulting ternary or greater solution is stirred. Next, additional water is added to the alkoxide solution in order to facilitate its gelation. Prior to gelation, the solution is poured into a mold of the desired shape.
After the solution gels, it is allowed to age at a temperature between 20.degree. C. and 100.degree. C. for a period of time between 1 hour and several weeks. The aged gel is then placed in a leaching bath in order to leach out some of the index modifying dopant, thus creating a concentration profile of the dopant. The leaching bath consists of water and one or more acids selected from the group consisting of hydrochloric acid and sulfuric acid, nitric acid.
After leaching, the gel is placed in an alcoholic fixing bath, preferably comprising methanol or ethanol, in order to fix the concentration profile in place. The gel then is dried to produce a porous oxide body with a greater percentage of index modifying dopants at its center than at its edge. Referring to FIG. 2, the dry gel then is sintered into glass by controlled heating to a temperature between 800.degree. C. and 1600.degree. C.
Gradient-index glass rods produced by this method can range in size from 0.5mm to 15mm. They also may have a delta-n up to 0.03. See FIG. 1. Finally, the gradient-index profile typically will be symmetrical and nearly parabolic in shape. See FIG. 3. The use of zirconium oxide as an index modifier will result in a lower index profile dispersion than when titanium oxide is used.
The addition of Al.sub.2 O.sub.3 to the gel helps to eliminate all of the problems inherent in a binary system. Gels containing Al.sub.2 O.sub.3 tend to have a lower density and coarser microstructure when they are dried. The coarse structure makes the dry gel more resistant to fracture while it is heated. It also allows gaseous reaction products formed during sintering to flow freely out of the gel, thus helping to avoid bloating. Al.sub.2 O.sub.3 tends to increase the temperature at which the gel collapses into glass, which means that the reactions which cause bloating are more likely to be completed before the gel collapses. When added to a gel containing TiO.sub.2 . helps to reduce the rate of crystallization and increase the temperature at which crystallization occurs.
The addition B.sub.2 O the gel helps to eliminate bloating because the B.sub.2 O.sub.3 gradient created during the leaching stage lowers the sintering temperature of the center of the gel relative to the outer portions of the gel. This means that the middle will sinter first, and released gases will therefore not be trapped within the collapsing gel. Also, B.sub.2 O.sub.3 substantially reduces the tendency of a gel containing TiO.sub.2 to crystallize at high temperature.
(GeO.sub.2, performs a similar function to B but in addition it makes a significant contribution to the total index change.
Tetramethoxy silane, or "TMOS", is the preferred silicon alkoxide for the source of silica in the gel. The preferred source of B.sub.2 O.sub.3 is triethyl borate or tributyl borate. The preferred sources of GeGeO.sub.2, ZrO.sub.2, and TiO.sub. 2 are the ethoxides, propoxides, and butoxides of germanium, zirconium, and titanium, respectively. The preferred source of A1203 is aluminum di(sec-butoxide) acetoacetic ester chelate. The metal oxides (SiO.sub.2, TiO.sub.2, ZrZrO.sub.2, Al.sub.2 O.sub. 3, and GeO.sub.2) are formed from their corresponding metal alkoxides by hydrolysis and polycondensation reactions. These reactions lead to the formation of a highly porous oxide gel.
The amount of SiO.sub.2 in the gel should be between 60 and 98 mole percent. Amounts less than 60% result in a gel which is too weak to withstand all of the processing steps. Amounts greater than 98% will not yield useful refractive index changes.
For gels incorporating TiO.sub. 2 as the main index modifier, the amount of TiO.sub.2 in the gel should be at least 0.1 mole percent but less than 25 mole percent. For gels incorporating ZrO.sub.2 as the main index modifier, the amount of ZrO.sub.2 should also be at least 0.1 mole percent but less than 25 mole percent. Gels containing more than 25% TiO.sub.2 or ZrO.sub.2 tend to dissolve during the leaching stage or crystallize during the sintering stage.
When 2 O.sub.3, Al.sub. 2 O.sub.3 or GeO.sub. 2 are used as gel modifiers, the amount of B.sub.2 O.sub. 3 should be less than 10 mole percent, the amount of Al.sub. 2 O.sub. 3 should be between 1 and 25 mole percent, and the amount of GeO.sub. 2 should be less than 20 mole percent.
The following are illustrative examples of specific embodiments of this invention.
Example 1
9.13ml of TMOS, 30.97ml of methanol, and 1.38ml of a 0.1M aqueous solution of hydrochloric acid are stirred together for 30 minutes. 2.17ml of titanium isopropoxide and 2.20ml of aluminum di(sec-butoxide) acetoacetic ester chelate then are added and the mixture is stirred for 2 hours. 4.14ml of water then is added and the mixture is stirred for 10 to 15 minutes. The resulting solution is poured into four 15.times. 90mm polypropylene test tubes which are immediately capped. The solution inside the test tubes forms a stiff gel within 3 hours at room temperature. The gels are kept closed inside the test tubes while they are aged for 1 day at 60.degree. C.
The gels then are placed into glass test tubes containing 50ml of a 32.6% aqueous solution of sulfuric acid. The glass tubes are rotated end over end to provide thorough agitation. After 19 hours the gels are removed from the acid and washed in methanol. The gels then are placed in large empty test tubes in an oven at 60.degree. C. to dry for 2 days. The gels are dried for 1 more day at 100.degree. C.
Next, the gels are heated at 5.degree. C. per minute to 500.degree. C., then at 10.degree. C. per minute to 900.degree. C., then at 5.degree. C. per minute to 1200.degree. C., then at 25.degree. C. per minute to 1450.degree. C. At 1450.degree. C., the resulting glass rods are removed from the furnace and cooled to room temperature. The heating is done in an oxygen atmosphere up to 900.degree. C., and in a helium atmosphere from 900.degree. at 1450.degree. C. See FIG. 2.
The resulting rods are 4.7mm in diameter and about 25mm long. They are transparent and free of defects. They have a nearly parabolic index of refraction gradient with a total index change of 0.007, and are suitable for making plane-faced rod lenses.
Example 2
8.26ml of TMOS, 30.21ml of methanol, and 1.01ml of aqueous 0.1M hydrochloric acid are stirred for 30 minutes. 2.22ml of titanium isopropoxide, 3.09ml of aluminum di(sec-butoxide) acetoacetic ester chelate, and 0.836ml of germanium ethoxide are then added and the mixture is stirred for 2 hours. 4.38ml of water is then added, and the mixture is stirred for 10 minutes. The resulting solution is poured into test tubes, aged, leached, dried, and sintered as in Example 1. The leaching time is only 9 hours in this case, however. The resulting gradient-index glass rods have a nearly parabolic refractive index profile with a total index change of 0.0143 and a diameter of 4.7mm.
Example 3
A solution prepared according to example 2 is poured into a single 25mm diameter teflon test tube. The rest of the processing is identical two Example 2 except that the gel is leached in 150ml of acid solution for 30 hours. The resulting glass rod is 8.1mm in diameter with an index change of 0.007.
Example 4
9.73ml of TMOS, 31.43ml of methanol, and 1.19ml of 0.1M hydrochloric acid are mixed together for 30 minutes. 2.42ml of zirconium n-propoxide and 0.87ml of germanium ethoxide are then added and the mixture is stirred for 2 hours. 4.41ml of water is then added and the mixture is stirred for 10 to 15 minutes. The resulting solution is poured into molds and aged as in Example 1. The gels are leached for 7 hours in a 12.5% aqueous hydrochloric acid solution, and then are washed and dried as in Example 1. The dry gels are converted into gradient-index glass by heating at 100.degree. C. per hour to 300.degree. C. for 1 hour, heating at 50.degree. C. per hour to 450.degree. C., then at 5.degree. C. per minute to 1350.degree. C., then cooled to room temperature. The heating was done in an oxygen atmosphere up to 700.degree. C., and in a helium atmosphere from 700.degree. C. to 1350.degree. C. The resulting gradient-index glass rods are similar to those produced in Example 1.
Example 5
Gels are prepared in a manner similar to that of Example 4, except that a combination of boron and aluminum alkoxides are used instead of a germanium alkoxide in preparing the initial solution. The chemicals used are 8.12ml of TMOS, 31.83ml of methanol, 0.99ml of 0.1M aqueous hydrochloric acid, 2.45ml of zirconium n-propoxide, 1.98ml of triethyl borate, 1.58ml of aluminum di(sec-butoxide) acetoacetic ester chelate, and 4.68ml of water. The gels are treated similar to the ones in Example 4 and yield gradient-index glass rods of similar quality.
Claims
We claim:
1. A gradient-index glass having a generally parabolic index of refraction about a central axis and which is produced from a sol-gel consisting essentially of at least three oxide components which are silicon dioxide (SiO.sub.2) and, an index modifying dopant generally uniformly decreasing radially outward from the axis and consisting of a metal oxide selected from the group consisting of titanium oxide TiO.sub.2) and zirconium oxide (ZrO.sub.2) and at least one additional oxide element for gel modification selected from the group consisting of oxides of aluminum (Al.sub.2 O.sub.3), boron (B.sub.2 O.sub.3) and germanium (GeO.sub.2), wherein said oxides are in an interconnected network and wherein the concentration of SiO.sub.2 in the gel is between 60 and 98 mole percent of the total oxide content in the gel, the concentration of the index modifying dopant oxide in the gel is between 0.1 and 25 mole percent of the total oxide content in the gel, and the concentration of the additional metal oxide is less than 25 mole percent of the total oxide content in the gel.
2. The gradient-index glass according to claim 1 wherein the index modifying dopant is titanium oxide.
3. The gradient-index glass according to claim 1 wherein the gel modification metal oxide element is aluminum oxide.
4. The gradient-index glass according to claim 1 wherein the gel modification metal oxide element is aluminum oxide and germanium oxide.
5. The gradient-index glass according to claim 1 wherein the index modifying dopant is zirconium oxide.