Transparent glass-ceramics

Abstract: Described are optically active glass-ceramic articles. They are free from ZnO and ZnF 2 exhibiting high optical clarity and containing essentially only one crystal phase consisting essentially, expressed in terms of mole percent, of SiO 2 20-35 PbF 2 19-23 AlO 1.5 10-20 YF 3 3-7 CdF 2 19-34 and PrF +3 at a concentration in the range of about 50 to 650 ppm; and, a transparent glass covering the surface of said elongated central member, but leaving exposed said first and second ends, consisting essentially, expressed in terms of weight percent on the oxide basis, of SiO 2 23-30 B 2 O 3 1-10 Al 2 O 3 0-3 PbO 49-60 Li 2 O 0-1 Na 2 O 0-2 K 2 O 5-11 BaO 0-8 Doped with Pr, Er, and Dy they are especially useful as waveguide amplifiers and lasers.

Description: The invention relates to optically active glass-ceramic articles, especially as optical waveguide amplifiers or lasers. Fluoride based glasses, especially those containing heavy metals as in U.S. Patent 4,674,835, suffer certain undesirable attributes which have restricted their applications, poor resistance to devitrification, crystallization and light scattering problems, and problems in forming large preforms. Crystallization at the interface between the core and cladding during the production of the preform causes problems in the most commonly used methods for preparing an optical fiber, as the glasses are prone to inhomogeneous nucleation, the consequence of which being crystallization at the core and cladding interfaces, particularly during the drawing of the optical fiber. The resulting fibers are subject to serious scattering losses due to crystals in the fibers. Devitrification of the glasses is aggravated when ions necessary to impart differences in indices of refraction to the core and cladding are added to the glass composition. Additional doping, for example with rare earth metal ions, also tends to reduce the stability of the glass. The glass ceramics of Y. Wang and J. Ohwaki in "New Transparent Vitroceramics Codoped with Er 3+ and Yb 3+ for Efficient Frequency Upconversion", Applied Physics Letters , 63 (24), 3268-3270, December 13, 1993, apparently show some improvement of transparency. Based upon those results, we hypothesized that, if those glass-ceramics were as transparent as described, they might also be useful as hosts in amplifier and/or laser devices. Nevertheless, we realized that, if the glass-ceramic materials were to comprise viable hosts for 1.3 µm amplifier devices, Yb would have to be eliminated from the composition because Pr, which is customarily utilized in materials designed for such devices, readily transfers electrons to Yb, that action resulting in the efficiency of the device being reduced. EP-A-0 716 050 claims the priority of November 25, 1994 and was published on June 12, 1996. Designated are the contracting states DE, FR, GB, IT, NL. This European patent application has to be considered, therefore, only under Article 54(3) and (4) EPC. This document discloses transparent glass-ceramics doped with PrF 3 . A particular example is given wherein each batch was doped with 200 ppm PrF 3 . A certain range for the dopant is not described. EP-A-0 640 571 discloses a high efficiency wavelength upconversion transparent glass ceramic composition containing rare earth ions, which can be applied for example to short wavelength solid lasers, full color displays and infrared light detecting sensors, with a chemical composition, in which fluoride fine crystals containing rare earth ions are preferentially precipitated. YbF 3 is mentioned as one rare earth element. Therefore, the objective of the present invention was to develop such glass-ceramic materials which, when doped with Pr, would exhibit excellent behavior as hosts in 1.3 µm amplifiers. Another specific objective of the instant invention was to develop optical fiber waveguides comprising said glass-ceramic materials as the high refractive index core surrounded by a cladding of lower refractive index material. Summary of the Invention In our initial laboratory investigations, we discovered that, when YbF 3 was removed from the Wang et al. composition, the resultant glass did not, upon heat treatment, crystallize in situ properly to produce relatively uniformly-sized, homogeneously dispersed, very fine-grained crystals to yield a transparent material. That is, the resulting material did not exhibit the controlled crystallization constituting the hallmark of a glass-ceramic body. X-ray diffraction studies of the material found no crystalline peaks when the precursor glass was exposed to temperatures within the 450°-500°C range and further heat treatments did not yield a transparent glass-ceramic body. The occurrence of this phenomenon indicates that Yb plays a critical role in the formation of the crystal phase, a role not recognized by Wang et al. Further laboratory studies disclosed that YbF 3 could be replaced without changing the basic crystallization characteristics or the crystal phase itself of the Wang et al. glass by either a combination of YF 3 with CdF 2 concentrations greater than that in the glass of Wang et al., or by a combination of YF 3 and ZnF 2 . Founded upon those two discoveries, the two compositions listed below, expressed in terms of mole percent, were adopted as base glasses: Glass I (A) Glass II (B) SiO 2 30 PbF 2 22 SiO 2 30 PbF 2 17 AlO 1.5 15 YF 3 4 AlO 1.5 15 YF 3 4 CdF 2 29 CdF 2 29 ZnF 2 5 . Each of these base glasses produced a high optical clarity glass- ceramic material when doped with up to 900 ppm by weight of Pr. In addition, a high optical clarity glass-ceramic resulted when these base glasses were doped with up to 5 mole % LuF 3 . The presence of at least 3 mole % YF 3 was determined to be required to assure the proper crystallization in situ to yield a transparent glass-ceramic material of optical clarity. Whereas both base glass compositions performed satisfactorily, the inclusion of ZnF 2 results in somewhat improved glass melting and crystallization behavior; hence, glasses containing ZnF 2 are preferred. In ZnF 2 -containing compositions the content of CdF 2 will range about 21-31 mole %. Where ZnF 2 is absent, CdF 2 will vary between about 19-34 mole %. In ZnF 2 -containing compositions the concentration of PbF 2 will range about 15-25 mole %, whereas in the absence of ZnF 2 , the PbF 2 content will be held between about 19-23 mole %. In order to determine whether additions and/or substitutions could be made to the base glasses, various composition excursions were tested. The general approach adopted comprised substituting fluorides for fluorides and oxides for oxides, thereby maintaining a relatively constant anion ratio. Satisfaction of the following two fundamental criteria was required: (1) the glass will crystallize in situ to a glass-ceramic containing essentially one crystal phase which, most preferably, is capable of accepting some rare earth metal doping; and (2) the glass-ceramic will display high optical clarity. Those excursions illustrated that B 2 O 3 , GeO 2 , P 2 O 5 , and, to a lesser extent, TiO 2 can be substituted into the oxide composition without encountering adverse effects upon the crystallization behavior of the glass. GaF 3 , HfF 4 , and InF 3 can be substituted into the fluoride composition area. Alkali metal and alkaline earth metal oxides and fluorides caused the glass melt to devitrify as it cooled. Compositions containing LaF 3 did not melt well, even at temperatures as high as 1200°C. Other rare earth metals demonstrated varying effects. For example, LuF 3 and satisfied the above two criteria in amounts up to 5 mole %; GdF 3 -containing compositions crystallized in situ with two crystal phases; and CeF 3 -containing melts devitrified spontaneously during cooling. Finally, some CdS can be substituted for CdF 2 . As a result of our laboratory investigations, we have determined that precursor glasses essentially free from ZnO and ZnF 2 capable of being crystallized in situ to glass-ceramic materials displaying high optical clarity and containing essentially one crystal phase can be prepared from compositions consisting essentially, expressed in terms of mole percent, of SiO 2 20-35 PbF 2 19-23 AlO 1.5 10-20 YF 3 3-7 . CdF 2 19-34 and PrF 3 at a concentration in the range of about 50-650 ppm, a PrF 3 concentration of 200 ppm being excluded. Where the precursor glass contains 3-7 mole % ZnF 2 , glass-ceramic materials exhibiting high optical clarity and containing essentially one crystal phase can be prepared from compositions consisting essentially, expressed in terms of mole percent, of SiO 2 20-35 PbF 2 15-25 ALo 1.5 10-20 YF 3 3-7 CdF 2 21-31 ZnF 2 3-7 . and PrF 3 at a concentration in the range of about 50-650 ppm, a PrF 3 concentration of 200 ppm being excluded. By the expression "essentially free from", it is meant that the glass does not contain sufficient ZnF 2 to alter the chemical and/or physical characteristics of the glass. Preferably, ZnF 2 will be absent altogether, but this is not always possible because the glass batch materials (including cullet added to the batch materials) may contain it as an impurity. By the expression "essentially one crystal phase", it is meant that the glass-ceramic does not contain a sufficient amount of a second crystal phase to alter the chemical and/or physical characteristics of the glass-ceramic, most particularly the optical clarity thereof. Again, most preferably, no amount of a second crystal phase will be present. Where rare earth metal ions are included as substitutes for yttrium, they will be present in the crystal phase(s). In the present specification and claims, the expressions "consisting essentially of" and "consist essentially of" are intended to permit the inclusion of minor amounts of inorganic components which do not detrimentally affect the characteristics of the precursor glass and/or those of the final glass-ceramic. In both of the above composition intervals, up to 17 mole % total of the following components in the indicated proportions selected from the group consisting of 0-7% BO 1.5 , 0-12% GeO 2 , 0-7% PO 2.5 , 0-3% TiO 2 , 0-7% GaF 3 , 0-7% HfF 4 , 0-7% InF 3 , 0-5% LuF 3 , 0-3% CdCl 2 , and 0-5% CdS may be present. Also 0-1% NbO 1.5 and 0-1% LaF 3 have been found to be compatible substitutions in the A and B glasses. Differential scanning calorimetry (DSC) measurements of the inventive glasses have indicated a transition temperature in the vicinity of 400°C and a sharp crystallization peak above 450°C for most compositions. The temperature of the heat treatment required to convert the precursor glass to a glass-ceramic was determined after first observing the position of the crystallization peak from the DSC curve, and then exposing the glass to temperatures in the vicinity of that peak. The length of the exposure was dependent upon the temperature employed relative to the peak crystallization temperature, it being well known that crystallization occurs more rapidly at higher temperatures. Thus, the period of exposure could be as short as a few minutes at elevated temperatures to many hours at temperatures below the peak crystallization temperature. Nevertheless, because crystal growth can be more closely controlled at lower temperatures to assure uniformly very fine-grained crystals, heat treatments of 2-8 hours, desirably about 4 hours, at temperatures slightly below the peak crystallization temperature were employed. X-ray diffractive analyses have indicated the presence of a crystal phase which has not been positively identified. The crystal structure has been tentatively identified as a derivative of either M (1-x) (Y,Ln) x F 2+x , wherein M comprises Pb and/or Cd, or (Pb, Cd)LnF 3+x , each of which is a cubic fluorite-like crystal. (Ln refers to a rare earth metal of the lanthanide series.) In either case it indicates the site of the rare earth metal ion in the crystal. X-ray diffraction analyses also indicated the size of the crystals to be about 100-300 Å (10-30 nm, 0.01-0.03 µm) and the crystal content of the material to be about 25-30% by volume. Those values were confirmed via transmission electron micrography. The linear coefficients of thermal expansion of the inventive glass-ceramic materials over the temperature range of 25°-300°C have been measured between about 95-112x10 -7 /°C. The densities of the glass-ceramics range about 5.7-5.9 g/cm 3 and their refractive indices between about 1.74-1.76. By doping with Pr, fluorescence lifetimes in excess of 100 microseconds are the norm with some examples measuring up to about 160 microseconds, that value being more than 50% longer than exhibited by Pr 3+ -doped ZBLAN. Pr is attractive as a dopant because it has an electron transition near 1300 nm, so it is ideal for fabricating optical amplifiers for the 1300 nm telecommunications window. Also reliable pump lasers are available. It was found that fluorescence lifetimes were greater than 120 microseconds with Pr +3 concentrations, in the base glasses, of up to about 500 ppm by weight(ppmw). A quenching effect began slightly above 500 ppmw and lifetimes continued an essentially linear decrease to about 70 microseconds at 900 ppmw. Thus the inventive glass-ceramic and the compatible covering or cladding glass described below can be formed into optically active devices, which may be optical amplifiers or lasers. These optically active devices comprise an elongated central member consisting essentially of either the A or B base glass and a compatible covering or cladding glass according to the composition consisting essentially, expressed in terms of weight percent on the oxide basis, of SiO 2 23-30 B 2 O 3 1-10 Al 2 O 3 0-3 PbO 49-60 Li 2 O 0-1 Na 2 O 0-2 . K 2 O 5-11 BaO 0-8 The central member may also be made up of metal oxides and metal fluorides chosen from the group consisting of 0-7% BO 1.5 , 0-12% GeO 2 , 0-7% PO 2.5 , 0-3% TiO 2 , 0-1% NbO 1.5 , 0-7% GaF 3 , 0-7% HfF 4 , 0-7% InF 3 , 0-5% LuF 3 , 0-1% LaF 3 , 0-3% CdCl 2 , and 0-5% CdS, which are substituted for the oxides and fluorides in the base glasses. About 17 mole % total substitution is acceptable. In general oxides and fluorides are substituted respectively for oxides and fluorides. Another aspect of the invention is a method for making the optically active devices. A major difficulty encountered in the method is avoiding crystal formation during the forming step. The central member glasses described above will form crystals during the forming step if the glass remains too long at a temperature near the peak crystallization temperature. Thus, if a double crucible technique is used, the elongated glass article, having a central member and a covering thereover, must be quickly cooled to a temperature below the peak crystallization temperature. This temperature varies depending upon central member glass composition but is readily determined by DSC of other methods well known in the art. In general the peak crystallization temperature lies in the range of about 400 to 500 °C. The double crucible technique is well known in the art and is described in numerous references, such as, "Fabrication of Long Single Mode and Multimode Fluoride Glass Fibers by the Double Crucible Technique", Tokiwa et al., Electronics Letters, #24, V. 21, 1985. The undesired crystal growth is suppressed by cooling the elongated glass article formed in the double crucible to a temperature below the crystallization temperature in about 1 minute. If an extrusion technique is used, the glass article does not require quenching since extrusion can be done at a viscosity less than or equal to about 10 9.5 poises, which about an order of magnitude above the viscosity whereat crystals can form. The extrusion technique is also well documented in the art for example in, "Shaping of Glass Melts by Continuous Pull Extrusion", Rammo et al., Glastechnische Berichte, #3, V. 67, 1994. If further shaping of the glass article is required after extrusion, a heating and quenching step would have to be added. Once the glass article has reached its final shape, the crystallization process may be carried out at or near the peak crystallization temperature. (Note crystallization as used herein is equivalent to transforming a glass into a glass-ceramic. This temperature is desirable because of the control one has in determining the size, the number and the spacing of the crystals. Thus the preferred temperature in general is in the range of about 400 to 500 °C and the time at temperature may vary 1/2 to 24 hours. One may choose a temperature whereat the required crystallization is complete in 2-8 hours. The ends of the optically active glass-ceramic article are left uncovered to allow access to the central member, which is the optically active part of the article. Pump light or signal light may launched into the central member and received after passing through the central member as would be the case for an optical amplifier. If used as a laser pump light would be inserted into the central member and the laser light would emerge from one or both of the ends. Description of Preferred Embodiments Table I below records a number of glass compositions expressed in terms of mole percent illustrating the present invention resulting from our laboratory investigations. Batches in 25 gram lots were prepared from pure oxides, fluorides, chlorides, and sulfides, hand tumbled to mix the components together, and then charged into 30 cm 3 platinum crucibles. Previous experimentation had established that the preferred PrF 3 concentration was in the range of about 200 to 500 ppmw. In these experimental melts, each batch was doped with 200 ppm PrF 3 . Glass-ceramics containing 200 ppm PrF 3 are excluded from the present invention. Hence, examples wherein each batch was doped with 200 ppm PrF 3 are not included in the scope of protection. The crucibles were moved into a furnace operating at temperatures between 1000°-1200°C for 0.5 hour. All compounding, mixing, and melting were carried out in a glove box under dry nitrogen. Although these glasses do not require melting under inert conditions, safety concerns because of the high concentrations of cadmium led to the practice of confining the melts. After melting, most compositions appeared to be clear, moderately fluid, quiescent liquids. When poured onto a steel block, the resultant slabs tended to break up into small fragments, the cause of the fragmentation being conjectured to be due to the formation of a few crystals therein. Larger bars having dimensions of 5 X 1 X 1 cm, could be cast without shattering, this capability being theorized to be due to a partial anneal received during cooling because of the larger volume of the article. A more thorough anneal was required when the material was to be cut and polished for testing. As was observed above, the crystallization heat treatment applied to each glass sample was determined after the position of the crystallization peak had been located from a DSC curve. The glass sample was heated to a temperature in the vicinity of the peak, the time of exposure being dependent upon the heat treatment temperature utilized vis-a-vis the peak crystallization temperature. In Table I the glass compositions are founded in base glasses A and B with various substitutions of constituents being recorded in terms of mole percent. As noted above, the crystallization heat treatment comprises a range of temperatures centered about the peak crystallization temperature. Because each change in composition can shift both the Tg and peak crystallization temperature of a glass, the thermal processing of each material varies. The heat treatment range for each composition, expressed in terms of °C, encompasses the temperature interval between the onset of the crystallization peak to its terminus. The breadth of the heat treatment ranges for some of the compositions is reported in Table I. Finally, whether the crystallized product (Product) exhibited the demanded optical clarity and whether it contained extremely fine-grained crystals of a single phase are also recorded (yes/no). Example Base Glass Substitution Heat Treatment Product 1002-27-1 1 B None 442-463 Yes 1002-31-4 2 A None 455-466 Yes 1002-3-3 3 A 7.5 ZnO for Al 2 O 3 No 1002-7-2 4 A 5 LiF for PbF 2 No 1002-7-3 5 A 5 NaF for PbF 2 No 1002-7-4 6 A 5 ZrF 4 for PbF 2 No 1002-7-5 7 A 5 HfF 4 for PbF 2 Yes 1002-7-6 8 A 5 SnF 2 for PbF 2 No 1002-7-7 9 A 5 SnO for SiO 2 No 1002-7-8 10 A 5 ZrO 2 for SiO 2 No 1002-7-9 11 A 1.25 TaO 1.5 for SiO 2 No 1002-9-1 12 A 1.25 NbO 1.5 for SiO 2 No 1002-9-3 13 A 5 GaF 3 for PbF 2 Yes 1002-11-1 14 A 2 GdF 3 for PbF 2 Yes 1002-11-3 15 A 5 LuF 3 for PbF 2 Yes 1002-11-4 16 A 2 InF 3 for PbF 2 439-456 Yes 1002-11-5 17 A 1 NbO 1.5 for PbF 2 410-451 Yes 1002-11-7 18 A 5 PO 2.5 for SiO 2 461-477 Yes 934-149-5 19 B 5 RbF for ZnF 2 No 934-149-6 20 B 5 SrF 2 for ZnF 2 No 934-149-7 21 B 5 BaF 2 for ZnF 2 No 934-149-8 22 B 5 CaF 2 for ZnF 2 No 934-149-9 23 B 5 LaF 3 for ZnF 2 No 934-151-1 24 B 5 InF 3 for ZnF 2 469-492 Yes 934-151-2 25 A 5 BO 1.5 for AlO 1.5 403-420 Yes 934-151-3 26 A 10 GeO 2 for SiO 2 465-479 Yes 934-151-5 27 A 2.5 CdS for CdF 2 448-461 Yes 934-151-6 28 A 1 TiO 2 for SiO 2 445-458 Yes 1002-55-5 29 B 3 CdCl 2 for CdF 2 440-460 Yes A chemical analysis was conducted on base glass B. The batch therefor was melted for 30 minutes at 1000°C in a platinum crucible. Element Batched, Weight % Melted, Weight % Si 6.9 5.3 Al 3.3 3.6 Cd 26.7 28.9 Pb 28.9 30.6 Y 2.9 3.3 Zn 2.7 3.0 F 17.8 12.8 Those data suggest that essentially only Si and F were lost during melting. Inasmuch as the F/Si ratio loss approximates 4, it is believed logical to conclude that SiF 4 comprises the principal volatilization product under the present melting conditions. The great resistance of the inventive glasses to devitrification permits the production of large preforms. Thus, crystallization at the interface between the core and cladding during the production of the preform is avoided in the most commonly used methods in preparing an optical fiber waveguide. That attribute led to investigations to discover cladding glasses exhibiting lower refractive indices than the inventive glass-ceramics, but demonstrating linear coefficients of thermal expansion, transition temperatures, and viscosity characteristics compatible with the inventive precursor glasses and glass-ceramics, so as to permit the fabrication of optical fiber waveguides. We have found a family of glasses in the K 2 O-PbO-B 2 O 3 -SiO 2 system which exhibit the necessary properties. Thus, they display refractive indices between 1.67-1.73, linear coefficients of thermal expansion over the temperature range of 25°-300°C of 98-110x10 -7 /°C, transition temperatures between 390°-425°C, and softening points between 475°-525°C. The composition ranges of operable glasses are set out below, expressed in terms of weight percent on the oxide basis, of SiO 2 23-30 B 2 O 3 1-10 Al 2 O 3 0-3 PbO 49-60 Li 2 O 0-1 Na 2 O 0-2 K 2 O 5-11 BaO 0-8 Examples of operable glass compositions, expressed in terms of weight percent on the oxide basis, are listed below in Table II. Also listed are the refractive index (η), the linear coefficient of thermal expansion (Exp) over the temperature range 25°-300°C expressed in terms of x10 - 7 /°C, and the softening point (S.P.) and transition temperature (Tg) expressed in terms of °C. The batch ingredients were compounded in 1000 gram lots, thoroughly blended together in a turbula mixer, and charged into platinum crucibles. The crucibles were moved into a furnace operating at 1200°C and the batches melted for three hours. The melts were cocktail mixed and then poured onto a steel plate to form glass patties having dimensions of about 6" x 6" x 0.5" (∼15 x 15 x 1.25 cm). Finally, the patties were annealed at 400°C. 1 2 3 4 5 6 SiO 2 26.0 25.5 24.4 29.2 27.2 26.0 PbO 58.0 52.3 50.6 54.0 54.0 58.0 K 2 O 9.0 10.3 11.4 7.7 7.7 8.0 B 2 O 3 3.0 3.0 3.0 6.0 8.0 2.0 Li 2 O -- -- -- 0.5 0.5 -- BaO -- 4.9 6.6 -- -- 2.0 Al 2 O 3 3.0 3.0 3.0 -- -- 2.0 Na 2 O -- -- -- 1.6 1.6 -- Sb 2 O 3 1.0 1.0 1.0 1.0 1.0 1.0 η 1.722 1.713 1.713 1.699 1.701 1.7175 Exp 97-109 97-113 103-118 98-116 95-110 92-104 S.P. -- -- -- 504 502 550 Tg 425 423 426 399 398 421 Sb 2 O 3 was included in the glasses to perform its conventional function as a fining agent. As can be appreciated, other fining agents such as As 2 O 3 , halides, and sulfates could be substituted therefor. As can be seen, minor amounts of Li 2 O and/or Na 2 O can be substituted for K 2 O. Such substitutions can improve the chemical durability of the glasses. Likewise, a minor amount of BaO can be substituted for PbO to modify the refractive index of the glass. The most preferred transparent glass-ceramic consists of Glass B doped with an amount of PrF 3 in the range of about 200 to 500 ppmw.

Claims: An optically active glass-ceramic article comprising: an elongated central member, having a first and a second end, consisting of, a transparent glass-ceramic essentially free from ZnO and ZnF 2 exhibiting high optical clarity and containing essentially only one crystal phase consisting essentially, expressed in terms of mole percent, of SiO 2 20-35 PbF 2 19-23 AlO 1.5 10-20 YF 3 3-7 CdF 2 19-34 and PrF 3 at a concentration in the range of about 50 to 650 ppm; a PrF 3 concentration of 200 ppm being excluded; and, a transparent glass covering the surface of said elongated central member, but leaving exposed said first and second ends, consisting essentially, expressed in terms of weight percent on the oxide basis, of SiO 2 23-30 B 2 O 3 1-10 Al 2 O 3 0-3 PbO 49-60 Li 2 O 0-1 Na 2 O 0-2 K 2 O 5-11 BaO 0-8 An optically active glass-ceramic article according to claim 1 wherein the concentration PrF 3 is in the range of about 200-550 ppmw, wherein 200 ppm is excluded. An optically active glass-ceramic article according to claim 2 also containing in said central member up to 17 mole percent total of at least one component selected from the group consisting of 0-7% BO 1.5 , 0-12% GeO 2 , 0-7% PO 2.5 , 0-3% TiO 2 , 0-1% NbO 1.5 , 0-7% GaF 3 , 0-7% HfF 4 , 0-7% InF 3 , 0-5% LuF 3 , 0-1% LaF 3 , 0-3% CdCl 2 , and 0-5% CdS. An optically active glass-ceramic article according to claim 2 wherein said optically active glass-ceramic article is an optical waveguide fiber amplifier. An optically active glass-ceramic article comprising: an elongated central member, having a first and a second end, consisting of a transparent glass-ceramic exhibiting high optical clarity and containing essentially only one crystal phase consisting essentially, expressed in terms of mole percent, of SiO 2 20-35 PbF 2 15-25 AlO 1.5 10-20 YF 3 3-7 CdF 2 21-31 ZnF 2 3-7 and PrF 3 at a concentration in the range of about 50 to 650 ppm, a PrF 3 concentration of 200 ppm being excluded; and, a transparent glass covering the surface of said elongated central member, but leaving exposed said first and second ends, consisting essentially, expressed in terms of weight percent on the oxide basis, of SiO 2 23-30 B 2 O 3 1-10 Al 2 O 3 0-3 PbO 49-60 Li 2 O 0-1 Na 2 O 0-2 K 2 O 5-11 BaO 0-8. An optically active glass-ceramic article according to claim 5 also containing in said central member up to 17 mole percent total of at least one component selected from the group consisting of 0-7% BO 1.5 , 0-12% GeO 2 , 0-7% PO 2.5 , 0-3% TiO 2 , 0-1 NbO 1.5 , 0-7% GaF 3 , 0-7% HfF 4 , 0-7% InF 3 , 0-5% LuF 3 , 0-1 LaF 3 , 0-3% CdCl 2 , and 0-5% CdS. An optically active glass-ceramic article according to claim 6 wherein said optically active glass-ceramic article is an optical waveguide fiber amplifier. An optically active glass-ceramic article according to claim 6 wherein said optically active glass-ceramic article is a laser. The optically active glass-ceramic article according to claim 5 wherein the concentration of PrF 3 is in the range of about 200-550 ppmw, 200 ppm being excluded. A method of making an optically active glass-ceramic article according to claim 5 comprising the steps: forming an elongated glass body, having a first and a second end, a center member consisting of a transparent glass consisting essentially, expressed in terms of mole percent, of SiO 2 20-35 PbF 2 15-25 AlO 1 . 5 10-20 YF 3 3-7 CdF 2 21-31 ZnF 2 3-7 and PrF 3 at a concentration in the range of about 50 to 650 ppm, wherein a PrF 3 concentration of 200 ppm is excluded; and, a transparent glass covering the surface of said elongated central member, but leaving exposed said first and second ends, consisting essentially, expressed in terms of weight percent on the oxide basis, of SiO 2 23-30 B 2 O 3 1-10 Al 2 O 3 0-3 PbO 49-60 Li 2 O 0-1 Na 2 O 0-2 K 2 O 5-11 BaO 0-8 ; and, heating said elongated glass body at a pre-selected temperature for a pre-selected time, to transform said center glass member into a transparent glass-ceramic exhibiting high optical clarity and containing essentially only one crystal phase. A method according to claim 10 wherein said forming step is carried out using a double crucible technique wherein the said center member glass and said transparent glass covering said center member are each heated to a temperature in the range of about 800-1300°C during forming and the formed glass is quenched to a temperature below the peak crystallization temperature in a time of less than 1 minute. The method according to claim 10 wherein said heating step is carried out using a pre-selected temperature near the peak crystallization temperature of said central member glass and the pre-selected time is in the range of about 1/2-24 hours. A method of making an optically active glass-ceramic article according to claim 1 comprising the steps: forming an elongated glass body, having a first and a second end, a center member consisting of a transparent glass essentially free from ZnO and ZnF 2 and consisting essentially, expressed in terms of cation percent, of SiO 2 20-35 PbF 2 19-23 AlO 1.5 10-20 YF 3 3-7 CdF 2 19-34 and PrF 3 at a concentration in the range of about 50 to 650 ppm, wherein 200 ppm is excluded; and, a transparent glass covering the surface of said elongated central member, but leaving exposed said first and second ends, consisting essentially, expressed in terms of weight percent on the oxide basis, of SiO 2 23-30 B 2 O 3 1-10 Al 2 O 3 0-3 PbO 49-60 Li 2 O 0-1 Na 2 O 0-2 K 2 O 5-11 BaO 0-8 ; and, heating said elongated glass body at a pre-selected temperature for a pre-selected time, to transform said center glass member into a transparent glass-ceramic exhibiting high optical clarity and containing essentially only one crystal phase.

Inventors: BORRELLI NICHOLAS F, CORNELIUS LAUREN K, NEWHOUSE MARK A, TICK PAUL A, BORRELLI, NICHOLAS F., CORNELIUS, LAUREN K., NEWHOUSE, MARK A., TICK, PAUL A.
Applicants: CORNING INC, CORNING INCORPORATED
Application year: 1996
Main classification: C03C13
IPC codes: C03C13, C03C10, H01S3, G02F1, C03C3, C03C4