Fatigue resistant optical fiber

Abstract: A silica-based optical fiber is provided, which has improved resistance to static fatigue. The fiber includes an outer layer 140 of modified, fused silica which contains zirconia and, optionally, alumina. The inventive fiber in one embodiement includes core 100, cladding 110, fused silica layer 120, fused silica layer 130, and anti-fatigue layer 140. According to an exemplary procedure, glass layers corresponding respectively, to the cladding and the core are first formed on the inner surface of a fused silica substrate tube by well-known MCVD methods. The substrate tube is collapsed, again by well-known methods, to form the inner portion of a fiber preform. The glass of the substrate tube corresponds to layer 120 of the ultimate fiber. The collapsed tube is placed within a second, fused silica tube, here referred to as the overcladding tube. The overcladding tube is then collapsed, exemplarily by heating it with oxyhydrogen torches on a vertical glass lathe, to form a solid, rod-like preform. The glass of the overcladding tube corresponds to layer 130. The material of the anti-fatigue layer is then applied.

Description: Field of the Invention This invention relates to the field of silica-based optical fibers, and more particularly to those fibers that have improved resistance to static fatigue. Background of the Invention It has long been known that silica-based optical fibers are susceptible to stress-assisted corrosion, also known as static fatigue, when the fiber is under stress in the presence of moisture. One approach to this problem has been to manufacture fiber having an outer layer which is under relatively high compressive stress. A stronger fiber is believed to result from such built-in stress. A method for making such fibers is disclosed, for example, in U.S. Patent No. 4,243,298, issued on January 6, 1981, to C.K. Kao, et al. Optical fibers having high-compression outer layers may have certain disadvantages. For example, fiber joints are conventionally made in an operation which includes the cleaving of the fiber ends that are to be joined. A predetermined tension is applied to each fiber by the cleaving machine in order to fracture the fiber at a desirable cleave angle, i.e., an angle which is preferably 0.0°, but which is more typically about 0.25°. It has been observed that in order to produce a desirable cleave angle in a fiber having a high-compression outer layer, the cleaving tension must be increased. This requirement is undesirable, because the extra step that is entailed is inconvenient for workmen making field installations, increases the cost of such installations, and increases the likelihood of error. Practitioners have hitherto failed to provide a silica-based optical fiber having a modified outer glass layer which offers improved resistance to static fatigue, but which is not in substantially higher compression than other regions of the fiber. One method of forming protective outer layers on optical fibers, generally applicable to layers containing oxides of elements of the boron, titanium, or carbon groups, is described in Patent Abstracts of Japan, Publication No. JP63117922, published May 21, 1988 under the title "Production of Optical Fiber". This method involves depositing a soot from a burner, followed by sintering. European patent application, Publication No. 0078749, published May 11, 1983 under the title "Reinforced and Chemically Resistant Optical Filament," describes an optical fiber overcoated with a thin, protective, zirconia-containing, metal oxide coating. However, the protective coating described there is selected to exert a compressive force on the optical fiber. Patent Abstract of JP-A-63117922 describes a method of manufacturing an optical fiber in which before drawing the fiber there is deposited a particulate layer comprising silica doped with zirconia. According to the present invention there is provided an optical fiber as defined in the claim. We have discovered a modified, silica glass composition which offers improved resistance to static fatigue. Accordingly, the invention, in one aspect, is a silica-based optical fiber which includes a modified silica-based outer layer, wherein the composition of the outer layer includes zirconia and alumina. The outer layer is substantially free of residual, compressive stress. (It should be noted in this regard that a method for making silica-based optical fiber codoped with zirconia and alumina is described in U.S. Patent No. 4,666,247, issued to J.B. MacChesney, et al., on May 19, 1987. However, that patent does not address the problem of static fatigue.) The fiber is exemplarily manufactured by drawing fiber from a solid, rod-like preform. According to the invention, the preform includes at least one outer portion of silica-based glass. Before the fiber is drawn, an outer glass layer which comprises silica doped with zirconia and alumina is formed on the outer surface of the preform. The amount of zirconia is effective for producing, in the resulting fiber, a stress corrosion parameter of 30 or more. The zirconium atomic number density in the outer layer, expressed as a fraction of the silicon density, is at least about 2% but not more than about 8%. The aluminum density, similarly expressed, does not exceed about 8%. Alumina is added in order to suppress crystallization in the outer layer, and the amount used should be effective for this purpose. In a currently preferred embodiment, the outer layer is formed initially as a particulate layer which is then sintered to form the glass layer. Brief Description of the Drawings FIG. 1 is a schematic, cross sectional end view of an exemplary optical fiber made according to the invention. FIG. 2 is a schematic drawing of a conventional torch which may be useful for manufacturing the inventive fiber, in one embodiment. FIG. 3 is a schematic drawing of a conventional aerosol delivery nozzle which may be useful for manufacturing the inventive fiber, in one embodiment. FIG. 4 is a map in a two-dimensional space which represents doping levels of alumina and zirconia in an outer glass layer made according to the invention. Indicated on the map is the region which represents selected compositions. Detailed Description The inventive fiber may be a single or multiple mode fiber having a core and a cladding, and having any of a broad range of dimensions. The only essential limitation in this regard is that at least an outer portion of the cladding should be made of silica-based glass, for example, glass which contains at least about 80% silicon dioxide by weight. The improved resistance to static fatigue which is the object of this invention is provided by forming an outer glass layer which comprises silica that is doped with zirconia and alumina. This outer layer is typically about 1 - 5 µm thick. The surface of the resulting fiber may be in tension because of the contraction of the outer layer when it is formed and cooled. This will tend to occur, for example, when the underlying cladding consists of substantially pure silica. In order to avoid excessive tension, and also in order to assure that the glass of the outer layer will be homogeneous, it is desirable to limit the ratio of the number density of zirconium atoms to the number density of silicon atoms (hereafter denoted Zr:Si) in the outer layer to about 8% or less, and to limit the analogous aluminum-to-silicon ratio, Al:Si, to about 8% or less. Although higher levels may be useful in some cases, it is generally preferable to limit the total of Zr:Si plus Al:Si to about 12% or less, and more preferably to about 10% or less. Alumina is a useful co-dopant for the purpose of enhancing the solubility of zirconia in the host silica glass. In practice, it is generally desirable to determine, first, the desired doping level of zirconia. Alumina should then be included in an amount sufficient to assure the solubility of the zirconia in the desired concentration. Incorporation of excessive alumina should be avoided because it may tend to weaken the resulting fiber. The amount of zirconia should be effective for raising the value of n of the resulting fiber to 30 or more. The parameter n is the "stress corrosion parameter." It is defined with reference to static stress tests, discussed below, in which the mean time to failure, t f , is determined as a function of the applied tension σ. The results of such tests generally obey an equation of the form t f = k σ - n , where k is an empirically determined constant. We have observed that adding as little as 0.5% zirconia (i.e., Zr:Si = 0.5%) or even less to pure silica can increase n from about 22 to about 30 or more. We have observed such an increase both with and without the concurrent addition of alumina to the glass. Significantly, doping with zirconia and with alumina provides values of n of 30 or more without placing the fiber under a substantial amount of compression. Instead, such doping has been observed to be neutral with respect to residual stress, or, as noted, may tend to contribute a modest amount of residual, tensile, stress in the outer glass layer (i.e., in layer 140 of FIG. 1). One widely used method for evaluating the resistance of the inventive fiber to static fatigue is provided by a standard two-point bend test for fatigue, in 90°C deionized water. (Such a test is hereafter referred to as the Standard Fatigue Test.) Representative samples of the inventive fiber were subjected to the Standard Fatigue Test as bare fibers (i.e., there was no polymer jacket). The samples were observed to survive the Standard Fatigue Test, on average, for more than 10 6 seconds at 500 ksi (3.44 GPa). By comparison, standard silica fiber exhibited the same initial strength as the inventive fiber (i.e., about 800 ksi, or 5.52 GPa), but was observed to survive the Standard Fatigue Test for 10 6 seconds only at 385 ksi (2.65 GPa) or less. With reference to FIG. 1, the inventive fiber in one embodiment includes core 100, cladding 110, fused silica layer 120, fused silica layer 130, and anti-fatigue layer 140. According to an exemplary procedure, glass layers corresponding, respectively, to the cladding and the core are first formed on the inner surface of a fused silica substrate tube by well-known MCVD methods. The substrate tube is collapsed, again by well-known methods, to form the inner portion of a fiber preform. The glass of the substrate tube corresponds to layer 120 of the ultimate fiber. The collapsed tube is placed within a second, fused silica tube, here referred to as the overcladding tube. The overcladding tube is then collapsed, exemplarily by heating it with oxyhydrogen torches on a vertical glass lathe, to form a solid, rod-like preform. The glass of the overcladding tube corresponds to layer 130. The material of the anti-fatigue layer is then applied. According to a currently preferred embodiment, the material is applied in particulate form, and is subsequently sintered to convert it to pore-free glass. The anti-fatigue layer typically contributes about 3% - 15% of the total glass in the ultimate fiber. According to one useful technique, the material is applied using a VAD torch of conventional design. With reference to FIG. 2, an appropriate such torch has a central orifice 200 and at least three concentric, annular passages numbered in the figure, from the innermost passage, 210, 220, and 230, respectively. As in conventional VAD processing, oxygen flows through passages 210 and 230, and hydrogen flows through passage 220. Also as in conventional VAD processing, a silica-containing gas, which comprises a mixture of oxygen and silicon tetrachloride, flows through the central orifice. However, in a departure from conventional VAD processing, the delivery end of injector tube 240 is inserted into the orifice for delivering the dopant material to the torch flame. The silica-containing gas is typically introduced by flowing it through port (or side-tube) 265 into tube 240. Reservoirs 250 and 260 are provided, respectively, for metallic aluminum and zirconium in the form of shot or wire. The metals in reservoirs 250 and 260 are heated to at least 300°C, and preferably to about 350°C, and chlorine gas is directed in separate streams over the respective metals. The metal-laden gas streams are combined and directed into injector tube 240, which extends to the outlet of orifice 200 and into the torch flame. In order to prevent condensation of zirconium tetrachloride on the inner walls of tube 240, the tube is wrapped with nichrome heating wire 270 and maintained at an effective temperature to prevent such condensation. In an alternate, and currently preferred, technique, material containing silicon, zirconium and aluminum is delivered to the torch as an aerosol, rather than as chloride vapors. The alternate embodiment is currently preferred because it avoids the use of chlorine gas. Chlorine is undesirable because its corrosive properties make it difficult to handle. According to the preferred embodiment, a sol is prepared by mixing alkoxides of silicon, zirconium and aluminum with an appropriate solvent. Exemplary alkoxides for this purpose are, respectively, TEOS (tetraethyl orthosilicate), zirconium isopropoxide and aluminum trisecbutoxide. An appropriate solvent is a mixture of water and an alcohol, exemplarily propanol. In order to prevent inhomogeneities in the resulting glass, the TEOS and the solvent are reacted together to cause hydrolysis before the sol is delivered to the torch. Inhomogeneities could otherwise occur, for example, as a result of reactions between unreacted alkoxides and moisture from by-products of the torch flame. Additionally, desirable complexes are formed when the zirconium and aluminum alkoxides are added to the mixture of TEOS and solvent. Relevant sol-gel chemical methods are well known, and are described, for example, in B.E. Yoldas, J. Materials Science 12 , (1977) 1203 - 1208, and B.E. Yoldas, J. Non-Cryst. Solids 63 , (1984) 145 - 154. The sol is delivered to the torch from, e.g., an airbrush-type nozzle 295 as depicted in FIG. 3. The nozzle is used as an injector in a manner which is analogous to the use of injector tube 240 of FIG. 2. The sol flows out through central orifice 300, and gas flows out through annular passage 310. An exemplary gas flow is oxygen at 4 liters per minute. After the particulate layer has been formed, it is sintered according to well known methods, in order to form a glass layer corresponding to anti-fatigue layer 140 of the ultimate fiber. Fiber is then drawn from the preform according to well known methods. During the sintering step, some care is necessary in order to prevent crystallization. That is, a separate, zirconia-rich phase tends to crystallize if the glass is heated for too long at too high a temperature. The heating time required to produce this effect grows shorter as the temperature is raised. For example, when glass doped with 5% Zr:Si and 2% Al:Si is heated for more than about ten seconds at 2200°C, a crystallized phase is observed to form upon cooling. At lower torch temperatures, it takes a longer heating period for crystallization to be induced, if at all. This effect can be controlled by judicious selection of the sintering temperature and heating duration. Moreover, co-doping with alumina increases the temperature and duration required to induce crystallization. Thus, for example, if glass doped with 5% Zr:Si and 3% Al:Si is sintered at 2200°C and permitted to cool, crystallization is easily avoided. A zirconia-rich phase can also crystallize out when fiber is pulled from the preform. Rapid quenching of the pulled fiber tends to inhibit crystallization. However, the residence time of the glass in the furnace is typically comparable to the sintering times which tend to promote crystallization. As a consequence, the advantage of rapid quenching may be at least partially canceled, and crystallization may occur, causing the resulting fiber to be weakened. Crystallization during fiber pull can be avoided by including an effective amount of alumina as a dopant. The minimum amount that is effective depends upon the zirconia content of the glass. FIG. 4 depicts the selected range for zirconia and alumina doping levels. As indicated, Zr:Si is at least about 2%, and the sum of Zr:Si plus Al:Si is less than or equal to about 12%. The minimum alumina content rises linearly with zirconia content (in excess of Zr:Si of about 2%) with a slope of about 0.67. The maximum alumina content (in excess of Al:Si of about 2%) rises linearly with a slope of about 1.5.

Claims: An optical fiber having a core and a cladding surrounding the core, at least a first portion of the cladding comprising silica-based glass, the cladding having at least one outer layer which surrounds the first portion, and the outer layer comprising silica doped with zirconia, CHARACTERIZED IN THAT a) the zirconia content of the outer layer is such that the ratio of the number density of zirconium atoms to the number density of silicon atoms, to be referred to as "Zr:Si", is greater than 2% but not more than about 8%; b) the outer layer further comprises alumina in an amount such that the ratio of the number density of aluminum atoms tu the number density of silicon atoms, to be referred to as "Al:Si", is at least about 0.67 times the excess of Zr:Si over 2%; c) Al:Si in the outer layer is not more than about 2% plus 1.5 times Zr:Si; and d) the sum of Zr:Si plus Al:Si is not more than about 12%.

Inventors: BROWNLOW DARRYL LENEIR, DIGIOVANNI DAVID JOHN, INNISS DARYL, BROWNLOW, DARRYL LENEIR, DIGIOVANNI, DAVID JOHN, INNISS, DARYL
Applicants: AT & T CORP, AT&T CORP.
Application year: 1992
Main classification: G02B6
IPC codes: G02B6, C03C13, C03B37, C03C25