CN102249533B - Method for manufacturing large-size low-water-peak prefabricated rod - Google Patents
Method for manufacturing large-size low-water-peak prefabricated rod Download PDFInfo
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- CN102249533B CN102249533B CN2011101101612A CN201110110161A CN102249533B CN 102249533 B CN102249533 B CN 102249533B CN 2011101101612 A CN2011101101612 A CN 2011101101612A CN 201110110161 A CN201110110161 A CN 201110110161A CN 102249533 B CN102249533 B CN 102249533B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/01413—Reactant delivery systems
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/012—Manufacture of preforms for drawing fibres or filaments
- C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
- C03B37/018—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD] by glass deposition on a glass substrate, e.g. by inside-, modified-, plasma-, or plasma modified- chemical vapour deposition [ICVD, MCVD, PCVD, PMCVD], i.e. by thin layer coating on the inside or outside of a glass tube or on a glass rod
- C03B37/01807—Reactant delivery systems, e.g. reactant deposition burners
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/08—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant
- C03B2201/12—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with fluorine
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2203/00—Fibre product details, e.g. structure, shape
- C03B2203/10—Internal structure or shape details
- C03B2203/22—Radial profile of refractive index, composition or softening point
- C03B2203/23—Double or multiple optical cladding profiles
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Abstract
The invention relates to a method for preparing a large-size low-water-peak prefabricated rod, which comprises the following steps of: 1, depositing a core layer and partial cladding material in a quartz glass lining tube by using an in-tube chemical vapor deposition method to meet the requirement of a waveguide structure and optimize fluorine doped components, wherein the F-doped refractive index contribution of an inner cladding layer prepared by an in-tube method is not more than -0.10 percent and the F-doped refractive index contribution of the core layer is not more than -0.03 percent; 2, melting and shrinking the quartz glass lining tube deposited with the core layer and the partial cladding material at the temperature of between 1,900 and 2,300DEG C into a solid core rod, and manufacturing a core rod of which the b/a is more than or equal to 1.5 and less than or equal to 3.0 and the c/a is more than or equal to 2.3 and less than 4.5; 3, cladding a proper amount of uniform quartz loose body on the outer surface of the core rod directly by using an outside vapor deposition method to obtain a loose body prefabricated rod; and 4, slowly heating the loose body prefabricated rod at high temperature for dehydration, and sintering to obtain the transparent large-size low-water-peak prefabricated rod. The advantage of doping of the in-tube method and the advantage of large size of the outside method are combined, the process is simple, and the method is suitable for producing large-size low-water-peak prefabricated rods at low cost on a large scale.
Description
Technical field
The present invention relates to a kind of interior method doping process advantage of pipe of utilizing and adopt the direct outer packet technology of plug to prepare the method for preform, namely adopt the interior method of pipe and the direct outsourcing technology of Soot to make the method for large-scale preformod of optical fiber with low water peak, belong to optical fiber and make the field.
Background technology
Preform is used for the optical fiber that wire drawing prepares communications.Optic fibre manufacturing technology comprises a lot of links and operation, and wherein master operation has two, and one of them is the prefabricated rods manufacturing.The manufacturing process of " two-step approach " is generally adopted in the production of present commercial prefabricated rods, i.e. the first step, the manufacturing of plug; Second step, the manufacturing of outsourcing with becomes excellent.Wherein the manufacturing process of plug typically has method gas-phase deposition in the pipe, improve chemical vapor deposition method and PCVD (plasma chemical vapor deposition) plasma exciatiaon chemical Vapor deposition process as MCVD (modified chemical vapor deposition), and the outer method gas-phase deposition of pipe, as OVD (outside vapor deposition) outside vapor deposition process and VAD (vapor axial deposition) external shaft to depositing operation.The at present typical technology of outer packet technology comprises RIT (rod in tube) and RIC (rod in cylinder) tiretube process, the direct epiboly of Soot, APVD plasma spraying process and sol-gel method.Wherein the direct epiboly of tiretube process and Soot mainly adopts the preparation of the realization clad material of similar plug outside vapor deposition process characteristics, the key distinction is relative plug manufacturing process, what tiretube process adopted is the off-line preparation method, and what the direct epiboly of Soot adopted is online preparation method.Therefore, add the feature of the current preform manufacturing process of outer packet technology ability full-time instruction with the plug manufacturing technology.As everyone knows, the waveguiding structure of plug and material are formed the transport property that has determined optical fiber, and for example: loss, bandwidth, cutoff wavelength, mode field diameter, dispersion property, useful area etc. also have decisive role to polarization mode dispersion (PMD) and physical strength etc.And the manufacturing cost of preform depends primarily on the out worker technology.The geometrical performance of optical fiber is relevant with the prefabricated rods global design with mechanical property.
The method of existing immediate large-scale preformod of optical fiber with low water peak is tiretube process, as US005837334A, US007089765B2.Tiretube process is to produce plug earlier at present, this plug is inserted the quartz glass tube of size match again, and making plug and sleeve pipe melt the fusion prolongation synchronously through heat becomes photoconductive fiber.Tiretube process be produce for routine with one of immediate technology of the present invention.But this tiretube process has the following disadvantages: the geometric accuracy height that large-sized sleeve pipe requires, and the manufacturing process complexity, the material unaccounted-for (MUF) in the sleeve pipe course of processing causes cost to increase.The interface of plug and sleeve pipe has increased the complexity of drawing optical fibers technology, the cleaning at interface and drying become stricter, and the interface has increased the probability that mechanical fiber optic strength weak link produces, increased the possibility of unit length fibercuts, the interface also has a negative impact to optical fiber water peak (being called the water peak owing to hydroxyl absorption peak in 1360nm～1460nm scope in the Optical Fiber Transmission), avoids added influence additional technical process in interface to increase the production cost of prefabricated rods.
Managing the direct epiboly of outer method+Soot is to be thought to make the first-selected operational path of low-cost large scale prefabricated rod by industry at present, as US005917109A.Especially along with VAD and OVD organize the technical development of shaking depositing operation to many modulated structures more, the direct epiboly of Soot has significantly reduced the manufacturing cost of preform.Because outside vapour deposition process VAD and OVD characteristics are that sedimentation rate height, starting material obtain easily, the direct outer packet technology of the outer method+Soot of pipe provides most commercial prefabricated rods at present, and typical two-step process route is VAD+OVD, OVD+OVD, VAD+VAD.But be the large scale prefabricated rod in the low water peak of preparation, also there is following deficiency in the technological line of managing the direct epiboly of outer method+Soot: well-known, manage outer method owing to have Soot preparation and vitrified separation process, mix in the relative pipe in aspect such as technology obviously deficiency of method altogether with Ge/F realizing the complex index of refraction section, therefore, utilize the direct epiboly manufacturing of the outer method+Soot of pipe to hang down in the large scale prefabricated rod in water peak homemade, based on production simple step single-mode fiber (being typically ITU-G.652.D), product type is difficult to switch; In addition, because simple relatively plug dopant material design, for the hydroxyl of avoiding directly outer packet procedures SMIS rod surface spreads to the core district in dehydration and sintering process, in low-water-peak fiber mandrel process design process, generally need to reserve the diameter in enough big inner cladding and core district than (being T/a), present measuring and calculating theoretical value can reach T/a and be not less than 3.8, generally near 4.5, this characteristic remarkable has reduced the annual capacity that is converted to optical fiber of separate unit plug equipment to representative value.In addition, well-known, manage the direct outer packet technology of outer method+Soot and prepare and contain the large scale prefabricated rod of mixing the fluorine covering deeply and mix at fluorine and face huge challenge aspect contribution amount (generally being difficult to be lower than-0.30%) and the technology stability.
The another kind of technology that approaches with the present invention is the PCVD+APVD technology.This technology be the plug that chemical vapor deposition method becomes in managing be the target rod, at it outside, adopt APVD technology that silica powder is sprayed on the quartzy target and make the compound surrounding layer of cheapness.Synthetic quartz target rod has been guaranteed the quality of optical fiber, and outer spray technique silica powder has higher deposition efficiency, is a kind of conventional technology cheaply of producing that has been used for.But this technology has following problem, because the silica powder that the sedimentation effect of APVD is high and employing is cheap, the purity of this silica powder and consistence are influenced by starting material and fluctuate bigger, some impurity that wherein contains has disadvantageous effect to the wire drawing intensity of optical fiber, and this starting material can not be purified and non-renewablely limited it and produce the popularization of large size prefabricated excellent technology.In addition, the large scale prefabricated rod of this technological line preparation is owing to the homogeneity remarkably influenced mechanical fiber optic performance of material, and typical breakpoint rate is more than the twice of the large scale prefabricated rod of Soot outsourcing prepared in the drawing process process.
The characteristics of PCVD technology are the very thin thickness of settled layer, can be by the accurate controls of charging, make the waveguiding structure design of optical fiber and material is formed and structure design reaches the unification of harmony.At material The Nomenclature Composition and Structure of Complexes design aspect, introduce the design of Functionally Graded Materials, namely by setting proper formula, make the footpath of plug or cross section of optic fibre upwards have continuous The Nomenclature Composition and Structure of Complexes graded, therefore and make the character gradual change of material, make no tangible interface in the prefabricated rods.When making each layer viscosity coupling, thermal stresses obtains relaxing, thus in the subsequent technique that optical fiber is made, just can residual thermal stress in the optical fiber and produce scission of link, thus reduced optical fiber decay, optimized characteristics such as PMD, warpage, welding and anti-hydrogen are aging.PCVD technology sandwich layer and optics covering are all mixed GeO
2And F, utilize the two difference to viscosity influence can be easy to realize sandwich layer and the covering coupling on viscosity, thereby even PCVD optical fiber without D
2Handle and also have good anti-hydrogen loss performance.PCVD technology is introduced F except the effect of landing low-refraction, also can significantly reduce under the condition of high temperature hydroxyl to the rate of diffusion in core district, reach the effect that reduces the water peak, therefore, (conversion is labeled as c for the diameter in the optical fiber by adjusting bushing pipe in the design of PCVD plug, equivalence is the T of pipe in the outer method plug manufacturing process) and PCVD doping inner cladding (conversion is labeled as b for the diameter in the optical fiber) and core diameter (convert is that diameter in the optical fiber is labeled as ratio and doping content a), can guarantee that plug external diameter and the ratio (c/a) of core diameter are not more than 4.5, this is that separate unit PCVD plug manufacturing capacity is converted to the major cause that the optical fiber production capacity is significantly higher than the outer method of pipe.In addition, an amount of F also can effectively reduce the defective in the optical fiber.In drawing process, optical fiber easily forms defectives such as Si, Ge, SiO and GeO, and these defectives not only can cause strong uv-absorbing, and its hangover influence is until the decay of 1550nm, and these defectives very easily are combined with H simultaneously, form strong absorption peak.Fluorine can be combined with these defectives, and defective is played a good healing effect, not only makes optical fiber have low decay, has also guaranteed the anti-hydrogen loss characteristic that optical fiber is good.PCVD process using gas ions effect deposition silica glass, fluorine has higher deposition efficiency, and for OVD and VAD technology, the sedimentation effect of fluorine is extremely low in the deposition process, great majority are mixed F and carry out (as feeding SiF4) in sintering processes.But be subjected to the restriction of deposit thickness, need adopt the repeatedly method of deposition-sintering, thereby mixing aspect the fluorine, PCVD technology has clear superiority.PCVD with its refractive index profile control accurately advantage especially be fit to make G652D, G.657, G.655, type fiber such as DCF.
Chinese patent CN00128165.8 discloses a kind of method of making large prefabricated optical fiber bar, it is characterized in that in quartz glass tube, depositing core and clad material and the molten plug that shortens into method in the pipe, sinter the transparent glass rod into outside method deposition outsourcing layer again, this patent does not relate to the concrete doping content of fiber core layer and covering, does not relate to the concrete processing parameter of PCVD technology and optical fiber parameter.Chinese patent CN01128430.7 discloses a kind of manufacture method of preform, it is characterized in that mixing the manufacturing preform by plasma activated chemical vapour deposition and two kinds of technologies of the outer vapour deposition of pipe, but this patent does not relate to the concrete processing parameter of plasma chemical vapor deposition, does not relate to optical fiber structure parameter and fiber optics performance perameter.
Terms more of the present invention are defined as:
Bushing pipe: the purity quartz glass pipe for high that vapour deposition is used in the pipe, reactant are deposited on Glass tubing behind inner reaction tube inwall forms thin layer of glass.
Plug: the solid prefabricated component that contains sandwich layer and PCVD deposition covering.
Refractive index profile: the relation between prefabricated rods/plug/optical fiber glass refraction and its radius.
Sleeve pipe: the heavy wall purity quartz glass pipe for high that meets certain sectional area requirement.
A value: the diameter of optical fiber center core layer.
B/a value: be defined as the cladding diameter of deposition in the pipe and the ratio of sandwich layer diameter.(the b value is the diameter of the fibre cladding of the clad section correspondence of deposition in the pipe.)
The c value: the plug conversion that is defined as method preparation in the pipe is the diameter in the optical fiber, is equivalent to the T in the outer method of pipe;
D value: be defined as the prefabricated rods conversion and be the diameter in the optical fiber.
Relative refractive index Δ i%:
Wherein ni is the specific refractory power of i layer fiber optic materials, n
0Specific refractory power for pure silica glass.
Loose body prefabricated rods: be the loose body prefabricated rods that comprises PCVD plug and Soot outsourcing.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists at above-mentioned prior art, and a kind of preparation method of large-scale preformod of optical fiber with low water peak is provided.Advantage in conjunction with PCVD and two kinds of technologies of the direct outsourcing of Soot, mix altogether by Ge/F or pure mode of mixing fluorine is made the accurately plug of control of low c/a, production specific refractory power with the PCVD method, with high-level efficiency, the technology direct epiboly of Soot deposition silica glass covering flexibly, to obtain large size preformod of optical fiber with low water peak cheaply.
The objective of the invention is to be realized by following method:
1, with method in the pipe, especially PCVD, deposition Ge/F mixes or pure core district and the part inner cladding material of mixing fluorine altogether in high purity, low-hydroxy-group squartz glass bushing pipe, wherein to be entrained in the inner cladding of method deposition in the pipe specific refractory power contribution amount representative value be that-0.10% to-1.00%, F is entrained in that specific refractory power contribution amount representative value is-0.03% to-0.20% in the sandwich layer to F.The viscosity coupling of fiber optic materials design can be effectively optimized in the design of this doping process, and for preventing that the surrounding layer hydroxyl from worsening optical fiber water peak performance to the diffusion of core district blocking layer than minimal thickness is provided.Be raising plug production capacity, preferred large size bushing pipe and high deposition rate PCVD technology, typical in the bushing pipe that is not less than the 31mm diameter and the PCVD technology that is not less than the 2.5g/min sedimentation rate, plug length is not less than 1000mm.Adopt low hydroxyl purity quartz glass pipe for high as bushing pipe, the hydroxy radical content of bushing pipe requires smaller or equal to 1000ppb, further requires less than 100ppb, further requires less than 10ppb.For satisfying the needs of waveguiding structure design, lining pipe also can the fluorine-doped quartz material of relative refractive index between 0～-0.30% to be pure quartz material.
2, with deposited tube molten solid mandrel that shortens under 1900 ℃-2300 ℃, make the plug of 1.5≤b/a≤3.0,2.3≤c/a≤4.5; For avoiding the outside hydroxyl of the direct outsourcing technology of Soot and drawing process to inner cladding and the diffusion of core district, by between bushing pipe hydroxy radical content, inner cladding/sandwich layer F doping specific refractory power contribution amount, b/a and three major influence factors of c/a, adjusting optimization.Usually, the hydroxy radical content of liner material generally is not more than 100ppb, when bushing pipe hydroxyl whole content is low, can mixes or hangs down b/a and the c/a value realizes low water peak maximization prefabricated rods by a small amount of F.The hydroxy radical content of liner material is not less than 3.0 as satisfying when c/a value when 20ppb is following, the inner cladding that appropriateness is mixed fluorine can be realized the level near b/a=1.5, perhaps mates under the suitable situation at waveguiding structure and viscosity of material, and b/a can be near c/a=2.3.Typically under the consistent relatively condition of liner material hydroxy radical content, be conducive to further reduce b/a and c/a value by increasing F doping (especially the F of inner cladding mixes), wherein typical c/a significantly is lower than the constitutional features that the direct outsourcing technology of the outer method+Soot of pipe is generally kept 4.2-5.0 between 3.0-4.2.Typically be and guarantee the required waveguiding structure of optical fiber, increasing F mixes and need additional Ge doping be accompanied by the risk that the loss of optical fiber intrinsic increases, general core district F doping specific refractory power contribution amount is not less than-0.20%, inner cladding F doping specific refractory power contribution amount is not less than-0.70%, in structure design and waveguide design also can the whole Ge/F of control mix altogether or the pure F of mixing concentration in utilize PCVD process advantage segmentation inner cladding to be the many structures of gradient, mix deeply near the bushing pipe zone (can realize-1.00%), reducing whole the doping near the core district, the risk that the intrinsic loss increases under the risk that the water peak increases when the low b/a of balance and c/a and the high-dopant concentration.In addition, in the plug doped structure that relates to the polycomponent doping, the viscosity coupling that needs the control material to form avoids introducing in the drawing process added losses.Directly deposition gained plug representative diameter scope is 18mm to 51mm.Because the diameter that method directly deposits the gained plug in the pipe is limited by the state-of-art of diameter of the nucleus equipment-resonator cavity of PCVD technology, in the large size prefabricated excellent technical process process of design, also can be divided into direct deposition part and the molten contracting part of off-line to the corresponding glass material of c part that bushing pipe is converted in the optical fiber, namely can directly be finished under the prerequisite of deposition by PCVD at guarantor b/a, bushing pipe selects the suitable diameter parent tube to finish PCVD technology and collapsar technics according to actual resonant cavity size, append suitable transition bushing pipe by the c/a design requirements then and carry out the molten contracting of secondary, 1.5≤b/a≤3.0 are satisfied in preparation, 2.3 the plug of≤c/a≤4.5.For improving the continuous wire drawing ability of single prefabricated rods, the gained plug can carry out length combination, or appends suitable transition bushing pipe after the combination and carry out the molten contracting of secondary or stretching, to realize that length is greater than the plug of the direct outsourcing technology of the confession of 1.5-3.0m.
3, coat an amount of quartzy loose body uniformly with the direct sedimentation of Soot at the outside surface of above-mentioned plug, form loose body prefabricated rods.Be specially: will melt plug after the contracting and be installed on the external sediment lathe around the rotation of plug axis, with chemical feedstocks gas and fuel gas with different pipelines towards blowtorch, make the flame of blowtorch spray to this target rod.The relative translation of paralleling to the axis takes place in plug and flame, makes the glass granules that generates in the torch flame be deposited on from level to level on the target rod, has formed the loose body prefabricated rods with enough cladding glass microparticle materials.Depositing operation need be according to dust density, and the external diameter of control dust rod makes it to satisfy how much requirements of final optical fiber d/a.For the impurity of avoiding low b/a and c/a value plug to cause because of interface pollution in Soot technology spreads to inner cladding and core district, generally need to plug polish or pre-etching to obtain unsalted surface, avoid the cracking in the dust deposit process simultaneously, reserve the bushing pipe external diameter in requisition for part.For realizing large size prefabricated rod and reduce the optical fiber manufacturing cost that preferred single rod group lamp equivalence sedimentation rate is not less than the direct outsourcing technology of Soot of 60g/min, also can adopt many rows to organize the lamp technology mode of deposition synchronously.Wherein the direct outsourcing technology of Soot can be to utilize SiCl
4Be OVD or the VAD of main raw material.Single rod group lamp typical case deposition length is not less than 1500mm.Because the present invention has significantly reduced c/a, design at present mainly serve T/a greater than the required plug size of the direct outsourcing equipment of 3.8 Soot less than the plug by OVD or VAD prepared, can not guarantee at Soot depositing device and follow-up dehydration-sintering oven under the condition of large size dust rod depositing operation more, can carry out preliminary draft to the plug of the direct deposition of PCVD or the molten contracting of secondary, when optimizing technical process, also can avoid PCVD plug primary depositing joint length to be difficult to break through the unfavorable of 1200mm.
4, will comprise in the prefabricated immigration dehydration-sintering oven of target rod and loose body, dewatering under 800-1200 ℃ the temperature condition and under the mixed atmosphere of proper ratio oxygen, chlorine and helium, progressively drive organism, moisture and the metallic impurity of loose body weight, sinter the transparent large-scale preformod of optical fiber with low water peak of no bubble in heat under 1400-1600 ℃ the temperature condition and under based on the mixed atmosphere of oxygen, argon gas and chlorine then.This prefabricated rods can be directly used in follow-up optical fiber preparation technologies such as wire drawing or the hot shaping of preform bar stretching.
The positively effect of characteristics of the present invention and generation is:
Method and two kinds of technologies of outside method combine in will managing, combine the advantage of two kinds of technologies, take full advantage of PCVD technology be easy to dark doping, composite mixed, accurately control the superiority of plug refractive index profile structure, thereby preparation fluorine doping sandwich layer and inner cladding obtain low decay and low water peak, with starting material be convenient to obtain, sedimentation effect height, the direct epiboly of Soot being convenient to maximize obtain low-cost prefabricated rods.The PCVD+OVD tiretube process directly deposits surrounding layer at plug relatively, has saved series of processes such as the necessary grinding of manufacturing sleeve pipe, polishing, stretching, has reduced manufacturing cost.Manage the direct depositing operation of outer method+Soot relatively, utilize PCVD to be convenient to that advantage that F mixes has prepared T/a low or the low water peak plug of c/a, significantly improved the annual capacity that is converted to optical fiber of separate unit plug equipment, overcome the direct depositing operation of the outer method+Soot of pipe simultaneously and be not easy the difficult problem that variant production technology is switched, be fit to the low-water-peak fiber series product of the complicated cross-section structure of preparation.The operational path that the present invention selects for use comprises to dewater and melt the process that contracts in the dehydration/sintering oven of the loose body of prefabricated rods has removed the fine structure defective of impurity atom and prefabricated rods inside, improve purity and the intensity of prefabricated rods material, can improve the physical strength of optical fiber.The method of the invention both can obtain the high optical waveguide structure of precision, had obtained high production efficiency again, was fit to make high-quality large-scale preformod of optical fiber with low water peak.The present invention has obtained the prefabricated rods that single rod can be produced low-water-peak fiber more than 3600 kilometers in the practice process.The optical fiber of producing with this prefabricated rods in the decay at 1310nm place less than 0.340dB/km, in the decay at 1383nm place less than 0.334dB/km, in the decay at 1550nm place less than 0.220dB/km.
Description of drawings
Fig. 1 is that Ge/F of the present invention mixes or pure F doping preformod of optical fiber with low water peak in large size material structure synoptic diagram altogether.
Fig. 2 a. is that the simple core of the present invention/covering Ge/F mixes common single mode low-water-peak fiber refractive index profile structure altogether
Fig. 2 b. is that the core/covering Ge/F of the many coverings of the present invention mixes single mode low-water-peak fiber refractive index profile structure altogether
Fig. 2 c. is that the present invention mixes fluorine covering single mode low-water-peak fiber refractive index profile structure deeply
Fig. 2 d. is that core of the present invention/covering Ge/F mixes counter-bending single mode low-water-peak fiber refractive index profile structure altogether
Embodiment
The present invention includes following steps: a, mix altogether or the pure fluorine of mixing forms mix deposition sandwich layer and inner cladding material with chemical Vapor deposition process Ge and F in the silica glass bushing pipe in the pipe, it is that-0.10% to-1.00%, F is entrained in that specific refractory power contribution amount representative value is-0.03% to-0.20% in the sandwich layer that F is entrained in the inner cladding specific refractory power contribution amount representative value; B, with deposited tube in 1900 ℃-2300 ℃ following molten solid mandrels that shorten into, plug satisfies 1.5≤b/a≤3.0,2.3≤c/a≤4.5 after converting optical fiber; C, coat quartzy loose body uniformly with the direct epiboly of Soot at the outside surface of plug, form loose body prefabricated rods; D, the slow heat of the body prefabricated rods of will loosening are dewatered, are sintered transparent large-scale preformod of optical fiber with low water peak into, and the prefabricated rods diameter is not less than 150mm, and the fiber lengths of continuous drawing is greater than 1500km.Chemical Vapor deposition process is plasma chemical vapor deposition in the described pipe, the nucleus equipment resonator cavity of plasma chemical vapor deposition allows that the bushing pipe size of direct deposition is not less than 28mm, typical case's sedimentation effect is not less than 2.5g/min., and the depositing operation round trip is not less than 1200mm.
Make the silica glass Glass tubing that plug uses and be synthetic quartz or significantly mix fluorine synthetic quartz material, its relative refractive index is 0 to-0.3%, and the hydroxy radical content of described Glass tubing is less than 1000ppb.The hydroxy radical content of preferred glass pipe is less than 100ppb.
More preferably the hydroxy radical content of Glass tubing is less than 10ppb.The F doping inner cladding of method preparation is uniform material in the pipe, or gradient F doping or gradual change F doped structure, the F doping refractive index contribution amount of the inner cladding in close core district is optimized, is optimized to-0.70% away from the inner cladding F doping refractive index contribution amount partly in core district to-0.10%.Described plug is that directly the interior method of pipe once melts contraction fully, or select for use earlier the thin-walled bushing pipe manage in plug after method deposition and the molten contracting, select for use the transition bushing pipe to carry out the plug that obtains after the molten contracting of secondary again, plug is directly used in subsequent technique, or carry out single plug preliminary draft or HF corrosion cold working, or select for use the transition bushing pipe to carry out preliminary draft after many plugs combinations or the combination.The direct epiboly of described Soot is OVD method or VAD method, and the starting material of use are SiCl
4The loose body prefabricated rods of the direct epiboly preparation of described Soot adopts dewatering process and transparence sintering process stage by stage to handle, or adopts the sintering process of vacuum outgas to handle; By dividing potential drop and the heat-up time of control fluoro-gas, the realization surrounding layer is partly mixed fluorine in the sintering process process.Large scale prefabricated rod behind the described sintering is directly used in follow-up drawing process, or carries out carrying out follow-up drawing process again after the preliminary draft.The optical fiber that described large-scale preformod of optical fiber with low water peak draws in the decay at 1310nm place less than 0.340dB/km, in the decay at 1383nm place less than 0.334dB/km, in the decay at 1550nm place less than 0.220dB/km.
The method of the invention is because adopt the PCVD prepared plug that is easy to realize the complex index of refraction section, therefore not only be suitable for preparing the general single mode fiber of simple section, also be fit to the single-mode fiber of the complicated cross-section structure of preparation, this is apparent to those skilled in the art.
Embodiment one: the embodiment of the large-scale low water peak prefabricated rods of single-mode fiber
By the inventive method, table 1 is listed the structural parameter to 3 kinds of specification prefabricated rods, and wherein the single mode plug all adopts existing PCVD prepared.
Table 1 prefabricated rods geometric parameter (and corresponding optical fiber geometric parameter)
The PCVD stage process is as follows: mixed gas feed requires to be O
2In water-content require to be less than or equal to 100ppb, C
2F
6In water-content require to be less than or equal to 1000ppb, the dynamic leakage rate of depositing lathe is less than or equal to 1.0 * 10
-5Mbar.l/s, the relative humidity of environment is less than 25% in the preparation process, and ambient relative humidity is less than 15% preferably, and more excellent ambient relative humidity is less than 5%.The minimum 28mm of used bushing pipe external diameter, maximum 46.5mm, its hydroxy radical content is not higher than 100ppb.Directly the single plug equivalence of deposition sedimentation rate is not less than 2.5g/min, preferred 3.0g/min.The deposition round trip is not less than 1200mm, is typically 1300mm, and single plug typical case effectively rod length is 1000mm, the minimum 18mm of external diameter, and maximum is no more than 51mm.Molten contracting stage process is as follows: stove speed is 18-30mm/min, is set in 1800-2100 ℃ according to different size and doping composition furnace temperature.
The loose body sintering stage process of prefabricated rods is as follows: the density of the loose body of OVD deposition prefabricated rods is 50%～60% of silica glass density, VAD prepared lower slightly, the compound loose body of prefabricated rods is vertically inserted in dehydration/sintering oven, feed O according to different size with being doping in the branch setting stove
2About 1500sccm and Cl
2The temperature rise rate of about 150sccm, the about 5-10 of rate of heating ℃/min makes furnace temperature rise to 1150 ℃, and constant temperature 60--150min with this understanding, remove moisture and other impurity, then, to dewater/sintering oven top local heating to 1400 ℃-1600 ℃, simultaneously around the loose body of prefabricated rods axis rotation, upwards promote prefabricated rods with the speed of 5-10mm/min, make the whole prefabricated rods body that loosens evenly be sintered to transparent preform.
For fibre profile structural representation such as Fig. 2 (a) of table 1 sequence number 1 correspondence, be a kind of simple common single mode low-water-peak fiber, comprise that Ge/F mixes the core district altogether and single Ge/F mixes inner cladding altogether.When plug prepares, when the hydroxy radical content representative value of bushing pipe when 100ppb is following, the specific refractory power contribution margin that its center core layer is mixed F is not less than-0.20%, the specific refractory power contribution margin of doped cladding layer F is lower than-0.20%, by increasing b/a near the c/a value, can realize the low water peak single mode fiber characteristic by 2.3 o'clock in that c/a is little.When the bushing pipe hydroxy radical content further descends, Ge/F mixes altogether and mixes the fluorine amount in the plug of core district and inner cladding and can reduce.This plug directly carries out OVD outsourcing technology after directly melting contracting, and carries out direct wire drawing, can realize the about 400km of single continuous wire drawing.
Fibre profile structural representation such as Fig. 2 (b) for table 1 sequence number 2 correspondences, it is characterized in that utilizing similar is to adopt to mix the fluorine material and deposit as the bushing pipe of PCVD, wherein bushing pipe is selected for use is-0.10%F mixes, hydroxy radical content is not more than 100ppb high purity quartz composite tube, PCVD technology center core layer is mixed the specific refractory power contribution margin of F-0.08%, the specific refractory power contribution margin of compound doped cladding layer F near the core district is-0.10---0.30%, be-0.25---0.70% to mix to optimize waveguiding structure by adjusting Ge away from core district part.By above doping design, be not more than the doping that can reduce Ge in the plug at 4.0 o'clock in less b/a value (about 1.7) and c/a, the loss that realization optical fiber is lower when guaranteeing low water peak performance and good bending property.After this plug directly melts contracting, cut combination for many, realize typical 1500mm, through HF corrosion back external diameter 39-48mm, be directly used in the vertical outsourcing technology of VAD and dewater with sintering after the prefabricated rods that obtains direct wire drawing.The continuous length of string of single prefabricated rods reaches about 1800km, the optical fiber that this prefabricated rods is produced in the decay at 1310nm place less than 0.340dB/km, in the decay at 1383nm place less than 0.334dB/km, in the decay at 1550nm place less than 0.220dB/km.
Fibre profile structural representation such as Fig. 2 (b) for table 1 sequence number 3 correspondences, it is characterized in that utilizing the technical characterictic of similar table 1 sequence number 2, F mixes and control bushing pipe hydroxy radical content by optimizing, in the plug deposition process, further reduce b/a and c/a, under the 46.5mm bushing pipe, prepare the large-size plug, select suitable bushing pipe to carry out the molten contracting increase of secondary c/a then and guarantee the low peak of optical fiber performance.What bushing pipe was selected for use in the specific implementation process is-0.10%F doping high purity quartz composite tube, sandwich layer is mixed the specific refractory power contribution margin of F-0.08%, the specific refractory power contribution margin of compound doped cladding layer F near the core district is-0.10---0.30%, be-0.25---0.70% to mix to optimize waveguiding structure by adjusting Ge away from core district part.After this plug directly melts contracting, 3 are made up, corrosion back select wall thickness 4mm, external diameter be 53mm, the about 3000mm of length-0.10%F doping high purity quartz composite tube combination stretching, realize the plug about representative value length 1500mm, external diameter 47mm, through be used further to high deposition rate OVD outsourcing technology after the HF corrosion and dewater and sintering after the prefabricated rods that obtains direct wire drawing.The continuous length of string of single prefabricated rods reaches about 3600km, the optical fiber that this prefabricated rods is produced in the decay at 1310nm place less than 0.330dB/km, in the decay at 1383nm place less than 0.325dB/km, in the decay at 1550nm place less than 0.200dB/km.
Embodiment two: the embodiment that mixes the large scale prefabricated rod of fluorine covering low water peak single mode fiber deeply
Adopt the plug manufacturing process of similar table 1 sequence number 1, the fibre profile structural representation utilizes PCVD technology to be easy to mix deeply the process advantage of fluorine shown in Fig. 2 (c), and the large scale prefabricated rod of fluorine low water peak single mode fiber is mixed in preparation.Bushing pipe is selected for use among this embodiment is-0.25---0.35%F mixes, hydroxy radical content is not more than 100ppb high purity quartz composite tube, the specific refractory power contribution margin that sandwich layer is mixed F is at-0.03---0.06%, the inner cladding of PCVD prepared is the pure F of mixing quartz material, mixing F specific refractory power contribution margin near the core district is-0.30---0.45%, be-0.40---0.70% that wherein c/a can be near 3.0 away from core district part.This plug directly adopts OVD technology to carry out outsourcing deposition, increases high-purity Si F4 gas in dewatering process, keeps low body of heater translational speed, carries out slow sintering under the SiF4 gas atmosphere containing then, realizes fluorine doping transparent prefabricated rods.The optical fiber that this prefabricated rods is produced in the decay at 1310nm place less than 0.320dB/km, in the decay at 1383nm place less than 0.330dB/km, in the decay at 1550nm place less than 0.185dB/km.
Embodiment three: the embodiment of the large scale prefabricated rod in large-scale low water peak G.657
Adopt the plug manufacturing process of similar table 1 sequence number 2, the fibre profile structural representation is shown in Fig. 2 (d), wherein bushing pipe is selected for use is-0.25---0.35%F mixes, hydroxy radical content is not higher than 100ppb high purity quartz composite tube, the specific refractory power contribution margin that sandwich layer is mixed F is at-0.03---0.12%, doped cladding layer F specific refractory power contribution margin is-0.10---0.25% to satisfy b/a simultaneously between 1.5-1.7.For satisfying the waveguiding structure requirement, core district and inner cladding can be adjusted the index distribution that suitable Ge mixes balance optical fiber.If the fluorine floor is mixed in the PCVD inner cladding increase away from core district part deeply, typical Ke Da-0.70%, the darkest reaching-1.00%, and its corresponding c/a can be near 3.0, and final prefabricated rods can guarantee good bending property and low water peak performance.Be directly used in Soot outsourcing technology after directly the plug of molten contracting can corrode, carry out the out worker skill after also can directly being drawn into suitable external diameter.
Claims (10)
1. method of making large-scale preformod of optical fiber with low water peak, may further comprise the steps: a, mix altogether or the pure fluorine of mixing forms mix deposition sandwich layer and inner cladding material with chemical Vapor deposition process Ge and F in the silica glass bushing pipe in the pipe, it is that-0.10% to-1.00%, F is entrained in that specific refractory power contribution amount representative value is-0.03% to-0.20% in the sandwich layer that F is entrained in the inner cladding specific refractory power contribution amount representative value; B, with deposited tube in 1900 ℃-2300 ℃ following molten solid mandrels that shorten into, plug satisfies 1.5≤b/a≤3.0,2.3≤c/a≤4.5 after converting optical fiber; C, coat quartzy loose body uniformly with the direct epiboly of Soot at the outside surface of plug, form loose body prefabricated rods; D, the slow heat of the body prefabricated rods of will loosening are dewatered, are sintered transparent large-scale preformod of optical fiber with low water peak into, and the prefabricated rods diameter is not less than 150mm, and the fiber lengths of continuous drawing is greater than 1500km.
2. a kind of method of making large-scale preformod of optical fiber with low water peak as claimed in claim 1, it is characterized in that chemical Vapor deposition process is plasma chemical vapor deposition in the described pipe, the nucleus equipment resonator cavity of plasma chemical vapor deposition allows that the bushing pipe size of direct deposition is not less than 28mm, typical case's sedimentation effect is not less than 2.5g/min., and the depositing operation round trip is not less than 1200mm.
3. a kind of method of making large-scale preformod of optical fiber with low water peak as claimed in claim 1, it is characterized in that making the silica glass Glass tubing that plug uses is synthetic quartz or significantly mixes fluorine synthetic quartz material, its relative refractive index is 0 to-0.3%, and the hydroxy radical content of described Glass tubing is less than 1000ppb.
4. a kind of method of making large-scale preformod of optical fiber with low water peak as claimed in claim 3 is characterized in that the hydroxy radical content of described Glass tubing is less than 100ppb.
5. a kind of method of making large-scale preformod of optical fiber with low water peak as claimed in claim 1, the F doping inner cladding of method preparation is uniform material in it is characterized in that managing, or gradient F doping or gradual change F doped structure, the F doping refractive index contribution amount of the inner cladding in close core district is optimized, is optimized to-0.70% away from the inner cladding F doping refractive index contribution amount partly in core district to-0.10%.
6. a kind of method of making large-scale preformod of optical fiber with low water peak according to claim 1, it is characterized in that described plug is that directly the interior method of pipe once melts contraction fully, or select for use earlier the thin-walled bushing pipe manage in plug after method deposition and the molten contracting, select for use the transition bushing pipe to carry out the plug that obtains after the molten contracting of secondary again, plug is directly used in subsequent technique, or carry out single plug preliminary draft or HF corrosion cold working, or select for use the transition bushing pipe to carry out preliminary draft after many plugs combinations or the combination.
7. a kind of method of making large-scale preformod of optical fiber with low water peak as claimed in claim 1 is characterized in that the direct epiboly of described Soot is OVD method or VAD method, and the starting material of use are SiCl
4
8. as claim 1 or 7 described a kind of methods of making large-scale preformod of optical fiber with low water peak, the loose body prefabricated rods that it is characterized in that the direct epiboly preparation of described Soot adopts dewatering process and transparence sintering process stage by stage to handle, or adopts the sintering process of vacuum outgas to handle; By dividing potential drop and the heat-up time of control fluoro-gas, the realization surrounding layer is partly mixed fluorine in the sintering process process.
9. as claim 1 or 7 described a kind of methods of making large-scale preformod of optical fiber with low water peak, it is characterized in that the large scale prefabricated rod behind the described sintering is directly used in follow-up drawing process, or carry out carrying out follow-up drawing process again after the preliminary draft.
10. a kind of method of making large-scale preformod of optical fiber with low water peak as claimed in claim 1, it is characterized in that optical fiber that described large-scale preformod of optical fiber with low water peak draws in the decay at 1310nm place less than 0.340dB/km, in the decay at 1383nm place less than 0.334dB/km, in the decay at 1550nm place less than 0.220dB/km.
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| CN102757179B (en) * | 2012-08-02 | 2015-04-08 | 长飞光纤光缆股份有限公司 | Method for preparing large-size optical fiber preform |
| CN103864291B (en) * | 2014-01-27 | 2016-08-24 | 长飞光纤光缆股份有限公司 | A kind of single-mode fiber prefabricated rods and preparation method thereof |
| CN109081576B (en) * | 2017-06-14 | 2021-05-14 | 中天科技精密材料有限公司 | Optical fiber preform and method for manufacturing the same |
| CN108863042B (en) * | 2018-08-15 | 2023-02-17 | 上海至纯洁净系统科技股份有限公司 | Method for manufacturing optical fiber preform core rod by PCVD (plasma chemical vapor deposition) process |
| CN109399909B (en) * | 2018-09-06 | 2023-05-09 | 上海至纯洁净系统科技股份有限公司 | Method for manufacturing low-hydroxyl optical fiber preform core rod by PCVD process |
| CN109665713B (en) * | 2019-01-29 | 2021-09-03 | 江苏永鼎股份有限公司 | Low water peak large-size optical fiber preform and manufacturing method thereof |
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| CN110590151A (en) * | 2019-09-29 | 2019-12-20 | 成都富通光通信技术有限公司 | Optical fiber preform production process and optical fiber preform thereof |
| CN110845133B (en) * | 2019-12-10 | 2021-10-01 | 中国电子科技集团公司第四十六研究所 | Method for preparing boron-doped stress rod with gradient isolation layer |
| CN111285599A (en) * | 2020-01-07 | 2020-06-16 | 武汉长盈通光电技术有限公司 | Method for preparing optical fiber preform cladding by in-tube chemical vapor deposition method |
| CN112266162B (en) * | 2020-11-03 | 2023-09-26 | 江苏亨通光导新材料有限公司 | Fluorine-doped quartz tube suitable for large-size optical fiber preform and preparation method thereof |
| CN113264670A (en) * | 2021-04-13 | 2021-08-17 | 江苏永鼎股份有限公司 | Method for preparing large-size fluorine-doped quartz tube and fluorine-doped quartz tube |
| CN113820782A (en) * | 2021-08-12 | 2021-12-21 | 江苏法尔胜光电科技有限公司 | High-precision homogenizing optical fiber and preparation method thereof |
| CN114853330A (en) * | 2022-04-07 | 2022-08-05 | 长飞光纤潜江有限公司 | Method for manufacturing large-size low-water-peak optical fiber preform |
| CN114907007B (en) * | 2022-06-15 | 2024-02-02 | 山东富通光导科技有限公司 | Method for doping fluorine in optical fiber preform loose body |
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