CN116924674A - Preparation method of fully doped hollow anti-resonance active optical fiber preform - Google Patents
Preparation method of fully doped hollow anti-resonance active optical fiber preform Download PDFInfo
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- 239000013307 optical fiber Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 27
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000010146 3D printing Methods 0.000 claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007639 printing Methods 0.000 claims abstract description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 15
- 238000000016 photochemical curing Methods 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 11
- 238000005286 illumination Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000003504 photosensitizing agent Substances 0.000 claims description 5
- -1 rare earth ions Chemical class 0.000 claims description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 abstract description 9
- 238000013461 design Methods 0.000 abstract description 6
- 238000005253 cladding Methods 0.000 description 20
- 230000005540 biological transmission Effects 0.000 description 13
- 239000000835 fiber Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 4
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 229960005323 phenoxyethanol Drugs 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
- C03B37/0128—Manufacture of preforms for drawing fibres or filaments starting from pulverulent glass
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Lasers (AREA)
Abstract
The invention provides a preparation method of a fully doped hollow anti-resonance active optical fiber preform, and belongs to the technical field of optical fiber preparation. According to the invention, firstly, nano silicon dioxide and photosensitive resin raw materials are mixed to obtain a printing base material, then DLP photo-curing 3D printing is carried out, the method can meet the design requirement of a complex structure of the optical fiber preform, the thickness is uniform, the method is simple, then organic monomers are removed through heat treatment, then rare earth source and/or bismuth source solutions are immersed for doping, the doping method is simple and uniform, finally, the silicon dioxide is densified through sintering, and then the fully doped hollow anti-resonance active optical fiber preform is obtained.
Description
Technical Field
The invention relates to the technical field of optical fiber preparation, in particular to a preparation method of a fully doped hollow anti-resonance active optical fiber preform.
Background
In the 21 st century, with the continuous explosive growth of information transmission capacity, the restriction of the intrinsic defects of the quartz optical fiber, such as nonlinearity, dispersion, irradiation damage, ultraviolet middle infrared light-blocking and the like, on the development of the optical communication field is more obvious. The antiresonant hollow-core optical fiber based on antiresonant reflection optical waveguide effect restrains light energy in the air fiber core, and compared with the solid optical fiber, the hollow-core optical fiber has been widely focused and studied because of low broadband transmission loss, small nonlinear coefficient and low transmission delay. The transmission loss of anti-resonant hollow-core optical fibers with various structures continuously reaches new low-loss records, and particularly the embedded ring non-node anti-resonant hollow-core optical fibers (Nested antiresonantnodeless hollow core fiberNANF). GregoryT Jasion et al, university of south Amton, england, realized a series of low loss NANF,2018, which resulted in six-ring NANF with transmission loss < 1.4dB/km, 40nm transmission bandwidth; in 2019, they achieved a low transmission loss of 0.65dB/km throughout the C+L communications band; in 2020, gregoryT Jasion et al further reduced transmission loss in the 1.51-1.6 μm band to 0.28dB/km by further improving the structural design; in 2022, gregory T Jasion et al realized low transmission loss recording of 0.174dB/km in C-band in a 5-ring NANF by adding a layer of nested structure. The transmission loss of the antiresonant hollow-Core optical fiber in the C+L communication band continuously reaches a new low value, and the Opportunities and Challenges for Long-Distance Transmission in Hollow-Core Fbiers theory published in JOURNAL OF LIGHTWAVE TECHNOLOGY in 2022 predicts that when the loss of the embedded ring node-free antiresonant hollow-Core optical fiber NANF is lower than that of a single-mode optical fiber, 200-300 km of unrepeatered amplified transmission can be realized, and if the doped antiresonant hollow-Core active optical fiber is realized, the ultra-long distance transmission can be possibly realized.
The existing method for preparing the antiresonant hollow-core optical fiber with the complex structure is a rod-tube stacking method: the glass tube is used for drawing a capillary tube with a required diameter, then the capillary tube is inserted into the quartz tube, and the capillary tube and the quartz tube are fused together by heating and melting, but the optical fiber preform prepared by the method has uneven thickness and can only be used for producing optical fibers with simpler structures, and the requirements of anti-resonant hollow-core optical fibers with complex structures cannot be met. Moreover, the existing way to actively dope hollow anti-resonance fibers is modified chemical vapor deposition MCVD or outside vapor deposition OVD. Chinese patent CN113497404B discloses a rare earth doped hollow anti-resonance fiber, which uses MCVD or OVD to perform rare earth doping on the entire cladding glass tube ring; chinese patent CN219065790U uses MCVD with no rotation to dope the nested outer tube with partially circumferential rare earth. Due to the inherent characteristics of the MCVD or OVD deposition mode, for the complete doping of the whole cladding tube ring, an undoped layer is required to be arranged outside or inside the doped tube, if the undoped region is to be removed, additional treatment is required to strip the undoped layer, the preparation cost is increased, the thickness of the optical fiber may be uneven after the stripping, and the performance of the optical fiber is affected.
In summary, the current method for preparing the doped hollow anti-resonance active optical fiber is difficult to meet the design requirement of the complex structure of the hollow anti-resonance optical fiber, and has the advantages of complex preparation method, uneven thickness of the prepared product and high preparation cost. Therefore, a preparation method of the fully doped hollow anti-resonance active optical fiber is needed, which can meet the design requirement of the complex structure of the hollow anti-resonance optical fiber, and has the advantages of simple and controllable implementation method and uniform thickness.
Disclosure of Invention
The invention aims to provide a preparation method of a fully doped hollow anti-resonance active optical fiber preform. The preparation method provided by the invention is simple, and the prepared active optical fiber preform has uniform thickness.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a fully doped hollow anti-resonance active optical fiber preform, which comprises the following steps:
(1) Mixing nano silicon dioxide and photosensitive resin raw materials to obtain a printing substrate;
(2) Performing DLP photo-curing 3D printing on the printing substrate obtained in the step (1) to obtain a blank;
(3) Performing heat treatment on the blank obtained in the step (2) to obtain a preform precursor;
(4) Dipping and doping the preform precursor obtained in the step (3) in a rare earth source and/or bismuth source solution to obtain a doped preform precursor;
(5) And (3) sintering the doped preform precursor obtained in the step (4) to obtain the fully doped hollow anti-resonance active optical fiber preform.
Preferably, the average particle diameter of the nano silica in the step (1) is 45-55 nm.
Preferably, the photosensitive resin raw material in the step (1) includes a resin monomer, a solvent, a crosslinking agent, a photosensitizer, and an ultraviolet absorber.
Preferably, in the step (1), the mass ratio of the nano silicon dioxide to the photosensitive resin raw material is (40-50): 100.
preferably, the illumination intensity of the DLP photo-curing 3D printing in the step (2) is 6-6.5 mW/cm 2 The illumination time is 1-1.5 s/layer, and the layer thickness is 0.04-0.06 mm.
Preferably, the heat treatment process in the step (3) is as follows: firstly, the temperature is raised to 60-80 ℃ from room temperature at the heating rate of 0.13-0.16 ℃/min and is kept for 3-5 hours, then the temperature is raised to 140-160 ℃ at the heating rate of 0.08-0.12 ℃/min and is kept for 3-5 hours, then the temperature is raised to 320-380 ℃ at the heating rate of 0.4-0.6 ℃/min and is kept for 3-5 hours, and finally the temperature is raised to 580-620 ℃ at the heating rate of 0.4-0.6 ℃/min and is kept for 1-3 hours.
Preferably, the concentration of rare earth ions in the rare earth source solution in the step (4) is 0.001-0.002 mol/L.
Preferably, the time of the soaking in the step (4) is 3-5 min.
Preferably, the temperature is firstly increased to 750-850 ℃ at the heating rate of 2-4 ℃/min for 1-2 h, and then is increased to 1150-1250 ℃ at the heating rate of 0.5-1.5 ℃/min for 1.5-2.5 h.
The invention provides a preparation method of a fully doped hollow anti-resonance active optical fiber preform, which comprises the following steps: (1) Mixing nano silicon dioxide and photosensitive resin raw materials to obtain a printing substrate; (2) Performing DLP photo-curing 3D printing on the printing substrate obtained in the step (1) to obtain a blank; (3) Performing heat treatment on the blank obtained in the step (2) to obtain a preform precursor; (4) Dipping and doping the preform precursor obtained in the step (3) in a rare earth source and/or bismuth source solution to obtain a doped preform precursor; (5) And (3) sintering the doped preform precursor obtained in the step (4) to obtain the fully doped hollow anti-resonance active optical fiber preform. According to the invention, firstly, nano silicon dioxide and photosensitive resin raw materials are mixed to obtain a printing base material, then DLP photo-curing 3D printing is carried out, the method has extremely high precision, can meet the design requirement of a complex structure of the optical fiber preform, has uniform thickness and simple method, then organic monomers are removed through heat treatment, then rare earth source and/or bismuth source solutions are immersed for doping, the doping method is simple and uniform, finally, the silicon dioxide is densified through sintering, and then the fully doped hollow anti-resonance active optical fiber preform is obtained.
Drawings
FIG. 1 is a schematic structural diagram of a fully doped hollow anti-resonant active optical fiber preform prepared in example 1 of the present invention;
FIG. 2 is a macroscopic view of a fully doped hollow-core antiresonant active optical fiber preform prepared according to example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a fully doped hollow anti-resonance active optical fiber preform, which comprises the following steps:
(1) Mixing nano silicon dioxide and photosensitive resin raw materials to obtain a printing substrate;
(2) Performing DLP photo-curing 3D printing on the printing substrate obtained in the step (1) to obtain a blank;
(3) Performing heat treatment on the blank obtained in the step (2) to obtain a preform precursor;
(4) Dipping and doping the preform precursor obtained in the step (3) in a rare earth source and/or bismuth source solution to obtain a doped preform precursor;
(5) And (3) sintering the doped preform precursor obtained in the step (4) to obtain the fully doped hollow anti-resonance active optical fiber preform.
The source of each raw material is not particularly limited unless specifically stated, and commercially available products known to those skilled in the art may be used.
The invention mixes nano silicon dioxide and photosensitive resin raw materials to obtain the printing base material.
In the present invention, the nano silica is preferably hydrophilic fumed silica.
In the present invention, the average particle diameter of the nanosilica is preferably 45 to 55nm, more preferably 50nm.
In the present invention, the photosensitive resin raw material preferably includes a resin monomer, a solvent, a crosslinking agent, a photosensitizer, and an ultraviolet absorber. In the present invention, the resin monomer preferably includes 2-hydroxyethyl methacrylate (HEMA); the solvent preferably comprises 2-Phenoxyethanol (POE); the cross-linking agent preferably comprises tetra (ethylene glycol) diacrylate (TEGDA); the photosensitizer preferably comprises (2, 4, 6-trimethylbenzoyl) Diphenyl Phosphine Oxide (DPO); the ultraviolet absorber preferably comprises hydroquinone (Hyd). In the invention, the volume ratio of the resin monomer to the solvent to the cross-linking agent is preferably 60:30:10, the mass of the photosensitizer is preferably 0.2% of the total mass of the nano-silica, the resin monomer, the solvent and the cross-linking agent, and the mass of the ultraviolet absorber is preferably 0.1% of the total mass of the nano-silica, the resin monomer, the solvent and the cross-linking agent, which is expressed as (60 HEMA-30POE-10TEGDA, vol%) + (0.2 DPO-0.1Hyd, wt%).
In the invention, the mass ratio of the nano silicon dioxide to the photosensitive resin raw material is preferably (40-50): 100, more preferably 45:100.
In the invention, the nano silicon dioxide is used as the optical fiber preform base material, firstly, the nano silicon dioxide is mixed with the photosensitive resin raw material, and then DLP photo-curing 3D printing is carried out, the photosensitive resin raw material undergoes curing reaction in the DLP photo-curing 3D printing process, so that various blanks with complex required structures can be formed, and the method is simple and has uniform thickness.
The invention limits the parameters of the particle diameter of nano silicon dioxide, the composition of photosensitive resin raw materials, the dosage of the nano silicon dioxide and the photosensitive resin raw materials, and the like in the above range, can have proper silicon dioxide content, is used for forming the optical fiber preform later, has higher density after sintering, and has proper photosensitive resin content so as to be beneficial to the implementation of DLP photocuring 3D printing.
After the printing substrate is obtained, the printing substrate is subjected to DLP photo-curing 3D printing to obtain a blank.
In the invention, the illumination intensity of the DLP photo-curing 3D printing is preferably 6-6.5 mW/cm 2 More preferably 6.2mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The illumination time is preferably 1 to 1.5 s/layer, more preferably 1.2 s/layer; the layer thickness is preferably 0.04 to 0.06mm, more preferably 0.05mm. According to the invention, the parameters of DLP photo-curing 3D printing are limited in the above range, so that the printing process can be smoothly carried out, and the thickness is even more.
The structure of the preform body is not particularly limited in the present invention, and an optical fiber preform structure well known to those skilled in the art may be employed.
After the blank is obtained, the blank is subjected to heat treatment to obtain a preform precursor.
In the present invention, the heat treatment process is preferably: firstly, raising the temperature to 60-80 ℃ from the room temperature at a heating rate of 0.13-0.16 ℃/min and preserving the temperature for 3-5 hours, then raising the temperature to 140-160 ℃ at a heating rate of 0.08-0.12 ℃/min and preserving the temperature for 3-5 hours, then raising the temperature to 320-380 ℃ at a heating rate of 0.4-0.6 ℃/min and preserving the temperature for 3-5 hours, and finally raising the temperature to 580-620 ℃ at a heating rate of 0.4-0.6 ℃/min and preserving the temperature for 1-3 hours; more preferably, the temperature is raised from room temperature to 70 ℃ at a heating rate of 0.15 ℃/min and kept for 3 to 5 hours, then raised to 150 ℃ at a heating rate of 0.1 ℃/min and kept for 4 hours, then raised to 350 ℃ at a heating rate of 0.5 ℃/min and kept for 4 hours, and finally raised to 600 ℃ at a heating rate of 0.5 ℃/min and kept for 2 hours. In the present invention, the heat treatment is used to remove the organic monomer. According to the invention, the heat treatment is carried out in a sectional manner, and the temperature and time of each stage are controlled within the range, so that the organic monomers can be fully removed without influencing the blank structure.
After the heat treatment is completed, the present invention preferably cools the heat treated product to obtain a preform precursor.
The cooling operation is not particularly limited in the present invention, and cooling techniques well known to those skilled in the art may be employed.
After the preform precursor is obtained, the doped preform precursor is obtained by dip-doping the preform precursor in a rare earth source and/or bismuth source solution.
In the present invention, the rare earth source preferably includes rare earth chloride; the bismuth source preferably comprises bismuth chloride. In the present invention, the rare earth element in the rare earth source solution preferably includes one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
In the present invention, the concentrations of the rare earth ions and bismuth ions in the rare earth source and/or bismuth source solution are independently preferably 0.001 to 0.002mol/L, more preferably 0.0015mol/L. The concentration of the rare earth source and/or bismuth source solution is limited in the range, so that the rare earth source and/or bismuth source can be fully dissolved and the subsequent doping is more uniform.
In the present invention, the solvent in the rare earth source and/or bismuth source solution is preferably ethanol.
The preparation method is characterized in that partial rare earth source and/or bismuth source solution is firstly dripped on the surface of the preform precursor for preliminary doping, and then the preform precursor is obtained by immersing the preform precursor into the rare earth source and/or bismuth source solution for deep doping.
The invention does not limit the dosage of rare earth source and/or bismuth source solution during preliminary doping, and the preform precursor is uniformly dripped. In the present invention, the preliminary doping is to prevent the preform precursor from being burst.
In the present invention, the time of the deep doping is preferably 3 to 5 minutes. The invention limits the time of deep doping in the above range, and can realize full doping.
After the deep doping is completed, the doped preform precursor is preferably obtained by drying the deep doped product.
The drying operation is not particularly limited, and a drying scheme well known to those skilled in the art may be adopted.
After the doped prefabricated rod precursor is obtained, the doped prefabricated rod precursor is sintered to obtain the fully doped hollow anti-resonance active optical fiber prefabricated rod.
In the present invention, the sintering process is preferably: firstly, the temperature is raised to 750-850 ℃ at the temperature rising rate of 2-4 ℃/min for 1-2 h, then the temperature is raised to 1150-1250 ℃ at the temperature rising rate of 0.5-1.5 ℃/min for 1.5-2.5 h, more preferably, the temperature is raised to 800 ℃ at the temperature rising rate of 3 ℃/min for 1.5h, and then the temperature is raised to 1200 ℃ at the temperature rising rate of 1 ℃/min for 2h. In the present invention, the sintering process is capable of densifying the preform precursor. The invention limits parameters such as temperature and time of sintering stage and each stage in the above range, and can further improve the compactness of the preform.
After sintering, the sintered product is preferably cooled to obtain the fully doped hollow anti-resonance active optical fiber preform.
The cooling operation is not particularly limited in the present invention, and cooling techniques well known to those skilled in the art may be employed.
In the embodiment of the present invention, the schematic structural diagram of the fully doped hollow anti-resonant active optical fiber preform is preferably shown in fig. 1, and the fully doped hollow anti-resonant active optical fiber preform comprises a cladding collar 2, an air fiber core 3 formed by surrounding the cladding collar and a supporting element 1 arranged on the outer layer of the cladding collar, wherein O p Is the center of an air fiber core, C p Is the point of tangency of the cladding collar with the support member. In the present invention, the number of cladding collars is preferably 6 to 8, more preferably 7; the inner diameter d of the cladding ring tube p Preferably 3.50 to 3.70mm; thickness t of the cladding collar p Preferably 0.40 to 0.50mm; the cladding collars are inscribed at equal intervals on the inner surface of the support member. In the present invention, the cladding collar surrounds the diameter D of the formed air core p Preferably 6.40 to 7.40mm. In the present invention, the outer diameter D of the supporting element is preferably 18 to 20mm, and the thickness T of the supporting element p Preferably 1.50 to 1.60mm, more preferably 1.55mm.
According to the invention, firstly, nano silicon dioxide and photosensitive resin raw materials are mixed to obtain ultraviolet sensitive monomers, then DLP photo-curing 3D printing is carried out, the method can meet the design requirement of a complex structure of the optical fiber preform, the thickness is uniform, the method is simple, then the organic monomers are removed through heat treatment, then rare earth and/or bismuth solution is immersed for doping, the doping method is simple and uniform, finally, the silicon dioxide is densified through sintering, and then the fully doped hollow anti-resonance active optical fiber preform is obtained.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Mixing hydrophilic fumed silica with an average particle size of 50nm with a photosensitive resin, wherein the photosensitive resin is composed of 2-hydroxyethyl methacrylate (HEMA), 2-Phenoxyethanol (POE), tetra (ethylene glycol) diacrylate (TEGDA), (2, 4, 6-trimethylbenzoyl) Diphenyl Phosphine Oxide (DPO) and hydroquinone (Hyd) according to the component ratio of (60 HEMA-30POE-10TEGDA, vol%) + (0.2 DPO-0.1Hyd, wt%) and the mass ratio of the silica to the photosensitive resin is 45:100, so as to obtain a printing substrate;
(2) DLP 3D printing blank by adopting printing base material, wherein the illumination intensity of 3D printing is 6.2mW/cm 2 The illumination time is 1.2 s/layer, and the layer thickness is 0.05mm;
(3) Placing the printed blank into a high-temperature furnace for heat treatment, wherein the heat treatment process comprises the following steps: firstly, heating the furnace to 70 ℃ from room temperature at a heating rate of 0.15 ℃/min and preserving heat for 4 hours, then heating to 150 ℃ at a heating rate of 0.1 ℃/min and preserving heat for 4 hours, then heating to 350 ℃ at a heating rate of 0.5 ℃/min and preserving heat for 4 hours, and finally heating to 600 ℃ at a heating rate of 0.5 ℃/min and preserving heat for 2 hours to obtain a preform precursor;
(4) Dripping an ethanol solution containing erbium chloride (with the concentration of 0.0015 mol/L) on the preform precursor by using a rubber head dropper for primary doping, and then immersing the preform precursor in the ethanol solution containing erbium chloride for 4min to realize full doping;
(5) Placing the doped structure into a high-temperature furnace for sintering, wherein the sintering process is as follows: raising the temperature of the furnace to 800 ℃ at a heating rate of 3 ℃/min and preserving heat for 1.5 hours, then raising the temperature of the furnace to 1200 ℃ at a heating rate of 1 ℃/min and preserving heat for 2 hours, and then cooling to room temperature to obtain the fully doped hollow anti-resonance active optical fiber preform; wherein the fully doped hollow anti-resonance active optical fiber preform consists of a cladding ring 2, an air fiber core 3 formed by surrounding the cladding ring and a supporting element 1 arranged on the outer layer of the cladding ring, wherein O p Is the center of an air fiber core, C p The number of the cladding rings is 7; the inner diameter d of the cladding ring tube p 3.60mm; thickness t of the cladding collar p 0.46mm; the cladding rings are inscribed on the inner surface of the supporting element at equal intervals, and the diameter D of the air fiber core formed by the cladding rings in a surrounding manner p Is 7.29mm, the outer diameter D of the supporting element is 19.14mm, and the thickness T of the supporting element p 1.55mm.
A macroscopic view of the fully doped hollow-core antiresonant optical fiber preform prepared in example 1 is shown in FIG. 2. As can be seen from FIG. 2, the thicknesses of the supporting layer and the cladding ring canal in the fully doped hollow anti-resonance optical fiber preform prepared by the method are uniform.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A preparation method of a fully doped hollow anti-resonance active optical fiber preform comprises the following steps:
(1) Mixing nano silicon dioxide and photosensitive resin raw materials to obtain a printing substrate;
(2) Performing DLP photo-curing 3D printing on the printing substrate obtained in the step (1) to obtain a blank;
(3) Performing heat treatment on the blank obtained in the step (2) to obtain a preform precursor;
(4) Dipping and doping the preform precursor obtained in the step (3) in a rare earth source and/or bismuth source solution to obtain a doped preform precursor;
(5) And (3) sintering the doped preform precursor obtained in the step (4) to obtain the fully doped hollow anti-resonance active optical fiber preform.
2. The method according to claim 1, wherein the average particle diameter of the nanosilica in the step (1) is 45 to 55nm.
3. The method according to claim 1, wherein the photosensitive resin material in the step (1) comprises a resin monomer, a solvent, a crosslinking agent, a photosensitizer and an ultraviolet absorber.
4. The preparation method according to claim 1 or 3, wherein the mass ratio of the nanosilicon dioxide to the photosensitive resin raw material in the step (1) is (40 to 50): 100.
5. the method according to claim 1, wherein the illumination intensity of the DLP photo-curing 3D printing in the step (2) is 6 to 6.5mW/cm 2 The illumination time is 1-1.5 s/layer, and the layer thickness is 0.04-0.06 mm.
6. The method according to claim 1, wherein the heat treatment in the step (3) is: firstly, the temperature is raised to 60-80 ℃ from room temperature at the heating rate of 0.13-0.16 ℃/min and is kept for 3-5 hours, then the temperature is raised to 140-160 ℃ at the heating rate of 0.08-0.12 ℃/min and is kept for 3-5 hours, then the temperature is raised to 320-380 ℃ at the heating rate of 0.4-0.6 ℃/min and is kept for 3-5 hours, and finally the temperature is raised to 580-620 ℃ at the heating rate of 0.4-0.6 ℃/min and is kept for 1-3 hours.
7. The method according to claim 1, wherein the concentration of rare earth ions in the rare earth source solution in the step (4) is 0.001 to 0.002mol/L.
8. The method according to claim 1, wherein the time of the impregnation in the step (4) is 3 to 5 minutes.
9. The method according to claim 1, wherein the sintering process in step (5) is: firstly, heating to 750-850 ℃ at a heating rate of 2-4 ℃/min, preserving heat for 1-2 h, and then heating to 1150-1250 ℃ at a heating rate of 0.5-1.5 ℃/min, preserving heat for 1.5-2.5 h.
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| CN117800586A (en) * | 2024-01-03 | 2024-04-02 | 重庆大学 | 3D printing additive preparation method for bismuth erbium quartz fiber |
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