CN105565810A - Preparation method of rare-earth-doped yttrium oxide laser ceramic optical fiber - Google Patents
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Abstract
The present invention discloses a preparation method of rare-earth-doped yttrium oxide laser ceramic optical fiber, and aims to provide a preparation method of rare-earth-doped yttrium oxide laser ceramic optical fiber with high density and good mechanical properties. The preparation method is as follows: high purity rare-earth-doped yttrium oxide nano powder is sieved and selected; a composite sintering additive, a monomer, a crosslinking agent, a dispersing agent and deionized water are added into the selected yttrium oxide powder for ball-mill mixing for preparation of slurry; bubbles in the slurry are removed, an initiator is added, the slurry is injected into a microporous plaster mold for solidification and mold release to obtain a fiber wet blank, and the fiber wet blank is dried and calcined; the fiber blank is sintered in two steps by hydrogen; and sintered ceramic fiber is annealed in oxygen to obtain the rare-earth-doped yttrium oxide laser ceramic optical fiber. Compared with the prior art, the preparation method is simple in process and lower in cost, and solves the problems of low density, low strength and easy fragmentation of yttrium oxide laser ceramic optical fiber in the prior art, and the rare-earth-doped yttrium oxide laser ceramic optical fiber can be used as a near-infrared high-power laser gain medium.
Description
Technical field
The present invention relates to a kind of laser ceramics optical fiber, specifically the present invention relates to a kind of preparation method of rare earth ion doped yttria laser ceramic optical fibre.
Background technology
Due to the widespread use in fields such as optical communication, optical data storage, sensing technology, medical science, optical fiber laser development is in recent years very rapid.Optical fiber laser compares slab laser, and volume is less, and quality is lighter, and power is higher.The normally used gain media of optical fiber laser is glass optical fiber.Laser apparatus is when high-power operation, and the thermal gradient that the lower thermal conductivity due to glass optical fiber causes, can cause mechanical failure and thermal lens successively, thus cause beam quality to reduce.Very long optical fiber can overcome these problems, but single mode operation can cause spontaneous Raman scattering and spontaneous Brillouin scatter.Compared with conventional glass optical fiber, monocrystalline oxide optical fiber has more high heat conductance, higher stimulated Brillouin scattering threshold value, higher melt temperature and excellent environmental stability.The preparation of monocrystalline oxide optical fiber generally adopts laser heated pedestal growth, EFG technique, micro-glass tube down-drawing and intercrystalline method.The scorification that but this several method institute growing single-crystal optical fiber is all complicated based on production technique and equipment, energy consumption is large, cost is high, thus limit development and the application of laser fiber.Relative to single crystal fiber, the advantages such as polycrystalline ceramics optical fiber has crystallization and sintering temperature is lower, doping content is high, structure easily designs, have important application prospect in superpower laser.
Yttrium (Yb
3+), neodymium (Nd
3+), erbium (Er
3+) rare earth ion has wide absorption and bandwidth of an emission as active ions, long fluorescence lifetime, can realize the Laser output of 1.03 microns, 1.06 microns, 1.54 microns equiwavelengths.Compared with yttrium aluminum garnet matrix, be all the yttrium oxide (Y of cube structure
2o
3) matrix not only has outstanding physical and chemical stability same with yttrium aluminum garnet, but also have higher thermal conductivity and lower thermal expansivity, be more applicable to developing to high brightness high-average power laser.But traditional method growth yttrium oxide monocrystalline mainly adopts Verneuil method, because its sintering temperature (2280 DEG C) is very close with melt temperature (2430 DEG C), be difficult to grow the yttrium oxide crystal of effective dimensions to form Laser output.
Adopt ceramic post sintering and fiber preparation process technology, crystallization and the sintering temperature of polycrystalline ceramics optical fiber can be reduced, to prepare ceramic optical fibre in the temperature far below yttrium oxide fusing point, thus make refractory oxide be used as laser medium to become possibility.The Ikesue etc. of Benshen island chemistry prepared polycrystalline yttrium aluminium garnet ceramic optical fibre and realized Laser output day.The Kim etc. of United States Air Force experiment, by extrusion moulding and vacuum sintering technology technology, obtains ~ yttrium aluminum garnet the ceramic optical fibre of 30 microns.The yttrium oxide mixing rare earth is a kind of outstanding laser gain material, relative to the thermal conductivity of silica glass 1.37W/mK, its thermal conductivity is up to ~ 13.1W/mK, and single doped yttrium oxide ceramic optical fibre can produce or bear higher laser power and can not produce beam aberration because of heat problem or gain material is damaged.Sol-gel method and method of electrostatic spinning are the main method preparing yttrium oxide nano-multicrystal ceramic fiber at present.But the ceramic optical fibre homogeneity that these methods obtain is poor, and in prior art, yttria laser ceramic optical fibre density is low, intensity is low, easily cracked.
Summary of the invention
The present invention is directed to above-mentioned problems of the prior art, a kind of step is proposed simple, cost is lower, rare earth ion doped yttria laser ceramic optical fibre that intensity is high, not easily broken and preparation method thereof, to solve in prior art, yttrium optical fiber density is low, intensity is low, easily cracked problem.
Above-mentioned purpose of the present invention can be reached by following measures, a kind of preparation method of rare earth ion doped yttria laser ceramic optical fibre, in the yttrium oxide powder that particle diameter 20 ~ 100 nanometer that it is characterized in that comprising the steps: to choose at sub-sieve, the yttrium of 0.1mol ~ 5mol%, neodymium, erbium are rear-earth-doped, rear-earth-doped yttrium oxide powder 1 by after screening: sintering aid 0.02: monomer 0.2: linking agent 0.01: dispersion agent 0.02: the mass ratio of deionized water 1.6 takes respectively or measures, and then ball milling is mixed to get the slurry of stable dispersion; The slurry that ball milling is good stirs at least 1 hour under vacuo, the bubble in removing slurry; The initiator adding powder quality 0.11wt% again mixes; Slurry is injected the micropore gypsum mold of diameter <60 micron, put into >=loft drier trigger monomer the polymerization reaction take place of 50 DEG C; Treat that the complete curing and demolding of slurry obtains ceramic fiber and to wet base, the ceramic fiber base base substrate that wets to be placed under the environment of low temperature and high relative humidity dry 24 hours, then in the loft drier transferring to 70 ° of C dry 24 hours; Dried base substrate is placed in tube type resistance furnace, by 1 DEG C/min speed, under oxygen atmosphere, is slowly raised to 800 DEG C is incubated 12 ~ 24 hours with removing organism wherein; Fiber body after the above-mentioned calcining tungsten coil furnace be placed under hydrogen atmosphere is carried out two step hydrogen sinterings; Ceramic fiber after sintering is annealed in oxygen atmosphere, obtains rare earth ion doped yttria laser ceramic optical fibre.
Beneficial effect of the present invention is:
Step is simple, and cost is lower.The present invention adopts the screening of (1) powder; (2) slurry preparation; (3) gel casting forming; (4) drying of fiber biscuit, calcining; (5) hydrogen two-step sintering; (6) oxygen annealing.The gel injection molding and forming technology wherein adopted, hinge structure, step is simple, and cost is lower.The ceramic sintering process working temperature adopted is low, and energy consumption is less.The average grain size of the ceramic optical fibre that the present invention obtains 0.3 ~ 2 micron, tensile strength 0.5 ~ 0.9GPa, has higher density and good mechanical property.The yttrium fibre diameter <50 micron of preparation, and not easily broken, solve in prior art that yttria laser ceramic optical fibre density is low, intensity is low, easily cracked problem.
The present invention utilizes yttrium (Yb
3+), neodymium (Nd
3+), erbium (Er
3+) rare earth ion is as active ions, they have the fluorescence lifetime of wide absorption and bandwidth of an emission and length, can realize the Laser output of 1.03 microns, 1.06 microns, 1.54 microns equiwavelengths.The rear-earth-doped yttria laser ceramic optical fibre that the present invention obtains can be used as the gain media of near infrared superpower laser.
Embodiment
In order to prepare rear-earth-doped yttria laser ceramic optical fibre, implementing according to technical solution of the present invention, providing experiment method and flow process: (1) powder sieves; (2) slurry preparation; (3) gel casting forming; (4) drying of fiber biscuit, calcining; (5) hydrogen two-step sintering; (6) oxygen annealing.Wherein:
(1) powder screening
Choose raw material, the yttrium oxide nano-powder of purity 99.99%, particle diameter 20 ~ 100 nanometer, doping 0.1mol ~ 5mol% rare earth ion (yttrium, neodymium, erbium) is carried out sub-sieve by 250 order nylon screens, get rid of the larger cluster of grains that do not sieve, choose the powder that sieves as raw material.
(2) slurry preparation
Be that 1:0.02:0.2:0.01:0.02:1.6 takes respectively or measures above raw material or reagent by the mass ratio of rear-earth-doped yttrium oxide powder, complex sintering aids, monomer, linking agent, dispersion agent and the deionized water of 0.1mol ~ 5mol% after screening, then ball milling is mixed to get the slurry of stable dispersion; Wherein, complex sintering aids is tetraethoxy and nano zirconium oxide powder, and monomer is acrylamide, and linking agent is N, N '-methylene-bisacrylamide, dispersion agent is polyacrylic acid; Ball grinder and grinding ball material are agate, and ball milling method is planetary ball mill, and the grinding machine time is 24 hours.For realizing low-temperature sintering and suppressing grain growing, in the tetraethoxy added and nano zirconium oxide powder complex sintering aids, the mass ratio of tetraethyl silicate, nano zircite and rare earth ion doped yttrium oxide is 0.016:0.004:1.
(3) gel casting forming
Slurry good for ball milling is stirred under vacuo the bubble at least 1 hour removing slurry; Then add initiator ammonium persulfate by 0.4% of powder quality to mix; Slurry is injected diameter <60 micrometer Millipore gypsum mold, puts into >=loft drier trigger monomer the polymerization reaction take place of 50 DEG C; Treat that the complete curing and demolding of slurry obtains wet base.
(4) drying of fiber body, calcining
The gained base that wets to be placed under the environment of low temperature and high relative humidity dry 24 hours, and then in the loft drier transferring to 70 DEG C dry 24 hours.Be placed in tube type resistance furnace by dried base substrate, under oxygen atmosphere, be slowly raised to 800 DEG C be incubated 12 ~ 24 hours with removing organism wherein, rate-controlling is at 1 DEG C/min.
(5) hydrogen atmosphere two-step sintering
The tungsten coil furnace that fiber body after above-mentioned calcining is placed under hydrogen atmosphere is sintered, first be warming up to 1000 DEG C with 5 DEG C/min, 1700 ~ 1800 DEG C are warming up to again with 2 DEG C/min, be incubated 1 ~ 2 hour, 1400 DEG C of insulations 10 hours are cooled to rapidly again with 50 DEG C/min, then 200 DEG C are cooled to 1 DEG C/min, last slowly furnace cooling.
(6) oxygen annealing
Annealed in oxygen atmosphere by ceramic optical fibre after sintering, annealing temperature 1200 DEG C ~ 1400 DEG C, annealing time 100 ~ 200 hours, obtains rare earth ion doped yttria laser ceramic optical fibre.
Embodiment 1:
(1) powder screening
99.99% high-purity yttrium oxide powder of particle diameter 20 ~ 60 nanometer 0.lmol% Er ions of purchase is sieved by 250 order nylon screens, gets rid of the larger cluster of grains that do not sieve, choose the powder 10 grams that sieves as raw material.
(2) slurry preparation
By the yttrium oxide powder of 10 grams of Er ions, tetraethoxy 0.16 gram, nano zirconium oxide powder 0.04 gram, acrylamide 2 grams, N, N '-methylene-bisacrylamide 0.1 gram, polyacrylic acid 0.2 gram, deionized water 16 grams join in agate jar.In planetary ball mill, ball milling 24 hours, obtains the slurry of stable dispersion.
(3) gel casting forming
Slurry good for ball milling is stirred under vacuo the bubble in 2 hours removing slurries; Then in slurry, add 0.11 gram of ammonium persulphate mix; Slurry is injected the gypsum mold of direct 50 microns, put into the loft drier trigger monomer polymerization reaction take place of 50 DEG C; Treat that the complete curing and demolding of slurry obtains wet base.
(4) drying of fiber biscuit, calcining
Base substrate to be placed under the environment of low temperature and high relative humidity dry 24 hours, and then in the loft drier transferring to 70 DEG C dry 24 hours.Be placed in tube type resistance furnace by dried base substrate, under oxygen atmosphere, be slowly raised to 800 DEG C be incubated 24 hours with removing organism wherein, rate-controlling is at 1 DEG C/min.
(5) hydrogen two-step sintering
The tungsten coil furnace that fiber body after above-mentioned calcining is placed under hydrogen atmosphere is carried out two-step sintering.5 DEG C/min are warming up to 1000 DEG C, then are warming up to 1700 DEG C with 2 DEG C/min, are incubated 1 hour, be cooled to rapidly 1400 DEG C of insulations 20 hours again, be then cooled to 200 DEG C with 1 DEG C/min with 50 DEG C/min, last slowly furnace cooling.
(6) oxygen annealing
Ceramic optical fibre after sintering is put into oxygen atmosphere stove anneal, and program is as follows.Temperature rise period: 0 ~ 1200 DEG C, heat-up rate is 0.5 DEG C/min; Holding stage: 1200 DEG C are incubated 200 hours; Temperature-fall period: 1200 DEG C ~ 300 DEG C, cooling rate is, 1 DEG C/min; Less than 300 DEG C Temperature fall are to room temperature.
Its erbium ion-doped yttria laser ceramic optical fibre prepared, diameter 40 microns, average grain size 0.3 micron, tensile strength 0.9GPa.
Embodiment 2:
(1) powder screening
High-purity (99.99%) yttrium oxide powder of particle diameter 40 ~ 100 nanometer 5mol% neodymium bought doping is sieved by 250 order nylon screens, gets rid of the larger cluster of grains that do not sieve, choose the powder 5 grams that sieves as raw material.
(2) slurry preparation
By the yttrium oxide powder of 5 grams of neodymiums doping, tetraethoxy 0.08 gram, nano zirconium oxide powder 0.02 gram, acrylamide 1 gram, N, N '-methylene-bisacrylamide 0.05 gram, polyacrylic acid 0.1 gram, deionized water 8 grams join in agate jar.In planetary ball mill, ball milling 24 hours, obtains the slurry of stable dispersion.
(3) gel casting forming
Slurry good for ball milling is stirred under vacuo the bubble in 1 hour removing slurry; In slurry, add 0.055 gram of agent ammonium persulphate mix; Slurry is injected the gypsum mold of direct 35 microns, put into the loft drier trigger monomer polymerization reaction take place of 60 DEG C; Treat that the complete curing and demolding of slurry obtains wet base.
(4) drying of fiber biscuit, calcining
Base substrate to be placed under the environment of low temperature and high relative humidity dry 24 hours, and then in the loft drier transferring to 70 DEG C dry 24 hours.Be placed in tube type resistance furnace by dried base substrate, under oxygen atmosphere, be slowly raised to 800 DEG C be incubated 12 hours with removing organism wherein, rate-controlling is at 1 DEG C/min.
(5) hydrogen two-step sintering
The tungsten coil furnace that fiber base after above-mentioned calcining is placed under hydrogen atmosphere is sintered, first be warming up to 1000 DEG C with 5 DEG C/min, 1800 DEG C are warming up to again with 2 DEG C/min, be incubated 1.5 hours, 1400 DEG C of insulations 10 hours are cooled to rapidly again with 50 DEG C/min, then 200 DEG C are cooled to 1 DEG C/min, last slowly furnace cooling;
(6) oxygen annealing
Ceramic optical fibre after sintering is put into oxygen atmosphere stove anneal, and program is as follows.Temperature rise period: 0 ~ 1200 DEG C, heat-up rate is 0.5 DEG C/min; Holding stage: 1400 DEG C are incubated 100 hours; Temperature-fall period: 1400 DEG C ~ 300 DEG C, cooling rate is, 1 DEG C/min; Less than 300 DEG C Temperature fall are to room temperature.
Its neodymium ion doped yttria laser ceramic optical fibre prepared, diameter 30 microns, average grain size 2 microns, tensile strength 0.5GPa.
Embodiment 3:
(1) powder screening
High-purity (99.99%) yttrium oxide powder of particle diameter 30 ~ 80 nanometer 1mol% doped yttrium bought is carried out sub-sieve by 250 order nylon screens, gets rid of the larger cluster of grains that do not sieve, choose the powder 10 grams that sieves as raw material.
(2) slurry preparation
Tetraethoxy 0.16 gram, nano zirconium oxide powder 0.04 gram, acrylamide 2 grams, N, N being added in the yttrium oxide powder of 10 grams of doped yttrium '-methylene-bisacrylamide 0.1 gram, polyacrylic acid 0.2 gram, deionized water 16 grams join in agate jar.In planetary ball mill, ball milling 24 hours, obtains the slurry of stable dispersion.
(3) gel casting forming
Slurry good for ball milling is stirred under vacuo the bubble in 1 hour removing slurry; Then in slurry, add 0.11 gram of ammonium persulphate mix; Slurry is injected the gypsum mold of direct 45 microns, put into the loft drier trigger monomer polymerization reaction take place of 50 DEG C; Treat that the complete curing and demolding of slurry obtains wet base.
(4) drying of fiber biscuit, calcining
Base substrate to be placed under the environment of low temperature and high relative humidity dry 24 hours, and then in the loft drier transferring to 70 DEG C dry 24 hours.Be placed in tube type resistance furnace by dried base substrate, under oxygen atmosphere, be slowly raised to 800 DEG C be incubated 20 hours with removing organism wherein, rate-controlling is at 1 DEG C/min.
(5) hydrogen two-step sintering
The tungsten coil furnace that fiber biscuit after above-mentioned calcining is placed under hydrogen atmosphere is sintered, first be warming up to 1000 DEG C with 5 DEG C/min, 1750 DEG C are warming up to again with 2 DEG C/min, be incubated 2 hours, 1400 DEG C of insulations 10 hours are cooled to rapidly again with 50 DEG C/min, then 200 DEG C are cooled to 1 DEG C/min, last slowly furnace cooling.
(6) oxygen annealing
Ceramic optical fibre after sintering is put into oxygen atmosphere stove anneal, and program is as follows.Temperature rise period: 0 ~ 1200 DEG C, heat-up rate is 0.5 DEG C/min; Holding stage: 1350 DEG C are incubated 100 hours; Temperature-fall period: 1350 DEG C ~ 300 DEG C, cooling rate is, 1 DEG C/min; Less than 300 DEG C Temperature fall are to room temperature.
The yttria laser ceramic optical fibre of its ruthenium ion doping prepared, diameter 35 microns, average grain size 1.6 microns, tensile strength 0.75GPa.
Claims (6)
1. the preparation method of a rare earth ion doped yttria laser ceramic optical fibre, in the yttrium oxide powder that particle diameter 20 ~ 100 nanometer that it is characterized in that comprising the steps: to choose at sub-sieve, the yttrium of 0.1mol ~ 5mol%, neodymium, erbium are rear-earth-doped, rear-earth-doped yttrium oxide powder 1 by after screening: sintering aid 0.02: monomer 0.2: linking agent 0.01: dispersion agent 0.02: the mass ratio of deionized water 1.6 takes respectively or measures, and then ball milling is mixed to get the slurry of stable dispersion; The slurry that ball milling is good stirs at least 1 hour under vacuo, the bubble in removing slurry; The initiator adding powder quality 0.11wt% again mixes; Slurry is injected the micropore gypsum mold of diameter <60 micron, put into >=loft drier trigger monomer the polymerization reaction take place of 50 DEG C; Treat that the complete curing and demolding of slurry obtains ceramic fiber and to wet base, the ceramic fiber base that wets to be placed under the environment of low temperature and high relative humidity dry 24 hours, then in the loft drier transferring to 70 DEG C dry 24 hours; Dried base substrate is placed in tube type resistance furnace, by 1 DEG C/min speed, under oxygen atmosphere, is slowly raised to 800 DEG C is incubated 12 ~ 24 hours with removing organism wherein; Fiber body after the above-mentioned calcining tungsten coil furnace be placed under hydrogen atmosphere is carried out two step hydrogen sinterings; Ceramic fiber after sintering is annealed in oxygen atmosphere, obtains rare earth ion doped yttria laser ceramic optical fibre.
2. rare earth ion doped yttria laser ceramic optical fibre preparation method according to claim 1, is characterised in that: by the yttrium (Yb of high-purity (99.99%) 0.1mol ~ 5mol% of particle diameter 20 ~ 100 nanometer
3+), neodymium (Nd
3+), erbium (Er
3+) rare earth ion doped yttrium oxide powder crosses 250 order nylon screens and sieve, and chooses raw material.
3. rare earth ion doped yttria laser ceramic optical fibre preparation method according to claim 1, it is characterized in that: in the gel casting forming operation of ceramic optical fibre, monomer is acrylamide, linking agent is N, N '-methylene-bisacrylamide, dispersion agent is polyacrylic acid, and initiator is ammonium persulphate, wherein rear-earth-doped yttrium oxide powder: monomer: linking agent: dispersion agent: initiator: the mass ratio of deionized water is 1:0.2:0.01:0.02:0.011:1.6.
4. rare earth ion doped yttria laser ceramic optical fibre preparation method according to claim 1, it is characterized in that: for realizing low-temperature sintering and suppressing grain growing, interpolation tetraethoxy and nano zirconium oxide powder are as complex sintering aids, and wherein the mass ratio of tetraethyl silicate, nano zircite and rare earth ion doped yttrium oxide is 0.016:0.004:1.
5. rare earth ion doped yttria laser ceramic optical fibre preparation method according to claim 1, it is characterized in that: in hydrogen atmosphere two-step sintering operation, first be warming up to 1000 DEG C with 5 DEG C/min, 1700 ~ 1800 DEG C are warming up to again with 2 DEG C/min, be incubated 1 ~ 2 hour, be cooled to rapidly 1400 DEG C of insulations 10 hours with 50 DEG C/min again, be then cooled to 200 DEG C with 1 DEG C/min, last slowly furnace cooling.
6. rare earth ion doped yttria laser ceramic optical fibre preparation method according to claim 1, it is characterized in that: in oxygen annealing operation, ceramic optical fibre after sintering is annealed, annealing temperature 1200 DEG C ~ 1400 DEG C, annealing time 100 ~ 200 hours, to obtain rare earth ion doped yttria laser ceramic optical fibre.
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Cited By (4)
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| CN106830935A (en) * | 2017-01-13 | 2017-06-13 | 中国计量大学 | A kind of yttria-base laser ceramics of Nd sensitizations and preparation method thereof |
| CN111825453A (en) * | 2020-07-24 | 2020-10-27 | 江苏师范大学 | Preparation method of transparent ceramic optical fiber with core-spun structure |
| CN112209715A (en) * | 2020-10-26 | 2021-01-12 | 南通大学 | YAG ceramic fiber and preparation method thereof |
| CN112753072A (en) * | 2018-09-24 | 2021-05-04 | 康宁股份有限公司 | Rare earth doped metal oxide ceramic waveguide quantum memory and manufacturing method thereof |
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| CN106830935B (en) * | 2017-01-13 | 2020-01-24 | 中国计量大学 | Nd-sensitized yttrium oxide-based laser ceramic and preparation method thereof |
| CN112753072A (en) * | 2018-09-24 | 2021-05-04 | 康宁股份有限公司 | Rare earth doped metal oxide ceramic waveguide quantum memory and manufacturing method thereof |
| CN111825453A (en) * | 2020-07-24 | 2020-10-27 | 江苏师范大学 | Preparation method of transparent ceramic optical fiber with core-spun structure |
| CN112209715A (en) * | 2020-10-26 | 2021-01-12 | 南通大学 | YAG ceramic fiber and preparation method thereof |
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