CN106830935B - Nd-sensitized yttrium oxide-based laser ceramic and preparation method thereof - Google Patents

Nd-sensitized yttrium oxide-based laser ceramic and preparation method thereof Download PDF

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CN106830935B
CN106830935B CN201710025333.3A CN201710025333A CN106830935B CN 106830935 B CN106830935 B CN 106830935B CN 201710025333 A CN201710025333 A CN 201710025333A CN 106830935 B CN106830935 B CN 106830935B
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yttrium
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CN106830935A (en
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王焕平
雷若姗
李银艳
杨清华
徐时清
黄立辉
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China University of Metrology
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Abstract

The crystal grain of the Nd sensitized yttrium oxide based laser ceramic has a core-shell structure, and the core layer is (Y, Nd, M)2O3The photo and shell layers are (Y, N)2O3And phase, wherein M is rare earth luminescent ion, and N is sintering aid. The preparation process comprises the following steps: firstly, yttrium compound, neodymium compound and M compound are mixed and calcined to obtain (Y, Nd, M)2O3Mixing yttrium compound and N compound, and calcining to obtain (Y, N)2O3Powder, and then mixing the two kinds of powder; or mixing yttrium compound with N compound, and directly adding (Y, Nd, M)2O3Mixing and calcining the powder; and carrying out isostatic pressing, vacuum sintering, cooling and annealing on the obtained mixed powder. The present invention utilizes (Y, N) having excellent sintering properties2O3Thin layer pair (Y, Nd, M)2O3The phase is coated, so that lattice distortion can be reduced on the basis of improving the sintering performance of the ceramic, and excellent laser performance can be obtained.

Description

Nd-sensitized yttrium oxide-based laser ceramic and preparation method thereof
Technical Field
The invention relates to an yttrium oxide-based laser ceramic and a preparation method thereof, in particular to Nd-sensitized yttrium oxide-based laser ceramic and a preparation method thereof, belonging to the technical field of material science.
Background
The yttrium oxide is a cubic crystal, has excellent light transmittance, has the advantages of high melting point, good chemical and photochemical stability, high thermal conductivity, wide optical transparency range (0.23-8.0 mu m) and the like, and particularly has over 80 percent of theoretical transmittance in an infrared region; the material has low phonon energy, is easy to realize the doping modification of rare earth ions, can inhibit radiationless transition to a certain extent, and improves the probability of radiation transition, thereby improving the luminous quantum efficiency, and is an important matrix material as a solid laser medium material.
Y2O3Has a melting temperature as high as 2430 ℃ and generates a cubic phase and a hexagonal phase at 2280 DEG CBecause of the polycrystalline phase change, it is difficult to grow Y by the conventional Czochralski method2O3And (3) single crystal. By adopting the traditional ceramic process, the temperature can be far lower than Y2O3The transparent ceramic is prepared at the temperature of the melting point, so that the production cost is saved, the production efficiency is improved, more importantly, the high doping of active ions is easily realized by the ceramic preparation process, the laser output power can be greatly improved, and the high-melting-point oxide can be used as an optical medium and a laser medium. The sintering temperature of the transparent yttria ceramic is generally above 2000 ℃, and after the vacuum sintering and nano powder preparation technology is adopted, the sintering temperature is reduced to 1700 ℃ which is 700 ℃ lower than the melting temperature thereof. The ceramic material is polycrystal, the grain boundary, air hole, lattice imperfection and the like of the ceramic material can increase the light scattering loss to cause the opacity of the ceramic material, and the Y is2O3The research of the base transparent ceramic finds that La3+And Zr4+Doping of (A) is effective in improving Y2O3The sintering property of the base transparent ceramic is improved2O3The compactness of the base ceramic improves the transmittance of the base ceramic.
Rare earth doped Y2O3The laser properties of the base transparent ceramics have been extensively studied, for example, Lu et al prepared Nd: Y with a doping concentration of 1.5 at%2O3The transparent ceramic obtained 160 mW of laser output at a pump power of 742 mW using an LD of 807 nm as a pump source. Akira first reported diode-pumped Yb Y2O3The femtosecond ceramic laser obtains laser output with the central wavelength of 1076.5 nm and the average power of 420 mW when absorbing the pumping power of 2.6W. Kong utilizes Yb: Y2O3The ceramic laser realizes laser output with wavelength of 1078 nm and maximum power of 4.2W. To further increase Y2O3Sintering property and luminous property of transparent ceramic, and La is used by the Yang Kazu theme group of Shanghai university2O3The lanthanum yttrium oxide laser ceramic with good transparency is prepared by adopting a low-temperature sintering method under a pressureless reducing atmosphere as a sintering aid, and the added La is found2O3Effectively improve Y2O3The transparent ceramic has sintering performance and good laser spectrum performance. United states of AmericaThe first report in the military laboratory is in Er3+:Y2O3The middle infrared laser output of 2.71 mu m is obtained in the transparent ceramic, and the maximum output power is 380 mW at room temperature.
Although yttrium oxide-based laser ceramics are widely researched and reported, the laser efficiency is low when the doping concentration of rare earth ions is low in the current research situation at home and abroad; although the laser performance can be improved by increasing the doping concentration of the rare earth ions in theory, related researches show that the laser ceramic has the problems of increased scattering, reduced beam quality factor and the like along with the increase of the doping concentration of the rare earth ions. Because of the very strong directionality of the laser light, any minor refraction will cause light refraction, causing errors and losses. Thus, in holding Y2O3On the premise of good chemical and photochemical properties of the base transparent ceramic, the material avoids large lattice distortion and reduces scattering loss, and simultaneously keeps good sintering property, namely Y2O3The key of wider application of the base laser ceramic.
Disclosure of Invention
The invention aims to provide Nd-sensitized yttrium oxide-based laser ceramic and a preparation method thereof, which enable crystal grains of the yttrium oxide-based laser ceramic to have a core-shell structure, lead Nd-sensitized rare earth ions to be dissolved in a core layer, and lead sintering aids to be dissolved in a shell layer, thereby being beneficial to improving the sintering performance and the laser performance of the yttrium oxide-based laser ceramic on the basis of reducing lattice distortion.
The Nd sensitized yttrium oxide based laser ceramic is characterized in that the crystal grain of the ceramic has a core-shell structure, and the core layer is (Y)1-x-yNdxMy)2O3The phase and shell layer are (Y)1-zNz)2O3Wherein x is more than or equal to 0.01 and less than or equal to 0.1, y is more than or equal to 0.005 and less than or equal to 0.1, z is more than or equal to 0.05 and less than or equal to 0.2, M is one of rare earth luminescent ions Er and Dy, N is one or more of sintering aids La, Zr, Ti, Mn, Al, Ca, Zn and Mg, and the molar ratio of the shell layer substances to the core layer substances is 0.01-0.2: 1.
The preparation method of the Nd sensitized yttrium oxide based laser ceramic comprises the following two schemes:
scheme 1:
a method of preparing Nd-sensitized yttria-based laser ceramics, comprising the steps of:
(1) weighing yttrium compound, neodymium compound and M element compound according to the amount of nuclear layer substances, putting the yttrium compound, neodymium compound and M element compound into deionized water, uniformly mixing, then taking zirconia balls as grinding media, carrying out ball milling and mixing for 4-24 hours, drying, and then calcining for 2-8 hours at 1250-1550 ℃ to obtain Nd and M solid solution, and adding Y2O3Of (Y, Nd, M)2O3Phase powder;
(2) weighing yttrium compound and N element compound according to the amount of shell substances, putting into deionized water, mixing uniformly, and adding the (Y, Nd, M) synthesized in the step (1)2O3Ball-milling and mixing the phase powder for 4-24 hours, and then carrying out spray drying on the mixture to remove deionized water;
(3) putting the powder obtained after spray drying into a mold, molding under the pressure of 10-40 MPa, heating to 1050-1250 ℃, preserving heat for 1-4 hours, cooling, putting into an isostatic press, and carrying out isostatic pressing under 180-300 MPa;
(4) and (3) placing the product subjected to isostatic pressing in a vacuum furnace, preserving heat for 4-24 hours at 1550-1750 ℃, cooling, and annealing in air at 900-1500 ℃ for 2-8 hours to obtain the Nd-sensitized yttrium oxide-based laser ceramic.
In the scheme, the yttrium compound is one or more of yttrium oxide, yttrium nitrate and yttrium acetate; the neodymium compound is one or more of neodymium oxide, neodymium nitrate and neodymium acetate; the compound of the M element is one of erbium oxide, erbium nitrate, erbium acetate, dysprosium oxide, dysprosium nitrate and dysprosium acetate; the compound of the N element is one or more of lanthanum nitrate, lanthanum acetate, zirconium nitrate, zirconium acetate, tetrabutyl titanate, titanium nitrate, manganese acetate, aluminum nitrate, aluminum acetate, calcium nitrate, calcium acetate, zinc nitrate, zinc acetate, magnesium nitrate and magnesium acetate.
Scheme 2:
a method of preparing Nd-sensitized yttria-based laser ceramics, comprising the steps of:
(1) weighing yttrium compound, neodymium compound and M element compound according to the amount of nuclear layer substances, putting the yttrium compound, neodymium compound and M element compound into deionized water, uniformly mixing, then taking zirconia balls as grinding media, carrying out ball milling and mixing for 4-24 hours, drying, and then calcining for 2-8 hours at 1250-1550 ℃ to obtain Nd and M solid solution, and adding Y2O3Of (Y, Nd, M)2O3Phase powder;
(2) weighing yttrium compound and N element compound according to the amount of shell substances, putting the yttrium compound and the N element compound into deionized water, uniformly mixing, then using zirconia balls as grinding media, performing ball milling and mixing for 4-24 hours, drying, calcining at 1050-1250 ℃ for 1-4 hours to obtain N solid solution, and adding Y2O3Middle (Y, N)2O3Phase powder;
(3) mixing the powder prepared in the step (1) and the powder prepared in the step (2), putting the mixture into a ball milling tank, and carrying out ball milling and mixing for 4-24 hours by taking zirconia balls as milling media to obtain mixed powder;
(4) and drying the mixed powder, then performing compression molding, performing cold isostatic pressing at 180-300 MPa, then placing in a vacuum furnace, preserving the heat at 1550-1750 ℃ for 4-24 hours, cooling, and then annealing in air at 900-1500 ℃ for 2-8 hours to obtain the Nd-sensitized yttrium oxide-based laser ceramic.
In the scheme, the yttrium compound is one or more of yttrium oxide, yttrium nitrate and yttrium acetate; the neodymium compound is one or more of neodymium oxide, neodymium nitrate and neodymium acetate; the compound of the M element is one of erbium oxide, erbium nitrate, erbium acetate, dysprosium oxide, dysprosium nitrate and dysprosium acetate; the compound of the N element is one or more of lanthanum oxide, lanthanum nitrate, lanthanum acetate, zirconium oxide, zirconium nitrate, zirconium acetate, titanium oxide, tetrabutyl titanate, titanium nitrate, manganese oxide, manganese nitrate, manganese acetate, aluminum oxide, aluminum nitrate, aluminum acetate, calcium oxide, calcium nitrate, calcium acetate, zinc oxide, zinc nitrate, zinc acetate, magnesium oxide, magnesium nitrate and magnesium acetate.
The invention has the following beneficial effects: firstly, carrying out ball milling and mixing on an yttrium compound, a neodymium compound and an M compound, and then calcining at 1250-1550 ℃, namelyCan obtain Nd and M solid solution into Y2O3Of (Y, Nd, M)2O3The phase powder has good luminescence performance due to the fact that Nd is a sensitizing agent and M is rare earth luminescent ions (one of Er and Dy); subsequently coating (Y, Nd, M) with a compound of yttrium and a compound of N2O3Or ball-milling and mixing yttrium compound and N compound, and calcining at 1050-1250 ℃ to obtain (Y, N)2O3Mixing with (Y, Nd, M)2O3Mixing the powder, because N is one or more of La, Zr, Ti, Mn, Al, Ca, Zn and Mg, Y, N)2O3The phase has good sintering activity; (Y, Nd, M)2O3The synthesis temperature of the powder is 1250-1550 ℃ (Y, N)2O3The synthesis temperature of the powder is 1050-1250 ℃, and due to the difference of the synthesis temperatures, (Y, N)2O3Particle size ratio of powder (Y, Nd, M)2O3The powder has much finer particle size, and when the two powders are mixed together, the fine (Y, N) can be obtained by controlling the ratio of the two powders2O3The powder is surrounded on the thick (Y, Nd, M)2O3The structure around the particles, after molding and sintering, can obtain a core layer of (Y, Nd, M)2O3The photo and shell layers are (Y, N)2O3Phase yttria-based ceramics. In order (Y, Nd, M)2O3Is a core layer, (Y, N)2O3Is the structure of the shell layer, realizes the separate doping of sensitizing ions/luminous ions and sintering aid ions, thereby reducing lattice distortion and improving the laser performance of the ceramic, and simultaneously, because of the (Y, N) doped with the sintering aid2O3The phase has good sintering performance, and the compactness and the light transmittance of the ceramic are effectively improved, so that the yttrium oxide-based ceramic has good laser performance. The preparation process is simple and controllable.
Detailed Description
The present invention is further described below with reference to examples.
Example 1: (Y)0.84Nd0.08Er0.08)2O3-0.01(Y0.95La0.05)2O3（x=0.08，y=0.08，z=0.05，M=Er，N=La）
Weighing 0.84 mol of yttrium nitrate, 0.08 mol of neodymium nitrate and 0.08 mol of erbium nitrate, putting the materials into deionized water, uniformly mixing, then using zirconia balls as grinding media, carrying out ball milling and mixing for 4 hours, drying, and then calcining for 2 hours at 1550 ℃ to obtain (Y, Nd, Er)2O3And (3) phase powder. Weighing 0.0095 mol of yttrium nitrate and 0.0005 mol of lanthanum nitrate, putting the yttrium nitrate and the lanthanum nitrate into deionized water, uniformly mixing, and then adding the synthesized (Y, Nd, Er)2O3The powder was ball milled for 4 hours and the mixture was then spray dried to remove the deionized water. Putting the powder obtained after spray drying into a mould, forming under the pressure of 10 MPa, then heating to 1050 ℃, preserving heat for 4 hours, cooling, then putting into an isostatic press, and carrying out isostatic pressing under 300 MPa; and putting the product subjected to isostatic pressing in a vacuum furnace, preserving heat for 4 hours at 1750 ℃, cooling, and annealing in 1500 ℃ air for 2 hours to obtain the Nd-sensitized yttrium oxide-based laser ceramic.
Example 2: (Y)0.985Nd0.01Dy0.005)2O3-0.2(Y0.88La0.09Zr0.03)2O3（x=0.01，y=0.005，z=0.12，M=Dy，N=La,Zr）
Weighing 0.45 mol of yttrium oxide, 0.085 mol of yttrium nitrate, 0.01 mol of neodymium nitrate and 0.005mol of dysprosium acetate, uniformly mixing in deionized water, then using zirconia balls as grinding media, ball-milling and mixing for 24 hours, drying, and calcining for 8 hours at 1250 ℃ to obtain (Y, Nd, Dy)2O3And (3) phase powder. Weighing 0.176 mol of yttrium nitrate, 0.018 mol of lanthanum nitrate and 0.006 mol of zirconium nitrate, putting the materials into deionized water, uniformly mixing, then using zirconia balls as grinding media, performing ball milling and mixing for 24 hours, drying, and calcining at 1050 ℃ for 1 hour to obtain (Y, La, Zr)2O3And (3) phase powder. Mixing the above prepared (Y, Nd, Dy)2O3Phase powder and (Y, La, Zr)2O3Mixing the phase powder, putting the mixture into a ball milling tank, taking zirconia balls as milling media, and ball milling and mixing the mixture for 24 hours to obtain a mixed powderMixing the powder; and drying the mixed powder, then pressing and molding, carrying out cold isostatic pressing at 180 MPa, then placing in a vacuum furnace, preserving heat for 24 hours at 1550 ℃, cooling, and then annealing in air at 900 ℃ for 8 hours to obtain the Nd-sensitized yttrium oxide-based laser ceramic.
Example 3: (Y)0.8Nd0.1Er0.1)2O3-0.1(Y0.8La0.1Ti0.05Al0.05)2O3（x=0.1，y=0.1，z=0.2，M=Er，N=La,Ti,Al）
Weighing 0.25 mol of yttrium oxide, 0.15 mol of yttrium nitrate, 0.15 mol of yttrium acetate, 0.1 mol of neodymium nitrate and 0.1 mol of erbium acetate, putting the materials into deionized water, uniformly mixing, then using zirconia balls as grinding media, carrying out ball milling and mixing for 12 hours, drying, and then calcining for 6 hours at 1500 ℃ to obtain (Y, Nd, Er)2O3And (3) phase powder. Weighing 0.04mol of yttrium nitrate, 0.04mol of yttrium acetate, 0.01 mol of lanthanum acetate, 0.005mol of tetrabutyl titanate and 0.005mol of aluminum nitrate, putting the mixture into deionized water, uniformly mixing, and then adding the synthesized (Y, Nd, Er)2O3The powder was ball milled for 12 hours and the mixture was then spray dried to remove the deionized water. Putting the powder obtained after spray drying into a mould, forming under the pressure of 20 MPa, then heating to 1250 ℃, preserving heat for 2 hours, cooling, then putting into an isostatic press, and carrying out isostatic pressing under the pressure of 200 MPa; and putting the product subjected to isostatic pressing in a vacuum furnace, preserving heat for 8 hours at 1650 ℃, cooling, and annealing in air at 1200 ℃ for 5 hours to obtain the Nd-sensitized yttrium oxide-based laser ceramic.
Example 4: (Y)0.87Nd0.05Dy0.08)2O3-0.1(Y0.9Zr0.04Mn0.03Ca0.03)2O3（x=0.05，y=0.08，z=0.1，M=Dy，N=Zr,Mn,Ca）
Weighing 0.3 mol of yttrium oxide, 0.1 mol of yttrium nitrate, 0.17 mol of yttrium acetate, 0.05 mol of neodymium acetate and 0.08 mol of dysprosium acetate, putting the materials into deionized water, uniformly mixing, then taking zirconia balls as grinding media, carrying out ball milling and mixing for 10 hours, and dryingDrying, calcining at 1450 deg.C for 7 hr to obtain (Y, Nd, Dy)2O3And (3) phase powder. Weighing 0.09 mol of yttrium acetate, 0.004 mol of zirconium acetate, 0.003 mol of manganese acetate and 0.003 mol of calcium acetate, putting the materials into deionized water, uniformly mixing, then using zirconia balls as grinding media, carrying out ball milling and mixing for 12 hours, drying, and then calcining for 2 hours at 1150 ℃ to obtain (Y, Zr, Mn, Ca)2O3And (3) phase powder. Mixing the above prepared (Y, Nd, Dy)2O3Phase powder and (Y, Zr, Mn, Ca)2O3Mixing the phase powder, putting the mixture into a ball milling tank, taking zirconia balls as milling media, and carrying out ball milling and mixing for 8 hours to obtain mixed powder; and drying the mixed powder, then pressing and molding, carrying out cold isostatic pressing at 250 MPa, then placing in a vacuum furnace, keeping the temperature at 1600 ℃ for 12 hours, cooling, and then annealing in air at 1300 ℃ for 3 hours to obtain the Nd-sensitized yttrium oxide-based laser ceramic.
Example 5: (Y)0.88Nd0.08Er0.04)2O3-0.15(Y0.88La0.1Zn0.01Mg0.01)2O3（x=0.08，y=0.04，z=0.12，M=Er，N=La,Zn,Mg）
Weighing 0.88 mol of yttrium nitrate, 0.08 mol of neodymium acetate and 0.04mol of erbium acetate, putting the materials into deionized water, uniformly mixing, then using zirconia balls as grinding media, carrying out ball milling and mixing for 24 hours, drying, and calcining at 1350 ℃ for 7 hours to obtain (Y, Nd, Er)2O3And (3) phase powder. Weighing 0.132 mol of yttrium nitrate, 0.015 mol of lanthanum nitrate, 0.0015 mol of zinc acetate and 0.0015 mol of magnesium acetate, putting the materials into deionized water, uniformly mixing, and then adding the synthesized (Y, Nd, Er)2O3The powder was ball milled for 6 hours and the mixture was then spray dried to remove the deionized water. Putting the powder obtained after spray drying into a mould, forming under the pressure of 15 MPa, then heating to 1100 ℃, preserving heat for 3 hours, cooling, then putting into an isostatic press, and carrying out isostatic pressing under the pressure of 200 MPa; putting the product after isostatic pressing in a vacuum furnace, preserving heat for 20 hours at 1550 ℃, cooling and then annealing for 3 hours in air at 1450 ℃ to obtain the Nd-sensitized yttrium oxide-based laser ceramicAnd (4) porcelain.

Claims (1)

1. A method for preparing Nd-sensitized yttria-based laser ceramic is characterized in that (Y) is adopted0.84Nd0.08Er0.08)2O3-0.01(Y0.95La0.05)2O3Weighing 0.84 mol of yttrium nitrate, 0.08 mol of neodymium nitrate and 0.08 mol of erbium nitrate, putting the materials into deionized water, uniformly mixing, then using zirconia balls as grinding media, carrying out ball milling and mixing for 4 hours, drying, and then calcining for 2 hours at 1550 ℃ to obtain (Y, Nd, Er)2O3Phase powder; weighing 0.0095 mol of yttrium nitrate and 0.0005 mol of lanthanum nitrate, putting the yttrium nitrate and the lanthanum nitrate into deionized water, uniformly mixing, and then adding the synthesized (Y, Nd, Er)2O3Ball milling and mixing the phase powder for 4 hours, then carrying out spray drying on the mixture, and removing deionized water; putting the powder obtained after spray drying into a mould, forming under the pressure of 10 MPa, then heating to 1050 ℃, preserving heat for 4 hours, cooling, then putting into an isostatic press, and carrying out isostatic pressing under 300 MPa; and putting the product subjected to isostatic pressing in a vacuum furnace, preserving heat for 4 hours at 1750 ℃, cooling, and annealing in 1500 ℃ air for 2 hours to obtain the Nd-sensitized yttrium oxide-based laser ceramic.
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