CN114163235A - High-transmittance Dy: Y2O3Method for preparing transparent ceramic - Google Patents
High-transmittance Dy: Y2O3Method for preparing transparent ceramic Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 41
- 238000002834 transmittance Methods 0.000 title claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 36
- 235000015895 biscuits Nutrition 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 239000012452 mother liquor Substances 0.000 claims abstract description 17
- 238000007873 sieving Methods 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000010413 mother solution Substances 0.000 claims abstract description 9
- 239000011858 nanopowder Substances 0.000 claims abstract description 9
- 238000005498 polishing Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims abstract description 6
- 229910009253 Y(NO3)3 Inorganic materials 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000004448 titration Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 238000012805 post-processing Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 abstract description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000012994 industrial processing Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
High-transmittance Dy: Y2O3Preparation method of transparent ceramic using Dy (NO)3)3、Y(NO3)3、La(NO3)3、ZrOCl2·8H2Preparing a mother solution by using the O solution as a raw material; by NH4OH aqueous solution is used as a precipitating agent; firstly, dripping a precipitator into mother liquor to generate precipitate, then carrying out cleaning and solid-liquid separation treatment to obtain precipitate, and sequentially drying, crushing and sieving the precipitate to obtain powder; calcining the powder to synthesize Dy: Y2O3Nano powder; crushing the powder by using a zirconia mortar, and then sieving; sequentially carrying out dry pressing and cold isostatic pressing on the sieved powder to obtain a biscuit; firstly, carrying out vacuum sintering on a biscuit, and then carrying out hot isostatic pressing sintering; firstly, annealing the sintered biscuit, and then polishing to obtain the high transparencyDegree Dy: Y2O3A transparent ceramic. The method can prepare the transparent ceramic for bearing the high-power laser, and the stability of the transparent ceramic is good.
Description
Technical Field
The invention belongs to the technical field of solid laser gain medium materials, and particularly relates to a high-transmittance Dy: Y2O3A preparation method of transparent ceramics.
Background
The 2.8-3.3 mu m intermediate infrared laser is positioned in 2 transmission windows (1-3 mu m and 3-5 mu m) of the atmosphere and covers a plurality of important molecular characteristic spectral lines, and due to the characteristic, the intermediate infrared laser has very wide application in the fields of military affairs, medical treatment, optical communication, environmental monitoring, industrial processing and the like.
One of the main ways to obtain 2.8-3.3 μm band laser at present is to generate laser directly through laser working medium, i.e. laser material doped with LD pumping rare earth ions or transition metal ions, and the rare earth ions capable of emitting light at 2.8-3.3 μm band at present stage include Er3+, Dy3+, Ho3+, Tm3+, etc., wherein Er3+Has abundant energy levels and can be excited by a plurality of light frequencies such as 514nm, 532nm, 667nm, 800nm, 980nm and 1480nm, and thus, has received much attention. But Er3+High-concentration doping is required for activating ions, so that the thermal conductivity of the material can be greatly reduced, the heat dissipation effect of the laser gain medium is not ideal, the quality of laser beams is reduced, the efficiency of a laser is reduced, and the stability is poor. Therefore, a more stable novel doped laser gain medium material is urgently needed to be developed to meet the requirement of a 2.8-3.3 μm mid-infrared band high-power laser on the gain medium material.
Disclosure of Invention
In view of the problems of the prior art, the present invention provides a high transmittance Dy: Y2O3The method for preparing the transparent ceramic can prepare the transparent ceramic for bearing the high-power laser, has good stability, and can meet the requirement of a 2.8-3.3 mu m mid-infrared band high-power laser on a gain medium material.
In order to achieve the above object, the present invention provides Dy: Y having high transmittance2O3The preparation method of the transparent ceramic specifically comprises the following steps:
the method comprises the following steps: preparing a solution;
by Dy (NO)3)3、Y(NO3)3、La(NO3)3、ZrOCl2·8H2O solution is used as raw material, and the four solutions are mixed according to a chemical formula (Dy)0.006Zr0.01La0.005Y0.979)2O3Mixing the raw materials to prepare a mother solution, wherein the molar concentration of Y ions in the mother solution is 0.05-0.6 mol/L, the molar ratio of Dy to Y ions is between 1/200 and 1/50, the molar ratio of Zr to Y ions is between 1/200 and 1/20, and the molar ratio of La to Y ions is between 1/200 and 1/20; reacting NH4OH is diluted into NH with the molar concentration of 0.4 to 2.0mol/L by water4OH aqueous solution is used as a precipitating agent;
step two: preparing a front driving body;
dropping the precipitant into mother liquid while stirring at high speed to make NH by forward titration4Carrying out chemical reaction on OH and mother liquor under high-speed stirring to generate a precipitate, wherein the pH value of the mother liquor can be continuously increased in the reaction process, and when the pH value reaches 8.5, stopping titration; then respectively cleaning with deionized water and absolute ethyl alcohol, and then carrying out solid-liquid separation by adopting a vacuum filtration method to obtain a precipitate, wherein the precipitate is a precursor of dysprosium-doped yttrium oxide; drying the obtained precursor, grinding the dried precursor by using a zirconia mortar, and sieving to obtain powder;
step three: calcining the powder;
calcining the powder obtained in the second step at 800-1300 ℃ for 2-10 hours to synthesize Dy Y2O3Nano powder;
step four: forming a biscuit;
crushing the powder obtained in the third step by using a zirconia mortar, then carrying out sieving treatment, filling the sieved powder into a stainless steel mold, and sequentially carrying out dry pressing forming under the pressure of 3-15 MPa and cold isostatic pressing forming under the pressure of 100-300 MPa to further densify to obtain a biscuit;
step five: sintering the biscuit;
firstly, the biscuit is sintered in vacuum, the vacuum degree is less than or equal to 10-2Pa, the sintering temperature is 1600-1800 ℃, and the sintering time is 2-15 hours;
hot isostatic pressing sintering is carried out on the biscuit, the hot isostatic pressing sintering temperature is 1600-1780 ℃, the atmosphere is high-purity argon, and the sintering time is 1-3 hours;
step six: post-processing;
firstly, annealing the sintered biscuit at 1200-1450 ℃ for 2-20 hours in air atmosphere; then polishing to obtain high-transparency Dy: Y2O3A transparent ceramic.
Further, in order to ensure the effect of the dropping, in the second step, the precipitant is dropped into the mother liquor at a rate of 4 to 25mL/min by feeding through a peristaltic pump.
Further, in order to ensure the cleaning effect, in the cleaning process of the second step, the number of times of cleaning with deionized water is 3-4 times, and the number of times of cleaning with absolute ethyl alcohol is 2-3 times.
Preferably, in the second step, the powder is sieved through a 200-mesh sieve for 3 times.
Preferably, in the fourth step, the sieving treatment is carried out by 3 times through a 140-mesh sieve.
Preferably, in the third step, the powder is calcined in a muffle furnace.
The invention adopts a chemical coprecipitation method to synthesize ZrO by using mixed solution of Dy (NO3)3, Y (NO3)3, La (NO3)3 and ZrOCl2 & 8H2O2，La2O3Co-doped Dy: Y2O3Ceramic powder of, in which Dy3+The ions being laser-activated ions, Y3+Ion as host ion, La3+And Zr4+The ion codoping is used as a composite sintering aid for sintering rare earth element sesquioxide ceramic. Due to Y2O3Has low phonon energy, high thermal conductivity and high laser damage threshold, is one of ideal laser gain medium materials, and is also rare earth Dy3+Of ionsAn ideal host material. The yttrium oxide has stable physicochemical property, is resistant to acid and alkali corrosion, can bear certain thermal shock, can be used for preparing high-transparency Dy: Y2O3 ceramic, can effectively solve the bottleneck problem of 2.8-3.3 mu m intermediate infrared band laser materials, and can realize high-power laser output of the band. Due to Dy3+High-concentration doping is not needed, the problem of heat conductivity loss caused by high doping can be effectively avoided, the stability of the laser gain medium can be greatly improved, and meanwhile, the manufacturing cost of the transparent ceramic can be effectively reduced. Due to La3+Ion radius ratio Y3+Ion size of La3+The doping of the ions can cause slight distortion of crystal lattices and is beneficial to accelerating the cation Y in the sintering process3+The diffusion improves the sintering activity, is beneficial to accelerating the migration of crystal boundary and promotes the discharge of air holes; in addition, Zr4+The incorporation of ions helps to reduce oxygen vacancies and interstitial cations Y3+The amount of (b) plays a role in inhibiting excessive growth of crystal grains. The obtained powder is treated by combining vacuum sintering with hot isostatic pressing sintering technology, so that a ceramic biscuit with high density can be prepared, the relative density can be more than 99.99 percent, the stability after sintering is good, the optical performance is excellent, and Dy Y with high transmittance can be prepared2O3A transparent ceramic. Compared with the prior art, the transparent ceramic material prepared by the invention has the advantages of moderate grain size, good uniformity, no impurities or air holes, high sintering compactness and high visible light transmittance, the maximum linear transmittance of a 1mm thick sample subjected to double-side polishing in a visible light wave band can reach more than 78 percent, and the requirement of a 2.8-3.3 mu m middle-infrared wave band high-power laser on a gain medium material can be effectively met. Meanwhile, the ceramic prepared by the method has wide application prospects in the fields of laser media, information detection, infrared windows, high-temperature windows, high-refractive-index optical lenses, comprehensive shielding materials and the like.
The preparation method has the advantages of simple process, low requirement on preparation conditions, convenient operation, good controllability, relatively simple sintering conditions, short combustion reaction time, easy production and the like.
Drawings
FIG. 1 is the present inventionY is Dy prepared by the invention2O3A physical picture of the transparent ceramic;
FIG. 2 shows Dy: Y prepared by the present invention2O3Graph of transmittance of transparent ceramics.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
the method specifically comprises the following steps:
the method comprises the following steps: preparing a solution;
by Dy (NO)3)3、Y(NO3)3、La(NO3)3、ZrOCl2·8H2O solution is used as raw material, and the four solutions are mixed according to a chemical formula (Dy)0.006Zr0.01La0.005Y0.979)2O3Mixing to prepare 5L of solution as mother solution, wherein the molar concentration of Y ions in the mother solution is 0.2mol/L, the molar ratio of Dy to Y ions is between 1/200 and 1/50, the molar ratio of Zr to Y ions is between 1/200 and 1/20, and the molar ratio of La to Y ions is between 1/200 and 1/20; reacting NH4OH is diluted into NH with the molar concentration of 0.6mol/L by water4OH aqueous solution is used as a precipitating agent;
step two: preparing a front driving body;
adopting a forward titration method, dripping a precipitator into the mother liquor at the speed of 10mL/min by a peristaltic pump, and simultaneously stirring at high speed to ensure that NH is added4Carrying out chemical reaction on OH and mother liquor under high-speed stirring to generate a precipitate, wherein the pH value of the mother liquor can be continuously increased in the reaction process, and when the pH value reaches 8.5, stopping titration; then washing with deionized water for 4 times, washing with anhydrous ethanol for 3 times, performing solid-liquid separation by vacuum filtration to obtain precipitate, wherein the precipitate is precursor of dysprosium-doped yttrium oxide, and the precursor is (Dy)0.006Zr0.01La0.005Y0.979)(OH)3A precursor; drying the obtained precursor, grinding the dried precursor by using a zirconia mortar, and sieving the ground precursor by using a 200-mesh sieve for 3 times to obtain powder;
step three: calcining the powder;
calcining the powder obtained in the step two by adopting a muffle furnace at 1100 ℃ for 5 hours to synthesize Dy Y2O3Nano powder ((Dy)0.006Zr0.01La0.005Y0.979)2O3Nanopowder);
step four: forming a biscuit;
grinding the powder obtained in the third step by using a zirconia mortar, sieving the powder for 3 times by using a 140-mesh sieve, filling the sieved powder into a stainless steel mould, performing double-sided compression molding under the condition of 4MPa, and performing cold isostatic pressing under the condition of 200MPa to obtain (Dy)0.006Zr0.01La0.005Y0.979)2O3A ceramic biscuit;
step five: sintering the biscuit;
firstly, the biscuit is sintered in vacuum, the vacuum degree is lower than 1.0 multiplied by 10-3Pa, the sintering temperature is 1700 ℃, and the sintering time is 7 hours;
hot isostatic pressing sintering is carried out on the biscuit, the pressure is 176MPa, the temperature is 1720 ℃, the atmosphere is high-purity argon (99.99 percent), and the sintering time is 3 hours;
step six: post-processing;
firstly, placing the sintered biscuit in a muffle furnace for annealing treatment, wherein the annealing temperature is 1400 ℃, and annealing for 15 hours in an air atmosphere; then polishing to obtain high-transparency Dy: Y2O3Transparent ceramic ((Dy)0.006Zr0.01La0.005Y0.979)2O3Transparent ceramics).
The sample obtained in example 1 was observed by scanning electron microscopy, and the surface of the sample was smooth and free of impurities and air holes. As can be seen from the sample photo (figure 1) and the transmittance curve (figure 2), characters and patterns at the bottom of the sample are clearly visible, and the transmittance can reach 78% at most, which indicates that the sample has good optical transmittance in the visible light band.
Example 2:
the method specifically comprises the following steps:
the method comprises the following steps: preparing a solution;
by Dy (NO)3)3、Y(NO3)3、La(NO3)3、ZrOCl2·8H2O solution is used as raw material, and the four solutions are mixed according to a chemical formula (Dy)0.006Zr0.01La0.005Y0.979)2O3Mixing to prepare 5L of solution as mother solution, wherein the molar concentration of Y ions in the mother solution is 0.1mol/L, the molar ratio of Dy to Y ions is between 1/200 and 1/50, the molar ratio of Zr to Y ions is between 1/200 and 1/20, and the molar ratio of La to Y ions is between 1/200 and 1/20; reacting NH4OH is diluted into NH with the molar concentration of 0.5mol/L by water4OH aqueous solution is used as a precipitating agent;
step two: preparing a front driving body;
adopting a forward titration method, dripping a precipitator into the mother liquor at the speed of 12mL/min by a peristaltic pump, and simultaneously stirring at high speed to ensure that NH is added4Carrying out chemical reaction on OH and mother liquor under high-speed stirring to generate a precipitate, wherein the pH value of the mother liquor can be continuously increased in the reaction process, and when the pH value reaches 8.5, stopping titration; then washing with deionized water for 3 times, washing with anhydrous ethanol for 3 times, performing solid-liquid separation by vacuum filtration to obtain precipitate, wherein the precipitate is precursor of dysprosium-doped yttrium oxide, and the precursor is (Dy)0.006Zr0.01La0.005Y0.979)(OH)3A precursor; drying the obtained precursor, grinding the dried precursor by using a zirconia mortar, and sieving the ground precursor by using a 200-mesh sieve for 3 times to obtain powder;
step three: calcining the powder;
calcining the powder obtained in the step two by adopting a muffle furnace at the temperature of 900 ℃ for 10 hours to synthesize Dy Y2O3Nano powder ((Dy)0.006Zr0.01La0.005Y0.979)2O3Nanopowder);
step four: forming a biscuit;
crushing the powder obtained in the third step by using a zirconia mortar, and then passing throughSieving with 140 mesh sieve for 3 times, filling the sieved powder into stainless steel mold, double-sided pressing under 8MPa, and cold isostatic pressing under 150MPa to obtain (Dy)0.006Zr0.01La0.005Y0.979)2O3A ceramic biscuit;
step five: sintering the biscuit;
firstly, the biscuit is sintered in vacuum, the vacuum degree is lower than 1.0 multiplied by 10-2Pa, the sintering temperature is 1600 ℃, and the sintering time is 10 hours;
hot isostatic pressing sintering is carried out on the biscuit, the pressure is 176MPa, the sintering temperature is 1780 ℃, the atmosphere is high-purity argon (99.99 percent), and the sintering time is 2 hours;
step six: post-processing;
firstly, placing the sintered biscuit in a muffle furnace for annealing treatment, wherein the annealing temperature is 1300 ℃, and annealing for 20 hours in an air atmosphere; then polishing to obtain high-transparency Dy: Y2O3Transparent ceramic ((Dy)0.006Zr0.01La0.005Y0.979)2O3Transparent ceramics).
The sample obtained in example 2 was observed by a scanning electron microscope, and the surface of the sample was smooth and clean, and had no impurities or air holes. In the observation process of a sample photo and a transmittance curve, characters and patterns at the bottom of the sample are clearly visible, and the transmittance can reach 76% at most, which indicates that the sample has good optical transmittance in a visible light wave band.
Example 3:
the method specifically comprises the following steps:
the method comprises the following steps: preparing a solution;
by Dy (NO)3)3、Y(NO3)3、La(NO3)3、ZrOCl2·8H2O solution is used as raw material, and the four solutions are mixed according to a chemical formula (Dy)0.006Zr0.01La0.005Y0.979)2O3Mixing to obtain 5L solution as mother liquor, wherein the molar concentration of Y ions in the mother liquor is 0.6mol/L, and Dy and Y ions are in molThe molar ratio is between 1/200 and 1/50, the molar ratio of Zr to Y ions is between 1/200 and 1/20, and the molar ratio of La to Y ions is between 1/200 and 1/20; reacting NH4OH is diluted into NH with the molar concentration of 1.0mol/L by water4OH aqueous solution is used as a precipitating agent;
step two: preparing a front driving body;
dropping the precipitant into the mother liquid at 20mL/min by peristaltic pump while stirring at high speed to make NH4Carrying out chemical reaction on OH and mother liquor under high-speed stirring to generate a precipitate, wherein the pH value of the mother liquor can be continuously increased in the reaction process, and when the pH value reaches 8.5, stopping titration; then washing with deionized water for 3 times, washing with anhydrous ethanol for 2 times, performing solid-liquid separation by vacuum filtration to obtain precipitate, wherein the precipitate is precursor of dysprosium-doped yttrium oxide, and the precursor is (Dy)0.006Zr0.01La0.005Y0.979)(OH)3A precursor; drying the obtained precursor, grinding the dried precursor by using a zirconia mortar, and sieving the ground precursor by using a 200-mesh sieve for 3 times to obtain powder;
step three: calcining the powder;
calcining the powder obtained in the step two by adopting a muffle furnace at 1300 ℃ for 3 hours to synthesize Dy Y2O3Nano powder ((Dy)0.006Zr0.01La0.005Y0.979)2O3Nanopowder);
step four: forming a biscuit;
grinding the powder obtained in the third step by using a zirconia mortar, sieving the powder for 3 times by using a 140-mesh sieve, filling the sieved powder into a stainless steel mould, performing double-sided compression molding under the condition of 15MPa, and performing cold isostatic pressing under the condition of 300MPa to obtain (Dy)0.006Zr0.01La0.005Y0.979)2O3A ceramic biscuit;
step five: sintering the biscuit;
firstly, the biscuit is sintered in vacuum, the vacuum degree is lower than 2.0 multiplied by 10-3Pa, sintering temperatureThe temperature is 1800 ℃, and the sintering time is 6 hours;
hot isostatic pressing sintering is carried out on the biscuit, the pressure is 176MPa, the temperature is 1700 ℃, the atmosphere is high-purity argon (99.99 percent), and the sintering time is 3 hours;
step six: post-processing;
firstly, placing the sintered biscuit in a muffle furnace for annealing treatment, wherein the annealing temperature is 1450 ℃, and annealing for 10 hours in an air atmosphere; then polishing to obtain high-transparency Dy: Y2O3Transparent ceramic ((Dy)0.006Zr0.01La0.005Y0.979)2O3Transparent ceramics).
The sample obtained in example 3 was observed by scanning electron microscopy, and the surface of the sample was smooth and clean, and had no impurities or pores. In the observation process of a sample photo and a transmittance curve, characters and patterns at the bottom of the sample are clearly visible, and the transmittance can reach 74% at most, which indicates that the sample has good optical transmittance in a visible light wave band.
The polishing processes of the embodiment 1, the embodiment 2 and the embodiment 3 are the same, the linear transmittances of the visible light wave bands are 78%, 76% and 74% respectively when measured under the same condition, and meanwhile, tests show that the transparent ceramics in the 3 embodiments can stably and reliably realize high-power laser output and can meet the high-power output requirement of the mid-infrared wave band laser with the wavelength of 2.8-3.3 microns.
In summary, the present invention provides a high transmittance Dy: Y2O3Transparent ceramic ((Dy)0.006Zr0.01La0.005Y0.979)2O3Transparent ceramic), the method has the advantages of simple process, low requirement on preparation conditions, convenient operation, good controllability, relatively simple sintering conditions, short combustion reaction time, easy production and the like. The transparent ceramic material prepared by the method has the advantages of moderate crystal grain size, good uniformity, no impurities and air holes, high sintering density and high visible light transmittance, and the maximum linear transmittance of a sample with the thickness of 1mm subjected to double-side polishing in a visible light wave band can reach over 78 percent, so that the maximum linear transmittance can effectively meet the requirement of 2.8-3.3 mu m mid-infraredThe requirement of band high power lasers for gain medium materials.
Claims (6)
1. High-transmittance Dy: Y2O3The preparation method of the transparent ceramic is characterized by comprising the following steps:
the method comprises the following steps: preparing a solution;
by Dy (NO)3)3、Y(NO3)3、La(NO3)3、ZrOCl2·8H2O solution is used as raw material, and the four solutions are mixed according to a chemical formula (Dy)0.006Zr0.01La0.005Y0.979)2O3Mixing the raw materials to prepare a mother solution, wherein the molar concentration of Y ions in the mother solution is 0.05-0.6 mol/L, the molar ratio of Dy to Y ions is between 1/200 and 1/50, the molar ratio of Zr to Y ions is between 1/200 and 1/20, and the molar ratio of La to Y ions is between 1/200 and 1/20; reacting NH4OH is diluted into NH with the molar concentration of 0.4-2.0 mol/L by water4OH aqueous solution is used as a precipitating agent;
step two: preparing a front driving body;
dropping the precipitant into mother liquid while stirring at high speed to make NH by forward titration4Carrying out chemical reaction on OH and mother liquor under high-speed stirring to generate a precipitate, wherein the pH value of the mother liquor can be continuously increased in the reaction process, and when the pH value reaches 8.5, stopping titration; then respectively cleaning with deionized water and absolute ethyl alcohol, and then carrying out solid-liquid separation by adopting a vacuum filtration method to obtain a precipitate, wherein the precipitate is a precursor of dysprosium-doped yttrium oxide; drying the obtained precursor, grinding the dried precursor by using a zirconia mortar, and sieving to obtain powder;
step three: calcining the powder;
calcining the powder obtained in the second step at 800-1300 ℃ for 2-10 hours to synthesize Dy Y2O3Nano powder;
step four: forming a biscuit;
crushing the powder obtained in the third step by using a zirconia mortar, then carrying out sieving treatment, filling the sieved powder into a stainless steel mold, and sequentially carrying out dry pressing forming under the pressure of 3-15 MPa and cold isostatic pressing forming under the pressure of 100-300 MPa to further densify to obtain a biscuit;
step five: sintering the biscuit;
firstly, the biscuit is sintered in vacuum, the vacuum degree is less than or equal to 10-2Pa, the sintering temperature is 1600-1800 ℃, and the sintering time is 2-15 hours;
hot isostatic pressing sintering is carried out on the biscuit, the hot isostatic pressing sintering temperature is 1600-1780 ℃, the atmosphere is high-purity argon, and the sintering time is 1-3 hours;
step six: post-processing;
annealing the sintered biscuit at 1200-1450 ℃ for 2-20 hours in air atmosphere; then polishing to obtain high-transparency Dy: Y2O3A transparent ceramic.
2. Y is the high-transmittance Dy according to claim 12O3The preparation method of the transparent ceramic is characterized in that in the second step, a precipitator is dripped into the mother liquor at a speed of 4-25 mL/min in a feeding mode of a peristaltic pump.
3. Y is Dy with high transmittance according to claim 1 or 22O3The preparation method of the transparent ceramic is characterized in that in the cleaning process in the second step, the cleaning times of deionized water are 3-4 times, and the cleaning times of absolute ethyl alcohol are 2-3 times.
4. Y is the high-transmittance Dy according to claim 32O3The preparation method of the transparent ceramic is characterized in that in the second step, the transparent ceramic is sieved for 3 times through a 200-mesh sieve during sieving treatment.
5. Y is the high-transmittance Dy according to claim 42O3The preparation method of the transparent ceramic is characterized in that in the fourth step, the transparent ceramic is sievedDuring treatment, the mixture is sieved by a 140-mesh sieve for 3 times.
6. Y is the high-transmittance Dy according to claim 52O3The preparation method of the transparent ceramic is characterized in that in the third step, a muffle furnace is adopted for calcining the powder.
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