CN103833348A - Self-stimulated emission absorbing material and preparation method thereof - Google Patents
Self-stimulated emission absorbing material and preparation method thereof Download PDFInfo
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- CN103833348A CN103833348A CN201310753337.5A CN201310753337A CN103833348A CN 103833348 A CN103833348 A CN 103833348A CN 201310753337 A CN201310753337 A CN 201310753337A CN 103833348 A CN103833348 A CN 103833348A
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- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 70
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- 238000000034 method Methods 0.000 claims abstract description 29
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- 238000001816 cooling Methods 0.000 claims description 16
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
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- DZGUJOWBVDZNNF-UHFFFAOYSA-N azanium;2-methylprop-2-enoate Chemical compound [NH4+].CC(=C)C([O-])=O DZGUJOWBVDZNNF-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention discloses a self-stimulated emission absorbing material, which belongs to the field of laser materials. The chemical formula of the self-stimulated emission absorbing material is Y3-x-y-zSmxScyLuzAl5O12, wherein x is more than 0 and no more than 0.215, y is no less than 0.03 and no more than 0.3, and z is no less than 0.03 and no more than 0.9. According to the invention, Sc<3+> and Lu<3+> ions with radii smaller than the radius of a Y<3+> ion are used to substitute a part of Y<3+> ions in Sm: YAG, so a novel Sm: YLSAG material is formed; the absorption peak of the novel Sm: YLSAG material at about 1068 nm blueshifts to 1065.8 nm, so the novel Sm: YLSAG material has a great absorption coefficient at a wave length of 1064 nm. Moreover, the invention further provides a preparation method for the self-stimulated emission absorbing material. The preparation method comprises the following steps: adding a rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu into an alcohol-water mixed suspension containing Al2O3 powder, a precipitating agent and a static stabilizing agent drop by drop; carrying out a chemical co-precipitation reaction so as to obtain a precipitate; and subjecting the precipitate to solid-phase reaction sintering so as to prepare the Sm: YLSAG material. According to the invention, chemical co-precipitation and solid-phase reaction sintering are combined together, and the method is simple and easily controllable, has good repeatability and stability and is applicable to large-scale industrial production.
Description
Technical Field
The invention relates to the field of laser materials, in particular to a self-excitation radiation absorbing material and a preparation method thereof.
Background
A solid laser doped with Nd-doped Yttrium aluminum Garnet (Nd: YAG) is a laser using Nd: YAG crystal (or ceramic) as working medium, and has many technical advantages of high conversion efficiency, high output power, good beam quality, compact structure, light weight and the like, and is widely applied to the fields of national defense, industrial processing, communication, medical treatment and the like. However, under the condition of high-power laser operation, 1064nm stray fluorescence generated by Self-excitation radiation in the Nd: YAG crystal generates Self-excitation radiation oscillation to form a Self-excitation radiation Amplification (ASE) effect, and the ASE effect of the fluorescence not only seriously reduces the laser conversion efficiency, but also destroys the beam quality of laser output by the solid laser. Therefore, it is necessary to suppress the ASE effect of the Nd: YAG solid laser.
At present, samarium-doped yttrium aluminum garnet (Sm: YAG) single crystal or transparent ceramic capable of absorbing 1064nm light is generally compounded on the periphery or side edge of an Nd: YAG working medium, and because the lattice structures of the Sm: YAG single crystal and the Sm: YAG transparent ceramic are high in matching performance with the lattice structure of the Nd: YAG, the Sm: YAG single crystal and the Sm: YAG transparent ceramic can be organically combined into a whole through a thermal diffusion bonding technology. When the Nd and YAG are in a laser operation state, the Sm and YAG single crystal or Sm and YAG transparent ceramic material compounded around or on the side of the Nd and YAG working medium can absorb 1064nm stray fluorescence generated by self-excitation radiation in the Nd and YAG working medium, so that the self-excitation radiation oscillation amplification can not be generated, and the purpose of inhibiting the ASE effect is achieved.
In the process of implementing the invention, the inventor finds that the prior art has at least the following problems:
the absorption peak of the Sm: YAG single crystal and the Sm: YAG transparent ceramic closest to the wavelength of 1064nm has a peak-valley value about 1068nm, and the matching property with the 1064nm stray fluorescence peak of Nd: YAG is poor, so that the Sm: YAG single crystal and the Sm: YAG transparent ceramic have small absorption coefficients at the wavelength of 1064 nm.
Disclosure of Invention
In order to solve the problem that in the prior art, the Sm: YAG single crystal and Sm: YAG transparent ceramic have small absorption coefficients at the wavelength of 1064nm, the embodiment of the invention provides a self-excitation radiation absorbing material and a preparation method thereof. The technical scheme is as follows:
in one aspect, an embodiment of the present invention provides a self-excitation radiation absorbing material, where the self-excitation radiation absorbing material has a chemical formula: y is3-x-y-zSmxScyLuzAl5O12Wherein x is more than 0 and less than or equal to 0.215, y is more than or equal to 0.03 and less than or equal to 0.3, and z is more than or equal to 0.03 and less than or equal to 0.9.
Specifically, preferably, the self-excitation radiation absorbing material is a transparent ceramic.
In another aspect, an embodiment of the present invention further provides a method for preparing a self-excitation radiation absorbing material, where the method includes:
step 1: preparing rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu, and Al2O3The alcohol-water mixed suspension of the powder, the precipitator and the electrostatic stabilizer is prepared according to the chemical formula: y is3-x-y-zSmxScyLuzAl5O12(x is more than 0 and less than or equal to 0.215, Y is more than or equal to 0.03 and less than or equal to 0.3, and z is more than or equal to 0.03 and less than or equal to 0.9) to determine the mass of the elements Y, Sm, Sc and Lu and the mass of Al in the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu2O3The mass of (c);
step 2: dropwise adding the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu into the solution containing Al2O3In the alcohol-water mixed suspension of the powder, the precipitator and the electrostatic stabilizer, and adjusting the pH value of the reaction system to 7.0-8.5;
and step 3: after titration, aging and separating the reaction system to obtain a precipitate, and washing, drying, grinding and calcining the precipitate to obtain nano-scale powder;
and 4, step 4: forming a mixed system by the nano-scale powder, grinding balls, sintering aids, a dispersing agent and absolute ethyl alcohol, and carrying out ball milling on the mixed system to obtain slurry;
and 5: and drying the slurry to obtain dry powder, and performing compression molding, roasting, vacuum sintering and annealing treatment on the dry powder to obtain the self-excitation radiation absorbing material.
Specifically, in the step 1, preferably, the preparing the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu is specifically:
mixing high-purity Y2O3、Sm2O3、Sc2O3And Lu2O3Dissolving the powder in concentrated nitric acid to obtain a rare earth nitrate solution containing Y, Sm, Sc and Lu;
adding deionized water to the rare earth nitrate solution containing Y, Sm, Sc and Lu with the molar concentration of 0.1 mol.L-1-1.0mol·L-1。
Specifically, preferably, in step 1: the mass ratio of the precipitant to the rare earth inorganic acid salt is 5:1-16: 1;
the mass ratio of the static stabilizer to the rare earth inorganic acid salt is 1:2-2: 1;
the precipitating agent is in the Al-containing state2O3Mixing powder, precipitator and electrostatic stabilizer with alcohol and waterThe molar concentration in the suspension was 0.2 mol. L-1-2.0mol·L-1；
The volume ratio of water to alcohol in the alcohol-water mixed suspension is 1:1-1: 0.
Specifically, preferably, the precipitant is selected from at least one of bicarbonate, carbonate, and oxalate;
the static stabilizer is at least one of sulfate and bisulfate.
Specifically, preferably, the precipitant is ammonium bicarbonate; the static stabilizer is ammonium sulfate.
Specifically, in the step 3, the temperature of the calcination is preferably 1000 ℃ to 1350 ℃.
Specifically, preferably, in the step 4, the grinding balls are selected from Al2O3Balls, agate balls, silicon nitride balls, ZrO2At least one of balls, wherein the mass ratio of the grinding ball to the nano powder is 1:1-5: 1;
the sintering aid is selected from at least one of ethyl orthosilicate, silicon dioxide, methyl orthosilicate, magnesium oxide, calcium oxide and lithium fluoride, and the mass of the sintering aid is 0.05-1.5% of that of the nano-scale powder;
the dispersing agent is selected from at least one of polyacrylic acid, polyethylene glycol, poly (ammonium methacrylate) and oleic acid, and the mass of the dispersing agent is 0.1-3% of that of the nano-scale powder;
the mass ratio of the absolute ethyl alcohol to the nano-scale powder is 1:2-8: 1.
Specifically, as a preferable mode, the step 5 specifically includes: drying and grinding the slurry in an oven at the temperature of more than 75 ℃, and sieving the ground slurry by a sieve with more than 100 meshes; or drying the slurry by spray drying, controlling the inlet temperature at 90-200 ℃ and the spraying speed at 1-20ml/min during the spray drying to obtain dried powder,
putting the dried powder into a die, pre-pressing into a ceramic blank by using the pressure higher than 5MPa, further pressing and molding by using a cold isostatic press under the pressure higher than 200MPa,
the ceramic blank formed by pressing is roasted for more than 2 hours at the temperature of 800-1100 ℃ in the atmosphere of atmosphere or flowing oxygen,
placing the baked ceramic body in a high-temperature vacuum furnace, sintering for 4-20h at 1700-1850 ℃ in vacuum, controlling the heating and cooling rate to be 1-10 ℃/min,
annealing the ceramic blank after vacuum sintering at 1200-1450 deg.c in atmosphere or oxygen atmosphere for over 10 hr to obtain ceramic,
and cooling to room temperature, taking out the ceramic, and polishing the surface of the ceramic to obtain the self-excitation radiation absorbing material.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
in one aspect, an embodiment of the present invention provides a self-excitation radiation absorbing material, which has a chemical formula: y is3-x-y-zSmxScyLuzAl5O12Wherein x is more than 0 and less than or equal to 0.215, y is more than or equal to 0.03 and less than or equal to 0.3, and z is more than or equal to 0.03 and less than or equal to 0.9. By ion radius ratio Y3+Sc having a small ionic radius3+Ions and Lu3+Ionic substitution of part Y in Sm: YAG lattice3+Ions form a novel samarium-yttrium-lutetium scandium aluminum garnet (Sm: YLAG) material with smaller lattice constant than Sm: YAG. The absorption peak-to-valley value of Sm: YLAG at about 1068nm was bluish to about 1065.8nm, as compared with Sm: YAG. Therefore, the absorption peak of Sm: YLAG is better matched with the stray fluorescence peak of Nd: YAG working medium, so that the absorption coefficient of Sm: YLAG at the wavelength of 1064nm is larger. In addition, the self-excitation radiation absorbing material provided by the embodiment of the invention comprises: the lattice structure of Sm: YLAG has good matching property with that of Nd: YAG, and thermal diffusion bonding technology can be usedAnd is organically combined with the Nd: YAG crystal to restrain the self-excitation radiation of the Nd: YAG.
On the other hand, the embodiment of the invention also provides a preparation method of the self-excitation radiation absorbing material, which is characterized in that the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu is dropwise added into the Al-containing rare earth inorganic acid salt solution2O3And carrying out chemical coprecipitation reaction on the powder, the precipitator and the electrostatic stabilizer in an alcohol-water mixed solution. Thereby improving the ion reaction activity in the reaction system, being beneficial to the separation and crystallization of rare earth ions and overcoming the problem of chemical solubility product (K) of the rare earth ion precipitate and the aluminum ion precipitateSPValue) are greatly different from each other, and thus the Sm: YLAG is liable to deviate from the garnet stoichiometric ratio. The Sm: YLAG material capable of inhibiting Nd: YAG self-excitation radiation is prepared by carrying out solid phase reaction sintering treatment on the precipitate prepared by chemical coprecipitation, raw materials can be mixed more uniformly, and Sm: YLAG powder with garnet phase and high sintering activity is directly prepared, so that Sm: YLAG transparent ceramics with high Sm ion doping concentration and high transparency can be relatively easily prepared. Therefore, the embodiment of the invention combines chemical coprecipitation and solid-phase reaction sintering, has simple process, easy control and good repeatability and stability, and is suitable for large-scale industrial production.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a self-excitation radiation absorbing material according to an embodiment of the present invention;
FIG. 2 is a transmission spectrum of Sm: YAG crystal, Sm: YAG ceramic and Sm: YLAG transparent ceramic according to still another embodiment of the present invention.
Wherein the wavelength of lambda (in nm),
t transmittance (unit%),
1 represents a transmission spectrum chart of Sm: YLAG transparent ceramics,
2 represents a transmission spectrum of Sm: YAG crystal,
3 represents a transmission spectrum of Sm: YAG ceramic.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The transmittance of the crystal and the ceramic body is measured by a JB/T9495.3-1999 optical crystal transmittance measuring method, and the absorption coefficient of the crystal or the ceramic body at a specific wavelength is determined according to the measured transmittance.
Example 1
The embodiment of the invention provides a self-excitation radiation absorbing material, which has a chemical formula as follows: y is3-x-y-zSmxScyLuzAl5O12Wherein x is more than 0 and less than or equal to 0.215, y is more than or equal to 0.03 and less than or equal to 0.3, and z is more than or equal to 0.03 and less than or equal to 0.9.
The self-excited radiation absorbing material provided by the embodiment of the invention is prepared by the ion radius ratio Y3+Sc having a small ionic radius3+Ions and Lu3+Ionic substitution of part Y in Sm: YAG lattice3+Ions form a novel samarium-yttrium-lutetium scandium aluminum garnet (Sm: YLAG) material with smaller lattice constant than Sm: YAG. The absorption peak at about 1068nm of Sm: YLAG blueshifted to about 1065.8nm compared to Sm: YAG. Therefore, the absorption peak of Sm: YLAG and Nd: YAG (YLSAG)Neodymium-doped yttrium aluminum Garnet) working medium has better stray fluorescence peak matching performance, so that the absorption coefficient of Sm: YLAG at the wavelength of 1064nm is larger. In addition, the self-excitation radiation absorbing material provided by the embodiment of the invention comprises: the lattice structure of Sm: YLAG is well matched with that of Nd: YAG, and Sm: YLAG can be organically combined with Nd: YAG crystal into a whole by thermal diffusion bonding technology.
The self-excitation radiation absorbing material expected by the embodiment of the invention not only needs to perform edge covering on the periphery or the side edge of the Nd: YAG crystal and can perform good thermal diffusion bonding with the Nd: YAG crystal, but also has the function of absorbing 1064nm stray fluorescence generated by the Nd: YAG crystal, so as to achieve the purpose of inhibiting Nd: YAG self-excitation radiation.
In the design and manufacturing process of practical high-power Nd: YAG solid laser, the allowable Nd: YAG crystal size is limited, and the thinner the 1064nm fluorescent self-excitation radiation absorbing material thermally bonded at the side edge or around the Nd: YAG crystal is, the better the material is, and the material is generally expected to be not more than 2 mm. So as not to increase the size of the Nd: YAG crystal. If the thickness of the self-excitation radiation absorbing material compounded on the working medium of Nd: YAG at a wavelength of 1064nm is too thick, the area or volume of the composite crystal (i.e., Nd: YAG with the self-excitation radiation absorbing material wrapped) is increased, which causes great difficulty in packaging and welding of the composite crystal element in the back-end application process. Meanwhile, in order to absorb 1064nm stray fluorescence generated in the Nd-YAG working medium in the working process and completely inhibit the ASE effect, the self-excitation radiation absorbing material at least needs to be compounded on the side edge and can absorb at least 90% of the stray self-excitation radiation fluorescence in the Nd-YAG working medium.
Taking the example of the Sm: YAG crystal, although the Sm: YAG crystal has absorption at the 1064nm wavelength, the absorption peak valley value of the Sm: YAG crystal near the 1064nm is deviated from 1064nm and is positioned at about 1068nm, so that the absorption coefficient of the Sm: YAG crystal at the 1064nm wavelength is small, and according to the Lambert-beer law (the concentration of doping ions in the crystal is in a linear relation with the absorption coefficient), the crystal must completely absorb spontaneous emission fluorescence of the Nd: YAG crystal within the thinnest possible thicknessIt must have an ultra-high doping concentration. The absorption coefficient of the YAG crystal at a wavelength of 1064nm and the minimum thickness required to achieve 90% absorption at 1064nm are listed in Table 1 for the different doping concentrations Sm. As can be seen from the data in the table, in order to achieve a fluorescence absorption of 90% by self-excitation radiation of the Nd: YAG crystal within a thickness of 2mm, at least an Sm: YAG single crystal or an Sm: YAG ceramic having a concentration of 11.7at% needs to be prepared. However, Sm is responsible for3+Ionic radius and Y3+Sm with large ionic radius difference and high concentration3+Ion incorporation into YAG crystals causes severe lattice distortion, generates severe stress, causes crystal cracking or generates impurity phases, and thus it is difficult to obtain the desired Sm: YAG material at such a high concentration, whether by single crystal growth techniques or transparent ceramic preparation techniques.
TABLE 1 absorption coefficient at 1064nm wavelength for different concentrations of Sm: YAG and the minimum thickness of Sm: YAG required to achieve 90% absorption at 1064nm light
Wherein,*the numerical value is calculated according to the Labby beer's law.
Based on the above principle, the self-excitation radiation absorbing material provided by the embodiment of the invention replaces Y ions on part of the host lattice by introducing ions with smaller ionic radius and without destroying the optical and spectral properties of the raw material into Sm: YAG crystal (or ceramic), so that the lattice constant of the host material is properly reduced. After the lattice constant is reduced, the influence of the crystal coordination field on the energy level structure of the rare earth ions is strengthened, so that the energy level is further split or the energy level spacing is enlarged. Thus, the absorption spectrum of the Sm: YAG crystal (or ceramic) can be suitably blue-shifted to bring the Sm: YAG crystal (or ceramic) to an absorption peak at a wavelength of 1068nm and blue-shifted to a wavelength closer to 1064nm, so that the Sm: YAG crystal (or ceramic) can have a larger absorption coefficient at a wavelength of 1064nm even at a lower doping concentration.
YAG (yttrium aluminum garnet) crystals are typically of the garnet structure and belong to the cubic system, where Y is3+The ions are in a dodecahedral lattice, in the Sm: YAG crystal, Sm3+Ion substitution of a portion of Y in the host lattice3+Ions, also in the dodecahedral lattice site. The inventor finds in the research process that for YAG crystal matrix, a proper amount of trivalent rare earth ions are adopted to substitute part of Y in dodecahedral lattice3+Ions, which do not cause structural damage, maintain the complete garnet structure, and the smaller the radius of the trivalent rare earth ions, the larger the allowable substitution amount. Therefore, the embodiment of the present invention uses the ion radius ratio Y3+Substituting part of Y on Sm-YAG crystal lattice by trivalent rare earth ions with small ionic radius3+Ions are added to reduce the lattice constant of Sm to YAG and to blue shift the absorption spectrum. The inventor researches and discovers that the ion radius ratio Y is3+Lu is used for doping a YAG matrix, and does not cause spectral characteristic change3+Ions and Sc3+Ions. Therefore, the embodiment of the invention introduces Lu with proper content into the Sm: YAG matrix3+Ions and Sc3+And ions are used for preparing Sm: YLAG crystal (or ceramic), so that the lattice constant of YAG is reduced, the absorption peak valley value of the original Sm: YAG matrix at 1068nm is blue-shifted to about 1065.8nm, the absorption peak valley value is more matched with the spontaneous emission fluorescence peak (1064 nm) of Nd: YAG crystal, and the Sm: YLAG has larger absorption coefficient at the wavelength of 1064 nm.
In summary, the self-excited radiation absorbing material provided by the invention has the following advantages: (1) the material has a large absorption coefficient at the wavelength of 1064nm, and can completely absorb stray fluorescence generated in Nd: YAG working medium in the thinnest possible thickness; (2) the lattice structure is similar to that of Nd, YAG working medium, and is more beneficial to the thermal diffusion bonding between the Nd and the YAG working medium, so that the Nd and the YAG working medium are organically combined into a whole; (3) the Nd-YAG working medium has good heat-conducting property and is beneficial to heat dissipation of the Nd-YAG working medium; (4) the material has no absorption to 808nm pump light in Nd-YAG working medium, has no loss when passing the pump light, and is suitable for being used as a wrapping self-excitation radiation absorption material of Nd-YAG crystal in Nd-YAG lasers of various pumping modes (side pump, end pump and the like). Therefore, the self-excitation radiation absorbing material with the wavelength of 1064nm provided by the embodiment of the invention has important significance for preparing the Nd-YAG composite working medium with the self-excitation radiation absorbing material wrapped outside, inhibiting the ASE effect of the high-power Nd-YAG solid laser and improving the beam quality and the conversion efficiency of the high-power Nd-YAG solid laser.
Preferably, the self-exciting radiation absorbing material is a transparent ceramic.
The self-excitation radiation absorbing material provided by the embodiment of the invention is preferably a transparent ceramic material, and compared with a single crystal, the transparent ceramic material retains all excellent characteristics of the single crystal material. Meanwhile, the transparent ceramic material is prepared by solid-phase reaction sintering, the whole crystal is composed of tiny crystal grains, and the crystal grain boundary buffering effect exists between the crystal grains, so that higher Sm is allowed3+Ion doping concentration, therefore, Lu is used in the examples of the present invention3+Ions and Sc3+Ionically substituted moiety Y3+The ionic Sm: YLAG is prepared into a transparent ceramic form, and can realize higher Sm3+The ion doping concentration can obtain larger 1064nm absorption coefficient. In addition, in the embodiment of the invention, the preparation period of the Sm: YLAG transparent ceramic is short, and the preparation process does not need to use expensive noble metal Ir, so that the production cost is obviously reduced.
Example 2
The embodiment of the invention provides a preparation method of a self-excitation radiation absorbing material, which comprises the following steps:
step 1: preparing rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu, and Al2O3An alcohol-water mixed solution of powder, a precipitator and an electrostatic stabilizer, according to the chemical formula: y is3-x-y-zSmxScyLuzAl5O12（0＜x≤0.215、0.03≤y≤0.3、0.03≤z≤0.9）The ratio of the atomic numbers of Y, Sm, Sc, Lu and Al in the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu is determined to determine the mass of Y, Sm, Sc and Lu elements and Al in the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu2O3The mass of (c);
step 2: dropwise adding the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu into the solution containing Al2O3In the alcohol-water mixed suspension of the powder, the precipitator and the electrostatic stabilizer, and adjusting the pH value of the reaction system to 7.0-8.5;
and step 3: after titration, aging and separating the reaction system to obtain a precipitate, and washing, drying, grinding and calcining the precipitate to obtain nano-scale powder;
and 4, step 4: forming a mixed system by the nano-scale powder, grinding balls, sintering aids, a dispersing agent and absolute ethyl alcohol, and carrying out ball milling on the mixed system to obtain slurry;
and 5: and drying the slurry to obtain dry powder, and performing compression molding, roasting, vacuum sintering and annealing treatment on the dry powder to obtain the self-excitation radiation absorbing material.
Specifically, in step 1: the preparation of the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu comprises the following steps: mixing high-purity Y2O3、Sm2O3、Sc2O3And Lu2O3Dissolving the powder in concentrated nitric acid to obtain a rare earth nitrate solution containing Y, Sm, Sc and Lu;
adding deionized water to the rare earth nitrate solution containing Y, Sm, Sc and Lu with the molar concentration of 0.1 mol.L-1-1.0mol·L-1。
In the process, the rare earth oxides react with concentrated nitric acid to obtain the rare earth nitrate. Wherein, the concentrated nitric acid is analytically pure or superior to analytically pure so as to avoid introducing impurities into the reaction system.
Optionally, the rare earth inorganic acid salt solution can also be a high-purity rare earth chloride salt or a high-purity sulfate salt solution.
Specifically, the mass ratio of the precipitant to the rare earth inorganic acid salt is 5:1-16:1,
the mass ratio of the static stabilizer to the rare earth inorganic acid salt is 1:2-2:1,
the precipitating agent is in the Al-containing state2O3The molar concentration of the alcohol-water mixed suspension of the powder, the precipitant and the electrostatic stabilizer is 0.2 mol.L-1-2.0mol·L-1，
The volume ratio of water to alcohol in the alcohol-water mixed suspension is 1:0-1: 1.
The precipitating agent is selected from at least one of bicarbonate, carbonate and oxalate, and the electrostatic stabilizer is selected from at least one of sulfate and bisulfate.
Preferably, the precipitant is ammonium bicarbonate, and the electrostatic stabilizer is ammonium sulfate.
In the examples of the present invention, Al is contained2O3The alcohol-water mixed suspension of the powder, the precipitator and the electrostatic stabilizer is specifically as follows: mixing Al2O3The powder and a proper amount of ammonium bicarbonate are prepared into ammonium bicarbonate with the molar concentration of 0.2 mol.L-1-2.0mol·L-1The volume ratio of the deionized water to the ethanol is between 1:0 and 1:1, the purity of the ammonium bicarbonate is better than 99 percent, and the mass ratio of the ammonium bicarbonate to the total mass ratio of the rare earth nitrate is between 5:1 and 16: 1. Then adding a proper amount of ammonium sulfate with the purity of more than 99 percent as a charge stabilizer into the mixed suspension, wherein the ratio of the mass of the ammonium sulfate to the total mass of the rare earth ions is 1:2 to 2: 1. The resulting suspension was then continuously stirred.
In the embodiment of the invention, according to the chemical formula: y is3-x-y-zSmxScyLuzAl5O12(x is more than 0 and less than or equal to 0.215, Y is more than or equal to 0.03 and less than or equal to 0.3, and z is more than or equal to 0.03 and less than or equal to 0.9) in the atoms of Y, Sm, Sc, Lu and AlThe ratio of the numbers to determine high purity Y2O3、Sm2O3、Sc2O3And Lu2O3Powder and Al2O3Mass of the powder. Then from a determined mass of high purity Y2O3、Sm2O3、Sc2O3And Lu2O3Powder and Al2O3The powder is prepared into the rare earth nitrate solution containing Y, Sm, Sc and Lu and the rare earth nitrate solution containing Al according to the specific preparation method2O3Alcohol-water mixed suspension of powder, precipitator and electrostatic stabilizer.
And dropwise adding the prepared rare earth nitrate solution into the ammonium bicarbonate mixed suspension for reaction to obtain precursor precipitates of carbonates of Y, Sm, Sc and Lu and mixed precipitates of ammonium aluminum carbonate precipitates and aluminum hydroxide precipitates.
In the titration process, the dropping speed is controlled to be 3ml/min-10ml/min, and simultaneously, the mixed suspension of the alumina powder and the ammonium bicarbonate is kept in a ceaseless stirring state, so that the generation of precipitates is favorably controlled, and the agglomeration of precipitated particles is prevented. In addition, a pH meter is utilized to monitor the pH value of the ammonium bicarbonate mixed solution, and concentrated nitric acid or concentrated ammonia water is used for adjusting the pH value of the mixed solution to be 7.0-8.5 so as to keep the reaction system in a stable pH value environment and facilitate the reaction.
And after the titration reaction is finished, aging the mixed suspension for a period of time. The aging temperature is controlled to be 20-60 ℃, and the aging time is 12-48 hours, so that the impurities occluded in the precipitate are removed, and the precipitate crystal growth is more uniform.
After the aging is finished, separating the precipitate, and purifying and washing the precipitate. The purification washing process can adopt a centrifugal and/or suction filtration mode. Washing with deionized water and/or absolute ethanol at least once to reduce impurities remaining in the precipitate as much as possible. For example, the precipitate can be washed clean with deionized water and then washed several times with absolute ethanol.
Drying the washed precipitate at a temperature above 75 deg.C
Grinding and calcining the dried precipitate to obtain the nano-grade high-purity Sm: YLAG powder.
Preferably, the calcination temperature is from 1000 ℃ to 1350 ℃.
And performing ball milling, drying, press forming, roasting, vacuum sintering and annealing treatment on the high-purity Sm/YLAG powder obtained by calcining to prepare the Sm/YLAG transparent ceramic. Wherein the grinding ball is selected from Al2O3Balls, agate balls, silicon nitride balls, ZrO2At least one of balls, wherein the mass ratio of the grinding ball to the nano powder is 1:1-5: 1; the sintering aid is selected from at least one of ethyl orthosilicate, silicon dioxide, methyl orthosilicate, magnesium oxide, calcium oxide and lithium fluoride, and the mass of the sintering aid is 0.05-1.5% of that of the nano-scale powder; the dispersing agent is selected from at least one of polyacrylic acid, polyethylene glycol, poly (ammonium methacrylate) and oleic acid, and the mass of the dispersing agent is 0.1-3% of that of the nano-scale powder; the mass ratio of the absolute ethyl alcohol to the nano-scale powder is 1:2-8: 1.
The step 5 specifically comprises the following steps: drying and grinding the slurry in an oven at the temperature of more than 75 ℃, and sieving the ground slurry by a sieve with more than 100 meshes; or drying the slurry by spray drying, controlling the inlet temperature at 90-200 ℃ and the spraying speed at 1-20ml/min during the spray drying to obtain dried powder,
and putting the dried powder into a die, prepressing the powder into a ceramic biscuit by using the pressure higher than 5MPa, and further pressing and molding the ceramic biscuit by using a cold isostatic press under the pressure higher than 200 MPa. The ceramic blank formed by pressing is roasted for more than 2 hours at the temperature of 800-1100 ℃ in the atmosphere of atmosphere or flowing oxygen. And placing the baked ceramic body in a high-temperature vacuum furnace, and sintering for 4-20h at 1700-1850 ℃ in vacuum, wherein the heating and cooling rate is controlled to be 1-10 ℃/min. And annealing the ceramic biscuit after vacuum sintering at the temperature of 1200-1450 ℃ for more than 10h in the atmosphere of air or oxygen to obtain the ceramic. And cooling to room temperature, taking out the ceramic, and polishing the surface of the ceramic to obtain the self-excitation radiation absorbing material, namely the Sm: YLAG transparent ceramic capable of inhibiting Nd: YAG self-excitation radiation is prepared.
Therefore, the preparation method of the self-excitation radiation absorbing material provided by the embodiment of the invention is to dropwise add the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu into the Al-containing rare earth inorganic acid salt solution2O3And carrying out chemical coprecipitation reaction in alcohol-water mixed suspension of the powder, the precipitator and the electrostatic stabilizer. Not only improves the ion reaction activity of the reaction system, but also is beneficial to the separation and crystallization of rare earth ions, and overcomes the problem that the traditional chemical coprecipitation method is formed by the chemical solubility product (K) of rare earth ion precipitate and aluminum ion precipitateSPValue) are greatly different, resulting in the problem that the prepared Sm: YLAG is liable to deviate from its stoichiometric ratio. The Sm: YLAG powder which has garnet phase and high sintering activity can be directly prepared, thereby being capable of relatively easily obtaining high transparency. The chemical coprecipitation and solid phase reaction sintering are combined, the process is simple and easy to control, and the method has good repeatability and stability and is suitable for large-scale industrial production.
Example 3
According to the formula Y2.1Sm0.15Sc0.15Lu0.6Al5O12The following oxide raw material masses required for producing 40g of Sm: YLAG ceramic powder were calculated, and Y having a purity of 99.99% was weighed by a balance2O314.6384g powder of Lu with purity of 99.99%2O37.3704g of powder, Sc with a purity of 99.99%2O30.6386g of powder Sm with the purity of 99.99 percent2O31.6151g of powder, 99.99% pure Al2O315.7375g of powder. Will Y2O3、Lu2O3、Sc2O3And Sm2O3Mixing the powders, dissolving in concentrated nitric acid, and preparing with deionized water to obtain rare earth ions with total molar concentration of 0.5 mol.L-1And (3) a rare earth nitrate mixed solution.
147.19g of ammonium bicarbonate with purity better than 99.9 percent are weighed, and the ammonium bicarbonate and the weighed Al are added2O3Dissolving the powder into a mixed solution of deionized water and absolute ethyl alcohol according to the volume ratio of 1:1 to form ammonium bicarbonate with the concentration of 0.2 mol.L-1Al of (2)2O3Mixing the powder and ammonium bicarbonate to obtain alcohol-water suspension, adding ammonium sulfate (NH) with purity of 99%4)2SO4) (the molar ratio of ammonium sulfate to rare earth nitrate is 1: 1) as a dispersant to obtain the Al-containing alloy2O3Powder, NH4HCO3、(NH4)2SO4The mixed suspension of (3).
Stirring the mixed suspension evenly, and dropwise adding the prepared rare earth nitrate solution into the Al-containing solution at the speed of 5ml/min2O3Powder, NH4HCO3、(NH4)2SO4The mixed suspension of (3). And continuously stirring the mixed suspension by using a stirrer, monitoring the pH value of the mixed solution by using an acidimeter, and adjusting the pH value of the solution to be between 7.0 and 7.5 by using ammonia water and nitric acid. After titration, the solution was allowed to stand and aged for 24 h. Then, the precipitate was filtered off, and washed with deionized water to 0.1 mol. L-1BaCl of2The solution was checked until no precipitate was formed in the filtrate, and the filtrate was washed with absolute ethanol 3 times. Then placed in an oven and dried at a temperature of 75 ℃ for 12 h. Taking out, grinding, sieving with 100 mesh sieve (150 μm), and calcining in muffle furnace at 1100 deg.C for 8 hr to obtain Sm: YLAG nanometer powder.
Putting the prepared Sm: YLAG nano-grade powder into a ball milling tank, adding 80g of absolute ethyl alcohol and 160g of alumina balls with the diameter of phi 5mm as ball milling media, and adding the alumina balls equivalent to oxidationTEOS 0.5% and MgO 0.1% of the total weight of the powder are used as sintering aids, and polyacrylic acid 0.1% of the total weight of the oxide powder is added as a dispersant. And performing ball milling and mixing for 24 hours at the rotating speed of 350rpm to obtain slurry. The slurry was spray dried. The inlet temperature was 160 deg.C, the outlet temperature was 100 deg.C, and the spray rate was 10 ml/min. 12g of the spray-dried powder was weighed each time, put into a steel die, and pressed into a wafer having a diameter of 40mm under a pressure of 10 MPa. And (3) packaging the wafer by using a latex bag, and keeping the pressure for 2min by using a cold isostatic press under 300 MPa. After being taken out, the formed green body is roasted for 12 hours in a muffle furnace at the temperature of 800 ℃ so as to remove residual organic matters. Then placing the blank in a vacuum furnace, starting a vacuum system, and vacuumizing to 1 × 10-3And after Pa, heating to 1780 ℃ at the heating rate of 3-5 ℃/min, preserving the heat for 20 hours, and then cooling to room temperature at the rate of 10 ℃/min to obtain the Sm: YLAG ceramic sample.
And putting the vacuum sintered Sm: YLAG ceramic sample into an atmosphere high-temperature furnace, raising the temperature to 1400 ℃ at the temperature rise rate of 5 ℃/min, annealing for 10 hours in the atmosphere, reducing the temperature to room temperature at the temperature drop rate of 5 ℃/min, and polishing to obtain the Sm: YLAG transparent ceramic. The Sm: YLAG transparent ceramic was subjected to a transmittance test to obtain a transmittance of 81.9% at 808nm, a closest absorption peak at a wavelength of 1064nm at 1065.8nm, and an absorption coefficient at 1064nm of 5.3cm-1(as shown in figure 2).
Under the same operating parameters as those required for example 3, preparation of a compound of formula Y2.85Sm0.15Al5O12Sm: YAG transparent ceramic and growing the chemical formula of Y2.91Sm0.09Al5O12And the transmittance of the Sm: YAG crystal is tested, and the Sm: YAG crystal is shown in the attached figure 2: the absorption peak of the Sm: YAG crystal at the wavelength closest to 1064nm is at 1068nm, and the absorption coefficient at 1064nm is 1.49cm-1. The absorption peak of the Sm: YAG transparent ceramic at the wavelength of 1064nm is positioned at 1068nm, and the absorption coefficient at 1064nm is 2.5cm-1。
On one hand, compared with Sm: YAG crystal and Sm: YAG transparent ceramic, the Sm: YLAG transparent ceramic provided by the embodiment of the invention has higher absorption coefficient at 1064nm, has higher capability of absorbing 1064nm stray fluorescence generated by Nd: YAG working medium, basically does not absorb pump light at 808nm, and is favorable for being used as ASE effect inhibiting material of Nd: YAG solid laser.
Example 4
According to the formula Y1.855Sm0.215Sc0.03Lu0.9Al5O12The mass of each oxide raw material required for preparing 40g of Sm: YLAG ceramic powder was calculated from the atomic number ratio of the medium elements, and Y having a purity of 99.99% was weighed on a balance2O312.2663g powder of Lu with purity of 99.99%2O310.4876g of powder, Sc with a purity of 99.99%2O30.1212g of powder Sm with a purity of 99.99%2O32.1960g of powder, 99.99% pure Al2O314.9290g of powder. Will Y2O3、Lu2O3、Sc2O3And Sm2O3The powder is evenly mixed and dissolved in concentrated hydrochloric acid of analytical purity, and deionized water is used for preparing the rare earth ions with the total molar concentration of 0.1 mol.L-1Mixed solution of rare earth chloride salt.
223.42g of ammonium bicarbonate with purity better than 99 percent is weighed, and the ammonium bicarbonate and the weighed Al are mixed2O3Dissolving the powder into a mixed solution consisting of deionized water and absolute ethyl alcohol according to the volume ratio of 1:0.5 to prepare the ammonium bicarbonate with the concentration of 0.4 mol.L-1Containing Al2O3Mixed alcohol-water suspension of powder and ammonium bicarbonate. To the mixed suspension was added ammonium bisulfate (NH) having a purity of 99.99%4HSO4) (controlling the mol ratio of ammonium bisulfate to rare earth chloride salt to be 2: 1) as a dispersant to obtain the Al-containing material2O3Powder, ammonium acetate, NH4HSO4The suspension is mixed.
After the mixed suspension is stirred evenly,dropwise adding the prepared rare earth chloride solution to Al at the speed of 10ml/min2O3Powder, NH4HCO3、NH4HSO4Mixing the suspension. In the process, the mixed suspension is continuously stirred by a stirrer, the pH value of the mixed solution is monitored by an acidimeter, and the pH value of the solution is adjusted to be between 7.5 and 8.0 by ammonia water or nitric acid. After titration, the reaction system solution is left to stand and aged for 24 hours. Then, the precipitate was filtered off, and washed with deionized water to 0.1 mol. L-1BaCl of2The solution was checked until no precipitate was formed in the filtrate, and the filtrate was washed with absolute ethanol 3 times. Then placed in an oven and dried at a temperature of 85 ℃ for 24 h. Taking out, grinding, sieving with 100 mesh sieve (150 μm), and calcining in muffle furnace at 1000 deg.C for 24 hr to obtain Sm: YLAG nanometer powder.
Putting the prepared Sm: YLAG nano-grade powder into a ball milling tank, adding 60g of absolute ethyl alcohol, 200g of agate balls with the diameter phi of 5mm as ball milling media, adding TEOS (tetraethyl orthosilicate) accounting for 0.5 percent of the total weight of the oxide powder and MgO accounting for 0.1 percent of the total weight of the oxide powder as sintering aids, and adding oleic acid accounting for 0.1 percent of the total weight of the oxide powder as a dispersing agent. And performing ball milling and mixing for 24 hours at the rotating speed of 300rpm to obtain slurry. Spray drying the slurry, wherein the inlet temperature is controlled to be 200 ℃, the outlet temperature is controlled to be 120 ℃ and the spraying speed is 10ml/min in the spray drying process. 12g of the spray-dried powder was weighed each time, put into a steel die, and pressed into a wafer having a diameter of 40mm under a pressure of 20 MPa. And (3) packaging the wafer by using a latex bag, and keeping the pressure for 5min by using a cold isostatic press under 200 MPa. And taking out, and roasting the formed blank in a muffle furnace at 1000 ℃ for 8h to remove residual organic matters. Then placing the blank in a vacuum furnace, starting a vacuum system, and vacuumizing to 1 × 10-3After Pa, the temperature is raised to 1780 ℃ at the heating rate of 3-5 ℃/min, and after 20 hours of heat preservation, the temperature is reduced to room temperature at the heating rate of 10 ℃/min, thus obtaining the Sm: YLAG ceramic sample.
And putting the vacuum sintered Sm: YLAG ceramic sample into an atmosphere high-temperature furnace, raising the temperature to 1400 ℃ at the temperature rise rate of 5 ℃/min, annealing for 10 hours in the atmosphere, reducing the temperature to room temperature at the temperature drop rate of 5 ℃/min, and polishing to obtain the Sm: YLAG transparent ceramic.
The Sm: YLAG transparent ceramic was subjected to a transmittance test to obtain a transmittance at 808nm of 79.5%, a nearest absorption peak at 1064nm of 1065.6nm, and an absorption coefficient at 1064nm of 8.6cm-1. It can be seen that the Sm: YLAG transparent ceramic provided by the embodiment of the invention has a higher absorption coefficient at 1064nm, namely, has a higher capability of absorbing 1064nm stray fluorescence generated by Nd: YAG working medium.
Example 5
According to the formula Y2.25Sm0.15Sc0.3Lu0.3Al5O12The mass of each oxide raw material required for preparing 40g of Sm: YLAG ceramic powder is calculated, and Y with the purity of 99.99 percent is weighed by a balance2O316.5099g powder of Lu with purity of 99.99%2O33.8793g of powder, Sc with a purity of 99.99%2O31.3444g of powder Sm with the purity of 99.99 percent2O31.7001g of powder, 99.99% pure Al2O316.5663g of powder.
Will Y2O3、Lu2O3、Sc2O3And Sm2O3Mixing the powders, dissolving in concentrated nitric acid, and preparing with deionized water to obtain rare earth ions with total molar concentration of 1.0 mol.L-1And (3) a rare earth nitrate mixed solution. Weighing 77.47g of ammonium oxalate with purity better than 99.99 percent, and weighing the ammonium oxalate and weighed Al2O3Dissolving the powder into a mixed solution of deionized water and absolute ethyl alcohol according to the volume ratio of 1:0.2 to prepare the ammonium oxalate with the concentration of 0.2 mol.L-1Containing Al2O3Powder and ammonium oxalate mixed alcohol-water suspension. To the mixed suspension was added ammonium sulfate ((NH) having a purity of 99.99%)4)2SO4) (the mol ratio of ammonium sulfate to rare earth nitrate is 2: 1) as a dispersant to obtain the Al-containing alloy2O3Powder, ammonium oxalate and (NH)4)2SO4The mixed suspension of (3).
Will contain Al2O3Powder, ammonium oxalate and (NH)4)2SO4After the mixed suspension is evenly stirred, the prepared rare earth nitrate solution is dropwise added into the Al-containing solution at the speed of 8ml/min2O3Powder, ammonium oxalate and (NH)4)2SO4The mixed suspension of (3). In the process, the mixed suspension is continuously stirred by a stirrer, the pH value of the mixed solution is monitored by an acidimeter, and the pH value of the solution is adjusted to 7.5-8.2 by ammonia water and/or nitric acid. After the titration is finished, the reaction system solution is aged for 48 hours. Then, it was filtered until precipitates were filtered off, and washed with deionized water to 0.1mol L-1BaCl of2The solution was checked until no precipitate was formed in the filtrate, and the filtrate was washed with absolute ethanol 3 times. Then placed in an oven and dried at a temperature of 80 ℃ for 24 h. Taking out the dried precipitate, grinding and sieving with a 100-mesh sieve (150 μm), and calcining in a muffle furnace at 1280 deg.C for 6h to obtain Sm: YLAG nanometer powder.
Putting the prepared Sm: YLAG nano-grade powder into a ball milling tank, adding 80g of absolute ethyl alcohol, 160g of silicon nitride balls with the diameter phi of 5mm as ball milling media, adding TEOS (tetraethyl orthosilicate) accounting for 0.5 percent of the total weight of the oxide powder and CaO accounting for 0.1 percent of the total weight of the oxide powder as sintering aids, and adding a mixture of oleic acid and polyethylene glycol accounting for 0.5 percent of the total weight of the oxide powder as a dispersing agent. And performing ball milling and mixing for 16h at the rotating speed of 400rpm to obtain slurry. The slurry was spray dried at an inlet temperature of 160 deg.C, an outlet temperature of 90 deg.C and a spray rate of 20ml/min during the spray drying process. 12g of spray-dried powder is weighed each time, put into a steel die and pressed into a wafer with phi of 40mm under the pressure of 5 MPa. And (3) packaging the wafer by using a latex bag, and keeping the pressure for 5min by using a cold isostatic press under 200 MPa. After being taken out, the formed green body is roasted for 24 hours in a muffle furnace at 850 ℃ to remove residual organic matters. Then placing the blank in a vacuum furnace, starting a vacuum system, and vacuumizing to 1 × 10-3After Pa, heating to 1740 ℃ at the heating rate of 3-5 ℃/min, preserving the heat for 16 hours, and then cooling to room temperature at the rate of 10 ℃/min to obtain the productTo Sm: YLAG ceramic samples.
Putting the vacuum sintered Sm: YLAG ceramic sample into an atmosphere high-temperature furnace, heating to 1320 ℃ at the heating rate of 5 ℃/min, annealing for 24 hours in the atmosphere, cooling to room temperature at the cooling rate of 5 ℃/min to obtain Sm: YLAG ceramic, and polishing by adopting the conventional polishing method to obtain Sm: YLAG transparent ceramic.
The Sm: YLAG transparent ceramic was subjected to a transmittance test to obtain a transmittance of 81.5% at 808nm, an absorption peak nearest to 1064nm at 1066.2nm, and an absorption coefficient at 1064nm of 4.6cm-1. Therefore, the Sm: YLAG transparent ceramic provided by the embodiment of the invention has a higher absorption coefficient at 1064nm, namely, has higher capability of absorbing 1064nm stray fluorescence generated by Nd: YAG working medium.
Example 6
According to the formula Y2.16Sm0.09Sc0.15Lu0.6Al5O12The raw material mass of each oxide required for preparing the YLAG ceramic powder is 40gSm, and the Y with the purity of 99.99 percent is weighed by a balance2O315.1429g powder of Lu with purity of 99.99%2O37.4126g of powder, Sc with a purity of 99.99%2O30.6422g of powder Sm with the purity of 99.99 percent2O30.9746g of powder, 99.99% pure Al2O315.8276g of powder. Will Y2O3、Lu2O3、Sc2O3And Sm2O3Mixing the powders, dissolving in concentrated nitric acid, and preparing with deionized water to obtain rare earth ions with total molar concentration of 0.5 mol.L-1And (3) a rare earth nitrate mixed solution.
148.02g of ammonium carbonate with a purity better than 99.99% was weighed, and the ammonium carbonate and weighed Al were added2O3The powder is dissolved in deionized water to form ammonium carbonate with the concentration of 2.0 mol.L-1Al of (2)2O3Mixing powder and ammonium carbonate to obtain mixed suspensionAdding into the mixture with the purity of 99.99 percent (NH)4)2SO4(the molar ratio of ammonium sulfate to rare earth nitrate is 1: 2) as a dispersant to obtain the Al-containing alloy2O3Powder, ammonium carbonate, (NH)4)2SO4The mixed suspension of (3).
Will contain Al2O3Powder, ammonium carbonate, (NH)4)2SO4After the mixed suspension is evenly stirred, the prepared rare earth nitrate solution is dropwise added into the Al-containing solution at the speed of 5ml/min2O3Powder, ammonium carbonate, (NH)4)2SO4The mixed suspension of (3). And continuously stirring the mixed suspension by using a stirrer, monitoring the pH value of the mixed solution by using an acidimeter, and adjusting the pH value of the solution to be between 8.0 and 8.5 by using ammonia water and nitric acid. After titration, the solution was allowed to stand and aged for 12 h. The precipitate is then filtered off and washed with deionized water to 0.1mol L-1BaCl of2The solution was checked until no precipitate was formed in the filtrate, and the filtrate was washed with anhydrous ethanol for 5 times. Then placed in an oven and dried at a temperature of 75 ℃ for 48 h. Taking out, grinding, sieving with 100 mesh sieve (150 μm), and calcining in muffle furnace at 1200 deg.C for 10 hr to obtain Sm: YLAG nanometer powder.
Putting the prepared Sm: YLAG nano-grade powder into a ball milling tank, adding 40g of absolute ethyl alcohol and 120g of ZrO with the diameter of phi 5mm2The ball is used as a ball milling medium, TEOS which is 0.6 percent of the total weight of the oxide powder and LiF which is 1.0 percent of the total weight of the oxide powder are added as sintering aids, and oleic acid which is 1.0 percent of the total weight of the oxide powder and polyacrylic acid which is 0.1 percent of the total weight of the oxide powder are added as dispersing agents. And performing ball milling and mixing for 8 hours at the rotating speed of 400rpm to obtain slurry. The slurry was spray dried at an inlet temperature of 90 ℃ and an outlet temperature of 70 ℃ during the spray drying process at a spray rate of 10 ml/min. 12g of spray-dried powder is weighed each time, put into a steel die and pressed into a wafer with phi of 40mm under the pressure of 5 MPa. And (3) packaging the wafer by using a latex bag, and keeping the pressure for 5min by using a cold isostatic press under 200 MPa. After being taken out, the formed green body is roasted for 24 hours in a muffle furnace at 1100 ℃ to remove residual organic matters. Then placing the blank in a vacuum furnace, and starting the vacuum furnaceVacuum system, vacuumize to 1 × 10-3After Pa, raising the temperature to 1700 ℃ at the heating rate of 5-10 ℃/min, and after heat preservation is carried out for 50h, reducing the temperature to room temperature at the rate of 10 ℃/min to obtain the Sm: YLAG ceramic sample.
Putting the vacuum-sintered Sm: YLAG ceramic sample into an atmospheric high-temperature furnace, heating to 1200 ℃ at the heating rate of 5 ℃/min, annealing for 24 hours in the atmosphere, cooling to room temperature at the cooling rate of 5 ℃/min, and then polishing by adopting the conventional polishing method to obtain Sm: YLAG transparent ceramic.
The Sm: YLAG transparent ceramic was subjected to a transmittance test to obtain a transmittance of 81.2% at 808nm, an absorption peak nearest to 1064nm at 1065.2nm, and an absorption coefficient at 1064nm of 3.1cm-1. Therefore, the Sm: YLAG transparent ceramic provided by the embodiment of the invention has a higher absorption coefficient at 1064nm, namely, has higher capability of absorbing 1064nm stray fluorescence generated by Nd: YAG working medium.
Example 7
According to the formula Y1.85Sm0.15Sc0.1Lu0.9Al5O12The mass of each oxide raw material required for preparing 40g Sm: YLAG ceramic powder is calculated according to the chemical composition of each element, and Y with the purity of 99.999 percent is weighed by a balance2O312.3612g powder of Lu with purity of 99.999%2O310.5974g of powder, Sc with purity of 99.999%2O30.4081g of powder Sm with the purity of 99.999%2O31.5481g of powder, 99.99% pure Al2O315.0852g of powder. Will Y2O3、Lu2O3、Sc2O3And Sm2O3Mixing the powders, dissolving in concentrated nitric acid, and preparing with deionized water to obtain rare earth ions with total molar concentration of 0.8 mol.L-1And (3) a rare earth nitrate mixed solution.
141.09g of ammonium bicarbonate with purity better than 99.99 percent is weighed, and the ammonium bicarbonate and the weighed Al are added2O3The powder is dissolved togetherIn ionized water, the concentration of ammonium bicarbonate is 2.0 mol.L-1Al of (2)2O3Mixing the powder with ammonium bicarbonate, adding ammonium sulfate (molar ratio of ammonium sulfate to rare earth nitrate is 2: 1) with purity of 99.99% as dispersant to obtain Al-containing solution2O3Powder, NH4HCO3And (NH)4)2SO4The mixed suspension of (3).
Will contain Al2O3Powder, NH4HCO3And (NH)4)2SO4After the mixed suspension is evenly stirred, the prepared rare earth nitrate solution is dropwise added into the Al-containing solution at the speed of 3ml/min2O3Powder, NH4HCO3And (NH)4)2SO4The mixed suspension of (3). And continuously stirring the mixed suspension by using a stirrer, monitoring the pH value of the mixed solution by using an acidimeter, and adjusting the pH value of the solution to be between 7.5 and 8.0 by using ammonia water and nitric acid. After titration, the solution was allowed to stand and aged for 24 h. The precipitate is then filtered off and washed with deionized water to 0.1mol L-1BaCl of2The solution was checked until no precipitate was formed in the filtrate, and the filtrate was washed with anhydrous ethanol for 5 times. Then placed in an oven and dried at a temperature of 75 ℃ for 36 h. Taking out, grinding, sieving with 100 mesh sieve (150 μm), and calcining in muffle furnace at 1350 deg.C for 12 hr to obtain Sm: YLAG nanometer powder.
Putting the prepared Sm: YLAG nano-grade powder into a ball milling tank, adding 20g of absolute ethyl alcohol, 120g of agate balls and silicon nitride balls with the diameter phi of 5mm as ball milling media, adding TEOS (tetraethyl orthosilicate) accounting for 0.6 percent of the total weight of the oxide powder and 0.1 percent of MgO as sintering aids, and adding oleic acid accounting for 1.0 percent of the total weight of the oxide powder and polyethylene glycol accounting for 0.5 percent of the total weight of the oxide powder as dispersing agents. Then ball milling and mixing are carried out for 8 hours at the rotating speed of 400rpm, and slurry is obtained. The slurry was dried in a vacuum oven at 75 ℃ for 48 h. Taking out the dried powder, grinding and sieving the powder by a 200-mesh sieve, weighing 12g of sieved powder each time, putting the powder into a steel die, and pressing the powder into wafers with phi of 40mm under the pressure of 10 MPa. Packaging the wafer with latex bag, and keeping pressure at 200MPa with cold isostatic pressAnd 5 min. After being taken out, the formed green body is roasted for 24 hours in a muffle furnace at 950 ℃ to remove residual organic matters. Then placing the blank in a vacuum furnace, starting a vacuum system, and vacuumizing to 1 × 10-3And after Pa, heating to 1740 ℃ at the heating rate of 1-5 ℃/min, preserving the temperature for 24 hours, and then cooling to room temperature at the speed of 10 ℃/min to obtain the vacuum-sintered Sm: YLAG ceramic sample.
Putting the vacuum sintered Sm: YLAG ceramic sample into an atmosphere high-temperature furnace, heating to 1450 ℃ at the heating rate of 5 ℃/min, annealing for 10h in the atmosphere, cooling to room temperature at the cooling rate of 5 ℃/min, and then polishing by adopting the conventional polishing method to obtain the Sm: YLAG transparent ceramic.
The Sm: YLAG transparent ceramic was subjected to a transmittance test to obtain a transmittance at 808nm of 82.2%, a closest absorption peak at 1064nm of 1065.2nm, and an absorption coefficient at 1064nm of 7.9cm-1. Therefore, the Sm: YLAG transparent ceramic provided by the embodiment of the invention has a higher absorption coefficient at 1064nm, namely, has higher capability of absorbing 1064nm stray fluorescence generated by Nd: YAG working medium.
Example 8
According to the formula Y2.52Sm0.15Sc0.3Lu0.03Al5O12The raw material mass of each oxide required for preparing the YLAG ceramic powder is 40gSm, and the Y with the purity of 99.999 percent is weighed by a balance2O319.2166g powder of Lu with purity of 99.999%2O30.4031g of powder, Sc with purity of 99.999%2O31.3972g of powder Sm with the purity of 99.999%2O31.7668g of powder, 99.999% pure Al2O317.2162g of powder. Will Y2O3、Lu2O3、Sc2O3And Sm2O3Mixing the powders, dissolving in concentrated nitric acid, and preparing with deionized water to obtain rare earth ions with total molar concentration of 0.5 mol.L-1And (3) a rare earth nitrate mixed solution.
193.21g of ammonium bicarbonate with purity better than 99.99 percent is weighed, and the ammonium bicarbonate and the weighed Al are added2O3The powder is dissolved in deionized water to form ammonium bicarbonate with concentration of 0.5 mol.L-1Containing Al2O3Mixing the powder with ammonium bicarbonate suspension, adding ammonium sulfate (molar ratio of ammonium sulfate to rare earth nitrate is 1: 1) with purity of 99.99% as dispersant to obtain Al-containing solution2O3Powder, NH4HCO3、(NH4)2SO4The suspension is mixed.
Will contain Al2O3Powder, NH4HCO3、(NH4)2SO4The mixed suspension is stirred evenly, and then the prepared rare earth nitrate solution is dropwise added to NH at the speed of 5ml/min4HCO3Mixing the suspension. And continuously stirring the mixed suspension by using a stirrer, monitoring the pH value of the mixed solution by using an acidimeter, and adjusting the pH value of the solution to be 7.5-8.0 by using ammonia water or nitric acid. After the titration is finished, the reaction system solution is aged for 28 hours. The precipitate is then filtered off and washed with deionized water to 0.1mol L-1BaCl of2The solution was checked until no precipitate was formed in the filtrate, and the filtrate was washed with absolute ethanol 3 times. Then placed in an oven and dried at a temperature of 75 ℃ for 48 h. Taking out, grinding, sieving with 100 mesh sieve (150 μm), and calcining in muffle furnace at 1100 deg.C for 12 hr to obtain Sm: YLAG nanometer powder.
Putting the prepared Sm: YLAG nano-grade powder into a ball milling tank, adding 320g of absolute ethyl alcohol, 120g of agate balls with the diameter of phi 5mm as ball milling media, and adding SiO which is 0.15 percent of the total weight of the oxide powder2And 0.1% of MgO as a sintering aid, and 1.0% of ammonium polymethacrylate and 2% of polyethylene glycol as dispersing agents, which are equivalent to the total weight of the oxide powder, are added. Then ball milling and mixing are carried out for 12 hours at the rotating speed of 400rpm, and slurry is obtained.
Spray drying the slurry, controlling the inlet temperature at 160 ℃, the outlet temperature at 90 ℃ and the spraying speed in the processIs 8 ml/min. 12g of the sieved powder is weighed each time and put into a steel die, and the powder is pressed into wafers with phi of 40mm under the pressure of 10 MPa. And (3) packaging the wafer by using a latex bag, and keeping the pressure for 5min by using a cold isostatic press under 200 MPa. And taking out, and roasting the formed blank in a muffle furnace at 800 ℃ for 24h to remove residual organic matters. Then placing the blank in a vacuum furnace, starting a vacuum system, and vacuumizing to 1 × 10-3After Pa, heating to 1850 ℃ at the heating rate of 1-5 ℃/min, preserving the heat for 5h, and then cooling to room temperature at the rate of 10 ℃/min to obtain a vacuum-sintered Sm: YLAG ceramic sample.
And putting the vacuum sintered Sm: YLAG ceramic sample into an atmosphere high-temperature furnace, raising the temperature to 1450 ℃ at the temperature rise rate of 5 ℃/min, annealing for 10 hours in the atmosphere, reducing the temperature to room temperature at the temperature fall rate of 5 ℃/min, and polishing to obtain the Sm: YLAG transparent ceramic.
The Sm: YLAG transparent ceramic was subjected to a transmittance test to obtain a transmittance at 808nm of 82.1%, a closest absorption peak at 1064nm of 1066.5nm, and an absorption coefficient at 1064nm of 4.9cm-1. Therefore, the Sm: YLAG transparent ceramic provided by the embodiment of the invention has a higher absorption coefficient at 1064nm, namely, has higher capability of absorbing 1064nm stray fluorescence generated by Nd: YAG working medium.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A self-exciting radiation absorbing material, wherein the self-exciting radiation absorbing material has a chemical formula: y is3-x-y-zSmxScyLuzAl5O12Wherein x is more than 0 and less than or equal to 0.215, y is more than or equal to 0.03 and less than or equal to 0.3, and z is more than or equal to 0.03 and less than or equal to 0.9.
2. A self-excitation radiation absorbing material according to claim 1, wherein the self-excitation radiation absorbing material is a transparent ceramic.
3. A method for preparing a self-exciting radiation absorbing material according to claim 1, comprising:
step 1: preparing rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu, and Al2O3The alcohol-water mixed suspension of the powder, the precipitator and the electrostatic stabilizer is prepared according to the chemical formula: y is3-x-y-zSmxScyLuzAl5O12(x is more than 0 and less than or equal to 0.215, Y is more than or equal to 0.03 and less than or equal to 0.3, and z is more than or equal to 0.03 and less than or equal to 0.9) to determine the mass of the elements Y, Sm, Sc and Lu and the mass of Al in the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu2O3The mass of (c);
step 2: dropwise adding the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu into the solution containing Al2O3In the alcohol-water mixed suspension of the powder, the precipitator and the electrostatic stabilizer, and adjusting the pH value of the reaction system to 7.0-8.5;
and step 3: after titration, aging and separating the reaction system to obtain a precipitate, and washing, drying, grinding and calcining the precipitate to obtain nano-scale powder;
and 4, step 4: forming a mixed system by the nano-scale powder, grinding balls, sintering aids, a dispersing agent and absolute ethyl alcohol, and carrying out ball milling on the mixed system to obtain slurry;
and 5: and drying the slurry to obtain dry powder, and performing compression molding, roasting, vacuum sintering and annealing treatment on the dry powder to obtain the self-excitation radiation absorbing material.
4. The method for preparing a self-excitation radiation absorbing material according to claim 3, wherein in the step 1, the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu is prepared by:
mixing high-purity Y2O3、Sm2O3、Sc2O3And Lu2O3Dissolving the powder in concentrated nitric acid to obtainObtaining a rare earth nitrate solution containing Y, Sm, Sc and Lu;
adding deionized water to the rare earth nitrate solution containing Y, Sm, Sc and Lu with the molar concentration of 0.1 mol.L-1-1.0mol·L-1。
5. A method for producing a self-excitation radiation absorbing material according to claim 3, wherein in the step 1: the mass ratio of the precipitant to the rare earth inorganic acid salt is 5:1-16: 1;
the mass ratio of the static stabilizer to the rare earth inorganic acid salt is 1:2-2: 1;
the precipitating agent is in the Al-containing state2O3The molar concentration of the alcohol-water mixed suspension of the powder, the precipitant and the electrostatic stabilizer is 0.2 mol.L-1-2.0mol·L-1；
The volume ratio of water to alcohol in the alcohol-water mixed solution is 1:1-1: 0.
6. The method for producing a self-excitation radiation absorbing material according to claim 5, wherein the precipitating agent is selected from at least one of bicarbonate, carbonate, and oxalate;
the static stabilizer is at least one of sulfate and bisulfate.
7. The method for producing a self-excitation radiation absorbing material according to claim 6, wherein the precipitant is ammonium bicarbonate; the static stabilizer is ammonium sulfate.
8. The method for producing a self-excitation radiation absorbing material as set forth in claim 3, wherein the temperature of the calcination in the step 3 is 1000 ℃ to 1350 ℃.
9. A method for preparing a self-exciting radiation absorbing material according to claim 3, wherein in the step 4, the grinding ball is selected from Al2O3Balls, agate balls, silicon nitride balls, ZrO2At least one of balls, wherein the mass ratio of the grinding ball to the nano powder is 1:1-5: 1;
the sintering aid is selected from at least one of ethyl orthosilicate, silicon dioxide, methyl orthosilicate, magnesium oxide, calcium oxide and lithium fluoride, and the mass of the sintering aid is 0.05-1.5% of that of the nano-scale powder;
the dispersing agent is selected from at least one of polyacrylic acid, polyethylene glycol, poly (ammonium methacrylate) and oleic acid, and the mass of the dispersing agent is 0.1-3% of that of the nano-scale powder;
the mass ratio of the absolute ethyl alcohol to the nano-scale powder is 1:2-8: 1.
10. The method for preparing a self-excitation radiation absorbing material according to claim 3, wherein the step 5 is specifically: drying and grinding the slurry in an oven at the temperature of more than 75 ℃, and sieving the ground slurry by a sieve with more than 100 meshes; or drying the slurry by spray drying, controlling the inlet temperature at 90-200 ℃ and the spraying speed at 1-20ml/min during the spray drying to obtain dried powder,
putting the dried powder into a die, pre-pressing into a ceramic blank by using the pressure higher than 5MPa, further pressing and molding by using a cold isostatic press under the pressure higher than 200MPa,
the ceramic blank formed by pressing is roasted for more than 2 hours at the temperature of 800-1100 ℃ in the atmosphere of atmosphere or flowing oxygen,
placing the baked ceramic body in a high-temperature vacuum furnace, sintering for 4-20h at 1700-1850 ℃ in vacuum, controlling the heating and cooling rate to be 1-10 ℃/min,
annealing the ceramic blank after vacuum sintering at 1200-1450 deg.c in atmosphere or oxygen atmosphere for over 10 hr to obtain ceramic,
and cooling to room temperature, taking out the ceramic, and polishing the surface of the ceramic to obtain the self-excitation radiation absorbing material.
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| CN104725051A (en) * | 2015-02-25 | 2015-06-24 | 江苏金石研磨有限公司 | Preparation method of nano zirconia coated alumina powder |
| CN108700525A (en) * | 2016-02-26 | 2018-10-23 | 于利奇研究中心有限公司 | Method for the surface characteristic for determining conductive target |
| CN112159220A (en) * | 2020-09-24 | 2021-01-01 | 徐州凹凸光电科技有限公司 | High-thermal-stability high-quantum-efficiency fluorescent ceramic for white light LED/LD and preparation method thereof |
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| CN104725051A (en) * | 2015-02-25 | 2015-06-24 | 江苏金石研磨有限公司 | Preparation method of nano zirconia coated alumina powder |
| CN108700525A (en) * | 2016-02-26 | 2018-10-23 | 于利奇研究中心有限公司 | Method for the surface characteristic for determining conductive target |
| CN108700525B (en) * | 2016-02-26 | 2021-02-23 | 于利奇研究中心有限公司 | Method for determining surface properties of a conductive target |
| CN112159220A (en) * | 2020-09-24 | 2021-01-01 | 徐州凹凸光电科技有限公司 | High-thermal-stability high-quantum-efficiency fluorescent ceramic for white light LED/LD and preparation method thereof |
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