CN103833348B - 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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- CN103833348B CN103833348B CN201310753337.5A CN201310753337A CN103833348B CN 103833348 B CN103833348 B CN 103833348B CN 201310753337 A CN201310753337 A CN 201310753337A CN 103833348 B CN103833348 B CN 103833348B
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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 present invention relates to laserable material field, particularly a kind of self-excitation radiation-absorbing material and preparation method thereof.
Background technology
Neodymium-doped yttrium-aluminum garnet (Neodymium-doped Yttrium Aluminium Garnet: hereinafter referred to as Nd:YAG) solid statelaser is a kind of laser apparatus using Nd:YAG crystal (or pottery) as working medium, it has that efficiency of conversion is high, output rating is high, good beam quality, compact construction, many technical superioritys such as lightweight, be widely used in the fields such as national defence, industrial processes, communication and medical treatment.But, under high power laser light operating condition, self-excitation radiated oscillations can be there is in the spuious fluorescence of 1064nm of Nd:YAG crystals self-excitation radiation formation, form self-excitation radiation and amplify (Amplification by Self-stimulated Emission:ASE) effect, the ASE effect of fluorescence not only seriously reduces laser-conversion efficiency, also can destroy the beam quality of solid statelaser Output of laser.Therefore, the suppression of ASE effect is carried out to Nd:YAG solid statelaser very necessary.
At present, usually can absorb 1064nm light mix samarium yttrium aluminum garnet (hereinafter referred to as: Sm:YAG) monocrystalline or crystalline ceramics are compounded in surrounding or the side of Nd:YAG working medium, due to Sm:YAG monocrystalline and the crystalline network of Sm:YAG crystalline ceramics and the crystal lattice match of Nd:YAG higher, the two can be organically combined as a whole by thermodiffusion bonding techniques.When Nd:YAG is in laser operation state, be compounded in around Nd:YAG working medium or the Sm:YAG monocrystalline of side or Sm:YAG transparent ceramic material can absorb the spuious fluorescence of 1064nm that Nd:YAG working medium inside produces by self-excitation radiation, make it that self-excitation radiated oscillations can not occur to amplify, thus reach the object suppressing ASE effect.
Realizing in process of the present invention, contriver finds that prior art at least exists following problem:
Sm:YAG monocrystalline and Sm:YAG crystalline ceramics are from the nearest absorption peak of 1064nm wavelength, its peak-to-valley value is positioned at about 1068nm, poor with the matching of the spuious fluorescence peak of the 1064nm of Nd:YAG, thus cause Sm:YAG monocrystalline and Sm:YAG crystalline ceramics less at the uptake factor at 1064nm wavelength place.
Summary of the invention
In order to solve Sm:YAG monocrystalline and Sm:YAG crystalline ceramics in prior art in the less problem of the uptake factor at 1064nm wavelength place, embodiments provide a kind of self-excitation radiation-absorbing material and preparation method thereof.Described technical scheme is as follows:
On the one hand, embodiments provide a kind of self-excitation radiation-absorbing material, the chemical formula of described self-excitation radiation-absorbing material is: Y
3-x-y-zsm
xsc
ylu
zal
5o
12, wherein, 0 < x≤0.215,0.03≤y≤0.3,0.03≤z≤0.9.
Particularly, as preferably, described self-excitation radiation-absorbing material is a kind of crystalline ceramics.
On the other hand, the embodiment of the present invention additionally provides a kind of preparation method of self-excitation radiation-absorbing material, and described method comprises:
Step 1: preparation containing the rare earth inorganic acid salt solution of Y, Sm, Sc and Lu, and contains Al
2o
3the alcohol water mixing suspension liquid of powder, precipitation agent and electrostatic stabilization agent, according to chemical formula: Y
3-x-y-zsm
xsc
ylu
zal
5o
12the ratio of the atom number of Y, Sm, Sc, Lu and Al in (0 < x≤0.215,0.03≤y≤0.3,0.03≤z≤0.9), determines the described quality containing Y, Sm, Sc and Lu element in the rare earth inorganic acid salt solution of Y, Sm, Sc and Lu and Al
2o
3quality;
Step 2: the described rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu is dropwise added described containing Al
2o
3in the alcohol water mixing suspension liquid of powder, precipitation agent and electrostatic stabilization agent, and regulate the pH value of reaction system between 7.0-8.5;
Step 3: titration is complete, carries out ageing to described reaction system and is separated being precipitated thing, wash described throw out, dry, grinding and calcining, obtains nanometer grade powder;
Step 4: by described nanometer grade powder, abrading-ball, sintering aid, dispersion agent and dehydrated alcohol composition mixed system, and ball milling is carried out to described mixed system, obtain slurry;
Step 5: carry out drying to described slurry, obtains dry powder, and repressed shaping, the roasting of the powder of described drying, vacuum sintering, anneal, obtain described self-excitation radiation-absorbing material.
Particularly, as preferably, in described step 1, the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu described in described preparation is specially:
By high-purity Y
2o
3, Sm
2o
3, Sc
2o
3and Lu
2o
3powder is dissolved in concentrated nitric acid, obtains the rare earth nitrate solution containing Y, Sm, Sc and Lu;
Adding deionized water to the described volumetric molar concentration containing the rare earth nitrate solution of Y, Sm, Sc and Lu is 0.1molL
-1-1.0molL
-1.
Particularly, as preferably, in described step 1: described precipitation agent is 5:1-16:1 with the ratio of the amount of substance of described rare earth inorganic acid salt;
Described electrostatic stabilization agent is 1:2-2:1 with the ratio of the amount of substance of described rare earth inorganic acid salt;
Described precipitation agent contains Al described
2o
3volumetric molar concentration in the alcohol water mixing suspension liquid of powder, precipitation agent and electrostatic stabilization agent is 0.2molL
-1-2.0molL
-1;
In described alcohol water mixing suspension liquid, the volume ratio of water and alcohol is 1:1-1:0.
Particularly, as preferably, described precipitation agent is selected from least one in supercarbonate, carbonate and oxalate;
Described electrostatic stabilization agent is selected from least one in vitriol, hydrosulfate.
Particularly, as preferably, described precipitation agent is ammonium hydrogencarbonate; Described electrostatic stabilization agent is ammonium sulfate.
Particularly, as preferably, in described step 3, the temperature of described calcining is 1000 DEG C-1350 DEG C.
Particularly, as preferably, in described step 4, described abrading-ball is selected from Al
2o
3ball, agate ball, silicon nitride ball, ZrO
2at least one in ball, the mass ratio of described abrading-ball and described nano-powder is 1:1-5:1;
Described sintering aid is selected from least one in tetraethoxy, silicon-dioxide, methyl silicate, magnesium oxide, calcium oxide and lithium fluoride, and the quality of described sintering aid is the 0.05%-1.5% of described nanometer grade powder quality;
Described dispersion agent is selected from least one in polyacrylic acid, polyoxyethylene glycol, polymethyl acrylic acid ammonia and oleic acid, and the quality of described dispersion agent is the 0.1%-3% of described nanometer grade powder quality;
The mass ratio of described dehydrated alcohol and described nanometer grade powder is 1:2-8:1.
Particularly, as preferably, described step 5 is specially: cross 100 orders with top sieve carry out drying, grinding to described slurry in the baking oven of temperature higher than 75 DEG C after; Or carry out drying by spraying dry to described slurry, temperature in when controlling described spraying dry is 90 DEG C-200 DEG C, and spray velocity is 1-20ml/min, obtains dried powder,
Dried powder is put into mould, utilizes the pressure higher than 5MPa to be pressed into ceramic body in advance, then use cold isostatic press compression moulding further under higher than the pressure of 200MPa,
By the ceramic body of compression moulding air or flowing oxygen atmosphere in, at the temperature of 800 DEG C-1100 DEG C, more than roasting 2h,
Ceramic body after roasting is put in vacuum high temperature furnace, at the temperature of 1700 DEG C-1850 DEG C, vacuum sintering 4-20h, controlling temperature rate is 1-10 DEG C/min,
By the ceramic body after vacuum sintering in the atmosphere of air or oxygen, at the temperature of 1200 DEG C-1450 DEG C, more than anneal 10h, obtains pottery,
Be cooled to room temperature, take out pottery, surface finish is carried out to it, obtains described self-excitation radiation-absorbing material.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
On the one hand, embodiments provide a kind of self-excitation radiation-absorbing material, its chemical formula is: Y
3-x-y-zsm
xsc
ylu
zal
5o
12, wherein, 0 < x≤0.215,0.03≤y≤0.3,0.03≤z≤0.9.By by ratio of ionic radii Y
3+the Sc that ionic radius is less
3+ion and Lu
3+part Y in ionic replacement Sm:YAG lattice
3+ion, formed a kind of newly, lattice parameter is less than Sm:YAG mixes samarium yttrium lutetium scandium aluminium garnet (hereinafter referred to as Sm:YLSAG) material.Compared with Sm:YAG, Sm:YLSAG will be blue shifted to about 1065.8nm at the absorption peak valley of about 1068nm.Therefore, the absorption peak of Sm:YLSAG and the spuious fluorescence peak matching of Nd:YAG working medium better, thus make Sm:YLSAG larger at the uptake factor at 1064nm wavelength place.In addition, the self-excitation radiation-absorbing material that the embodiment of the present invention provides: Sm:YLSAG, its crystalline network is same with the crystalline network of Nd:YAG good matching, can utilize thermodiffusion bonding techniques, organically be combined into one with Nd:YAG crystal, suppress the self-excitation radiation of Nd:YAG.
On the other hand, the embodiment of the present invention additionally provides a kind of preparation method of self-excitation radiation-absorbing material, described containing Al by dropwise being added by the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu
2o
3in the alcohol water mixed solution of powder, precipitation agent and electrostatic stabilization agent, carry out chemical coprecipitation reaction.Thus improve reaction system intermediate ion reactive behavior, be beneficial to precipitation and the crystallization of rare earth ion, and overcome by rare earth ion throw out and aluminum ion throw out because of the long-pending (K of chemical solubility
sPvalue) difference is comparatively large and the Sm:YLSAG that causes easily departs from the problem of garnet stoichiometric ratio.The throw out prepared by chemical coprecipitation carries out solid state reaction sintering processes, prepare the material Sm:YLSAG that can suppress Nd:YAG self-excitation radiation provided by the invention, can be mixedly more even by raw material, directly prepare and there is garnet phase, Sm:YLSAG powder that sintering activity is high, thus relatively easily can prepare the Sm:YLSAG crystalline ceramics with high Sm ion doping concentration and high-clarity.Visible, chemical coprecipitation-solid state reaction sintering combines by the embodiment of the present invention, and technique is simple, easy to control, have good repeatability and stability, is suitable for large-scale industrial and produces.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is preparation method's schema of the self-excitation radiation-absorbing material that the embodiment of the present invention provides;
Fig. 2 be further embodiment of this invention provide Sm:YAG crystal, Sm:YAG pottery with Sm:YLSAG crystalline ceramics through spectrogram.
Wherein, λ wavelength (unit nm),
T transmitance (unit %),
1 represent Sm:YLSAG crystalline ceramics through spectrogram,
2 represent Sm:YAG crystal through spectrogram,
3 represent Sm:YAG pottery through spectrogram.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
The embodiment of the present invention measures the transmitance of crystal and ceramic body by JB/T 9495.3-1999 optical crystal Transmissivity measurement method, and determines above-mentioned crystal or the ceramic body uptake factor in certain wave strong point according to measured transmitance.
Embodiment 1
Embodiments provide a kind of self-excitation radiation-absorbing material, the chemical formula of described self-excitation radiation-absorbing material is: Y
3-x-y-zsm
xsc
ylu
zal
5o
12, wherein, 0 < x≤0.215,0.03≤y≤0.3,0.03≤z≤0.9.
The self-excitation radiation-absorbing material that the embodiment of the present invention provides, by by ratio of ionic radii Y
3+the Sc that ionic radius is less
3+ion and Lu
3+part Y in ionic replacement Sm:YAG lattice
3+ion, formed a kind of newly, lattice parameter is less than Sm:YAG mixes samarium yttrium lutetium scandium aluminium garnet (hereinafter referred to as Sm:YLSAG) material.Compared with Sm:YAG, Sm:YLSAG will be blue shifted to about 1065.8nm at the absorption peak of about 1068nm.Therefore, the absorption peak of Sm:YLSAG and Nd:YAG(Neodymium-doped YttriumAluminium Garnet neodymium-doped yttrium-aluminum garnet) the spuious fluorescence peak matching of working medium is better, thus make Sm:YLSAG larger at the uptake factor at 1064nm wavelength place.In addition, the self-excitation radiation-absorbing material that the embodiment of the present invention provides: Sm:YLSAG, the crystal lattice match of its crystalline network and Nd:YAG is better, can utilize thermodiffusion bonding techniques, organically be combined into one with Nd:YAG crystal.
Self-excitation radiation-absorbing material desired by the embodiment of the present invention, not only will around Nd:YAG crystal or side carry out bound edge, can and Nd:YAG crystal between carry out good thermodiffusion bonding, but also the spuious fluorescence of 1064nm absorbing Nd:YAG crystal and produce will be had, reach the object suppressing Nd:YAG self-excitation radiation.
In the superpower Nd:YAG solid statelaser design and manufaction process of reality, the Nd:YAG crystalline size allowed is limited, usually need thermal bonding Nd:YAG crystal side or around 1064nm fluorescence self-excitation radiation-absorbing material get over Bao Yuehao, general wish to be no more than 2mm.Not increase the size of Nd:YAG crystal.If the self-excitation radiation-absorbing material thickness being compounded in the 1064nm wavelength place on Nd:YAG working medium is blocked up, the area of composite crystal (namely bound edge has the Nd:YAG of self-excitation radiation-absorbing material) or volume will be caused to increase, and this can cause very large difficulty to the encapsulation of the composite crystal element in backend application process and welding.Simultaneously, in order to absorb the spuious fluorescence of the 1064nm produced in Nd:YAG working medium in working process, thorough suppression ASE effect, at least needs the self-excitation radiation-absorbing material of side compound at least can absorb the spuious self-excitation radiofluorescence of in Nd:YAG working medium 90%.
For Sm:YAG crystal, although Sm:YAG crystal has absorption at 1064nm wavelength place, but its absorption peak valley near 1064nm deviates from 1064nm, be positioned at about 1068nm, cause Sm:YAG less at the uptake factor at 1064nm wavelength place, known according to Lang Bo-Beer's law (in crystal the concentration of dopant ion and uptake factor linear), want in thickness thin as far as possible, realize the absorption completely to Nd:YAG crystal spontaneous radiation fluorescence, crystal must have the doping content of superelevation.List uptake factor at 1064nm wavelength place of the different levels of doping Sm:YAG crystal that tests out in table 1 and realize to 1064nm absorb reach 90% time required minimum thickness.As can be seen from data in table, want the fluorescent absorption realized in 2mm thickness the self-excitation of Nd:YAG crystal gives off and reach 90%, at least need to prepare Sm:YAG monocrystalline or the Sm:YAG pottery that concentration reaches 11.7at%.But, due to Sm
3+ionic radius and Y
3+ionic radius difference is comparatively large, the Sm of excessive concentrations
3+ion mixes in YAG crystal can cause serious lattice distortion, produce serious stress, cause crystal cleavage or produce impurity phase, no matter being therefore utilize Crystal Growth Technique or crystalline ceramics technology of preparing, being all difficult to the Sm:YAG material of the expectation obtaining high density like this.
Uptake factor at 1064nm wavelength place of the Sm:YAG of table 1 different concns and the minimum thickness of required Sm:YAG when realizing reaching 90% to 1064nm photoabsorption
Wherein,
*for the numerical value calculated according to bright vigorous Beer's law.
Based on above-mentioned principle, the self-excitation radiation-absorbing material that the embodiment of the present invention provides, by introducing the ion that ionic radius is less, can not destroy starting material optics and spectrum property in Sm:YAG crystal (or pottery) simultaneously, replace the Y ion on fraction matrix lattice, substrate material lattice parameter is suitably reduced.Because after lattice parameter diminishes, the level structure impact of crystal ligand field on rare earth ion is strengthened, and causes the further splitting of energy level or level spacing to widen.So, the suitable blue shift of absorption spectrum of Sm:YAG crystal (or pottery) can be made, thus Sm:YAG crystal (or pottery) is in the absorption peak at 1068nm wavelength place, blue shift is to closer to 1064nm wavelength place, even if under lower doping content, also larger uptake factor can be had at 1064nm wavelength place to make Sm:YAG crystal (or pottery).
YAG(yttrium aluminum garnet) crystal is typical garnet structure, belongs to isometric system, wherein Y
3+ion is in Dodecahedral sites, in Sm:YAG crystal, and Sm
3+part Y in ionic replacement parent lattice
3+ion, is also in Dodecahedral sites.Contriver finds in research process, for YAG crystal substrate, adopts appropriate trivalent rare earth ions replacement part to be in the Y of Dodecahedral sites
3+ion, can't cause structural destruction, still can keep complete garnet structure, and trivalent rare earth ions radius is less, and the substitution amount of permission is larger.So the embodiment of the present invention adopts ratio of ionic radii Y
3+the trivalent rare earth ions that ionic radius is little replaces the part Y on Sm:YAG lattice
3+ion, makes the lattice parameter of Sm:YAG diminish, absorption spectrum blue shift.Contriver studies discovery, in various trivalent rare earth ions, and ratio of ionic radii Y
3+ionic radius is little, and out-shell electron is full full state, and after mixing YAG matrix, what spectral response curve can not be caused to change has Lu
3+ion and Sc
3+ion.Therefore, the embodiment of the present invention, by Sm:YAG matrix, introduces the Lu of proper content
3+ion and Sc
3+ion, prepare Sm:YLSAG crystal (or pottery), thus reduce the lattice parameter of YAG, former Sm:YAG matrix is made to be blue shifted to about 1065.8nm at the absorption peak valley at 1068nm place, it absorbs peak valley and more mates with the spontaneous radiation fluorescence peak (1064nm) of Nd:YAG crystal, thus makes Sm:YLSAG have larger uptake factor at 1064nm wavelength place.
In sum, self-excitation radiation-absorbing material provided by the invention, has the following advantages: (1) has large uptake factor at 1064nm wavelength, in thickness thin as far as possible, all can be absorbed by the spuious fluorescence that Nd:YAG working medium inside produces; (2) crystalline structure of crystalline network and Nd:YAG working medium is close, is more conducive to the thermodiffusion bonding between the two, thus is organically combined as a whole; (3) there is good heat conductivility, be beneficial to the heat radiation of Nd:YAG working medium; (4) do not absorb 808nm pump light in Nd:YAG working medium, pump light, by not having loss, is suitable as the bound edge self-excitation radiation-absorbing material of Nd:YAG crystal in the Nd:YAG laser apparatus of various pump mode (mode such as side pump, end pump).Visible, the self-excitation radiation-absorbing material at the 1064nm wavelength place that the embodiment of the present invention provides, for the Nd:YAG compound working medium of the outer bound edge of preparation self-excitation radiation-absorbing material, suppress the ASE effect of superpower Nd:YAG solid statelaser, improve beam quality and the efficiency of conversion of superpower Nd:YAG solid statelaser, have great importance.
Preferably, described self-excitation radiation-absorbing material is a kind of crystalline ceramics.
The self-excitation radiation-absorbing material preferably transparent stupalith that the embodiment of the present invention provides, compare with monocrystalline, crystalline ceramics remains all good characteristics of monocrystal material.Meanwhile, because transparent ceramic material prepares through solid state reaction sintering, bulk crystal is made up of crystal grain small one by one, there is crystal boundary shock absorption between crystal grain, therefore allows higher Sm
3+ion doping concentration, therefore, by Lu in the embodiment of the present invention
3+ion and Sc
3+ionic replacement part Y
3+the Sm:YLSAG of ion is prepared into crystalline ceramics form, can realize higher Sm
3+ion doping concentration, obtains larger 1064nm uptake factor.In addition, in the embodiment of the present invention, shorter, the preparation process of the preparation cycle of Sm:YLSAG crystalline ceramics is without the need to using expensive precious metal Ir, significantly reduces production cost.
Embodiment 2
Embodiments provide a kind of preparation method of self-excitation radiation-absorbing material, described method comprises:
Step 1: preparation containing the rare earth inorganic acid salt solution of Y, Sm, Sc and Lu, and contains Al
2o
3the alcohol water mixed solution of powder, precipitation agent and electrostatic stabilization agent, according to chemical formula: Y
3-x-y-zsm
xsc
ylu
zal
5o
12the ratio of the atom number of Y, Sm, Sc, Lu and Al in (0 < x≤0.215,0.03≤y≤0.3,0.03≤z≤0.9), determines the described quality containing Y, Sm, Sc and Lu element in the rare earth inorganic acid salt solution of Y, Sm, Sc and Lu and Al
2o
3quality;
Step 2: the described rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu is dropwise added described containing Al
2o
3in the alcohol water mixing suspension liquid of powder, precipitation agent and electrostatic stabilization agent, and regulate the pH value of reaction system between 7.0-8.5;
Step 3: titration is complete, carries out ageing to described reaction system and is separated being precipitated thing, wash described throw out, dry, grinding and calcining, obtains nanometer grade powder;
Step 4: by described nanometer grade powder, abrading-ball, sintering aid, dispersion agent and dehydrated alcohol composition mixed system, and ball milling is carried out to described mixed system, obtain slurry;
Step 5: carry out drying to described slurry, obtains dry powder, and repressed shaping, the roasting of the powder of described drying, vacuum sintering, anneal, obtain described self-excitation radiation-absorbing material.
Particularly, in step 1: the described rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu of preparation is specially: by high-purity Y
2o
3, Sm
2o
3, Sc
2o
3and Lu
2o
3powder is dissolved in concentrated nitric acid, obtains the rare earth nitrate solution containing Y, Sm, Sc and Lu;
Adding deionized water to the described volumetric molar concentration containing the rare earth nitrate solution of Y, Sm, Sc and Lu is 0.1molL
-1-1.0molL
-1.
In this process, above-mentioned each rare earth oxide and concentrated nitric acid are obtained by reacting rare earth nitrate.Wherein, concentrated nitric acid is analytical pure or is better than analytical pure, to avoid introducing impurity in reaction system.
Alternatively, this rare earth inorganic acid salt solution also can be high-purity rare-earth villaumite or high-purity sulphuric acid salts solution.
Particularly, described precipitation agent is 5:1-16:1 with the ratio of the amount of substance of described rare earth inorganic acid salt,
Described electrostatic stabilization agent is 1:2-2:1 with the ratio of the amount of substance of described rare earth inorganic acid salt,
Described precipitation agent contains Al described
2o
3volumetric molar concentration in the alcohol water mixing suspension liquid of powder, precipitation agent and electrostatic stabilization agent is 0.2molL
-1-2.0molL
-1,
In described alcohol water mixing suspension liquid, the volume ratio of water and alcohol is 1:0-1:1.
Described precipitation agent is selected from least one in supercarbonate, carbonate and oxalate, and described electrostatic stabilization agent is selected from least one in vitriol, hydrosulfate.
As preferably, described precipitation agent is ammonium hydrogencarbonate, and described electrostatic stabilization agent is ammonium sulfate.
In the embodiment of the present invention, preparation is containing Al
2o
3the alcohol water mixing suspension liquid of powder, precipitation agent and electrostatic stabilization agent is specially: by Al
2o
3the volumetric molar concentration that powder is mixed with ammonium hydrogencarbonate together with appropriate bicarbonate of ammonia is 0.2molL
-1-2.0molL
-1alcohol water (volume ratio of deionized water and ethanol is between 1:0 to 1:1) mix suspension liquid, the purity of bicarbonate of ammonia is better than 99%, and its amount and the total amount of rare earth nitrate are than between 5:1 to 16:1.Then in mixing suspension liquid, add appropriate purity and be better than the ammonium sulfate of 99% as charge stable agent, the ratio of the amount of ammonium sulfate and the total amount of rare earth ion is between 1:2 to 2:1.Then the mixing suspension liquid that is mixed with of continuously stirring.
In the embodiment of the present invention, according to chemical formula: Y
3-x-y-zsm
xsc
ylu
zal
5o
12in (0 < x≤0.215,0.03≤y≤0.3,0.03≤z≤0.9), the ratio of the atom number of Y, Sm, Sc, Lu and Al, determines high-purity Y
2o
3, Sm
2o
3, Sc
2o
3and Lu
2o
3powder and Al
2o
3the quality of powder.Then by the high-purity Y determining quality
2o
3, Sm
2o
3, Sc
2o
3and Lu
2o
3powder and Al
2o
3powder, according to above-mentioned concrete compound method, preparation obtains containing the rare earth nitrate solution of Y, Sm, Sc and Lu and containing Al respectively
2o
3the alcohol water mixing suspension liquid of powder, precipitation agent and electrostatic stabilization agent.
Then the above-mentioned above-mentioned rare earth nitrate solution prepared dropwise is added drop-wise in bicarbonate of ammonia mixing suspension liquid, is obtained by reacting the mixed sediment of the pioneer precipitate of the carbonate of Y, Sm, Sc and Lu and aluminium carbonate ammonium, aluminum hydroxide precipitate.
In titration process, the speed controlling to drip is 3ml/min-10ml/min, keeps alumina powder jointed simultaneously, bicarbonate of ammonia mixing suspension liquid is in and do not stop whipped state, be beneficial to control sedimentary generation, prevent the reunion of deposit seeds.In addition, utilize pH meter to monitor the pH value of bicarbonate of ammonia mixing solutions, and regulate the pH value of mixed solution between 7.0-8.5 with concentrated nitric acid or strong aqua, to keep reaction system to be in stable pH value environment, be beneficial to the carrying out of reaction.
After above-mentioned drop reaction, suspension liquid ageing for some time will be mixed.The temperature controlling ageing is 20 DEG C-60 DEG C, and the time of ageing is 12-48 hour, to remove the impurity contained in throw out, and allows throw out crystal growth make its homogenizing more.
Ageing is complete, is separated by throw out, carries out purification and washing to this throw out.Purification and washing process can adopt mode that is centrifugal and/or suction filtration.Utilize deionized water and/or absolute ethanol washing at least one times, thus reduce the impurity retained in throw out as much as possible.Such as, available deionized water by throw out washes clean, then with absolute ethanol washing number time.
Carry out drying to the throw out after washing, described sedimentary drying temperature is higher than 75 DEG C
Dried throw out is carried out grind, calcine after can prepare nano level high-purity Sm:YLSAG powder.
Preferably, this calcining temperature is 1000 DEG C-1350 DEG C.
The high-purity Sm:YLSAG powder above-mentioned calcining obtained carries out ball milling, drying, compression moulding, roasting, vacuum sintering, anneal to prepare Sm:YLSAG crystalline ceramics.Wherein, described abrading-ball is selected from Al
2o
3ball, agate ball, silicon nitride ball, ZrO
2at least one in ball, the mass ratio of described abrading-ball and described nano-powder is 1:1-5:1; Described sintering aid is selected from least one in tetraethoxy, silicon-dioxide, methyl silicate, magnesium oxide, calcium oxide and lithium fluoride, and the quality of described sintering aid is the 0.05%-1.5% of described nanometer grade powder quality; Described dispersion agent is selected from least one in polyacrylic acid, polyoxyethylene glycol, polymethyl acrylic acid ammonia and oleic acid, and the quality of described dispersion agent is the 0.1%-3% of described nanometer grade powder quality; The mass ratio of described dehydrated alcohol and described nanometer grade powder is 1:2-8:1.
Step 5 is specially: cross 100 orders with top sieve carry out drying, grinding to described slurry in the baking oven of temperature higher than 75 DEG C after; Or carry out drying by spraying dry to described slurry, temperature in when controlling described spraying dry is 90 DEG C-200 DEG C, and spray velocity is 1-20ml/min, obtains dried powder,
Dried powder is put into mould, utilizes the pressure higher than 5MPa to be pressed into biscuit of ceramics in advance, then use cold isostatic press compression moulding further under higher than the pressure of 200MPa.By the ceramic body of compression moulding air or flowing oxygen atmosphere in, at the temperature of 800 DEG C-1100 DEG C, more than roasting 2h.Be put in vacuum high temperature furnace by the ceramic body after roasting, at the temperature of 1700 DEG C-1850 DEG C, vacuum sintering 4-20h, controlling temperature rate is 1-10 DEG C/min.By the biscuit of ceramics after vacuum sintering in the atmosphere of air or oxygen, at the temperature of 1200 DEG C-1450 DEG C, more than anneal 10h, obtains pottery.Be cooled to room temperature, take out pottery, surface finish is carried out to it, obtains described self-excitation radiation-absorbing material, namely prepare the Sm:YLSAG crystalline ceramics that can suppress Nd:YAG self-excitation radiation.
Visible, the preparation method of the self-excitation radiation-absorbing material that the embodiment of the present invention provides, described containing Al by the rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu is dropwise added
2o
3in the alcohol water mixing suspension liquid of powder, precipitation agent and electrostatic stabilization agent, carry out chemical coprecipitation reaction.Both improve reaction system ionic reaction active, be conducive to again precipitation and the crystallization of rare earth ion, and overcome traditional chemical coprecipitation method by rare earth ion throw out with aluminum ion throw out because chemical solubility amasss (K
sPvalue) difference is comparatively large and the prepared Sm:YLSAG that causes easily departs from the problem of its stoichiometric ratio.The throw out prepared by chemical coprecipitation carries out solid state reaction sintering processes, prepare the material Sm:YLSAG suppressing (namely absorbing) Nd:YAG self-excitation radiation provided by the invention, can be mixedly more even by raw material, directly prepare and there is garnet phase, Sm:YLSAG powder that sintering activity is high, thus can relatively easily obtain high transparency.Chemical coprecipitation-solid state reaction sintering combines, and technique is simple, easy to control, have good repeatability and stability, is suitable for large-scale industrial and produces.
Embodiment 3
According to chemical formula Y
2.1sm
0.15sc
0.15lu
0.6al
5o
12the ratio of atom number of each element, calculate the following oxide raw material quality needed for preparation 40g Sm:YLSAG ceramic powder, and the purity that weighs with scale is the Y of 99.99%
2o
3powder 14.6384g, purity is the Lu of 99.99%
2o
3powder 7.3704g, purity is the Sc of 99.99%
2o
3powder 0.6386g, purity is the Sm of 99.99%
2o
3powder 1.6151g, purity is the Al of 99.99%
2o
3powder 15.7375g.By Y
2o
3, Lu
2o
3, Sc
2o
3and Sm
2o
3powder mixes, and is dissolved in the pure concentrated nitric acid of top grade, and is mixed with rare earth ion total mol concentration at 0.5molL with deionized water
-1rare earth nitrate mixed solution.
Take the bicarbonate of ammonia that 147.19g purity is better than 99.9%, by bicarbonate of ammonia and the Al weighed
2o
3powder is dissolved in the mixing solutions be made up of for 1:1 by volume deionized water and dehydrated alcohol together, and formation ammonium bicarbonate concentration is 0.2molL
-1al
2o
3powder, bicarbonate of ammonia alcohol mixture aqueous suspension, in mixing suspension liquid, add purity is 99% ammonium sulfate ((NH
4)
2sO
4) (mol ratio of ammonium sulfate and rare earth nitrate is 1:1) as dispersion agent, obtain containing Al
2o
3powder, NH
4hCO
3, (NH
4)
2sO
4mixing suspension liquid.
Above-mentioned mixing suspension liquid is stirred, the rare earth nitrate solution of preparation is dropwise added drop-wise to containing Al with the speed of 5ml/min
2o
3powder, NH
4hCO
3, (NH
4)
2sO
4mixing suspension liquid in., be ceaselessly uniformly mixed suspension liquid with agitator therebetween, and by the pH value of acidometer monitoring mixed solution, by ammoniacal liquor and nitric acid regulator solution pH value between 7.0-7.5.After titration, solution is quiet puts aging 24h.Then throw out is leached, with deionized water wash to 0.1molL
-1baCl
2solution detects filtrate without till precipitation generation, then uses absolute ethanol washing 3 times.Then be put in baking oven, at the temperature of 75 DEG C, dry 12h.Take out, after ground 100 mesh sieves (150 μm), in the temperature lower calcination 8h of 1100 DEG C in retort furnace, obtain Sm:YLSAG nanometer grade powder.
By the Sm:YLSAG nanometer grade powder prepared, put into ball grinder, add 80g dehydrated alcohol, the alumina balls of 160g diameter of phi 5mm are as ball-milling medium, the MgO adding TEOS and 0.1% being equivalent to oxide powder gross weight 0.5% as sintering aid, add be equivalent to oxide powder gross weight 0.1% polyacrylic acid as dispersion agent.With the rotating speed of 350rpm, after ball milling mixing 24h, obtain slip.This slurry is carried out spraying dry.Temperature in is 160 DEG C, and temperature out is 100 DEG C, and spray speed is 10ml/min.Powder after each weighing 12g spraying dry, puts into punching block, with the pressure of 10MPa, is pressed into the disk of Φ 40mm.By disk with after latex rubber bag encapsulation, with cold isostatic press pressurize 2min under 300MPa.After taking-up, by shaping base substrate in the retort furnace of 800 DEG C, roasting 12h, to remove residual organism.Then base substrate is put in vacuum oven, opens vacuum system, be evacuated to 1 × 10
-3after Pa, with the temperature rise rate of 3 ~ 5 DEG C/min, rise to 1780 DEG C, after insulation 20h, then be down to room temperature with the speed of 10 DEG C/min, obtain Sm:YLSAG ceramics sample.
The Sm:YLSAG ceramics sample of this vacuum sintering is put in air High Temperature Furnaces Heating Apparatus, 1400 DEG C are risen to, air annealing 10h with the temperature rise rate of 5 DEG C/min, then after being down to room temperature with the rate of temperature fall of 5 DEG C/min, polished finish is carried out to it, obtains Sm:YLSAG crystalline ceramics.Carry out transmission measurement to this Sm:YLSAG crystalline ceramics, obtaining its transmitance at 808nm place is 81.9%, and the absorption peak nearest at 1064nm wavelength place is positioned at 1065.8nm, and the uptake factor at 1064nm place is 5.3cm
-1(as shown in Figure 2).
Under the condition identical with embodiment 3 desired operating parameter, preparative chemistry formula is Y
2.85sm
0.15al
5o
12sm:YAG crystalline ceramics, and to grow chemical formula be Y
2.91sm
0.09al
5o
12sm:YAG crystal, and carry out transmission measurement to it, as shown in Figure 2: Sm:YAG crystal is positioned at 1068nm place at the absorption peak nearest from 1064nm wavelength place, its uptake factor at 1064nm place is 1.49cm
-1.Sm:YAG crystalline ceramics is positioned at 1068nm place at nearest from 1064nm wavelength place absorption peak, and its uptake factor at 1064nm place is 2.5cm
-1.
Visible, the Sm:YLSAG crystalline ceramics that the embodiment of the present invention provides, on the one hand, compare with Sm:YAG crystalline ceramics with Sm:YAG crystal, the Sm:YLSAG crystalline ceramics that the embodiment of the present invention provides has higher uptake factor at 1064nm place, there is the ability of the spuious fluorescence of 1064nm that higher absorption Nd:YAG working medium produces, and to the pump light at 808nm place substantially without absorbing, be beneficial to the ASE effect suppression material as Nd:YAG solid statelaser.
Embodiment 4
According to chemical formula Y
1.855sm
0.215sc
0.03lu
0.9al
5o
12in the ratio of atom number of element, calculate each oxide raw material quality needed for preparation 40g Sm:YLSAG ceramic powder, and the purity that weighs with scale is the Y of 99.99%
2o
3powder 12.2663g, purity is the Lu of 99.99%
2o
3powder 10.4876g, purity is the Sc of 99.99%
2o
3powder 0.1212g, purity is the Sm of 99.99%
2o
3powder 2.1960g, purity is the Al of 99.99%
2o
3powder 14.9290g.By Y
2o
3, Lu
2o
3, Sc
2o
3and Sm
2o
3powder Homogeneous phase mixing, is dissolved in analytically pure concentrated hydrochloric acid, and is mixed with rare earth ion total mol concentration at 0.1molL with deionized water
-1rare earth villaumite mixing solutions.
Take the bicarbonate of ammonia that 223.42g purity is better than 99%, by bicarbonate of ammonia and the Al weighed
2o
3powder is dissolved in the mixing solutions be made up of for 1:0.5 by volume deionized water and dehydrated alcohol together, and being mixed with bicarbonate of ammonia ammonium concentration is 0.4molL
-1containing Al
2o
3the alcohol mixture aqueous suspension of powder, bicarbonate of ammonia.Monoammonium sulfate (the NH that purity is 99.99% is added in this mixing suspension liquid
4hSO
4) (mol ratio controlling monoammonium sulfate and rare earth villaumite is 2:1) as dispersion agent, obtain containing Al
2o
3powder, ammonium acetate, NH
4hSO
4mixing suspension liquid.
After being stirred by above-mentioned mixing suspension liquid, the rare earth chloride solution of preparation is dropwise added drop-wise to Al with the speed of 10ml/min
2o
3powder, NH
4hCO
3, NH
4hSO
4in mixing suspension liquid.In this process, be ceaselessly uniformly mixed suspension liquid with agitator, and by the pH value of acidometer monitoring mixed solution, by ammoniacal liquor or nitric acid regulator solution pH value between 7.5-8.0.After titration, put aging 24h by quiet for reaction system solution.Then throw out is leached, with deionized water wash to 0.1molL
-1baCl
2solution detects filtrate without till precipitation generation, then uses absolute ethanol washing 3 times.Then be put in baking oven, at the temperature of 85 DEG C, dry 24h.Take out, after ground 100 mesh sieves (150 μm), in the temperature lower calcination 24h of 1000 DEG C in retort furnace, obtain Sm:YLSAG nanometer grade powder.
By the Sm:YLSAG nanometer grade powder prepared, put into ball grinder, add 60g dehydrated alcohol, the agate ball of 200g diameter of phi 5mm is as ball-milling medium, the MgO adding TEOS and 0.1% being equivalent to oxide powder gross weight 0.5% as sintering aid, add be equivalent to oxide powder gross weight 0.1% oleic acid as dispersion agent.With the rotating speed of 300rpm, after ball milling mixing 24h, obtain slip.This slurry is carried out spraying dry, and controlling temperature in spray-drying process is 200 DEG C, and temperature out is 120 DEG C, and spray speed is 10ml/min.Powder after each weighing 12g spraying dry, puts into punching block, with the pressure of 20MPa, is pressed into the disk of Φ 40mm.By disk with after latex rubber bag encapsulation, with cold isostatic press pressurize 5min under 200MPa.After taking-up, by shaping base substrate in the retort furnace of 1000 DEG C, roasting 8h, to remove residual organism.Then base substrate is put in vacuum oven, opens vacuum system, be evacuated to 1 × 10
-3after Pa, with the temperature rise rate of 3-5 DEG C/min, rise to 1780 DEG C, after insulation 20h, then be down to room temperature with the speed of 10 DEG C/min, obtain Sm:YLSAG ceramics sample.
The Sm:YLSAG ceramics sample of this vacuum sintering is put in air High Temperature Furnaces Heating Apparatus, 1400 DEG C are risen to, air annealing 10h with the temperature rise rate of 5 DEG C/min, then after being down to room temperature with the rate of temperature fall of 5 DEG C/min, polished finish is carried out to it, obtains Sm:YLSAG crystalline ceramics.
Carry out transmission measurement to this Sm:YLSAG crystalline ceramics, obtaining it in 808nm place transmitance is 79.5%, and be positioned at 1065.6nm at the absorption peak nearest from 1064nm place, the uptake factor at 1064nm place is 8.6cm
-1.Visible, the Sm:YLSAG crystalline ceramics that the embodiment of the present invention provides has higher uptake factor at 1064nm place, namely has the ability of the spuious fluorescence of 1064nm that higher absorption Nd:YAG working medium produces.
Embodiment 5
According to chemical formula Y
2.25sm
0.15sc
0.3lu
0.3al
5o
12in the chemical constitution metering ratio of each element, calculate each oxide raw material quality needed for preparation 40g Sm:YLSAG ceramic powder, and the purity that weighs with scale is the Y of 99.99%
2o
3powder 16.5099g, purity is the Lu of 99.99%
2o
3powder 3.8793g, purity is the Sc of 99.99%
2o
3powder 1.3444g, purity is the Sm of 99.99%
2o
3powder 1.7001g, purity is the Al of 99.99%
2o
3powder 16.5663g.
By Y
2o
3, Lu
2o
3, Sc
2o
3and Sm
2o
3powder mixes, and is dissolved in the pure concentrated nitric acid of top grade, and is mixed with rare earth ion total mol concentration at 1.0molL with deionized water
-1rare earth nitrate mixed solution.Weigh and get the ammonium oxalate that 77.47g purity is better than 99.99%, by ammonium oxalate and the Al weighed
2o
3powder is dissolved in the mixing solutions be made up of for 1:0.2 by volume deionized water and dehydrated alcohol together, and being mixed with ammonium formiate concentration is 0.2molL
-1containing Al
2o
3the alcohol mixture aqueous suspension of powder, ammonium oxalate.The ammonium sulfate ((NH that purity is 99.99% is added in this mixing suspension liquid
4)
2sO
4) (mol ratio of ammonium sulfate and rare earth nitrate is 2:1) as dispersion agent, obtain containing Al
2o
3powder, ammonium oxalate and (NH
4)
2sO
4mixing suspension liquid.
Will containing Al
2o
3powder, ammonium oxalate and (NH
4)
2sO
4mixing suspension liquid stir after, the above-mentioned rare earth nitrate solution prepared dropwise is added drop-wise to containing Al with the speed of 8ml/min
2o
3powder, ammonium oxalate and (NH
4)
2sO
4mixing suspension liquid in.In the process, be ceaselessly uniformly mixed suspension liquid with agitator, and by the pH value of acidometer monitoring mixed solution, by ammoniacal liquor and/or nitric acid regulator solution pH value between 7.5-8.2.After titration, by reaction system ageing of solution 48h.Then it is filtered to and leaches throw out, with deionized water wash to 0.1molL
-1baCl
2solution detects filtrate without till precipitation generation, then uses absolute ethanol washing 3 times.Then be put in baking oven, at the temperature of 80 DEG C, dry 24h.Take out dried throw out, after ground 100 mesh sieves (150 μm), in the temperature lower calcination 6h of 1280 DEG C in retort furnace, obtain Sm:YLSAG nanometer grade powder.
By the Sm:YLSAG nanometer grade powder prepared, put into ball grinder, add 80g dehydrated alcohol, the silicon nitride ball of 160g diameter of phi 5mm is as ball-milling medium, the CaO adding TEOS and 0.1% being equivalent to oxide powder gross weight 0.5%, as sintering aid, adds the mixture of the oleic acid and polyoxyethylene glycol being equivalent to oxide powder gross weight 0.5% as dispersion agent.With the rotating speed of 400rpm, after ball milling mixing 16h, obtain slip.Carry out spraying dry to this slurry, controlling temperature in spray-drying process is 160 DEG C, and temperature out is 90 DEG C, and spray speed is 20ml/min.Powder after each weighing 12g spraying dry, puts into punching block, with the pressure of 5MPa, is pressed into the disk of Φ 40mm.By disk with after latex rubber bag encapsulation, with cold isostatic press pressurize 5min under 200MPa.After taking-up, by shaping base substrate in the retort furnace of 850 DEG C, roasting 24h, to remove residual organism.Then base substrate is put in vacuum oven, opens vacuum system, be evacuated to 1 × 10
-3after Pa, with the temperature rise rate of 3 ~ 5 DEG C/min, rise to 1740 DEG C, after insulation 16h, then be down to room temperature with the speed of 10 DEG C/min, obtain Sm:YLSAG ceramics sample.
The Sm:YLSAG ceramics sample of this vacuum sintering is put in air High Temperature Furnaces Heating Apparatus, 1320 DEG C are risen to the temperature rise rate of 5 DEG C/min, air annealing 24h, after being down to room temperature with the rate of temperature fall of 5 DEG C/min again, obtain Sm:YLSAG pottery, adopt existing finishing method to carry out polished finish to it, obtain Sm:YLSAG crystalline ceramics.
Carry out transmission measurement to this Sm:YLSAG crystalline ceramics, obtaining it in 808nm place transmitance is 81.5%, and be positioned at 1066.2nm at the absorption peak nearest from 1064nm place, the uptake factor at 1064nm place is 4.6cm
-1.Visible, the Sm:YLSAG crystalline ceramics that the embodiment of the present invention provides has higher uptake factor at 1064nm place, namely has the ability of the spuious fluorescence of 1064nm that higher absorption Nd:YAG working medium produces.
Embodiment 6
According to chemical formula Y
2.16sm
0.09sc
0.15lu
0.6al
5o
12in the chemical constitution of each element calculate each oxide raw material quality needed for preparation 40gSm:YLSAG ceramic powder, and the purity that weighs with scale is the Y of 99.99%
2o
3powder 15.1429g, purity is the Lu of 99.99%
2o
3powder 7.4126g, purity is the Sc of 99.99%
2o
3powder 0.6422g, purity is the Sm of 99.99%
2o
3powder 0.9746g, purity is the Al of 99.99%
2o
3powder 15.8276g.By Y
2o
3, Lu
2o
3, Sc
2o
3and Sm
2o
3powder mixes, and is dissolved in the pure concentrated nitric acid of top grade, and is mixed with rare earth ion total mol concentration at 0.5molL with deionized water
-1rare earth nitrate mixed solution.
Take the volatile salt that 148.02g purity is better than 99.99%, by volatile salt and the Al weighed
2o
3powder is dissolved in by deionized water together, and forming volatile salt concentration is 2.0molL
-1al
2o
3powder, volatile salt mixing suspension liquid, in mixing suspension liquid, add purity is 99.99% (NH
4)
2sO
4(mol ratio of ammonium sulfate and rare earth nitrate is 1:2), as dispersion agent, obtains containing Al
2o
3powder, volatile salt, (NH
4)
2sO
4mixing suspension liquid.
Will containing Al
2o
3powder, volatile salt, (NH
4)
2sO
4mixing suspension liquid stir after, the rare earth nitrate solution of preparation is dropwise added drop-wise to containing Al with the speed of 5ml/min
2o
3powder, volatile salt, (NH
4)
2sO
4mixing suspension liquid in., be ceaselessly uniformly mixed suspension liquid with agitator therebetween, and by the pH value of acidometer monitoring mixed solution, by ammoniacal liquor and nitric acid regulator solution pH value between 8.0-8.5.After titration, solution is quiet puts aging 12h.Then throw out is leached, with deionized water wash to 0.1molL
-1baCl
2solution detects filtrate without till precipitation generation, then uses absolute ethanol washing 5 times.Then be put in baking oven, at the temperature of 75 DEG C, dry 48h.Take out, after ground 100 mesh sieves (150 μm), in the temperature lower calcination 10h of 1200 DEG C in retort furnace, obtain Sm:YLSAG nanometer grade powder.
By the Sm:YLSAG nanometer grade powder prepared, put into ball grinder, add 40g dehydrated alcohol, the ZrO of 120g diameter of phi 5mm
2ball is as ball-milling medium, and the LiF adding TEOS and 1.0% being equivalent to oxide powder gross weight 0.6%, as sintering aid, adds the polyacrylic acid of oleic acid and 0.1% being equivalent to oxide powder gross weight 1.0% as dispersion agent.With the rotating speed of 400rpm, after ball milling mixing 8h, obtain slip.Carry out spraying dry to this slurry, controlling temperature in spray-drying process is 90 DEG C, and temperature out is 70 DEG C, and spray speed is 10ml/min.Powder after each weighing 12g spraying dry, puts into punching block, with the pressure of 5MPa, is pressed into the disk of Φ 40mm.By disk with after latex rubber bag encapsulation, with cold isostatic press pressurize 5min under 200MPa.After taking-up, by shaping base substrate in the retort furnace of 1100 DEG C, roasting 24h, to remove residual organism.Then base substrate is put in vacuum oven, opens vacuum system, be evacuated to 1 × 10
-3after Pa, with the temperature rise rate of 5-10 DEG C/min, rise to 1700 DEG C, after insulation 50h, then be down to room temperature with the speed of 10 DEG C/min, obtain Sm:YLSAG ceramics sample.
The Sm:YLSAG ceramics sample of this vacuum sintering is put in air High Temperature Furnaces Heating Apparatus, 1200 DEG C are risen to, air annealing 24h with the temperature rise rate of 5 DEG C/min, then after being down to room temperature with the rate of temperature fall of 5 DEG C/min, adopt existing finishing method to carry out polished finish to it, obtain Sm:YLSAG crystalline ceramics.
Carry out transmission measurement to this Sm:YLSAG crystalline ceramics, obtaining it in 808nm place transmitance is 81.2%, and be positioned at 1065.2nm at the absorption peak nearest from 1064nm place, the uptake factor at 1064nm place is 3.1cm
-1.Visible, the Sm:YLSAG crystalline ceramics that the embodiment of the present invention provides has higher uptake factor at 1064nm place, namely has the ability of the spuious fluorescence of 1064nm that higher absorption Nd:YAG working medium produces.
Embodiment 7
According to chemical formula Y
1.85sm
0.15sc
0.1lu
0.9al
5o
12in the chemical constitution of each element calculate each oxide raw material quality needed for preparation 40g Sm:YLSAG ceramic powder, and the purity that weighs with scale is the Y of 99.999%
2o
3powder 12.3612g, purity is the Lu of 99.999%
2o
3powder 10.5974g, purity is the Sc of 99.999%
2o
3powder 0.4081g, purity is the Sm of 99.999%
2o
3powder 1.5481g, purity is the Al of 99.99%
2o
3powder 15.0852g.By Y
2o
3, Lu
2o
3, Sc
2o
3and Sm
2o
3powder mixes, and is dissolved in the pure concentrated nitric acid of top grade, and is mixed with rare earth ion total mol concentration at 0.8molL with deionized water
-1rare earth nitrate mixed solution.
Take the bicarbonate of ammonia that 141.09g purity is better than 99.99%, by bicarbonate of ammonia and the Al weighed
2o
3powder is dissolved in by deionized water together, and formation ammonium bicarbonate concentration is 2.0molL
-1al
2o
3powder, bicarbonate of ammonia mixing suspension liquid, to mixing suspension liquid in add purity be 99.99% ammonium sulfate (mol ratio of ammonium sulfate and rare earth nitrate is 2:1) as dispersion agent, obtain contain Al
2o
3powder, NH
4hCO
3(NH
4)
2sO
4mixing suspension liquid.
Will containing Al
2o
3powder, NH
4hCO
3(NH
4)
2sO
4mixing suspension liquid stir after, the rare earth nitrate solution of preparation is dropwise added drop-wise to containing Al with the speed of 3ml/min
2o
3powder, NH
4hCO
3(NH
4)
2sO
4mixing suspension liquid in., be ceaselessly uniformly mixed suspension liquid with agitator therebetween, and by the pH value of acidometer monitoring mixed solution, by ammoniacal liquor and nitric acid regulator solution pH value between 7.5-8.0.After titration, solution is quiet puts aging 24h.Then throw out is leached, with deionized water wash to 0.1molL
-1baCl
2solution detects filtrate without till precipitation generation, then uses absolute ethanol washing 5 times.Then be put in baking oven, at the temperature of 75 DEG C, dry 36h.Take out, after ground 100 mesh sieves (150 μm), in the temperature lower calcination 12h of 1350 DEG C in retort furnace, obtain Sm:YLSAG nanometer grade powder.
By the Sm:YLSAG nanometer grade powder prepared, put into ball grinder, add 20g dehydrated alcohol, the agate ball of 120g diameter of phi 5mm and silicon nitride ball are as ball-milling medium, the MgO adding TEOS and 0.1% being equivalent to oxide powder gross weight 0.6%, as sintering aid, adds the polyoxyethylene glycol of oleic acid and 0.5% being equivalent to oxide powder gross weight 1.0% as dispersion agent.Then with the rotating speed of 400rpm, after ball milling mixing 8h, slip is obtained.By this slurry in the vacuum drying oven of 75 DEG C, dry 48h.Take out dry powder, after ground 200 mesh sieves, each 12g that weighs sieves powder, puts into punching block, with the pressure of 10MPa, is pressed into the disk of Φ 40mm.By disk with after latex rubber bag encapsulation, with cold isostatic press pressurize 5min under 200MPa.After taking-up, by shaping base substrate in the retort furnace of 950 DEG C, roasting 24h, to remove residual organism.Then base substrate is put in vacuum oven, opens vacuum system, be evacuated to 1 × 10
-3after Pa, with the temperature rise rate of 1 ~ 5 DEG C/min, rise to 1740 DEG C, after insulation 24h, then be down to room temperature with the speed of 10 DEG C/min, obtain the Sm:YLSAG ceramics sample of vacuum sintering.
The Sm:YLSAG ceramics sample of this vacuum sintering is put in air High Temperature Furnaces Heating Apparatus, 1450 DEG C are risen to, air annealing 10h with the temperature rise rate of 5 DEG C/min, then after being down to room temperature with the rate of temperature fall of 5 DEG C/min, adopt existing finishing method to carry out polished finish, obtain Sm:YLSAG crystalline ceramics.
Carry out transmission measurement to this Sm:YLSAG crystalline ceramics, obtaining it in 808nm place transmitance is 82.2%, and be positioned at 1065.2nm at the absorption peak nearest from 1064nm place, the uptake factor at 1064nm place is 7.9cm
-1.Visible, the Sm:YLSAG crystalline ceramics that the embodiment of the present invention provides has higher uptake factor at 1064nm place, namely has the ability of the spuious fluorescence of 1064nm that higher absorption Nd:YAG working medium produces.
Embodiment 8
According to chemical formula Y
2.52sm
0.15sc
0.3lu
0.03al
5o
12in the chemical constitution of each element calculate each oxide raw material quality needed for preparation 40gSm:YLSAG ceramic powder, and the purity that weighs with scale is the Y of 99.999%
2o
3powder 19.2166g, purity is the Lu of 99.999%
2o
3powder 0.4031g, purity is the Sc of 99.999%
2o
3powder 1.3972g, purity is the Sm of 99.999%
2o
3powder 1.7668g, purity is the Al of 99.999%
2o
3powder 17.2162g.By Y
2o
3, Lu
2o
3, Sc
2o
3and Sm
2o
3powder mixes, and is dissolved in the pure concentrated nitric acid of top grade, and is mixed with rare earth ion total mol concentration at 0.5molL with deionized water
-1rare earth nitrate mixed solution.
Take the bicarbonate of ammonia that 193.21g purity is better than 99.99%, by bicarbonate of ammonia and the Al weighed
2o
3powder is dissolved in by deionized water together, and formation ammonium bicarbonate concentration is 0.5molL
-1containing Al
2o
3powder, bicarbonate of ammonia mixing suspension liquid, to mixing suspension liquid in add purity be the ammonium sulfate (mol ratio of ammonium sulfate and rare earth nitrate is 1:1) of 99.99% as dispersion agent, obtain contain Al
2o
3powder, NH
4hCO
3, (NH
4)
2sO
4mixing suspension liquid.
Will containing Al
2o
3powder, NH
4hCO
3, (NH
4)
2sO
4mixing suspension liquid stirs, and then the rare earth nitrate solution of preparation is dropwise added drop-wise to NH with the speed of 5ml/min
4hCO
3in mixing suspension liquid., be ceaselessly uniformly mixed suspension liquid with agitator therebetween, and by the pH value of acidometer monitoring mixed solution, by ammoniacal liquor or nitric acid regulator solution pH value between 7.5-8.0.After titration, by reaction system ageing of solution 28h.Then throw out is leached, with deionized water wash to 0.1molL
-1baCl
2solution detects filtrate without till precipitation generation, then uses absolute ethanol washing 3 times.Then be put in baking oven, at the temperature of 75 DEG C, dry 48h.Take out, after ground 100 mesh sieves (150 μm), in the temperature lower calcination 12h of 1100 DEG C in retort furnace, obtain Sm:YLSAG nanometer grade powder.
By the Sm:YLSAG nanometer grade powder prepared, put into ball grinder, add 320g dehydrated alcohol, the agate ball of 120g diameter of phi 5mm, as ball-milling medium, adds the SiO being equivalent to oxide powder gross weight 0.15%
2with 0.1% MgO as sintering aid, add the polyoxyethylene glycol of polymethyl acrylic acid ammonia and 2% being equivalent to oxide powder gross weight 1.0% as dispersion agent.Then with the rotating speed of 400rpm, after ball milling mixing 12h, slip is obtained.
Described slurry is carried out spraying dry, and in control process, temperature in is 160 DEG C, and temperature out is 90 DEG C, and spray speed is 8ml/min.Each weighing 12g sieves powder, puts into punching block, with the pressure of 10MPa, is pressed into the disk of Φ 40mm.By disk with after latex rubber bag encapsulation, with cold isostatic press pressurize 5min under 200MPa.After taking-up, by shaping base substrate in the retort furnace of 800 DEG C, roasting 24h, to remove residual organism.Then base substrate is put in vacuum oven, opens vacuum system, be evacuated to 1 × 10
-3after Pa, with the temperature rise rate of 1-5 DEG C/min, be warming up to 1850 DEG C, after insulation 5h, then be down to room temperature with the speed of 10 DEG C/min, obtain the Sm:YLSAG ceramics sample of vacuum sintering.
The Sm:YLSAG ceramics sample of this vacuum sintering is put in air High Temperature Furnaces Heating Apparatus, 1450 DEG C are risen to, air annealing 10h with the temperature rise rate of 5 DEG C/min, then after being down to room temperature with the rate of temperature fall of 5 DEG C/min, polished finish is carried out to it, obtains Sm:YLSAG crystalline ceramics.
Carry out transmission measurement to this Sm:YLSAG crystalline ceramics, obtaining it in 808nm place transmitance is 82.1%, and be positioned at 1066.5nm place at the absorption peak nearest from 1064nm place, the uptake factor at 1064nm place is 4.9cm
-1.Visible, the Sm:YLSAG crystalline ceramics that the embodiment of the present invention provides has higher uptake factor at 1064nm place, namely has the ability of the spuious fluorescence of 1064nm that higher absorption Nd:YAG working medium produces.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a self-excitation radiation-absorbing material, is characterized in that, the chemical formula of described self-excitation radiation-absorbing material is: Y
3-x-y-zsm
xsc
ylu
zal
5o
12, wherein, 0 < x≤0.215,0.03≤y≤0.3,0.03≤z≤0.9.
2. self-excitation radiation-absorbing material according to claim 1, is characterized in that, described self-excitation radiation-absorbing material is a kind of crystalline ceramics.
3. a preparation method for self-excitation radiation-absorbing material according to claim 1, is characterized in that, described method comprises:
Step 1: preparation containing the rare earth inorganic acid salt solution of Y, Sm, Sc and Lu, and contains Al
2o
3the water of powder, precipitation agent and electrostatic stabilization agent or alcohol water mixing suspension liquid, according to chemical formula: Y
3-x-y-zsm
xsc
ylu
zal
5o
12the ratio of the atom number of middle Y, Sm, Sc, Lu and Al, determines the described quality containing Y, Sm, Sc and Lu element in the rare earth inorganic acid salt solution of Y, Sm, Sc and Lu and Al
2o
3quality, described chemical formula: Y
3-x-y-zsm
xsc
ylu
zal
5o
12in, 0 < x≤0.215,0.03≤y≤0.3,0.03≤z≤0.9, in described water or alcohol water mixing suspension liquid, the volume ratio of water and alcohol is 1:1-1:0;
Step 2: the described rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu is dropwise added described containing Al
2o
3in the water of powder, precipitation agent and electrostatic stabilization agent or alcohol water mixing suspension liquid, and regulate the pH value of reaction system between 7.0-8.5;
Step 3: titration is complete, carries out ageing to described reaction system and is separated being precipitated thing, wash described throw out, dry, grinding and calcining, obtains nanometer grade powder;
Step 4: by described nanometer grade powder, abrading-ball, sintering aid, dispersion agent and dehydrated alcohol composition mixed system, and ball milling is carried out to described mixed system, obtain slurry;
Step 5: carry out drying to described slurry, obtains dry powder, and repressed shaping, the roasting of the powder of described drying, vacuum sintering, anneal, obtain described self-excitation radiation-absorbing material.
4. the preparation method of self-excitation radiation-absorbing material according to claim 3, is characterized in that, in described step 1, the described rare earth inorganic acid salt solution containing Y, Sm, Sc and Lu of preparation is specially:
By high-purity Y
2o
3, Sm
2o
3, Sc
2o
3and Lu
2o
3powder is dissolved in concentrated nitric acid, obtains the rare earth nitrate solution containing Y, Sm, Sc and Lu;
Adding deionized water to the described volumetric molar concentration containing the rare earth nitrate solution of Y, Sm, Sc and Lu is 0.1molL
-1-1.0molL
-1.
5. the preparation method of self-excitation radiation-absorbing material according to claim 3, is characterized in that, in described step 1: described precipitation agent is 5:1-16:1 with the ratio of the amount of substance of described rare earth inorganic acid salt;
Described electrostatic stabilization agent is 1:2-2:1 with the ratio of the amount of substance of described rare earth inorganic acid salt;
Described precipitation agent contains Al described
2o
3volumetric molar concentration in the water of powder, precipitation agent and electrostatic stabilization agent or alcohol water mixing suspension liquid is 0.2molL
-1-2.0molL
-1.
6. the preparation method of self-excitation radiation-absorbing material according to claim 5, is characterized in that, described precipitation agent is selected from least one in supercarbonate, carbonate and oxalate;
Described electrostatic stabilization agent is selected from least one in vitriol, hydrosulfate.
7. the preparation method of self-excitation radiation-absorbing material according to claim 6, is characterized in that, described precipitation agent is bicarbonate of ammonia; Described electrostatic stabilization agent is ammonium sulfate.
8. the preparation method of self-excitation radiation-absorbing material according to claim 3, is characterized in that, in described step 3, the temperature of described calcining is 1000 DEG C-1350 DEG C.
9. the preparation method of self-excitation radiation-absorbing material according to claim 3, is characterized in that, in described step 4, described abrading-ball is selected from Al
2o
3ball, agate ball, silicon nitride ball, ZrO
2at least one in ball, the mass ratio of described abrading-ball and described nano-powder is 1:1-5:1;
Described sintering aid is selected from least one in tetraethoxy, silicon-dioxide, methyl silicate, magnesium oxide, calcium oxide and lithium fluoride, and the quality of described sintering aid is the 0.05%-1.5% of described nanometer grade powder quality;
Described dispersion agent is selected from least one in polyacrylic acid, polyoxyethylene glycol, ammonium polymethacrylate and oleic acid, and the quality of described dispersion agent is the 0.1%-3% of described nanometer grade powder quality;
The mass ratio of described dehydrated alcohol and described nanometer grade powder is 1:2-8:1.
10. the preparation method of self-excitation radiation-absorbing material according to claim 3, is characterized in that, described step 5 is specially: cross 100 orders with top sieve carry out drying, grinding to described slurry in the baking oven of temperature higher than 75 DEG C after; Or carry out drying by spraying dry to described slurry, temperature in when controlling described spraying dry is 90 DEG C-200 DEG C, and spray velocity is 1-20ml/min, obtains dried powder,
Dried powder is put into mould, utilizes the pressure higher than 5MPa to be pressed into ceramic body in advance, then use cold isostatic press compression moulding further under higher than the pressure of 200MPa,
By the ceramic body of compression moulding air or flowing oxygen atmosphere in, at the temperature of 800 DEG C-1100 DEG C, more than roasting 2h,
Ceramic body after roasting is put in vacuum high temperature furnace, at the temperature of 1700 DEG C-1850 DEG C, vacuum sintering 4-20h, controlling temperature rate is 1-10 DEG C/min,
By the ceramic body after vacuum sintering in the atmosphere of air or oxygen, at the temperature of 1200 DEG C-1450 DEG C, more than anneal 10h, obtains pottery,
Be cooled to room temperature, take out pottery, surface finish is carried out to it, obtains described self-excitation radiation-absorbing material.
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