CN103253937A - Yttrium oxide laser transparent ceramic material with incentive elements in continuous gradient distribution and preparation method thereof - Google Patents
Yttrium oxide laser transparent ceramic material with incentive elements in continuous gradient distribution and preparation method thereof Download PDFInfo
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- CN103253937A CN103253937A CN2013102091532A CN201310209153A CN103253937A CN 103253937 A CN103253937 A CN 103253937A CN 2013102091532 A CN2013102091532 A CN 2013102091532A CN 201310209153 A CN201310209153 A CN 201310209153A CN 103253937 A CN103253937 A CN 103253937A
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Abstract
The invention discloses a yttrium oxide laser transparent ceramic material with incentive elements in continuous gradient distribution and a preparation method thereof, wherein a host material is Y2O3; and the incentive elements RE are Yb, Tm or Nd. The yttrium oxide laser transparent ceramic material is characterized in that the concentration of the incentive elements RE in the host material is in a continuous gradient distribution along the axial direction of the host material. The preparation method comprises the steps of (1) preparing Y(NO3)3 solution, RE(NO3)3 solution and urea solution; (2) preparing RE:Y2O3 spherical nano-powder; (3) preparing Y2O3 spherical nano-powder; (4) mixing the Y2O3 spherical nano-powder and the RE:Y2O3 spherical nano-powder which are the same in particle size to prepare mixed powder; ball-milling, dispersing and ultrasonically dispersing to obtain slurry with high suspending stability; (5) centrifugally separating and removing a liquid phase, and drying to obtain a gradient blank; and (6) sintering in vacuum after biscuiting, and finally annealing. By adopting the preparation technology of a common ceramic material, the preparation method is simple in process, low in cost and suitable for large-scale production.
Description
Technical field
The invention belongs to the material technology field, particularly a kind of element that encourages is yttria laser transparent ceramic material that continuous gradient distributes and preparation method thereof.
Background technology
Advantages such as laser diode-pumped all solid state laser has that volume is little, efficient is high, good stability and life-span are long have important use in fields such as national defence, photoelectronic industry, optical communication and health cares.Along with constantly improving and development of high power semiconductor lasers technology, the high-power diode light-pumped solid state laser has become the research focus of Chinese scholars, these researchs mainly concentrate on and improve laser output power how effectively and improve the laser beam quality aspect, in high-power pumping process, the part heat that solid laser medium absorbs adds the heat that nonradiative transition produces, make that on the one hand laser crystals self temperature raises, on the other hand, the temperature of laser crystals raises, acting in conjunction with cooling system, formation temperature gradient in crystal, produce thermal lensing effect, phenomenons such as thermic diffraction loss and thermal rupture, running to laser apparatus brings disadvantageous effect, has had a strong impact on the beam quality of laser and output efficiency and the power of laser apparatus.
The heat effect of laser crystals derives from gain media greatly to the inhomogeneous absorption of pump light; Because the present solid state laser gain medium crystal of single doping content normally, gain media produces index to pump light and absorbs during work, has higher temperature and thermograde near making incident end face; Doping content is more big, and its uptake factor is more big, and the absorptive pumping energy is more many when causing pump light through the crystal end-face center, and its end face core temperature is more high; Because its uptake factor is more big, along with pump light enters crystal, the pump energy decay is more fast again, finally causes the more high germ nucleus axle temperature degree decay of doping content more fast.
Adopt multistage composite gain medium can alleviate working-laser material to the non-homogeneous absorption of pumping light, improve the heat effect problem of laser crystals.The laser crystals of single relatively doping content, its temperature distribution evenness of composite gain medium of end pumping is greatly improved, and the segments of laser crystals is more many, and longitudinal temperature distributes also more even.But multistage composite gain medium, do not eliminate the formed interface of compound tense between section and the section fully, its excitation concentration of element still is to a certain degree " ladder " and distributes in matrix, heat effect problem in can't fundamentally solving every section also just can not be eliminated heat effect that the interface causes and to the influence of laser beam.
Summary of the invention
The objective of the invention is the shortcoming and defect at existing multistage recombination laser crystal, provide a kind of element that encourages to be yttria laser transparent ceramic material that continuous gradient distributes and preparation method thereof.
The substrate material that excitation element of the present invention is the yttria laser transparent ceramic material of continuous gradient distribution is Y
2O
3, the excitation elements RE is Yb, Tm or Nd, the concentration of excitation elements RE in substrate material axially is continuous gradient along substrate material and distributes.
Above-mentioned excitation element is in the yttria laser transparent ceramic material of continuous gradient distribution, and when RE was Yb, its composition contained Yb1 ~ 20% by atomic percent, and surplus is Y
2O
3When RE was Tm, its composition contained Tm0.1 ~ 10% by atomic percent, and surplus is Y
2O
3When RE was Nd, its composition contained Nd0.5 ~ 10% by atomic percent, and surplus is Y
2O
3
Above-mentioned excitation element is the single-phase yttrium oxide polycrystal that is organized as of yttria laser transparent ceramic material that continuous gradient distributes.
Excitation element of the present invention is the yttria laser transparent ceramic preparation methods of continuous gradient distribution to carry out according to the following steps:
1, the preparation volumetric molar concentration is the Y(NO of 0.01 ~ 0.5M
3)
3Solution, and regulate pH=1 ~ 5; The preparation volumetric molar concentration is the RE(NO of 0.01 ~ 0.5M
3)
3Solution, and regulate pH=1 ~ 5; The preparation volumetric molar concentration is the urea soln of 0.5 ~ 2M;
2, preparation RE:Y
2O
3The ball shaped nano powder:
2.1, with Y(NO
3)
3Solution, RE(NO
3)
3Solution and urea soln mix makes rare earth doped yttrium oxide female salts solution, wherein Y(NO
3)
3With RE(NO
3)
3Mol ratio be 1:(0.1 ~ 0.5), Y(NO
3)
3And RE(NO
3)
3Total amount and the mol ratio of urea be 1:(1 ~ 30); The female salts solution of rare earth doped yttrium oxide is warming up to 75 ~ 98 ℃ in 0.5 ~ 4h, is incubated 0.5 ~ 5 hour, obtain white precipitate; Filter to collect white precipitate, clean then, 60 ~ 150 ℃ of dryings 2 ~ 48 hours, obtain rare earth doped yttrium oxide precursor powder again;
2.2, be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with rare earth doped yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and rare earth doped yttrium oxide precursor powder is 1:(4 ~ 12), the mass ratio of rare earth doped yttrium oxide precursor powder and dehydrated alcohol is 1:(2 ~ 12), polycarboxylate accounts for 0.1 ~ 4% of rare earth doped yttrium oxide precursor powder gross weight, and the ball milling time is 4 ~ 24h; Material behind the ball milling 60 ~ 150 ℃ of dryings 2 ~ 48 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 1 ~ 8h under 800 ~ 1100 ℃ and air atmosphere, obtain RE:Y
2O
3Ball shaped nano powder, particle diameter are at 100 ~ 500nm, and density is 5.09 ~ 5.4g/cm
3
3, preparation Y
2O
3The ball shaped nano powder:
3.1, with Y(NO
3)
3Solution and urea soln mix makes yttrium oxide female salts solution, wherein Y(NO
3)
3With the mol ratio of urea be 1:(1 ~ 30); The female salts solution of yttrium oxide is warming up to 75 ~ 98 ℃ in 0.5 ~ 4h, is incubated 0.5 ~ 5 hour, obtain white precipitate; Filter to collect white precipitate, clean then, 60 ~ 150 ℃ of dryings 2 ~ 48 hours, obtain yttrium oxide precursor powder again;
3.2, be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and yttrium oxide precursor powder is 1:(4 ~ 12), the mass ratio of yttrium oxide precursor powder and dehydrated alcohol is 1:(2 ~ 12), polycarboxylate accounts for 0.1 ~ 4% of yttrium oxide precursor powder gross weight, and the ball milling time is 4 ~ 24h; Material behind the ball milling 60 ~ 150 ℃ of dryings 2 ~ 48 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 1 ~ 8h under 800 ~ 1100 ℃ and air atmosphere, obtain Y
2O
3Ball shaped nano powder, particle diameter are at 100 ~ 500nm, and density is 5.01 ~ 5.03g/cm
3
4, Y that particle diameter is identical
2O
3Ball shaped nano powder and RE:Y
2O
3The ball shaped nano powder is mixed and made into mixed powder, Y
2O
3Ball shaped nano powder and RE:Y
2O
3The blending ratio of ball shaped nano powder is 1:0.01 ~ 0.5 in molar ratio; Being ball-milling medium with water, is dispersion agent with the polycarboxylate, and with the mixed powder Ball milling, the volume ratio of mixed powder and water is (0.01 ~ 0.4): 1, and dispersion agent accounts for 0.1 ~ 4% of mixed powder gross weight; Material behind the ball milling is carried out ultra-sonic dispersion, and the time is 5 ~ 30min, obtains higher suspension stability slurry;
5, with higher suspension stability slurry centrifugal 0.5 ~ 2h under 500 ~ 10000rpm condition, separate then and remove liquid phase; The dry moisture of removing in the solid phase under 60 ~ 120 ℃ of conditions obtains the gradient base substrate again;
6, with the biscuiting under the air or oxygen atmospheric condition of gradient base substrate, the biscuiting temperature is 1200 ~ 1400 ℃, and the time is 4 ~ 24h; Vacuum sintering then, the vacuum sintering temperature is 1600 ~ 1800 ℃, control vacuum tightness≤1 * 10 during vacuum sintering
-3Pa, the vacuum sintering time is 5 ~ 24h; 4 ~ the 24h that anneals under 1000 ~ 1400 ℃ of conditions at last obtains the excitation element and is the yttria laser transparent ceramic material that continuous gradient distributes.
Select ammonium polyacrylate or ammonium polymethacrylate for use as the polycarboxylate of dispersion agent in the aforesaid method.
The reagent of regulating the pH employing in the aforesaid method is the salpeter solution of concentration 0.1 ~ 1M.
Cleaning in the aforesaid method refers to that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, does not have nitrate ion to white precipitate.
The viscosity of the higher suspension stability slurry that obtains in the aforesaid method is 0.001 ~ 1Pa.
The principle of method of the present invention is: two kinds of monodisperse spherical powders that density is different with the particle diameter unanimity utilize the formed separating substances phenomenon of difference of powder granule density as raw material, in conjunction with the centrifuging process parameter adjustment, realize RE in the polycrystalline ceramics
3+The continuous gradientization of doping content.The Stokes sedimentation formula of revising can the accurate description centrifugal action under the sedimentation behavior of spheroidal particle.For diameter in the liquid slurry be
dThe rigidity bead, under centrifugal action, it will set up an equilibrium rate with moment
vSedimentation, above-mentioned sedimentation formula is:
Wherein,
ηBe liquid viscosity,
Be solid content,
dBe particle diameter,
ρ sBe pellet density,
ρ wBe fluid density,
ωBe circular frequency,
rIt is centrifugal radius.
The present invention as raw material, is about to the particle size unanimity and two kinds of monodisperse spherical powders of doping content difference (thereby density difference) are that (for example doping content is 0 Y to raw material with the isometrical bead that satisfies Stokes sedimentation formula establishment condition
2O
3Powder and Yb:Y
2O
3Powder, the perhaps Yb:Y of two kinds of different levels of doping
2O
3Powder etc.), can realize RE:Y
2O
3" structure " of crystalline ceramics compositional gradient, acquisition can be eliminated the crystalline ceramics gain medium of non-homogeneous absorption pumping light, solve the heat effect problem of end pumped laser crystal, not only can significantly improve the output rating of laser apparatus and improve beam quality, also will bring very big degree of freedom to the design of laser device structure, pumping mode and resonator cavity.On the other hand, RE:Y
2O
3Be a kind of extremely promising solid laser material, because laser ceramics can obtain doping content and the luminous efficiency higher than monocrystalline, realize RE:Y
2O
3Excitation element doping content is the continuous gradient distribution in the polycrystalline laser transparent ceramic, the lifting of laser beam quality and mean power will be brought, can aspect national defence, science and technology, industry and other civilian technology important application prospects arranged for the preparation of the super high power laser apparatus of nucleosynthesis and laser weapon.
Method of the present invention can prepare the excitation element and be the RE:Y that continuous gradient distributes
2O
3The polycrystalline laser transparent ceramic, eliminate between multistage recombination laser gain media stage casing and the segment limit face thermal stresses and to the influence of laser beam, and can not ftracture.The present invention adopts common ceramic material technology, and technology is simple, and is with low cost, is fit to scale operation.
Description of drawings
Fig. 1 is the rare earth doped yttrium oxide precursor powder SEM pattern photo figure of the embodiment of the invention 1.
Fig. 2 is the fracture SEM pattern photo figure of the gradient base substrate of the embodiment of the invention 1.
Fig. 3 is Yb in the yttria laser transparent ceramic material that continuous gradient distributes for the excitation element of the embodiment of the invention 1
3+The concentration gradient scatter chart.
Fig. 4 is the straight line transmittance curve figure of the yttria laser transparent ceramic material of continuous gradient distribution for the excitation element of the embodiment of the invention 1.
Embodiment
In the embodiment of the invention during ball milling working speed of ball mill be 200rpm.
The ultra-sonic dispersion equipment that adopts in the embodiment of the invention is the ultrasonic disruption instrument, and operating frequency is 20 ~ 25KHz.
The material of the centrifuge tube of the centrifugation apparatus that adopts in the embodiment of the invention is stainless steel or tetrafluoroethylene.
The Y(NO that adopts in the embodiment of the invention
3)
3Be commercial product, weight purity is 99.99%.
The Yb(NO that adopts in the embodiment of the invention
3)
3Be commercial product, weight purity is 99.95%.
The Tm(NO that adopts in the embodiment of the invention
3)
3Be commercial product, weight purity is 99.95%.
The Nd(NO that adopts in the embodiment of the invention
3)
3Be commercial product, weight purity is 99.95%.
The urea that adopts in the embodiment of the invention is commercial analytical reagent.
The ammonium polyacrylate that adopts in the embodiment of the invention and ammonium polymethacrylate are commercial product.
The equipment that the vacuum sintering of adopting in the embodiment of the invention is adopted is VSF-7 type vacuum sintering furnace.
The test and excitation element is the Yb of the yttria laser transparent ceramic material of continuous gradient distribution in the embodiment of the invention
3+The equipment that the concentration gradient distribution is adopted is inductive coupling plasma emission spectrograph.
To be the equipment that the straight line transmitance of the yttria laser transparent ceramic material that continuous gradient distributes adopts be the UV-VIS spectrophotometer to the test and excitation element in the embodiment of the invention.
Embodiment 1
The preparation volumetric molar concentration is the Y(NO of 0.01M
3)
3Solution, and adopt the salpeter solution of concentration 0.1M to regulate pH=1; The preparation volumetric molar concentration is the Yb(NO of 0.01M
3)
3Solution, and adopt the salpeter solution of concentration 0.1M to regulate pH=1; The preparation volumetric molar concentration is the urea soln of 0.5M;
Preparation Yb:Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution, Yb(NO
3)
3Solution and urea soln mix makes rare earth doped yttrium oxide female salts solution, wherein Y(NO
3)
3With Yb(NO
3)
3Mol ratio be 1:0.2, Y(NO
3)
3And Yb(NO
3)
3Total amount and the mol ratio of urea be 1:10; The female salts solution of rare earth doped yttrium oxide is warming up to 90 ℃ in 0.5h, is incubated 5 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 150 ℃ of dryings 2 hours, obtain rare earth doped yttrium oxide precursor powder, its SEM pattern photo as shown in Figure 1;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with rare earth doped yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and rare earth doped yttrium oxide precursor powder is 1:4, the mass ratio of rare earth doped yttrium oxide precursor powder and dehydrated alcohol is 1:2, polycarboxylate accounts for 0.1% of rare earth doped yttrium oxide precursor powder gross weight, and the ball milling time is 24h; Material behind the ball milling 60 ℃ of dryings 48 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 1h under 1100 ℃ and air atmosphere, obtain Yb:Y
2O
3Ball shaped nano powder, particle diameter be at 220 ± 20nm, density 5.24g/cm
3
Preparation Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution and urea soln mix makes yttrium oxide female salts solution, wherein Y(NO
3)
3With the mol ratio of urea be 1:15; The female salts solution of yttrium oxide is warming up to 85 ℃ in 0.5h, is incubated 5 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 150 ℃ of dryings 2 hours, obtain yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and yttrium oxide precursor powder is 1:4, the mass ratio of yttrium oxide precursor powder and dehydrated alcohol is 1:2, polycarboxylate accounts for 0.1% of yttrium oxide precursor powder gross weight, and the ball milling time is 24h; Material behind the ball milling 60 ℃ of dryings 48 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 1h under 1100 ℃ and air atmosphere, obtain Y
2O
3Ball shaped nano powder, particle diameter be at 220 ± 10nm, density 5.01 g/cm
3
With above-mentioned Y
2O
3Ball shaped nano powder and Yb:Y
2O
3The ball shaped nano powder is mixed and made into mixed powder, Y
2O
3Ball shaped nano powder and Yb:Y
2O
3The blending ratio of ball shaped nano powder is 1:0.3 in molar ratio; Being ball-milling medium with water, is dispersion agent with the polycarboxylate, and with the mixed powder Ball milling, the volume ratio of mixed powder and water is 0.4:1, and dispersion agent accounts for 4% of mixed powder gross weight; Material behind the ball milling is carried out ultra-sonic dispersion, and the time is 30min, obtains higher suspension stability slurry, and viscosity is 0.32Pa;
With higher suspension stability slurry centrifugal 0.5h under the 10000rpm condition, separate then and remove liquid phase; The dry moisture of removing in the solid phase under 60 ~ 120 ℃ of conditions obtains the gradient base substrate again, and its fracture SEM pattern photo as shown in Figure 2;
With the biscuiting under the air atmosphere condition of gradient base substrate, the biscuiting temperature is 1200 ℃, and the time is 24h; Vacuum sintering then, the vacuum sintering temperature is 1600 ℃, control vacuum tightness≤1 * 10 during vacuum sintering
-3Pa, the vacuum sintering time is 24h; The 24h that anneals under 1000 ℃ of conditions at last obtains the excitation element and is the yttria laser transparent ceramic material that continuous gradient distributes, and thickness is 20mm, its Yb
3+The concentration gradient distribution curve as shown in Figure 3; The excitation element of intercepting thickness 1mm is the yttria laser transparent ceramic material that continuous gradient distributes, and its straight line transmittance curve figure as shown in Figure 4;
Above-mentioned polycarboxylate is ammonium polyacrylate;
The composition that the excitation element is the yttria laser transparent ceramic material of continuous gradient distribution on average contains Yb3.8% by atomic percent, and surplus is Y
2O
3
The excitation element is the single-phase yttrium oxide polycrystal that is organized as of yttria laser transparent ceramic material that continuous gradient distributes.
The preparation volumetric molar concentration is the Y(NO of 0.5M
3)
3Solution, and adopt the salpeter solution of concentration 1M to regulate pH=5; The preparation volumetric molar concentration is the Yb(NO of 0.5M
3)
3Solution, and adopt the salpeter solution of concentration 1M to regulate pH=5; The preparation volumetric molar concentration is the urea soln of 2M;
Preparation Yb:Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution, Yb(NO
3)
3Solution and urea soln mix makes rare earth doped yttrium oxide female salts solution, wherein Y(NO
3)
3With Yb(NO
3)
3Mol ratio be 1:0.5, Y(NO
3)
3And Yb(NO
3)
3Total amount and the mol ratio of urea be 1:30; The female salts solution of rare earth doped yttrium oxide is warming up to 82 ℃ in 1h, is incubated 3 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 60 ℃ of dryings 48 hours, obtain rare earth doped yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with rare earth doped yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and rare earth doped yttrium oxide precursor powder is 1:12, the mass ratio of rare earth doped yttrium oxide precursor powder and dehydrated alcohol is 1:12, polycarboxylate accounts for 4% of rare earth doped yttrium oxide precursor powder gross weight, and the ball milling time is 4h; Material behind the ball milling 120 ℃ of dryings 8 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 8h under 800 ℃ and air atmosphere, obtain Yb:Y
2O
3Ball shaped nano powder, particle diameter be at 230 ± 10nm, density 5.4g/cm
3
Preparation Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution and urea soln mix makes yttrium oxide female salts solution, wherein Y(NO
3)
3With the mol ratio of urea be 1:30; The female salts solution of yttrium oxide is warming up to 82 ℃ in 1h, is incubated 3 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 60 ℃ of dryings 48 hours, obtain yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and yttrium oxide precursor powder is 1:12, the mass ratio of yttrium oxide precursor powder and dehydrated alcohol is 1:12, polycarboxylate accounts for 4% of yttrium oxide precursor powder gross weight, and the ball milling time is 4h; Material behind the ball milling 120 ℃ of dryings 8 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 8h under 800 ℃ and air atmosphere, obtain Y
2O
3Ball shaped nano powder, particle diameter be at 230 ± 10nm, density 5.01g/cm
3
With above-mentioned Y
2O
3Ball shaped nano powder and Yb:Y
2O
3The ball shaped nano powder is mixed and made into mixed powder, Y
2O
3Ball shaped nano powder and Yb:Y
2O
3The blending ratio of ball shaped nano powder is 1:0.5 in molar ratio; Being ball-milling medium with water, is dispersion agent with the polycarboxylate, and with the mixed powder Ball milling, the volume ratio of mixed powder and water is 0.01:1, and dispersion agent accounts for 0.1% of mixed powder gross weight; Material behind the ball milling is carried out ultra-sonic dispersion, and the time is 5min, obtains higher suspension stability slurry, and viscosity is 0.005Pa;
With higher suspension stability slurry centrifugal 2h under the 500rpm condition, separate then and remove liquid phase; The dry moisture of removing in the solid phase under 60 ~ 120 ℃ of conditions obtains the gradient base substrate again;
With the biscuiting under the air atmosphere condition of gradient base substrate, the biscuiting temperature is 1300 ℃, and the time is 16h; Vacuum sintering then, the vacuum sintering temperature is 1800 ℃, control vacuum tightness≤1 * 10 during vacuum sintering
-3Pa, the vacuum sintering time is 5h; The 4h that anneals under 1400 ℃ of conditions at last obtains the excitation element and is the yttria laser transparent ceramic material that continuous gradient distributes;
Above-mentioned polycarboxylate is ammonium polymethacrylate;
The composition that the excitation element is the yttria laser transparent ceramic material of continuous gradient distribution on average contains Yb11.1% by atomic percent, and surplus is Y
2O
3
The excitation element is the single-phase yttrium oxide polycrystal that is organized as of yttria laser transparent ceramic material that continuous gradient distributes.
Embodiment 3
The preparation volumetric molar concentration is the Y(NO of 0.1M
3)
3Solution, and adopt the salpeter solution of concentration 0.2M to regulate pH=35; The preparation volumetric molar concentration is the Yb(NO of 0.1M
3)
3Solution, and adopt the salpeter solution of concentration 0.2M to regulate pH=3; The preparation volumetric molar concentration is the urea soln of 1M;
Preparation Yb:Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution, Yb(NO
3)
3Solution and urea soln mix makes rare earth doped yttrium oxide female salts solution, wherein Y(NO
3)
3With Yb(NO
3)
3Mol ratio be 1:0.1, Y(NO
3)
3And Yb(NO
3)
3Total amount and the mol ratio of urea be 1:10; The female salts solution of rare earth doped yttrium oxide is warming up to 98 ℃ in 4h, is incubated 0.5 hour, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 100 ℃ of dryings 24 hours, obtain rare earth doped yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with rare earth doped yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and rare earth doped yttrium oxide precursor powder is 1:8, the mass ratio of rare earth doped yttrium oxide precursor powder and dehydrated alcohol is 1:8, polycarboxylate accounts for 2% of rare earth doped yttrium oxide precursor powder gross weight, and the ball milling time is 12h; Material behind the ball milling 100 ℃ of dryings 24 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 6h under 900 ℃ and air atmosphere, obtain RE:Y
2O
3Ball shaped nano powder, particle diameter be at 360 ± 10nm, density 5.12g/cm
3
Preparation Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution and urea soln mix makes yttrium oxide female salts solution, wherein Y(NO
3)
3With the mol ratio of urea be 1:10; The female salts solution of yttrium oxide is warming up to 98 ℃ in 4h, is incubated 0.5 hour, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 100 ℃ of dryings 24 hours, obtain yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and yttrium oxide precursor powder is 1:8, the mass ratio of yttrium oxide precursor powder and dehydrated alcohol is 1:8, polycarboxylate accounts for 2% of yttrium oxide precursor powder gross weight, and the ball milling time is 12h; Material behind the ball milling 100 ℃ of dryings 24 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 6h under 900 ℃ and air atmosphere, obtain Y
2O
3Ball shaped nano powder, particle diameter be at 360 ± 10nm, density 5.02g/cm
3
With above-mentioned Y
2O
3Ball shaped nano powder and Yb:Y
2O
3The ball shaped nano powder is mixed and made into mixed powder, Y
2O
3Ball shaped nano powder and Yb:Y
2O
3The blending ratio of ball shaped nano powder is 1:0.2 in molar ratio; Being ball-milling medium with water, is dispersion agent with the polycarboxylate, and with the mixed powder Ball milling, the volume ratio of mixed powder and water is 0.2:1, and dispersion agent accounts for 1.5% of mixed powder gross weight; Material behind the ball milling is carried out ultra-sonic dispersion, and the time is 12min, obtains higher suspension stability slurry, and viscosity is 0.145Pa;
With higher suspension stability slurry centrifugal 1h under the 1000rpm condition, separate then and remove liquid phase; The dry moisture of removing in the solid phase under 60 ~ 120 ℃ of conditions obtains the gradient base substrate again;
With the biscuiting under the oxygen atmosphere condition of gradient base substrate, the biscuiting temperature is 1400 ℃, and the time is 4h; Vacuum sintering then, the vacuum sintering temperature is 1700 ℃, control vacuum tightness≤1 * 10 during vacuum sintering
-3Pa, the vacuum sintering time is 16h; The 20h that anneals under 1200 ℃ of conditions at last obtains the excitation element and is the yttria laser transparent ceramic material that continuous gradient distributes;
Above-mentioned polycarboxylate is ammonium polymethacrylate;
The composition that the excitation element is the yttria laser transparent ceramic material of continuous gradient distribution on average contains Yb1.5% by atomic percent, and surplus is Y
2O
3
The excitation element is the single-phase yttrium oxide polycrystal that is organized as of yttria laser transparent ceramic material that continuous gradient distributes.
The preparation volumetric molar concentration is the Y(NO of 0.02M
3)
3Solution, and adopt the salpeter solution of concentration 0.2M to regulate pH=2; The preparation volumetric molar concentration is the Tm(NO of 0.02M
3)
3Solution, and adopt the salpeter solution of concentration 0.2M to regulate pH=2; The preparation volumetric molar concentration is the urea soln of 0.8M;
Preparation Tm:Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution, Tm(NO
3)
3Solution and urea soln mix makes rare earth doped yttrium oxide female salts solution, wherein Y(NO
3)
3With Tm(NO
3)
3Mol ratio be 1:0.2, Y(NO
3)
3And Tm(NO
3)
3Total amount and the mol ratio of urea be 1:2; The female salts solution of rare earth doped yttrium oxide is warming up to 90 ℃ in 3h, is incubated 1 hour, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 80 ℃ of dryings 36 hours, obtain rare earth doped yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with rare earth doped yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and rare earth doped yttrium oxide precursor powder is 1:5, the mass ratio of rare earth doped yttrium oxide precursor powder and dehydrated alcohol is 1:3, polycarboxylate accounts for 0.5% of rare earth doped yttrium oxide precursor powder gross weight, and the ball milling time is 20h; Material behind the ball milling 60 ℃ of dryings 48 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 1h under 1100 ℃ and air atmosphere, obtain RE:Y
2O
3Ball shaped nano powder, particle diameter be at 480 ± 10nm, density 5.09g/cm
3
Preparation Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution and urea soln mix makes yttrium oxide female salts solution, wherein Y(NO
3)
3With the mol ratio of urea be 1:2; The female salts solution of yttrium oxide is warming up to 90 ℃ in 3h, is incubated 1 hour, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 80 ℃ of dryings 36 hours, obtain yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and yttrium oxide precursor powder is 1:5, the mass ratio of yttrium oxide precursor powder and dehydrated alcohol is 1:3, polycarboxylate accounts for 0.5% of yttrium oxide precursor powder gross weight, and the ball milling time is 20h; Material behind the ball milling 60 ℃ of dryings 48 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 1h under 1100 ℃ and air atmosphere, obtain Y
2O
3Ball shaped nano powder, particle diameter be at 480 ± 10nm, density 5.03g/cm
3
With above-mentioned Y
2O
3Ball shaped nano powder and Tm:Y
2O
3The ball shaped nano powder is mixed and made into mixed powder, Y
2O
3Ball shaped nano powder and Tm:Y
2O
3The blending ratio of ball shaped nano powder is 1:0.02 in molar ratio; Being ball-milling medium with water, is dispersion agent with the polycarboxylate, and with the mixed powder Ball milling, the volume ratio of mixed powder and water is 0.03:1, and dispersion agent accounts for 0.6% of mixed powder gross weight; Material behind the ball milling is carried out ultra-sonic dispersion, and the time is 10min, obtains higher suspension stability slurry, and viscosity is 0.022Pa;
With higher suspension stability slurry centrifugal 0.5h under the 10000rpm condition, separate then and remove liquid phase; The dry moisture of removing in the solid phase under 60 ~ 120 ℃ of conditions obtains the gradient base substrate again;
With the biscuiting under the air atmosphere condition of gradient base substrate, the biscuiting temperature is 1200 ℃, and the time is 20h; Vacuum sintering then, the vacuum sintering temperature is 1700 ℃, control vacuum tightness≤1 * 10 during vacuum sintering
-3Pa, the vacuum sintering time is 18h; The 9h that anneals under 1300 ℃ of conditions at last obtains the excitation element and is the yttria laser transparent ceramic material that continuous gradient distributes;
Above-mentioned polycarboxylate is ammonium polyacrylate;
The composition that the excitation element is the yttria laser transparent ceramic material of continuous gradient distribution on average contains Tm0.33% by atomic percent, and surplus is Y
2O
3
The excitation element is the single-phase yttrium oxide polycrystal that is organized as of yttria laser transparent ceramic material that continuous gradient distributes.
Embodiment 5
The preparation volumetric molar concentration is the Y(NO of 0.4M
3)
3Solution, and adopt the salpeter solution of concentration 0.8M to regulate pH=3; The preparation volumetric molar concentration is the Tm(NO of 0.4M
3)
3Solution, and adopt the salpeter solution of concentration 0.8M to regulate pH=4; The preparation volumetric molar concentration is the urea soln of 1.6M;
Preparation Tm:Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution, Tm(NO
3)
3Solution and urea soln mix makes rare earth doped yttrium oxide female salts solution, wherein Y(NO
3)
3With Tm(NO
3)
3Mol ratio be 1:0.15, Y(NO
3)
3And Tm(NO
3)
3Total amount and the mol ratio of urea be 1:25; The female salts solution of rare earth doped yttrium oxide is warming up to 80 ℃ in 1h, is incubated 4 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 120 ℃ of dryings 12 hours, obtain rare earth doped yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with rare earth doped yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and rare earth doped yttrium oxide precursor powder is 1:10, the mass ratio of rare earth doped yttrium oxide precursor powder and dehydrated alcohol is 1:10, polycarboxylate accounts for 3% of rare earth doped yttrium oxide precursor powder gross weight, and the ball milling time is 6h; Material behind the ball milling 150 ℃ of dryings 2 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 8h under 800 ℃ and air atmosphere, obtain RE:Y
2O
3Ball shaped nano powder, particle diameter be at 200 ± 20nm, density 5.19g/cm
3
Preparation Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution and urea soln mix makes yttrium oxide female salts solution, wherein Y(NO
3)
3With the mol ratio of urea be 1:25; The female salts solution of yttrium oxide is warming up to 80 ℃ in 1h, is incubated 4 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 120 ℃ of dryings 12 hours, obtain yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and yttrium oxide precursor powder is 1:10, the mass ratio of yttrium oxide precursor powder and dehydrated alcohol is 1:10, polycarboxylate accounts for 3% of yttrium oxide precursor powder gross weight, and the ball milling time is 6h; Material behind the ball milling 150 ℃ of dryings 2 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 8h under 800 ℃ and air atmosphere, obtain Y
2O
3Ball shaped nano powder, particle diameter be at 200 ± 20nm, density 5.01g/cm
3
With above-mentioned Y
2O
3Ball shaped nano powder and Tm:Y
2O
3The ball shaped nano powder is mixed and made into mixed powder, Y
2O
3Ball shaped nano powder and Tm:Y
2O
3The blending ratio of ball shaped nano powder is 1:0.4 in molar ratio; Being ball-milling medium with water, is dispersion agent with the polycarboxylate, and with the mixed powder Ball milling, the volume ratio of mixed powder and water is 0.33:1, and dispersion agent accounts for 2.6% of mixed powder gross weight; Material behind the ball milling is carried out ultra-sonic dispersion, and the time is 25min, obtains higher suspension stability slurry, and viscosity is 0.75Pa;
With higher suspension stability slurry centrifugal 2h under the 500rpm condition, separate then and remove liquid phase; The dry moisture of removing in the solid phase under 60 ~ 120 ℃ of conditions obtains the gradient base substrate again;
With the biscuiting under the air atmosphere condition of gradient base substrate, the biscuiting temperature is 1400 ℃, and the time is 6h; Vacuum sintering then, the vacuum sintering temperature is 1600 ℃, control vacuum tightness≤1 * 10 during vacuum sintering
-3Pa, the vacuum sintering time is 20h; The 22h that anneals under 1000 ℃ of conditions at last obtains the excitation element and is the yttria laser transparent ceramic material that continuous gradient distributes;
Above-mentioned polycarboxylate is ammonium polymethacrylate;
The composition that the excitation element is the yttria laser transparent ceramic material that continuous gradient distributes atomic percent by weight on average contains Tm3.7%, and surplus is Y
2O
3
The excitation element is the single-phase yttrium oxide polycrystal that is organized as of yttria laser transparent ceramic material that continuous gradient distributes.
The preparation volumetric molar concentration is the Y(NO of 0.3M
3)
3Solution, and adopt the salpeter solution of concentration 0.6M to regulate pH=5; The preparation volumetric molar concentration is the Tm(NO of 0.3M
3)
3Solution, and adopt the salpeter solution of concentration 0.6M to regulate pH=4; The preparation volumetric molar concentration is the urea soln of 1.2M;
Preparation Tm:Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution, Tm(NO
3)
3Solution and urea soln mix makes rare earth doped yttrium oxide female salts solution, wherein Y(NO
3)
3With Tm(NO
3)
3Mol ratio be 1:0.2, Y(NO
3)
3And Tm(NO
3)
3Total amount and the mol ratio of urea be 1:20; The female salts solution of rare earth doped yttrium oxide is warming up to 92 ℃ in 2h, is incubated 3 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 100 ℃ of dryings 24 hours, obtain rare earth doped yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with rare earth doped yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and rare earth doped yttrium oxide precursor powder is 1:9, the mass ratio of rare earth doped yttrium oxide precursor powder and dehydrated alcohol is 1:8, polycarboxylate accounts for 1% of rare earth doped yttrium oxide precursor powder gross weight, and the ball milling time is 18h; Material behind the ball milling 100 ℃ of dryings 24 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 3h under 1000 ℃ and air atmosphere, obtain RE:Y
2O
3Ball shaped nano powder, particle diameter be at 300 ± 10nm, density 5.17g/cm
3
Preparation Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution and urea soln mix makes yttrium oxide female salts solution, wherein Y(NO
3)
3With the mol ratio of urea be 1:20; The female salts solution of yttrium oxide is warming up to 88 ℃ in 1h, is incubated 4 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 90 ℃ of dryings 30 hours, obtain yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and yttrium oxide precursor powder is 1:9, the mass ratio of yttrium oxide precursor powder and dehydrated alcohol is 1:8, polycarboxylate accounts for 1% of yttrium oxide precursor powder gross weight, and the ball milling time is 18h; Material behind the ball milling 100 ℃ of dryings 24 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 3h under 1000 ℃ and air atmosphere, obtain Y
2O
3Ball shaped nano powder, particle diameter be at 300 ± 10nm, density 5.01g/cm
3
With above-mentioned Y
2O
3Ball shaped nano powder and Tm:Y
2O
3The ball shaped nano powder is mixed and made into mixed powder, Y
2O
3Ball shaped nano powder and Tm:Y
2O
3The blending ratio of ball shaped nano powder is 1:0.3 in molar ratio; Being ball-milling medium with water, is dispersion agent with the polycarboxylate, and with the mixed powder Ball milling, the volume ratio of mixed powder and water is 0.18:1, and dispersion agent accounts for 1.5% of mixed powder gross weight; Material behind the ball milling is carried out ultra-sonic dispersion, and the time is 20min, obtains higher suspension stability slurry, and viscosity is 0.12Pa;
With higher suspension stability slurry centrifugal 1h under the 1000rpm condition, separate then and remove liquid phase; The dry moisture of removing in the solid phase under 60 ~ 120 ℃ of conditions obtains the gradient base substrate again;
With the biscuiting under the oxygen atmosphere condition of gradient base substrate, the biscuiting temperature is 1300 ℃, and the time is 12h; Vacuum sintering then, the vacuum sintering temperature is 1800 ℃, control vacuum tightness≤1 * 10 during vacuum sintering
-3Pa, the vacuum sintering time is 10h; The 14h that anneals under 1200 ℃ of conditions at last obtains the excitation element and is the yttria laser transparent ceramic material that continuous gradient distributes;
Above-mentioned polycarboxylate is ammonium polymethacrylate;
The composition that the excitation element is the yttria laser transparent ceramic material of continuous gradient distribution on average contains Tm3.8% by atomic percent, and surplus is Y
2O
3
The excitation element is the single-phase yttrium oxide polycrystal that is organized as of yttria laser transparent ceramic material that continuous gradient distributes.
Embodiment 7
The preparation volumetric molar concentration is the Y(NO of 0.06M
3)
3Solution, and adopt the salpeter solution of concentration 0.2M to regulate pH=1; The preparation volumetric molar concentration is the Nd(NO of 0.06M
3)
3Solution, and adopt the salpeter solution of concentration 0.2M to regulate pH=3; The preparation volumetric molar concentration is the urea soln of 0.9M;
Preparation Nd:Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution, Nd(NO
3)
3Solution and urea soln mix makes rare earth doped yttrium oxide female salts solution, wherein Y(NO
3)
3With Nd(NO
3)
3Mol ratio be 1:0.4, Y(NO
3)
3And Nd(NO
3)
3Total amount and the mol ratio of urea be 1:3; The female salts solution of rare earth doped yttrium oxide is warming up to 75 ℃ in 0.5h, is incubated 5 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 150 ℃ of dryings 2 hours, obtain rare earth doped yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with rare earth doped yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and rare earth doped yttrium oxide precursor powder is 1:6, the mass ratio of rare earth doped yttrium oxide precursor powder and dehydrated alcohol is 1:4, polycarboxylate accounts for 0.3% of rare earth doped yttrium oxide precursor powder gross weight, and the ball milling time is 22h; Material behind the ball milling 150 ℃ of dryings 2 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 6h under 900 ℃ and air atmosphere, obtain RE:Y
2O
3Ball shaped nano powder, particle diameter be at 330 ± 30nm, density 5.11g/cm
3
Preparation Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution and urea soln mix makes yttrium oxide female salts solution, wherein Y(NO
3)
3With the mol ratio of urea be 1:3; The female salts solution of yttrium oxide is warming up to 84 ℃ in 3h, is incubated 4 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 120 ℃ of dryings 8 hours, obtain yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and yttrium oxide precursor powder is 1:6, the mass ratio of yttrium oxide precursor powder and dehydrated alcohol is 1:4, polycarboxylate accounts for 0.3% of yttrium oxide precursor powder gross weight, and the ball milling time is 22h; Material behind the ball milling 150 ℃ of dryings 2 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 6h under 900 ℃ and air atmosphere, obtain Y
2O
3Ball shaped nano powder, particle diameter be at 330 ± 30nm, density 5.02g/cm
3
With above-mentioned Y
2O
3Ball shaped nano powder and Nd:Y
2O
3The ball shaped nano powder is mixed and made into mixed powder, Y
2O
3Ball shaped nano powder and Nd:Y
2O
3The blending ratio of ball shaped nano powder is 1:0.03 in molar ratio; Being ball-milling medium with water, is dispersion agent with the polycarboxylate, and with the mixed powder Ball milling, the volume ratio of mixed powder and water is 0.05:1, and dispersion agent accounts for 0.9% of mixed powder gross weight; Material behind the ball milling is carried out ultra-sonic dispersion, and the time is 9min, obtains higher suspension stability slurry, and viscosity is 0.023Pa;
With higher suspension stability slurry centrifugal 0.5h under the 10000rpm condition, separate then and remove liquid phase; The dry moisture of removing in the solid phase under 60 ~ 120 ℃ of conditions obtains the gradient base substrate again;
With the biscuiting under the oxygen atmosphere condition of gradient base substrate, the biscuiting temperature is 1400 ℃, and the time is 18h; Vacuum sintering then, the vacuum sintering temperature is 1600 ℃, control vacuum tightness≤1 * 10 during vacuum sintering
-3Pa, the vacuum sintering time is 21h; The 19h that anneals under 1000 ℃ of conditions at last obtains the excitation element and is the yttria laser transparent ceramic material that continuous gradient distributes;
Above-mentioned polycarboxylate is ammonium polyacrylate;
The composition that the excitation element is the yttria laser transparent ceramic material of continuous gradient distribution on average contains Nd0.83% by atomic percent, and surplus is Y
2O
3
The excitation element is the single-phase yttrium oxide polycrystal that is organized as of yttria laser transparent ceramic material that continuous gradient distributes.
The preparation volumetric molar concentration is the Y(NO of 0.5M
3)
3Solution, and adopt the salpeter solution of concentration 1M to regulate pH=4; The preparation volumetric molar concentration is the Nd(NO of 0.5M
3)
3Solution, and adopt the salpeter solution of concentration 1M to regulate pH=1; The preparation volumetric molar concentration is the urea soln of 2M;
Preparation Nd:Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution, Nd(NO
3)
3Solution and urea soln mix makes rare earth doped yttrium oxide female salts solution, wherein Y(NO
3)
3With Nd(NO
3)
3Mol ratio be 1:0.1, Y(NO
3)
3And Nd(NO
3)
3Total amount and the mol ratio of urea be 1:27; The female salts solution of rare earth doped yttrium oxide is warming up to 98 ℃ in 4h, is incubated 1 hour, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 90 ℃ of dryings 40 hours, obtain rare earth doped yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with rare earth doped yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and rare earth doped yttrium oxide precursor powder is 1:11, the mass ratio of rare earth doped yttrium oxide precursor powder and dehydrated alcohol is 1:11, polycarboxylate accounts for 4% of rare earth doped yttrium oxide precursor powder gross weight, and the ball milling time is 4h; Material behind the ball milling 90 ℃ of dryings 24 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 1h under 1100 ℃ and air atmosphere, obtain Nd:Y
2O
3Ball shaped nano powder, particle diameter be at 420 ± 30nm, density 5.15g/cm
3
Preparation Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution and urea soln mix makes yttrium oxide female salts solution, wherein Y(NO
3)
3With the mol ratio of urea be 1:27; The female salts solution of yttrium oxide is warming up to 90 ℃ in 3h, is incubated 2.5 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 60 ℃ of dryings 48 hours, obtain yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and yttrium oxide precursor powder is 1:11, the mass ratio of yttrium oxide precursor powder and dehydrated alcohol is 1:11, polycarboxylate accounts for 4% of yttrium oxide precursor powder gross weight, and the ball milling time is 24h; Material behind the ball milling 90 ℃ of dryings 24 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 1h under 1100 ℃ and air atmosphere, obtain Y
2O
3Ball shaped nano powder, particle diameter be at 420 ± 30nm, density 5.03g/cm
3
With above-mentioned Y
2O
3Ball shaped nano powder and Nd:Y
2O
3The ball shaped nano powder is mixed and made into mixed powder, Y
2O
3Ball shaped nano powder and Nd:Y
2O
3The blending ratio of ball shaped nano powder is 1:0.45 in molar ratio; Being ball-milling medium with water, is dispersion agent with the polycarboxylate, and with the mixed powder Ball milling, the volume ratio of mixed powder and water is 0.4:1, and dispersion agent accounts for 3% of mixed powder gross weight; Material behind the ball milling is carried out ultra-sonic dispersion, and the time is 28min, obtains higher suspension stability slurry, and viscosity is 0.98Pa;
With higher suspension stability slurry centrifugal 2h under the 500rpm condition, separate then and remove liquid phase; The dry moisture of removing in the solid phase under 60 ~ 120 ℃ of conditions obtains the gradient base substrate again;
With the biscuiting under the air atmosphere condition of gradient base substrate, the biscuiting temperature is 1300 ℃, and the time is 15h; Vacuum sintering then, the vacuum sintering temperature is 1800 ℃, control vacuum tightness≤1 * 10 during vacuum sintering
-3Pa, the vacuum sintering time is 6h; The 8h that anneals under 1400 ℃ of conditions at last obtains the excitation element and is the yttria laser transparent ceramic material that continuous gradient distributes;
Above-mentioned polycarboxylate is ammonium polyacrylate;
The composition that the excitation element is the yttria laser transparent ceramic material of continuous gradient distribution on average contains Nd2.8% by atomic percent, and surplus is Y
2O
3
The excitation element is the single-phase yttrium oxide polycrystal that is organized as of yttria laser transparent ceramic material that continuous gradient distributes.
Embodiment 9
The preparation volumetric molar concentration is the Y(NO of 0.1M
3)
3Solution, and adopt the salpeter solution of concentration 0.3M to regulate pH=5; The preparation volumetric molar concentration is the Nd(NO of 0.1M
3)
3Solution, and adopt the salpeter solution of concentration 0.3M to regulate pH=4; The preparation volumetric molar concentration is the urea soln of 1M;
Preparation Nd:Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution, Nd(NO
3)
3Solution and urea soln mix makes rare earth doped yttrium oxide female salts solution, wherein Y(NO
3)
3With Nd(NO
3)
3Mol ratio be 1:0.2, Y(NO
3)
3And Nd(NO
3)
3Total amount and the mol ratio of urea be 1:10; The female salts solution of rare earth doped yttrium oxide is warming up to 80 ℃ in 3h, is incubated 4.5 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 60 ℃ of dryings 48 hours, obtain rare earth doped yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with rare earth doped yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and rare earth doped yttrium oxide precursor powder is 1:10, the mass ratio of rare earth doped yttrium oxide precursor powder and dehydrated alcohol is 1:9, polycarboxylate accounts for 2% of rare earth doped yttrium oxide precursor powder gross weight, and the ball milling time is 10h; Material behind the ball milling 80 ℃ of dryings 36 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 8h under 800 ℃ and air atmosphere, obtain RE:Y
2O
3Ball shaped nano powder, particle diameter be at 190 ± 10nm, density 5.19g/cm
3
Preparation Y
2O
3The ball shaped nano powder:
With Y(NO
3)
3Solution and urea soln mix makes yttrium oxide female salts solution, wherein Y(NO
3)
3With the mol ratio of urea be 1:10; The female salts solution of yttrium oxide is warming up to 80 ℃ in 3h, is incubated 4 hours, obtain white precipitate; Filter and collect white precipitate and cleaning, cleaning is that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, and cleaning to white precipitate does not have nitrate ion; Clean the back 60 ℃ of dryings 48 hours, obtain yttrium oxide precursor powder;
Be ball-milling medium with the dehydrated alcohol, be dispersion agent with the polycarboxylate, with yttrium oxide precursor powder Ball milling, wherein the mass ratio (ratio of grinding media to material) of abrading-ball and yttrium oxide precursor powder is 1:10, the mass ratio of yttrium oxide precursor powder and dehydrated alcohol is 1:9, polycarboxylate accounts for 2% of yttrium oxide precursor powder gross weight, and the ball milling time is 10h; Material behind the ball milling 80 ℃ of dryings 36 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 8h under 800 ℃ and air atmosphere, obtain Y
2O
3Ball shaped nano powder, particle diameter be at 190 ± 10nm, density 5.01g/cm
3
With above-mentioned Y
2O
3Ball shaped nano powder and Nd:Y
2O
3The ball shaped nano powder is mixed and made into mixed powder, Y
2O
3Ball shaped nano powder and Nd:Y
2O
3The blending ratio of ball shaped nano powder is 1:0.2 in molar ratio; Being ball-milling medium with water, is dispersion agent with the polycarboxylate, and with the mixed powder Ball milling, the volume ratio of mixed powder and water is 0.25:1, and dispersion agent accounts for 2.2% of mixed powder gross weight; Material behind the ball milling is carried out ultra-sonic dispersion, and the time is 24min, obtains higher suspension stability slurry, and viscosity is 0.38Pa;
With higher suspension stability slurry centrifugal 1h under the 1000rpm condition, separate then and remove liquid phase; The dry moisture of removing in the solid phase under 60 ~ 120 ℃ of conditions obtains the gradient base substrate again;
With the biscuiting under the air atmosphere condition of gradient base substrate, the biscuiting temperature is 1200 ℃, and the time is 24h; Vacuum sintering then, the vacuum sintering temperature is 1700 ℃, control vacuum tightness≤1 * 10 during vacuum sintering
-3Pa, the vacuum sintering time is 15h; The 17h that anneals under 1100 ℃ of conditions at last obtains the excitation element and is the yttria laser transparent ceramic material that continuous gradient distributes;
Above-mentioned polycarboxylate is ammonium polyacrylate;
The composition that the excitation element is the yttria laser transparent ceramic material of continuous gradient distribution on average contains Nd2.8% by atomic percent, and surplus is Y
2O
3
The excitation element is the single-phase yttrium oxide polycrystal that is organized as of yttria laser transparent ceramic material that continuous gradient distributes.
Claims (6)
1. one kind is encouraged element to be the yttria laser transparent ceramic material that continuous gradient distributes, and its substrate material is Y
2O
3, the excitation elements RE is Yb, Tm or Nd, it is characterized in that: the concentration of excitation elements RE in substrate material axially is continuous gradient along substrate material and distributes.
2. a kind of element that encourages according to claim 1 is the yttria laser transparent ceramic material that continuous gradient distributes, and it is characterized in that when RE was Yb, its composition contained Yb1 ~ 20% by atomic percent, and surplus is Y
2O
3When RE was Tm, its composition contained Tm0.1 ~ 10% by atomic percent, and surplus is Y
2O
3When RE was Nd, its composition contained Nd0.5 ~ 10% by atomic percent, and surplus is Y
2O
3
3. the described a kind of element that encourages of claim 1 is the yttria laser transparent ceramic preparation methods that continuous gradient distributes, and it is characterized in that carrying out according to the following steps:
(1) the preparation volumetric molar concentration is the Y(NO of 0.01 ~ 0.5M
3)
3Solution, and regulate pH=1 ~ 5; The preparation volumetric molar concentration is the RE(NO of 0.01 ~ 0.5M
3)
3Solution, and regulate pH=1 ~ 5; The preparation volumetric molar concentration is the urea soln of 0.5 ~ 2M;
(2) preparation RE:Y
2O
3The ball shaped nano powder:
(2.1) with Y(NO
3)
3Solution, RE(NO
3)
3Solution and urea soln mix makes rare earth doped yttrium oxide female salts solution, wherein Y(NO
3)
3With RE(NO
3)
3Mol ratio be 1:(0.1 ~ 0.5), Y(NO
3)
3And RE(NO
3)
3Total amount and the mol ratio of urea be 1:(1 ~ 30); The female salts solution of rare earth doped yttrium oxide is warming up to 75 ~ 98 ℃ in 0.5 ~ 4h, is incubated 0.5 ~ 5 hour, obtain white precipitate; Filter to collect white precipitate, clean then, 60 ~ 150 ℃ of dryings 2 ~ 48 hours, obtain rare earth doped yttrium oxide precursor powder again;
(2.2) with the dehydrated alcohol be ball-milling medium, be dispersion agent with the polycarboxylate, with rare earth doped yttrium oxide precursor powder Ball milling, wherein the mass ratio of abrading-ball and rare earth doped yttrium oxide precursor powder is 1:(4 ~ 12), the mass ratio of rare earth doped yttrium oxide precursor powder and dehydrated alcohol is 1:(2 ~ 12), polycarboxylate accounts for 0.1 ~ 4% of rare earth doped yttrium oxide precursor powder gross weight, and the ball milling time is 4 ~ 24h; Material behind the ball milling 60 ~ 150 ℃ of dryings 2 ~ 48 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 1 ~ 8h under 800 ~ 1100 ℃ and air atmosphere, obtain RE:Y
2O
3Ball shaped nano powder, particle diameter are at 100 ~ 500nm, and density is 5.09 ~ 5.4g/cm
3
(3) preparation Y
2O
3The ball shaped nano powder:
(3.1) with Y(NO
3)
3Solution and urea soln mix makes yttrium oxide female salts solution, wherein Y(NO
3)
3With the mol ratio of urea be 1:(1 ~ 30); The female salts solution of yttrium oxide is warming up to 75 ~ 98 ℃ in 0.5 ~ 4h, is incubated 0.5 ~ 5 hour, obtain white precipitate; Filter to collect white precipitate, clean then, 60 ~ 150 ℃ of dryings 2 ~ 48 hours, obtain yttrium oxide precursor powder again;
(3.2) with the dehydrated alcohol be ball-milling medium, be dispersion agent with the polycarboxylate, with yttrium oxide precursor powder Ball milling, wherein the mass ratio of abrading-ball and yttrium oxide precursor powder is 1:(4 ~ 12), the mass ratio of yttrium oxide precursor powder and dehydrated alcohol is 1:(2 ~ 12), polycarboxylate accounts for 0.1 ~ 4% of yttrium oxide precursor powder gross weight, and the ball milling time is 4 ~ 24h; Material behind the ball milling 60 ~ 150 ℃ of dryings 2 ~ 48 hours, is crossed 100 mesh sieves then, and the material that will sieve is calcined 1 ~ 8h under 800 ~ 1100 ℃ and air atmosphere, obtain Y
2O
3Ball shaped nano powder, particle diameter are at 100 ~ 500nm, and density is 5.01 ~ 5.03g/cm
3
(4) Y that particle diameter is identical
2O
3Ball shaped nano powder and RE:Y
2O
3The ball shaped nano powder is mixed and made into mixed powder, Y
2O
3Ball shaped nano powder and RE:Y
2O
3The blending ratio of ball shaped nano powder is 1:0.01 ~ 0.5 in molar ratio; Being ball-milling medium with water, is dispersion agent with the polycarboxylate, and with the mixed powder Ball milling, the volume ratio of mixed powder and water is (0.01 ~ 0.4): 1, and dispersion agent accounts for 0.1 ~ 4% of mixed powder gross weight; Material behind the ball milling is carried out ultra-sonic dispersion, and the time is 5 ~ 30min, obtains higher suspension stability slurry;
(5) with higher suspension stability slurry centrifugal 0.5 ~ 2h under 500 ~ 10000rpm condition, separate then and remove liquid phase; The dry moisture of removing in the solid phase under 60 ~ 120 ℃ of conditions obtains the gradient base substrate again;
(6) with the biscuiting under the air or oxygen atmospheric condition of gradient base substrate, the biscuiting temperature is 1200 ~ 1400 ℃, and the time is 4 ~ 24h; Vacuum sintering then, the vacuum sintering temperature is 1600 ~ 1800 ℃, control vacuum tightness≤1 * 10 during vacuum sintering
-3Pa, the vacuum sintering time is 5 ~ 24h; 4 ~ the 24h that anneals under 1000 ~ 1400 ℃ of conditions at last obtains the excitation element and is the yttria laser transparent ceramic material that continuous gradient distributes.
4. a kind of element that encourages according to claim 3 is the yttria laser transparent ceramic preparation methods that continuous gradient distributes, and it is characterized in that described polycarboxylate selects ammonium polyacrylate or ammonium polymethacrylate for use.
5. a kind of element that encourages according to claim 3 is the yttria laser transparent ceramic preparation methods that continuous gradient distributes, it is characterized in that described cleaning refers to that first water cleans and filters white precipitate, with dehydrated alcohol white precipitate is cleaned and filters again, to white precipitate, do not have nitrate ion.
6. a kind of element that encourages according to claim 3 is the yttria laser transparent ceramic preparation methods that continuous gradient distributes, and it is characterized in that the viscosity of described higher suspension stability slurry is 0.001 ~ 1Pa.
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| CN106631022A (en) * | 2017-01-13 | 2017-05-10 | 中国计量大学 | Tm sensitized yttria-based laser ceramic and preparation method |
| CN109896851A (en) * | 2017-12-07 | 2019-06-18 | 上海航空电器有限公司 | Ceramic composite, preparation method and light supply apparatus with concentration gradient |
| CN114956109A (en) * | 2022-06-09 | 2022-08-30 | 陕西科技大学 | Ultrahigh-temperature rare earth hexaboride powder and preparation method thereof |
| CN115490257A (en) * | 2022-08-31 | 2022-12-20 | 贵州大学 | N-doped submicron spherical Y 2 O 3 Preparation method of (1) |
| CN116003124A (en) * | 2022-03-21 | 2023-04-25 | 无锡宜雅科技合伙企业(有限合伙) | Gradient zirconia ceramic block and preparation method thereof |
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| CN115490257B (en) * | 2022-08-31 | 2023-06-27 | 贵州大学 | N-doped submicron spherical Y 2 O 3 Is prepared by the preparation method of (2) |
| CN116354721A (en) * | 2023-03-24 | 2023-06-30 | 沈阳大学 | Activated ion concentration continuous gradient distribution lutetium oxide laser transparent ceramic material and preparation method thereof |
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