CN103482970A - Laser transparent ceramics and preparation method thereof - Google Patents
Laser transparent ceramics and preparation method thereof Download PDFInfo
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- CN103482970A CN103482970A CN201310411462.8A CN201310411462A CN103482970A CN 103482970 A CN103482970 A CN 103482970A CN 201310411462 A CN201310411462 A CN 201310411462A CN 103482970 A CN103482970 A CN 103482970A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 41
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- 238000000034 method Methods 0.000 claims abstract description 104
- 239000000843 powder Substances 0.000 claims abstract description 64
- 238000007731 hot pressing Methods 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 238000005498 polishing Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000003825 pressing Methods 0.000 claims abstract description 21
- 238000005303 weighing Methods 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 37
- 238000010792 warming Methods 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 28
- 238000009413 insulation Methods 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000004448 titration Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 9
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052691 Erbium Inorganic materials 0.000 claims description 8
- 229910052771 Terbium Inorganic materials 0.000 claims description 8
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 8
- 229910003460 diamond Inorganic materials 0.000 claims description 8
- 239000010432 diamond Substances 0.000 claims description 8
- -1 rare earth nitrate Chemical class 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
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Abstract
The present invention discloses a laser transparent ceramics preparation method, which comprises: weighing raw materials and preparing powder; carrying out dry pressing molding on the powder to obtain a half finished product; carrying out a low temperature heat treatment on the half finished product, wherein a temperature of the low temperature heat treatment is 500-1100 DEG C; carrying out hot pressing vibration sintering on the low temperature heat treated half finished product, wherein a sintering temperature of the hot pressing vibration is 1500-2000 DEG C, and a pressure is 4-55 Mpa; carrying out an annealing treatment on the sintered half finished product, wherein a sintering temperature is 900-1500 DEG C; and burnishing and polishing the obtained half finished product to obtain the Re:YAG laser transparent ceramics. Accordingly the present invention further discloses a laser transparent ceramics prepared by using the preparation method. According to the present invention, requirements of short time-consuming and excellent product performance of the sintering process can be met.
Description
Technical field
The present invention relates to the crystalline ceramics field, particularly laser transparent ceramic of a kind of rear-earth-doped YAG and preparation method thereof.
Background technology
The YAG transparent ceramic material of doping Nd is the of paramount importance innovation achievement of working-laser material preparation field in recent ten years.With respect to monocrystalline, polycrystalline YAG pottery has better optical property and mechanical behavior under high temperature, and preparation technology is simple, with low cost, and alternative monocrystalline YAG, be widely regarded as very excellent laser host material.
Nineteen ninety, the employing chemical coprecipitations such as Japanese scholars M.sekita prepare the YAG powder, make the YAG pottery of different neodymium-doped amounts with isostatic pressing and vacuum sintering technology, wherein the lat%Nd:YAG pottery is except having larger background absorption, and other spectrum property is almost identical with monocrystalline Nd:YAG.Nineteen ninety-five, Japan A.Ikesue utilized highly purified Al first
2o
3, Y
2o
3, Nd
2o
3for raw material, with SiO
2for sintering aid, adopt the solid phase vacuum sintering technology to prepare the Nd:YAG pottery of highly transparent, relative density is 99.98%, its specific refractory power and thermal conductivity and monocrystalline are suitable.Developed on this basis the transparent Nd:YAG ceramic laser that the first in the world platform can compare favourably with Nd:YAG monocrystalline laser apparatus.Under promoting, this make Nd:YAG crystalline ceramics technology of preparing obtain develop rapidly.Subsequently, day Benshen island (Konoshima) chemical company adopts a kind of new method: nanotechnology prepares powder and vacuum sintering technique has successfully been prepared high transparent Nd:YAG pottery.The optical properties such as absorption, emission and fluorescence lifetime of transparent Nd:YAG pottery are almost consistent with monocrystalline, and the laser device laser output rating prepared with this pottery reaches 317mw.
In February, 2007, the Nd:YAG crystalline ceramics that the scientists in U.S. Lao Lunsi Livermore laboratory utilizes Japanese Konoshima chemical company to produce, all solid state capacitance laser (the SSHC of development, employing is of a size of 100,100, the 20mm transparent laser ceramic is as working-laser material) realize that peak power output reaches 67kw, it can in 7 seconds, by 25mm, thick steel plate punctures.The very big concern that this has caused various countries defense sectors, make the Nd:YAG laser ceramic material replace laser crystals to become the important option that the following Solid State Laser weapon of US military is used material.It has represented the highest level of Solid State Laser technical development so far, and will become following 10 years most important demonstration demonstrations.
The domestic research about the YAG crystalline ceramics starts from 2000.2004, Northeastern University adopted high-purity A1
2o
3and Nd
2o
3and employing Y
2(OH)
5(NO
3) nH
2the homemade Y of O pyrolysis
2o
3ultrafine powder is raw material, adopts solid phase reaction process, has obtained the Nd:YAG pottery of high printing opacity, and it is 63% in visible region maximum transmission rate, and the transmittance in the infrared light district approaches 70%.In May, 2006, Shanghai Silicate Inst., Chinese Academy of Sciences, through the correlative study of nearly 6 years and a large amount of experiment, tests, adopts high-purity business A1
2o
3, Nd
2o
3and Y
2o
3ultrafine powder has successfully prepared high-quality Nd:YAG crystalline ceramics more than being incubated 10h as raw material, under 1650 ~ 1780 ℃ of vacuum conditions, has realized first at home the Laser output of Nd:YAG crystalline ceramics.
From current existing document and patent analyses, the preparation method of more ripe YAG crystalline ceramics adopts solid phase method or Liquid preparation methods oxide compound or YAG powder, then work in-process is carried out to vacuum sintering.Although vacuum sintering technology can be prepared quality sample preferably, this sintering process cycle is long, and approximately 2 ~ 3 days, limited resource was more as heat-up rate, soaking time and cooling rate etc., and wayward, cost is higher.
In addition, while adopting vacuum sintering, need to coordinate the use of multiple sintering aid, as TEOS, MgO, CaO or SiO
2deng, just make the product densified sintering product.But the too much additives such as use sintering aid, can introduce impurity, reduce the purity of goods.
Summary of the invention
Technical problem to be solved by this invention is, a kind of preparation method of laser transparent ceramic is provided, and it,, guaranteeing that product obtains under the prerequisite of excellent properties, still can reduce sintering process consuming time, reduces costs.
Technical problem to be solved by this invention is, a kind of preparation method of laser transparent ceramic is provided, and reduces the use of sintering aid.
Technical problem to be solved by this invention also is, the laser transparent ceramic that provides a kind of preparation method who adopts above-mentioned laser transparent ceramic to make.
For reaching above-mentioned technique effect, the invention provides a kind of preparation method of laser transparent ceramic, comprising:
Raw material is pressed to Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing, make powder;
Described powder is carried out dry-pressing formed, obtain work in-process;
Described work in-process are carried out to low-temperature heat treatment, and wherein, the temperature of described low-temperature heat treatment is 500 ~ 1100 ℃;
To carry out hot pressing vibratory sintering through the described work in-process of low-temperature heat treatment, wherein, the sintering temperature of described hot pressing vibration is 1500 ~ 2000 ℃, and pressure is 4 ~ 55Mpa;
To carry out anneal through the described work in-process of hot pressing vibratory sintering, annealing temperature is 900 ~ 1500 ℃;
Described work in-process sanding and polishing by annealed processing, make the Re:YAG laser transparent ceramic.
As the improvement of such scheme, the step that will carry out through the described work in-process of low-temperature heat treatment hot pressing vibratory sintering comprises:
At first, described work in-process are warming up to 800-1200 ℃ with the speed of 8-12 ℃/minute;
Then, described work in-process are warming up to 1500-2000 ℃ with the speed of 4-8 ℃/minute, and insulation 1-3h, pressure is 10-30T;
Finally, by described work in-process furnace cooling.
As the improvement of such scheme, the step that will carry out through the described work in-process of low-temperature heat treatment hot pressing vibratory sintering comprises:
At first, described work in-process are warming up to 1000 ℃ with the speed of 10 ℃/minute;
Then, described work in-process are warming up to 1760 ℃ with the speed of 6 ℃/minute, and insulation 2h, pressure is 20T;
Finally, by described work in-process furnace cooling.
As the improvement of such scheme, raw material is pressed to Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing, make powder by solid phase method, comprise the following steps:
Adopt A1
2o
3, Y
2o
3with rare earth oxide be main raw material, press Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing;
Take described raw material as base-material, add sintering aid and solvent ball milling 24 ~ 72h, obtain slurry;
Described slurry is put into to oven drying, and drying temperature is 50 ~ 100 ℃, then grinds 100 ~ 250 mesh sieves, obtains powder.
As the improvement of such scheme, raw material is pressed to Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing, make powder by coprecipitation method, comprise the following steps:
Adopting aluminum nitrate, Yttrium trinitrate and rare earth nitrate is main raw material, presses Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing, be configured to the metal salt solution that concentration is 0.08mol/L ~ 1.2mol/L;
The ammonium bicarbonate soln that is 0.08mol/L ~ 2.4mol/L by concentration is titrated to described metal salt solution, titration while stirring by certain speed;
Precipitated liquid at room temperature after slaking 15-30h, is carried out to suction filtration, washing, alcohol wash, drying, grinding to it, obtain pre-powder, wherein, drying temperature is 50 ~ 100 ℃;
Described pre-powder is calcined to 2-4h under 900 ~ 1200 ℃, make the Re:YAG powder;
The described Re:YAG powder of take is base-material, adds sintering aid and solvent ball milling 24 ~ 72h, obtains slurry;
Described slurry is put into to oven drying, and drying temperature is 50 ~ 100 ℃, then grinds 100 ~ 250 mesh sieves, obtains powder.
As the improvement of such scheme, described sintering aid is tetraethoxy, 0 ~ 2wt% that the addition of described sintering aid is described raw materials quality;
Described solvent is water or dehydrated alcohol, and the addition of described solvent and the mass ratio of described raw material are 1:3 ~ 3:1.
As the improvement of such scheme, described ball milling step adopts Al
2o
3ball and ZrO
2ball is ball-milling medium.
As the improvement of such scheme, described Y
3al
5o
12and Re
xy
3-xal
5o
12in, x=0 ~ 3, Re is one or more in Nd, Cr, Yb, Er, Tb rare earth element.
As the improvement of such scheme, by the described work in-process sanding and polishing of annealed processing, the step that makes the Re:YAG laser transparent ceramic comprises:
The described work in-process of annealed processing are polished through diamond wheel, and described polishing comprises surface corase grind and fine grinding;
To carry out polished finish through diamond paste through the described work in-process of polishing, make the Re:YAG laser transparent ceramic.
Correspondingly, the invention provides a kind of laser transparent ceramic, it adopts A1
2o
3, Y
2o
3with rare earth oxide be main raw material, or to adopt aluminum nitrate, Yttrium trinitrate and rare earth nitrate be main raw material, and described main raw material is pressed to Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing, and make by the preparation method of laser transparent ceramic as described in claim 1-9 any one;
Wherein, x=0 ~ 3, Re is one or more in Nd, Cr, Yb, Er, Tb rare earth element.
Implement the present invention and there is following beneficial effect:
One, the invention provides a kind of laser transparent ceramic and preparation method thereof, adopt with in the past different hot pressing vibratory sintering methods and make above-mentioned laser transparent ceramic, can be guaranteeing that product obtains that high densification, uniform crystal particles, pore are few, crystal boundary and lattice imperfection few, the transmitance height waits under the prerequisite of excellent properties, still the sintering period can be shortened, reduce sintering process consuming time, reduce costs.
At first, adopt hot pressing vibratory sintering technique, be sintered material when applying constant force up and down, apply the vibration force of an adjustable amplitude and frequency, what apply up and down like this is that constant force adds variable force simultaneously, and stack just produces vibration force.It is fine and close that material is accelerated diffusion in hot pressing.
Secondly, material, when hot pressing vibratory sintering, is subject to two sizes identical, the power of opposite direction.This two power also earthquake constantly, constantly reach a kind of dynamic balance, had more a thrust surface than the uniaxial pressure of original traditional hot pressed sintering like this, can make material be issued to the densification of maximum possible in such two-way function, thereby reach the optimum performance of this material.
Again, in the diffusion in hot pressing later stage, climb the stage of moving, material internal is followed contraction, its most of pore is got rid of, the contraction speed of pore can significantly reduce, and the pore major part becomes the hole of holding one's breath, and the isolated hole of holding one's breath is subject to diffusion and climbs the stress influence moved and still can constantly shrink each other.And, along with the sealed porosity internal pressure increases, further get rid of these isolated pores and just become more difficult.It is to remove the key of sealed porosity that the speed of moving is climbed in diffusion.And hot pressing vibratory sintering technique of the present invention, the additional vibration force of variable frequency and amplitude provides exitation factor, has increased diffusion and has climbed the speed of moving.Reached the effect of last eliminating pore.Therefore, hot pressing vibratory sintering is mainly to have utilized to vibrate this, makes material form more uniform internal structure under the condition of high temperature, can make material fine and close as much as possible.
In a word, hot pressing vibratory sintering technique, in the material high temperature sintering, is given the additional pressure of material, makes material carry out sintering under pressure state, and like this, material easily obtains full densification.And, can make material form more uniform internal structure under the condition of high temperature, can shorten like this sintering period to 10 of laser transparent ceramic of the present invention ~ the 20h left and right, the sintering period is obviously faster than vacuum sintering, and heat-up rate is fast, soaking time is short, the water-cooled fast cooling, effectively reduces costs.Simultaneously, also can reach better performance, higher index, high (the density reachable 4.60g/cm of prepared laser transparent ceramic density
3), uniform crystal particles, pore is few, crystal boundary and lattice imperfection are few, transmitance is high, at the visible region transmittance 70%, the infrared region transmittance>80%.
What two, adopt due to the present invention is hot pressing vibratory sintering, can exert pressure and vibrate powder when sintering and can make the densification of product Fast Sintering, therefore, the present invention only need adopt a kind of sintering aid tetraethoxy can reach corresponding effect, and its addition is 0 ~ 2wt%, avoided the excessive use sintering aid, reduce the introducing of impurity, improve purity, the density of goods, simplified preparation technology.
The accompanying drawing explanation
Fig. 1 is the schema of preparation method one embodiment of a kind of laser transparent ceramic of the present invention;
Fig. 2 is the schema of the another embodiment of preparation method of a kind of laser transparent ceramic of the present invention.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, the present invention is described in further detail.
The preparation process of transparent laser ceramic is roughly the same with general ceramic, comprises the powder preparation, moulding, the techniques such as sintering and aftertreatment.But the preparation of crystalline ceramics also has the characteristics of himself; When light when a certain medium, because the effects such as absorption, reflection, scattering and refraction of medium make its strength retrogression.In absorbing very little polycrystalline material, scattering may be the major cause that weakens light intensity, and this is also one of difficulty prepared crystalline ceramics.The major cause of scattering is the pore in polycrystalline, non-principal crystalline phase, composition gradient variation, crystal boundary and lattice imperfection etc. at one in mutually.Therefore to make pottery there is light transmission, just should technique, reduce scattering of light and the absorption that the various defects such as pore, impurity, crystal boundary cause as far as possible, thereby prepare fine and close transparent ceramic body.
In order to obtain the crystalline ceramics of high permeability, just require to consider the technological factors such as heat-up rate, soaking time and cooling rate when vacuum sintering, by slow intensification, insulation for a long time and slow cooling etc., make pottery can obtain the excellent properties such as high-compactness, uniform crystal particles, low porosity, crystal boundary and lattice imperfection are little, high permeability, this just makes sintering process length consuming time, limited resource is more, cost is higher.
That is, the preparation method of existing laser transparent ceramic can not meet the requirement of sintering process short, excellent product performance consuming time simultaneously.
Referring to Fig. 1, the invention provides the preparation method's of laser transparent ceramic a embodiment, comprising:
S101, adopt A1
2o
3, Y
2o
3with rare earth oxide be main raw material, press Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing.
Described Y
3al
5o
12and Re
xy
3-xal
5o
12in, x=0 ~ 3, Re is one or more in Nd, Cr, Yb, Er, Tb rare earth element.
Preferably, Re is any in Yb, Er, Tb rare earth element.
S102, take described raw material as base-material, adds sintering aid and solvent ball milling 24 ~ 72h, obtains slurry.
Concrete, described sintering aid is preferentially selected tetraethoxy, 0 ~ 2wt% that the addition of described sintering aid is described raw materials quality; Described solvent is preferentially selected water or dehydrated alcohol, and the addition of described solvent and the mass ratio of described raw material are 1:3 ~ 3:1.
Described ball milling step adopts Al
2o
3ball and ZrO
2ball is ball-milling medium.
S103, put into oven drying by described slurry, and drying temperature is 50 ~ 100 ℃, then grinds 100 ~ 250 mesh sieves, obtains powder.
S104, carry out described powder dry-pressing formed, obtains work in-process.
Concrete, step S104 comprises:
Described powder is placed in to mould;
The mould that is filled with described powder is placed in to press and carries out dry-pressing formedly, obtain work in-process, the nominal pressure of described press is 20 ~ 200T.
Preferably, dry-pressing formed pressure is 38 ~ 60T.
Better, dry-pressing formed pressure is 40 T, 45 T, 50 T or 55T.
It should be noted that, this step shape and size required according to laser transparent ceramic are produced corresponding mould, then will be placed in this mould through pretreated powder, through press, exert pressure and carry out dry-pressing formedly, obtain dense green.
S105, carry out low-temperature heat treatment by described work in-process, and wherein, the temperature of described low-temperature heat treatment is 500 ~ 1100 ℃.
Preferably, the temperature of low-temperature heat treatment is 500 ~ 1000 ℃.
Better, the temperature of low-temperature heat treatment is 600 ~ 800 ℃.
S106, will carry out hot pressing vibratory sintering through the described work in-process of low-temperature heat treatment, and wherein, the sintering temperature of described hot pressing vibration is 1500 ~ 2000 ℃, and pressure is 4 ~ 55Mpa.
Preferably, the sintering temperature of described hot pressing vibratory sintering is 1600 ~ 1900 ℃, and pressure is 5 ~ 50MPa.
Further, described hot pressing vibratory sintering is warming up to different temperature by different speed, then carries out sintering at different temperature, can make that sintering reaction is more abundant, homogenizing.Concrete, the sintering mechanism of described hot pressing vibratory sintering is as follows: at first, described work in-process are warming up to 800-1200 ℃ with the speed of 8-12 ℃/minute; Then, described work in-process are warming up to 1500-2000 ℃ with the speed of 4-8 ℃/minute, and insulation 1-3h, pressure is 10-30T; Finally, by described work in-process furnace cooling.
Better, the concrete sintering mechanism of hot pressing vibratory sintering is as follows: at first, described work in-process are warming up to 1000 ℃ with the speed of 10 ℃/minute; Then, described work in-process are warming up to 1760 ℃ with the speed of 6 ℃/minute, and insulation 2h, pressure is 20T; Finally, by described work in-process furnace cooling.
At the beginning, at lower temperature, when (room temperature ~ 1000 ℃), goods not yet have sintering reaction, and contraction is not arranged yet, can be suitably with being rapidly heated of 10 ℃ of/minute clock rate, can shorten sintering process consuming time; And, when temperature is 1000 ~ 1760 ℃, having the solid phase method of YAG to answer, also progressively densification of goods, now reduce temperature rise rate, can make more abundant, the homogenizing of reaction.Finally, furnace cooling, slow cooling.By the sintering temperature of above-mentioned three different stepss, the control of lifting/lowering temperature speed, can make pottery obtain high-compactness, uniform crystal particles, low porosity, crystal boundary and the excellent properties such as lattice imperfection is little, high permeability.
S107, will carry out anneal through the described work in-process of hot pressing vibratory sintering, and annealing temperature is 900 ~ 1500 ℃.
Preferably, described annealing temperature is 1000 ~ 1400 ℃.
Better, described work in-process, in the anneal process, rise to 1200 ℃ and be incubated 1 ~ 10h with 2-8 ℃/minute from room temperature.
S108, the described work in-process sanding and polishing by annealed processing, make the Re:YAG laser transparent ceramic.
Concrete, step S108 comprises:
The described work in-process of annealed processing are polished through diamond wheel, and described polishing comprises surface corase grind and fine grinding;
To carry out polished finish through diamond paste through the described work in-process of polishing, make the Re:YAG laser transparent ceramic.
Referring to Fig. 2, the invention provides the preparation method's of laser transparent ceramic another embodiment, comprising:
S201, adopting aluminum nitrate, Yttrium trinitrate and rare earth nitrate is main raw material, presses Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing, be configured to the metal salt solution that concentration is 0.08mol/L ~ 1.2mol/L.
Described Y
3al
5o
12and Re
xy
3-xal
5o
12in, x=0 ~ 3, Re is one or more in Nd, Cr, Yb, Er, Tb rare earth element.
Preferably, Re is any in Yb, Er, Tb rare earth element.
S202, the ammonium bicarbonate soln that is 0.08mol/L ~ 2.4mol/L by concentration is titrated to described metal salt solution, titration while stirring by certain speed.
Preferably, described rate of titration be 20-60 drip/minute.
Better, described rate of titration is 40 droplets/minute.
S203, at room temperature after slaking 15-30h, carry out suction filtration, washing, alcohol wash, drying, grinding to it by precipitated liquid, obtains pre-powder, and wherein, drying temperature is 50 ~ 100 ℃.
S204 calcines 2-4h by described pre-powder under 900 ~ 1200 ℃, makes the Re:YAG powder.
S205, the described Re:YAG powder of take is base-material, adds sintering aid and solvent ball milling 24 ~ 72h, obtains slurry.
Concrete, described sintering aid is preferentially selected tetraethoxy, 0 ~ 2wt% that the addition of described sintering aid is described raw materials quality; Described solvent is preferentially selected water or dehydrated alcohol, and the addition of described solvent and the mass ratio of described raw material are 1:3 ~ 3:1.
Described ball milling step adopts Al
2o
3ball and ZrO
2ball is ball-milling medium.
S206, put into oven drying by described slurry, and drying temperature is 50 ~ 100 ℃, then grinds 100 ~ 250 mesh sieves, obtains powder.
S207, carry out described powder dry-pressing formed, obtains work in-process.
Concrete, step S207 comprises:
Described powder is placed in to mould;
The mould that is filled with described powder is placed in to press and carries out dry-pressing formedly, obtain work in-process, the nominal pressure of described press is 20 ~ 200T.
Preferably, dry-pressing formed pressure is 38 ~ 60T.
Better, dry-pressing formed pressure is 40 T, 45 T, 50 T or 55T.
It should be noted that, this step shape and size required according to laser transparent ceramic are produced corresponding mould, then will be placed in this mould through pretreated powder, through press, exert pressure and carry out dry-pressing formedly, obtain dense green.
S208, carry out low-temperature heat treatment by described work in-process, and wherein, the temperature of described low-temperature heat treatment is 500 ~ 1100 ℃.
Preferably, the temperature of low-temperature heat treatment is 500 ℃ ~ 1000 ℃.
Better, the temperature of low-temperature heat treatment is 600 ℃ ~ 800 ℃.
S209, will carry out hot pressing vibratory sintering through the described work in-process of low-temperature heat treatment, and wherein, the sintering temperature of described hot pressing vibration is 1500 ~ 2000 ℃, and pressure is 4 ~ 55Mpa.
Preferably, the sintering temperature of described hot pressing vibratory sintering is 1600 ~ 1900 ℃, and pressure is 5 ~ 50MPa.
Further, described hot pressing vibratory sintering is warming up to different temperature by different speed, then carries out sintering at different temperature, can make that sintering reaction is more abundant, homogenizing.Concrete, the sintering mechanism of described hot pressing vibratory sintering is as follows: at first, described work in-process are warming up to 800-1200 ℃ with the speed of 8-12 ℃/minute; Then, described work in-process are warming up to 1500-2000 ℃ with the speed of 4-8 ℃/minute, and insulation 1-3h, pressure is 10-30T; Finally, by described work in-process furnace cooling.
Better, the concrete sintering mechanism of hot pressing vibratory sintering is as follows: at first, described work in-process are warming up to 1000 ℃ with the speed of 10 ℃/minute; Then, described work in-process are warming up to 1760 ℃ with the speed of 6 ℃/minute, and insulation 2h, pressure is 20T; Finally, by described work in-process furnace cooling.
At the beginning, at lower temperature, when (room temperature ~ 1000 ℃), goods not yet have sintering reaction, and contraction is not arranged yet, can be suitably with being rapidly heated of 10 ℃ of/minute clock rate, can shorten sintering process consuming time; And, when temperature is 1000 ~ 1760 ℃, having the solid phase method of YAG to answer, also progressively densification of goods, now reduce temperature rise rate, can make more abundant, the homogenizing of reaction.Finally, furnace cooling, slow cooling.By the sintering temperature of above-mentioned three different stepss, the control of lifting/lowering temperature speed, can make pottery obtain high-compactness, uniform crystal particles, low porosity, crystal boundary and the excellent properties such as lattice imperfection is little, high permeability.
S210, will carry out anneal through the described work in-process of hot pressing vibratory sintering, and annealing temperature is 900 ~ 1500 ℃.
Preferably, described annealing temperature is 1000 ~ 1400 ℃.
Better, described work in-process, in the anneal process, rise to 1200 ℃ and be incubated 1 ~ 10h with 2-8 ℃/minute from room temperature.
S211, the described work in-process sanding and polishing by annealed processing, make the Re:YAG laser transparent ceramic.
Concrete, step S211 comprises:
The described work in-process of annealed processing are polished through diamond wheel, and described polishing comprises surface corase grind and fine grinding;
To carry out polished finish through diamond paste through the described work in-process of polishing, make the Re:YAG laser transparent ceramic.
Compared with prior art, the embodiment shown in Fig. 1 and Fig. 2 all adopts hot pressing vibratory sintering technique to carry out the sintering processes of crystalline ceramics:
At first, adopt hot pressing vibratory sintering technique, be sintered material when applying constant force up and down, apply the vibration force of an adjustable amplitude and frequency, what apply up and down like this is that constant force adds variable force simultaneously, and stack just produces vibration force.It is fine and close that material is accelerated diffusion in hot pressing.
Secondly, material, when hot pressing vibratory sintering, is subject to two sizes identical, the power of opposite direction.This two power also earthquake constantly, constantly reach a kind of dynamic balance, had more a thrust surface than the uniaxial pressure of original traditional hot pressed sintering like this, can make material be issued to the densification of maximum possible in such two-way function, thereby reach the optimum performance of this material.
Again, in the diffusion in hot pressing later stage, climb the stage of moving, material internal is followed contraction, its most of pore is got rid of, the contraction speed of pore can significantly reduce, and the pore major part becomes the hole of holding one's breath, and the isolated hole of holding one's breath is subject to diffusion and climbs the stress influence moved and still can constantly shrink each other.And, along with the sealed porosity internal pressure increases, further get rid of these isolated pores and just become more difficult.It is to remove the key of sealed porosity that the speed of moving is climbed in diffusion.And hot pressing vibratory sintering technique of the present invention, the additional vibration force of variable frequency and amplitude provides exitation factor, has increased diffusion and has climbed the speed of moving.Reached the effect of last eliminating pore.Therefore, hot pressing vibratory sintering is mainly to have utilized to vibrate this, makes material form more uniform internal structure under the condition of high temperature, can make material fine and close as much as possible.
In a word, hot pressing vibratory sintering technique, in the material high temperature sintering, is given the additional pressure of material, makes material carry out sintering under pressure state, and like this, material easily obtains full densification.And, can make material form more uniform internal structure under the condition of high temperature, can shorten like this sintering period to 10 of laser transparent ceramic of the present invention ~ the 20h left and right, the sintering period is obviously faster than vacuum sintering, and heat-up rate is fast, soaking time is short, the water-cooled fast cooling, effectively reduces costs.Simultaneously, also can reach better performance, higher index, high (the density reachable 4.60g/cm of prepared laser transparent ceramic density
3), uniform crystal particles, pore is few, crystal boundary and lattice imperfection are few, transmitance is high, at the visible region transmittance 70%, the infrared region transmittance>80%.
That is, the present invention can be guaranteeing that product obtains that high densification, uniform crystal particles, pore are few, crystal boundary and lattice imperfection few, transmitance is high to be waited under the prerequisite of excellent properties, still can shorten the sintering period, the reduction sintering process is consuming time, reduces costs.
In addition, due to the present invention's employing is hot pressing vibratory sintering, can exert pressure and vibrate powder when sintering and can make the densification of product Fast Sintering, therefore, the present invention only need adopt a kind of sintering aid tetraethoxy can reach corresponding effect, and its addition is 0 ~ 2wt%, avoided the excessive use sintering aid, reduce the introducing of impurity, improve purity, the density of goods, simplified preparation technology.And while adopting vacuum sintering, due to the effect that there is no impressed pressure, sintering process is slow, and needs multiple sintering aid as TEOS, MgO, CaO or SiO
2deng wherein one or more, just make the product densified sintering product.
Below with specific embodiment, the present invention is further elaborated, to disclose more ins and outs:
Embodiment 1
(1) by 17g α-Al
2o
3powder, 22.374gY
2o
3powder, 0.35gNd
2o
3powder and 0.1986g tetraethoxy are put into the ball grinder that 120g high purity aluminium oxide ball is housed, and add dehydrated alcohol 30ml, and then ball milling mixing 48h obtains slurry; (2) slurry is dry in the baking oven of 60 ℃, then cross 100 mesh sieves, then dry-pressing formed, pressure is 50T, obtains the work in-process biscuit; (3) biscuit is heat-treated to insulation 0.5h in 600 ℃; (4) by the sintering in the vibration hot pressing furnace of the biscuit after thermal treatment, concrete sintering mechanism is as follows: first with the speed of 10 ℃/minute, be warming up to 1000 ℃, then with the speed of 6 ℃/minute, be warming up to 1760 ℃, and be incubated 2h, pressure is 20T, then with stove nature water-cooled cooling.(5) sample anneal in the Si-Mo rod stove of obtaining of vibration hot pressed sintering, mechanism of anneal is for rising to 1200 ℃ and be incubated 2h with 5 ℃/minute from room temperature, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample of finally anneal being crossed is polished, polishing obtains high permeability.
Embodiment 2
(1) by 17g α-Al
2o
3powder, 22.374gY
2o
3powder, 0.35gNd
2o
3powder and 0.1986g tetraethoxy are put into the ball grinder that 120g high purity aluminium oxide ball is housed, and add dehydrated alcohol 30ml, and then ball milling mixing 48h obtains slurry; (2) slurry is dry in the baking oven of 60 ℃, then cross 100 mesh sieves, then dry-pressing formed, pressure is 50T, obtains the work in-process biscuit; (3) biscuit is heat-treated to insulation 1h in 800 ℃; (4) by the sintering in the vibration hot pressing furnace of the biscuit after thermal treatment, concrete sintering mechanism is as follows: first with the speed of 8 ℃/minute, be warming up to 1000 ℃, then with the speed of 4 ℃/minute, be warming up to 1560 ℃, and be incubated 3h, pressure is 10T, then with stove nature water-cooled cooling.(5) sample anneal in the Si-Mo rod stove of obtaining of vibration hot pressed sintering, mechanism of anneal is for rising to 1200 ℃ and be incubated 5h with 6 ℃/minute from room temperature, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample of finally anneal being crossed is polished, polishing obtains high permeability.
Embodiment 3
(1) by 17g α-Al
2o
3powder, 22.374gY
2o
3powder, 0.35gNd
2o
3powder and 0.1986g tetraethoxy are put into the ball grinder that 120g high purity aluminium oxide ball is housed, and add dehydrated alcohol 30ml, and then ball milling mixing 48h obtains slurry; (2) slurry is dry in the baking oven of 60 ℃, then cross 100 mesh sieves, then dry-pressing formed, pressure is 50T, obtains the work in-process biscuit; (3) biscuit is heat-treated to insulation 2h in 700 ℃; (4) by the sintering in the vibration hot pressing furnace of the biscuit after thermal treatment, concrete sintering mechanism is as follows: first with the speed of 12 ℃/minute, be warming up to 1100 ℃, then with the speed of 7 ℃/minute, be warming up to 1900 ℃, and be incubated 1h, pressure is 10T, then with stove nature water-cooled cooling.(5) sample anneal in the Si-Mo rod stove of obtaining of vibration hot pressed sintering, mechanism of anneal is for rising to 1200 ℃ and be incubated 8h with 4 ℃/minute from room temperature, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample of finally anneal being crossed is polished, polishing obtains high permeability.
Embodiment 4
(1) 37.5g aluminum nitrate, 22.75g Yttrium trinitrate and 0.21g neodymium nitrate adding distil water are configured to the metal salt solution of 333ml, 31.62g bicarbonate of ammonia adding distil water are configured to the solution of 667ml; (2) ammonium bicarbonate soln is titrated in metal salt solution, titration while stirring, rate of titration is 40 droplets/minute; (3) titration complete after by throw out slaking 24h, then filter, washing, alcohol wash, then put into 60 ℃ of oven dry of baking oven; (4) powder is ground and is placed on silicon carbide rod furnace in 1100 ℃ of calcinings, insulation 3h; (5) burnt powder and 0.1g tetraethoxy are put into to the ball grinder that 80g high purity aluminium oxide ball is housed, add dehydrated alcohol 15ml, then ball milling mixing 24h obtains slurry; (2) slurry is dry in the baking oven of 60 ℃, then cross 150 mesh sieves, then dry-pressing formed, pressure is 50T, obtains the work in-process biscuit; (3) biscuit is heat-treated to insulation 0.5h in 600 ℃; (4) by the sintering in the vibration hot pressing furnace of the biscuit after thermal treatment, concrete sintering mechanism is as follows: first with the speed of 10 ℃/minute, be warming up to 1000 ℃, then with the speed of 6 ℃/minute, be warming up to 1760 ℃, and be incubated 2h, pressure is 20T, then with stove nature water-cooled cooling; (5) sample anneal in the Si-Mo rod stove of obtaining of vibration hot pressed sintering, mechanism of anneal is for rising to 1200 ℃ and be incubated 2h with 5 ℃/minute from room temperature, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample of finally anneal being crossed is polished, polishing obtains high permeability.
Embodiment 5
(1) 37.5g aluminum nitrate, 22.75g Yttrium trinitrate and 0.21g neodymium nitrate adding distil water are configured to the metal salt solution of 333ml, 31.62g bicarbonate of ammonia adding distil water are configured to the solution of 667ml; (2) ammonium bicarbonate soln is titrated in metal salt solution, titration while stirring, rate of titration is 40 droplets/minute; (3) titration complete after by throw out slaking 24h, then filter, washing, alcohol wash, then put into 60 ℃ of oven dry of baking oven; (4) powder is ground and is placed on silicon carbide rod furnace in 1100 ℃ of calcinings, insulation 3h; (5) burnt powder and 0.1g tetraethoxy are put into to the ball grinder that 80g high purity aluminium oxide ball is housed, add dehydrated alcohol 15ml, then ball milling mixing 24h obtains slurry; (2) slurry is dry in the baking oven of 60 ℃, then cross 150 mesh sieves, then dry-pressing formed, pressure is 50T, obtains the work in-process biscuit; (3) biscuit is heat-treated to insulation 1h in 500 ℃; (4) by the sintering in the vibration hot pressing furnace of the biscuit after thermal treatment, concrete sintering mechanism is as follows: first with the speed of 9 ℃/minute, be warming up to 900 ℃, then with the speed of 5 ℃/minute, be warming up to 1660 ℃, and be incubated 3h, pressure is 25T, then with stove nature water-cooled cooling; (5) sample anneal in the Si-Mo rod stove of obtaining of vibration hot pressed sintering, mechanism of anneal is for rising to 1200 ℃ and be incubated 2h with 6 ℃/minute from room temperature, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample of finally anneal being crossed is polished, polishing obtains high permeability.
Embodiment 6
(1) 37.5g aluminum nitrate, 22.75g Yttrium trinitrate and 0.21g neodymium nitrate adding distil water are configured to the metal salt solution of 333ml, 31.62g bicarbonate of ammonia adding distil water are configured to the solution of 667ml; (2) ammonium bicarbonate soln is titrated in metal salt solution, titration while stirring, rate of titration is 40 droplets/minute; (3) titration complete after by throw out slaking 24h, then filter, washing, alcohol wash, then put into 60 ℃ of oven dry of baking oven; (4) powder is ground and is placed on silicon carbide rod furnace in 1100 ℃ of calcinings, insulation 3h; (5) burnt powder and 0.1g tetraethoxy are put into to the ball grinder that 80g high purity aluminium oxide ball is housed, add dehydrated alcohol 15ml, then ball milling mixing 24h obtains slurry; (2) slurry is dry in the baking oven of 60 ℃, then cross 150 mesh sieves, then dry-pressing formed, pressure is 50T, obtains the work in-process biscuit; (3) biscuit is heat-treated to insulation 1.5h in 700 ℃; (4) by the sintering in the vibration hot pressing furnace of the biscuit after thermal treatment, concrete sintering mechanism is as follows: first with the speed of 11 ℃/minute, be warming up to 1050 ℃, then with the speed of 5 ℃/minute, be warming up to 1800 ℃, and be incubated 2.5h, pressure is 15T, then with stove nature water-cooled cooling; (5) sample anneal in the Si-Mo rod stove of obtaining of vibration hot pressed sintering, mechanism of anneal is for rising to 1200 ℃ and be incubated 2h with 5 ℃/minute from room temperature, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample of finally anneal being crossed is polished, polishing obtains high permeability.
Comparative Examples 1
(1) by 17g α-Al
2o
3powder, 22.374gY
2o
3powder, 0.35gNd
2o
3powder and 0.2g TEOS, 0.2gSiO
2put into the ball grinder that 120g high purity aluminium oxide ball is housed, add dehydrated alcohol 30ml, then ball milling mixing 48h obtains slurry; (2) slurry is dry in the baking oven of 60 ℃, then cross 100 mesh sieves, then dry-pressing formed, pressure is 50T, obtains the work in-process biscuit; (3) biscuit is heat-treated to insulation 0.5h in 600 ℃; (4) biscuit after thermal treatment is carried out to 1750 ℃ of vacuum sinterings, insulation 10h.(5) sample that vacuum sintering obtains anneal in the Si-Mo rod stove, mechanism of anneal is for rising to 1200 ℃ and be incubated 2h with 5 ℃/minute from room temperature, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample of finally anneal being crossed is polished, polishing obtains high permeability.
Comparative Examples 2
(1) 37.5g aluminum nitrate, 22.75g Yttrium trinitrate and 0.21g neodymium nitrate adding distil water are configured to the metal salt solution of 333ml, 31.62g bicarbonate of ammonia adding distil water are configured to the solution of 667ml; (2) ammonium bicarbonate soln is titrated in metal salt solution, titration while stirring, rate of titration is 40 droplets/minute; (3) titration complete after by throw out slaking 24h, then filter, washing, alcohol wash, then put into 60 ℃ of oven dry of baking oven; (4) powder is ground and is placed on silicon carbide rod furnace in 1100 ℃ of calcinings, insulation 3h; (5) by burnt powder and 0.2g CaO and 0.1gSiO
2put into the ball grinder that 80g high purity aluminium oxide ball is housed, add dehydrated alcohol 15ml, then ball milling mixing 24h obtains slurry; (2) slurry is dry in the baking oven of 60 ℃, then cross 150 mesh sieves, then dry-pressing formed, pressure is 50T, obtains the work in-process biscuit; (3) biscuit is heat-treated to insulation 0.5h in 600 ℃; (4) biscuit after thermal treatment is carried out to 1750 ℃ of vacuum sinterings, insulation 10h; (5) sample that vacuum sintering obtains anneal in the Si-Mo rod stove, mechanism of anneal is for rising to 1200 ℃ and be incubated 2h with 5 ℃/minute from room temperature, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample of finally anneal being crossed is polished, polishing obtains high permeability.
The prepared laser transparent ceramic of embodiment 1-6 is made to following technology for detection, and adopts the crystalline ceramics that vacuum sintering makes to compare with Comparative Examples 1-2, record the technical parameter in each preparation process simultaneously, result as shown in Table 1:
The density average out to 4.60g/cm of the laser transparent ceramic that as shown in Table 1, (1) the present invention makes
3, its density is high, and the density of the existing laser transparent ceramic made by vacuum sintering reaches 4.55g/cm
3, its density is also high;
(2) the pore quantity of the laser transparent ceramic that the present invention makes is within 0 ~ 5, and its pore is few, and the pore quantity of the existing laser transparent ceramic made by vacuum sintering is within 3 ~ 5, and its pore is also few;
(3) laser transparent ceramic that the present invention makes is at the visible region transmittance > 70%, the infrared region transmittance > 80%, its transmitance is high, and the existing laser transparent ceramic made by vacuum sintering is at the visible region transmittance > 68%, the infrared region transmittance > 82%, its transmitance is also high;
(4) sintering period of the laser transparent ceramic that the present invention makes, its cycle was short in about 10 ~ 20h, and the sintering period of the existing laser transparent ceramic made by vacuum sintering in the 48-72h left and right, its cycle is long;
(5) in the preparation process of laser transparent ceramic of the present invention, only need to use a kind of sintering aid, be exactly tetraethoxy, and its addition is 0 ~ 2wt%, and, in the preparation process of existing laser transparent ceramic, need to coordinate the use of multiple sintering aid, as TEOS, MgO, CaO or SiO
2deng, and its addition is greater than 3wt%.
Therefore, the preparation method of existing laser transparent ceramic can not meet the requirement of sintering process short, excellent product performance consuming time simultaneously; And the preparation method of laser transparent ceramic of the present invention can meet the requirement of sintering process short, excellent product performance consuming time simultaneously.
In addition, the present invention only need adopt a kind of sintering aid tetraethoxy can reach corresponding effect, and its addition is 0 ~ 2wt%, has avoided the excessive use sintering aid, reduces the introducing of impurity, improves purity, the density of goods, has simplified preparation technology.And while adopting vacuum sintering, due to the effect that there is no impressed pressure, sintering process is slow, and needs multiple sintering aid as TEOS, MgO, CaO or SiO
2deng wherein one or more, just make the product densified sintering product.
It should be noted that other details of the vacuum sintering in Comparative Examples 1-2 can be carried out with reference to existing vacuum sintering technique.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
Claims (10)
1. the preparation method of a laser transparent ceramic, is characterized in that, comprising:
Raw material is pressed to Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing, make powder;
Described powder is carried out dry-pressing formed, obtain work in-process;
Described work in-process are carried out to low-temperature heat treatment, and wherein, the temperature of described low-temperature heat treatment is 500 ~ 1100 ℃;
To carry out hot pressing vibratory sintering through the described work in-process of low-temperature heat treatment, wherein, the sintering temperature of described hot pressing vibration is 1500 ~ 2000 ℃, and pressure is 4 ~ 55Mpa;
To carry out anneal through the described work in-process of hot pressing vibratory sintering, annealing temperature is 900 ~ 1500 ℃;
Described work in-process sanding and polishing by annealed processing, make the Re:YAG laser transparent ceramic.
2. the preparation method of laser transparent ceramic as claimed in claim 1, is characterized in that, the step that will carry out through the described work in-process of low-temperature heat treatment hot pressing vibratory sintering comprises:
At first, described work in-process are warming up to 800-1200 ℃ with the speed of 8-12 ℃/minute;
Then, described work in-process are warming up to 1500-2000 ℃ with the speed of 4-8 ℃/minute, and insulation 1-3h, pressure is 10-30T;
Finally, by described work in-process furnace cooling.
3. the preparation method of laser transparent ceramic as claimed in claim 2, is characterized in that, the step that will carry out through the described work in-process of low-temperature heat treatment hot pressing vibratory sintering comprises:
At first, described work in-process are warming up to 1000 ℃ with the speed of 10 ℃/minute;
Then, described work in-process are warming up to 1760 ℃ with the speed of 6 ℃/minute, and insulation 2h, pressure is 20T;
Finally, by described work in-process furnace cooling.
4. the preparation method of laser transparent ceramic as claimed in claim 1, is characterized in that, raw material is pressed to Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing, make powder by solid phase method, comprise the following steps:
Adopt A1
2o
3, Y
2o
3with rare earth oxide be main raw material, press Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing;
Take described raw material as base-material, add sintering aid and solvent ball milling 24 ~ 72h, obtain slurry;
Described slurry is put into to oven drying, and drying temperature is 50 ~ 100 ℃, then grinds 100 ~ 250 mesh sieves, obtains powder.
5. the preparation method of laser transparent ceramic as claimed in claim 1, is characterized in that, raw material is pressed to Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing, make powder by coprecipitation method, comprise the following steps:
Adopting aluminum nitrate, Yttrium trinitrate and rare earth nitrate is main raw material, presses Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing, be configured to the metal salt solution that concentration is 0.08mol/L ~ 1.2mol/L;
The ammonium bicarbonate soln that is 0.08mol/L ~ 2.4mol/L by concentration is titrated to described metal salt solution, titration while stirring by certain speed;
Precipitated liquid at room temperature after slaking 15-30h, is carried out to suction filtration, washing, alcohol wash, drying, grinding to it, obtain pre-powder, wherein, drying temperature is 50 ~ 100 ℃;
Described pre-powder is calcined to 2-4h under 900 ~ 1200 ℃, make the Re:YAG powder;
The described Re:YAG powder of take is base-material, adds sintering aid and solvent ball milling 24 ~ 72h, obtains slurry;
Described slurry is put into to oven drying, and drying temperature is 50 ~ 100 ℃, then grinds 100 ~ 250 mesh sieves, obtains powder.
6. as the preparation method of claim 4 or 5 described laser transparent ceramics, it is characterized in that, described sintering aid is tetraethoxy, 0 ~ 2wt% that the addition of described sintering aid is described raw materials quality;
Described solvent is water or dehydrated alcohol, and the addition of described solvent and the mass ratio of described raw material are 1:3 ~ 3:1.
7. the preparation method of laser transparent ceramic as claimed in claim 6, is characterized in that, described ball milling step adopts Al
2o
3ball and ZrO
2ball is ball-milling medium.
8. as the preparation method of the described laser transparent ceramic of claim 1-5 any one, it is characterized in that described Y
3al
5o
12and Re
xy
3-xal
5o
12in, x=0 ~ 3, Re is one or more in Nd, Cr, Yb, Er, Tb rare earth element.
9. the preparation method of laser transparent ceramic as claimed in claim 1, is characterized in that, by the described work in-process sanding and polishing of annealed processing, the step that makes the Re:YAG laser transparent ceramic comprises:
The described work in-process of annealed processing are polished through diamond wheel, and described polishing comprises surface corase grind and fine grinding;
To carry out polished finish through diamond paste through the described work in-process of polishing, make the Re:YAG laser transparent ceramic.
10. a laser transparent ceramic, is characterized in that, it adopts A1
2o
3, Y
2o
3with rare earth oxide be main raw material, or to adopt aluminum nitrate, Yttrium trinitrate and rare earth nitrate be main raw material, and described main raw material is pressed to Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio carry out weighing, and make by the preparation method of laser transparent ceramic as described in claim 1-9 any one;
Wherein, x=0 ~ 3, Re is one or more in Nd, Cr, Yb, Er, Tb rare earth element.
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| CN109620442A (en) * | 2018-12-20 | 2019-04-16 | 四川华柚医疗器械有限公司 | A kind of novel artificial tooth and preparation method thereof |
| CN110418773A (en) * | 2017-03-13 | 2019-11-05 | Ａｇｃ株式会社 | Light transparent ceramic sintered body and its manufacturing method |
| CN111606699A (en) * | 2020-06-04 | 2020-09-01 | 景德镇陶瓷大学 | Lightweight porous daily fine porcelain and preparation method thereof |
| CN113548894A (en) * | 2021-07-15 | 2021-10-26 | 中国科学院上海硅酸盐研究所 | Ytterbium-yttria up-conversion luminescent transparent ceramic and preparation method thereof |
| CN114523433A (en) * | 2021-09-27 | 2022-05-24 | 杭州大和江东新材料科技有限公司 | Processing method of convex point type sucking disc |
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| CN110418773A (en) * | 2017-03-13 | 2019-11-05 | Ａｇｃ株式会社 | Light transparent ceramic sintered body and its manufacturing method |
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| CN111606699A (en) * | 2020-06-04 | 2020-09-01 | 景德镇陶瓷大学 | Lightweight porous daily fine porcelain and preparation method thereof |
| CN111606699B (en) * | 2020-06-04 | 2023-01-24 | 景德镇陶瓷大学 | Lightweight porous daily fine porcelain and preparation method thereof |
| CN113548894A (en) * | 2021-07-15 | 2021-10-26 | 中国科学院上海硅酸盐研究所 | Ytterbium-yttria up-conversion luminescent transparent ceramic and preparation method thereof |
| CN114523433A (en) * | 2021-09-27 | 2022-05-24 | 杭州大和江东新材料科技有限公司 | Processing method of convex point type sucking disc |
| CN114523433B (en) * | 2021-09-27 | 2023-10-24 | 杭州大和江东新材料科技有限公司 | Processing method of convex point type sucker |
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| CN103482970B (en) | 2015-12-09 |
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Denomination of invention: The invention relates to a laser transparent ceramic and a preparation method thereof Effective date of registration: 20211221 Granted publication date: 20151209 Pledgee: China Co. truction Bank Corp Foshan branch Pledgor: GUANGDONG JINGANG NEW MATERIAL CO.,LTD. Registration number: Y2021980015830 |
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Denomination of invention: A Laser Transparent Ceramic and Its Preparation Method Effective date of registration: 20231211 Granted publication date: 20151209 Pledgee: China Co. truction Bank Corp Foshan branch Pledgor: GUANGDONG JINGANG NEW MATERIAL CO.,LTD. Registration number: Y2023980070458 |