CN103482970B - A kind of laser transparent ceramic and preparation method thereof - Google Patents
A kind of laser transparent ceramic and preparation method thereof Download PDFInfo
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- CN103482970B CN103482970B CN201310411462.8A CN201310411462A CN103482970B CN 103482970 B CN103482970 B CN 103482970B CN 201310411462 A CN201310411462 A CN 201310411462A CN 103482970 B CN103482970 B CN 103482970B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000005245 sintering Methods 0.000 claims abstract description 148
- 238000000034 method Methods 0.000 claims abstract description 116
- 239000000843 powder Substances 0.000 claims abstract description 60
- 238000007731 hot pressing Methods 0.000 claims abstract description 50
- 230000008569 process Effects 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 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
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 26
- 238000010792 warming Methods 0.000 claims description 26
- 238000000498 ball milling Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 230000007246 mechanism Effects 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
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 229960000935 dehydrated alcohol Drugs 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
- 238000001035 drying Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 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
- 238000003756 stirring Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 238000000643 oven drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 24
- 235000015895 biscuits Nutrition 0.000 description 24
- 239000011148 porous material Substances 0.000 description 20
- 239000013078 crystal Substances 0.000 description 17
- 238000009413 insulation Methods 0.000 description 14
- 239000011222 crystalline ceramic Substances 0.000 description 12
- 229910002106 crystalline ceramic Inorganic materials 0.000 description 12
- 230000035699 permeability Effects 0.000 description 12
- 238000000280 densification Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 230000006872 improvement Effects 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- 229910006295 Si—Mo Inorganic materials 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
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- 239000000243 solution Substances 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a kind of preparation method of laser transparent ceramic, raw material is carried out weighing obtained powder; Described powder is carried out dry-pressing formed, obtains work in-process; Described work in-process are carried out low-temperature heat treatment, and wherein, the temperature of described low-temperature heat treatment is 500 ~ 1100 DEG C; Described work in-process through low-temperature heat treatment are carried out hot pressing vibratory sintering, and wherein, the sintering temperature of described hot pressing vibration is 1500 ~ 2000 DEG C, and pressure is 4 ~ 55Mpa; Described work in-process through hot pressing vibratory sintering are carried out anneal, and annealing temperature is 900 ~ 1500 DEG C; By the described work in-process sanding and polishing of annealed process, obtained Re:YAG laser transparent ceramic.Accordingly, the invention also discloses a kind of laser transparent ceramic adopting above-mentioned preparation method to obtain.Adopt the present invention, the requirement of sintering process short, excellent product performance consuming time can be met simultaneously.
Description
Technical field
The present invention relates to crystalline ceramics field, particularly the laser transparent ceramic and preparation method thereof of a kind of rear-earth-doped YAG.
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.Relative 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, is widely regarded as very excellent laser host material.
Nineteen ninety, Japanese scholars M.sekita etc. adopt chemical coprecipitation to prepare YAG powder, obtain the YAG pottery of different neodymium-doped amount with isostatic pressing and vacuum sintering technology, wherein 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 solid phase vacuum sintering technology to prepare the Nd:YAG pottery of highly transparent, relative density is 99.98%, and its specific refractory power is suitable with monocrystalline with thermal conductivity.Have developed the transparent Nd:YAG ceramic laser that the first in the world platform can compare favourably with Nd:YAG monocrystalline laser apparatus on this basis.Under this promotes, make Nd:YAG crystalline ceramics technology of preparing obtain develop rapidly.Subsequently, namely day Benshen island (Konoshima) chemical company adopts a kind of new method: nanotechnology prepares powder and vacuum sintering technique has successfully prepared high transparency Nd:YAG pottery.Absorption, the transmitting of transparent Nd:YAG pottery are almost consistent with monocrystalline with optical properties such as fluorescence lifetimes, reach 317mw with the laser device laser output rating of this ceramic preparation.
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 100,100,20mm transparent laser ceramic is as working-laser material) realize peak power output and reach 67kw, steel plate thick for 25mm can puncture by it in 7 seconds.Which results in the very big concern of defense sector of various countries, make Nd:YAG laser ceramic material replace laser crystals to become the important option of US military following Solid State Laser weapon use material.It represent the highest level of Solid State Laser technical development so far, and the most important demonstration of coming 10 years will be become prove item.
The domestic research about YAG crystalline ceramics starts from 2000.2004, Northeastern University adopted high-purity A1
2o
3and Nd
2o
3and adopt Y
2(OH)
5(NO
3) nH
2the homemade Y of O pyrolysis
2o
3ultrafine powder is raw material, adopts solid phase reaction process, and obtain the Nd:YAG pottery of high printing opacity, it is 63% in visible region maximum transmission rate, and the transmittance in infrared light district is close to 70%.In May, 2006, Shanghai Silicate Inst., Chinese Academy of Sciences, through the correlative study of nearly 6 years and a large amount of experiments, test, adopts high-purity business A1
2o
3, Nd
2o
3and Y
2o
3ultrafine powder as raw material, be incubated more than 10h under 1650 ~ 1780 DEG C of vacuum conditions, successfully prepared high-quality Nd:YAG crystalline ceramics, has been achieved the Laser output of Nd:YAG crystalline ceramics at home first.
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 vacuum sintering.Although vacuum sintering technology can prepare the good sample of quality, this sintering process cycle is long, about 2 ~ 3 days, and limited resource is more as heat-up rate, soaking time and cooling rate etc., and wayward, cost is higher.
In addition, when adopting vacuum sintering, the use coordinating multiple sintering aid is needed, as TEOS, MgO, CaO or SiO
2deng, just make product densified sintering product.But the additives such as too much use sintering aid, can introduce impurity, reduce the purity of goods.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of preparation method of laser transparent ceramic, and it, under ensureing that product obtains the prerequisite of excellent properties, still can reduce sintering process consuming time, reduce costs.
Technical problem to be solved by this invention is, provides a kind of preparation method of laser transparent ceramic, reduces the use of sintering aid.
Technical problem to be solved by this invention is also, provides a kind of laser transparent ceramic adopting the preparation method of 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 Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio weigh, obtained powder;
Described powder is carried out dry-pressing formed, obtains work in-process;
Described work in-process are carried out low-temperature heat treatment, and wherein, the temperature of described low-temperature heat treatment is 500 ~ 1100 DEG C;
Described work in-process through low-temperature heat treatment are carried out hot pressing vibratory sintering, and wherein, the sintering temperature of described hot pressing vibration is 1500 ~ 2000 DEG C, and pressure is 4 ~ 55MPa;
Described work in-process through hot pressing vibratory sintering are carried out anneal, and annealing temperature is 900 ~ 1500 DEG C;
By the described work in-process sanding and polishing of annealed process, obtained Re:YAG laser transparent ceramic.
As the improvement of such scheme, the step that the described work in-process through low-temperature heat treatment carry out hot pressing vibratory sintering is comprised:
First, described work in-process are warming up to 800-1200 DEG C with the speed of 8-12 DEG C/min;
Then, described work in-process are warming up to 1500-2000 DEG C with the speed of 4-8 DEG C/min, and are incubated 1-3h, pressure is 10-30T;
Finally, by described work in-process furnace cooling.
As the improvement of such scheme, the step that the described work in-process through low-temperature heat treatment carry out hot pressing vibratory sintering is comprised:
First, described work in-process are warming up to 1000 DEG C with the speed of 10 DEG C/min;
Then, described work in-process are warming up to 1760 DEG C with the speed of 6 DEG C/min, and are incubated 2h, pressure is 20T;
Finally, by described work in-process furnace cooling.
As the improvement of such scheme, raw material is pressed Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio weigh, obtain powder by solid phase method, comprise the following steps:
Adopt A1
2o
3, Y
2o
3be main raw material with rare earth oxide, by Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio weigh;
With described raw material for base-material, add sintering aid and solvent ball milling 24 ~ 72h, obtain slurry;
Described slurry is put into oven drying, and drying temperature is 50 ~ 100 DEG C, and then ground 100 ~ 250 mesh sieves, obtain powder.
As the improvement of such scheme, raw material is pressed Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio weigh, obtain powder by coprecipitation method, comprise the following steps:
Aluminum nitrate, Yttrium trinitrate and rare earth nitrate is adopted to be main raw material, by Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio weigh, be configured to the metal salt solution that concentration is 0.08mol/L ~ 1.2mol/L;
Be that the ammonium bicarbonate soln of 0.08mol/L ~ 2.4mol/L is titrated to described metal salt solution by certain speed, titration while stirring by concentration;
After precipitated liquid at room temperature slaking 15-30h, carry out suction filtration, washing, alcohol wash, drying, grinding to it, obtain pre-powder, wherein, drying temperature is 50 ~ 100 DEG C;
Described pre-powder is calcined 2-4h at 900 ~ 1200 DEG C, obtained Re:YAG powder;
With described Re:YAG powder for base-material, add sintering aid and solvent ball milling 24 ~ 72h, obtain slurry;
Described slurry is put into oven drying, and drying temperature is 50 ~ 100 DEG C, and then ground 100 ~ 250 mesh sieves, obtain powder.
As the improvement of such scheme, described sintering aid is tetraethoxy, and the addition of described sintering aid is 0 ~ 2wt% of 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 process, the step of obtained Re:YAG laser transparent ceramic comprises:
Polished through diamond wheel by the described work in-process of annealed process, described polishing comprises surface corase grind and fine grinding;
Described work in-process through polishing are carried out polished finish through diamond paste, obtained Re:YAG laser transparent ceramic.
Correspondingly, the invention provides a kind of laser transparent ceramic, it adopts A1
2o
3, Y
2o
3be main raw material with rare earth oxide, or adopt aluminum nitrate, Yttrium trinitrate and rare earth nitrate to be main raw material, described main raw material is pressed Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio weigh, and by as described in any one of claim 1-9 laser transparent ceramic preparation method obtain;
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 and make above-mentioned laser transparent ceramic with in the past different hot pressing vibratory sintering methods, can obtain that high densification, uniform crystal particles, pore are few at guarantee product, crystal boundary and lattice imperfection few, under transmitance height waits the prerequisite of excellent properties, still the sintering period can be shortened, reduce sintering process consuming time, reduce costs.
First, adopt hot pressing vibratory sintering technique, be sintered material while 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 superposition just produces vibration force.Material adds fast diffusion densification in hot pressing.
Secondly, material, when hot pressing vibratory sintering, is subject to two sizes identical, the power that direction is contrary.These two power moment are also in variation, moment reaches a kind of dynamic balance, the uniaxial pressure of the hot pressed sintering that such ratio is originally traditional has had more a thrust surface, material can be made to be issued to the densification of maximum possible in such two-way function, thus reach the optimum performance of this material.
Again, the stage of moving is climbed in the diffusion of phase after hot-pressing, and material internal is with shrinking, its most of pore is got rid of, the contraction speed of pore can significantly reduce, and pore major part becomes hole of holding one's breath, and hole of holding one's breath isolated is each other subject to spreading to be climbed the stress influence moved and still can constantly shrink.And along with the increase of sealed porosity internal pressure, get rid of these isolated pores further and just become more difficult.It is 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 applied vibration power of variable frequency and amplitude provides exitation factor, adds diffusion and climbs the speed of moving.Reach the last effect getting rid of pore.Therefore, hot pressing vibratory sintering mainly make use of vibration this, material is formed at high operating temperatures evenly internal structure, material can be made fine and close as much as possible.
In a word, hot pressing vibratory sintering technique is while material high temperature sintering, and to the additional pressure of material, material is sintered under pressure state, and like this, material easily obtains full densification.And, material can be made to be formed at high operating temperatures evenly internal structure, can shorten sintering period to 10 ~ about the 20h of laser transparent ceramic of the present invention like this, the sintering period is obviously faster than vacuum sintering, and heat-up rate is fast, soaking time is short, water-cooled fast cooling, effectively reduces costs.Meanwhile, also can reach better performance, higher index, obtained laser transparent ceramic density is high, and (density can reach 4.60g/cm
3), uniform crystal particles, pore is few, crystal boundary and lattice imperfection few, transmitance is high, at visible region transmittance >70%, infrared region transmittance >80%.
Two, due to the present invention's employing is hot pressing vibratory sintering, can pressure be applied to powder and vibrate to make product Fast Sintering fine and close when sintering, therefore, the present invention only need adopt a kind of sintering aid tetraethoxy can reach corresponding effect, and its addition is 0 ~ 2wt%, avoid excessive use sintering aid, reduce the introducing of impurity, improve purity, the density of goods, simplify preparation technology.
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 object, technical solutions and advantages of the present invention clearly, 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 powder preparation, shaping, the techniques such as sintering and aftertreatment.But the preparation of crystalline ceramics also has the feature of himself; When light is by a certain medium, make its strength retrogression due to effects such as the absorption of medium, reflection, scattering and refractions.Absorbing in very little polycrystalline material, scattering may be the major cause weakening light intensity, and this is also one of difficulty preparing crystalline ceramics.The major cause of scattering be the pore in polycrystalline, non-principal crystalline phase, one mutually in composition gradient change, crystal boundary and lattice imperfection etc.Therefore pottery to be made to have light transmission, technique, just should reduce scattering of light and absorption that the various defects such as pore, impurity, crystal boundary cause as far as possible, thus 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 slowly heating up, pottery can the be obtained excellent properties such as high-compactness, uniform crystal particles, low porosity, crystal boundary and lattice imperfection are little, high permeability such as long-time heat preservation and slow cooling, 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.
See Fig. 1, the invention provides an embodiment of the preparation method of laser transparent ceramic, comprising:
S101, adopts A1
2o
3, Y
2o
3be main raw material with rare earth oxide, by Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio weigh.
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 one in Yb, Er, Tb rare earth element.
S102, with described raw material for base-material, adds sintering aid and solvent ball milling 24 ~ 72h, obtains slurry.
Concrete, described sintering aid preferentially selects tetraethoxy, and the addition of described sintering aid is 0 ~ 2wt% of described raw materials quality; Described solvent preferentially selects 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, puts into oven drying by described slurry, and drying temperature is 50 ~ 100 DEG C, and then ground 100 ~ 250 mesh sieves, obtain powder.
S104, is undertaken dry-pressing formed by described powder, obtains work in-process.
Concrete, step S104 comprises:
Described powder is placed in mould;
The mould being filled with described powder is placed in press to carry out dry-pressing formed, obtains work in-process, and the nominal pressure of described press is 20 ~ 200T.
Preferably, dry-pressing formed pressure is 38 ~ 60T.
Better, dry-pressing formed pressure is 40T, 45T, 50T or 55T.
It should be noted that, the shape and size of this step needed for laser transparent ceramic produce corresponding mould, then will be placed in this mould through pretreated powder, apply pressure and carry out dry-pressing formed, obtain dense green through press.
Described work in-process are carried out low-temperature heat treatment by S105, and wherein, the temperature of described low-temperature heat treatment is 500 ~ 1100 DEG C.
Preferably, the temperature of low-temperature heat treatment is 500 ~ 1000 DEG C.
Better, the temperature of low-temperature heat treatment is 600 ~ 800 DEG C.
Described work in-process through low-temperature heat treatment are carried out hot pressing vibratory sintering by S106, and wherein, the sintering temperature of described hot pressing vibration is 1500 ~ 2000 DEG C, and pressure is 4 ~ 55MPa.
Preferably, the sintering temperature of described hot pressing vibratory sintering is 1600 ~ 1900 DEG C, and pressure is 5 ~ 50MPa.
Further, described hot pressing vibratory sintering, then to be sintered to different temperature at different temperature by different ramp, can make that sintering reaction is more abundant, homogenizing.Concrete, the sin-tering mechanism of described hot pressing vibratory sintering is as follows: first, and described work in-process are warming up to 800-1200 DEG C with the speed of 8-12 DEG C/min; Then, described work in-process are warming up to 1500-2000 DEG C with the speed of 4-8 DEG C/min, and are incubated 1-3h, pressure is 10-30T; Finally, by described work in-process furnace cooling.
Better, the concrete sin-tering mechanism of hot pressing vibratory sintering is as follows: first, and described work in-process are warming up to 1000 DEG C with the speed of 10 DEG C/min; Then, described work in-process are warming up to 1760 DEG C with the speed of 6 DEG C/min, and are incubated 2h, pressure is 20T; Finally, by described work in-process furnace cooling.
At the beginning, at a lower temperature time (room temperature ~ 1000 DEG C), goods not yet have sintering reaction, also do not have contraction, can being rapidly heated suitably with 10 DEG C/min of speed, can shorten sintering process consuming time; And when temperature is 1000 ~ 1760 DEG C, have YAG solid phase method should, goods also progressively densification, now reduces temperature rise rate, can make that reaction is more abundant, homogenizing.Finally, furnace cooling, slow cooling.By the sintering temperature of above-mentioned three different stepss, the control of lifting/lowering temperature speed, the excellent properties such as pottery acquisition high-compactness, uniform crystal particles, low porosity, crystal boundary and lattice imperfection are little, high permeability can be made.
Described work in-process through hot pressing vibratory sintering are carried out anneal by S107, and annealing temperature is 900 ~ 1500 DEG C.
Preferably, described annealing temperature is 1000 ~ 1400 DEG C.
Better, described work in-process, in annealing process, rise to 1200 DEG C with 2-8 DEG C/min from room temperature and are incubated 1 ~ 10h.
S108, by the described work in-process sanding and polishing of annealed process, obtained Re:YAG laser transparent ceramic.
Concrete, step S108 comprises:
Polished through diamond wheel by the described work in-process of annealed process, described polishing comprises surface corase grind and fine grinding;
Described work in-process through polishing are carried out polished finish through diamond paste, obtained Re:YAG laser transparent ceramic.
See Fig. 2, the invention provides the another embodiment of the preparation method of laser transparent ceramic, comprising:
S201, adopts aluminum nitrate, Yttrium trinitrate and rare earth nitrate to be main raw material, by Y
3al
5o
12and Re
xy
3-xal
5o
12stoichiometric ratio weigh, 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 one in Yb, Er, Tb rare earth element.
Concentration is that the ammonium bicarbonate soln of 0.08mol/L ~ 2.4mol/L is titrated to described metal salt solution by certain speed by S202, titration while stirring.
Preferably, described rate of titration be 20-60 drip/minute.
Better, described rate of titration is 40 droplets/minute.
S203, after precipitated liquid at room temperature slaking 15-30h, carries out suction filtration, washing, alcohol wash, drying, grinding to it, obtains pre-powder, and wherein, drying temperature is 50 ~ 100 DEG C.
S204, calcines 2-4h by described pre-powder at 900 ~ 1200 DEG C, obtained Re:YAG powder.
S205, with described Re:YAG powder for base-material, adds sintering aid and solvent ball milling 24 ~ 72h, obtains slurry.
Concrete, described sintering aid preferentially selects tetraethoxy, and the addition of described sintering aid is 0 ~ 2wt% of described raw materials quality; Described solvent preferentially selects 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, puts into oven drying by described slurry, and drying temperature is 50 ~ 100 DEG C, and then ground 100 ~ 250 mesh sieves, obtain powder.
S207, is undertaken dry-pressing formed by described powder, obtains work in-process.
Concrete, step S207 comprises:
Described powder is placed in mould;
The mould being filled with described powder is placed in press to carry out dry-pressing formed, obtains work in-process, and the nominal pressure of described press is 20 ~ 200T.
Preferably, dry-pressing formed pressure is 38 ~ 60T.
Better, dry-pressing formed pressure is 40T, 45T, 50T or 55T.
It should be noted that, the shape and size of this step needed for laser transparent ceramic produce corresponding mould, then will be placed in this mould through pretreated powder, apply pressure and carry out dry-pressing formed, obtain dense green through press.
Described work in-process are carried out low-temperature heat treatment by S208, and wherein, the temperature of described low-temperature heat treatment is 500 ~ 1100 DEG C.
Preferably, the temperature of low-temperature heat treatment is 500 DEG C ~ 1000 DEG C.
Better, the temperature of low-temperature heat treatment is 600 DEG C ~ 800 DEG C.
Described work in-process through low-temperature heat treatment are carried out hot pressing vibratory sintering by S209, and wherein, the sintering temperature of described hot pressing vibration is 1500 ~ 2000 DEG C, and pressure is 4 ~ 55MPa.
Preferably, the sintering temperature of described hot pressing vibratory sintering is 1600 ~ 1900 DEG C, and pressure is 5 ~ 50MPa.
Further, described hot pressing vibratory sintering, then to be sintered to different temperature at different temperature by different ramp, can make that sintering reaction is more abundant, homogenizing.Concrete, the sin-tering mechanism of described hot pressing vibratory sintering is as follows: first, and described work in-process are warming up to 800-1200 DEG C with the speed of 8-12 DEG C/min; Then, described work in-process are warming up to 1500-2000 DEG C with the speed of 4-8 DEG C/min, and are incubated 1-3h, pressure is 10-30T; Finally, by described work in-process furnace cooling.
Better, the concrete sin-tering mechanism of hot pressing vibratory sintering is as follows: first, and described work in-process are warming up to 1000 DEG C with the speed of 10 DEG C/min; Then, described work in-process are warming up to 1760 DEG C with the speed of 6 DEG C/min, and are incubated 2h, pressure is 20T; Finally, by described work in-process furnace cooling.
At the beginning, at a lower temperature time (room temperature ~ 1000 DEG C), goods not yet have sintering reaction, also do not have contraction, can being rapidly heated suitably with 10 DEG C/min of speed, can shorten sintering process consuming time; And when temperature is 1000 ~ 1760 DEG C, have YAG solid phase method should, goods also progressively densification, now reduces temperature rise rate, can make that reaction is more abundant, homogenizing.Finally, furnace cooling, slow cooling.By the sintering temperature of above-mentioned three different stepss, the control of lifting/lowering temperature speed, the excellent properties such as pottery acquisition high-compactness, uniform crystal particles, low porosity, crystal boundary and lattice imperfection are little, high permeability can be made.
Described work in-process through hot pressing vibratory sintering are carried out anneal by S210, and annealing temperature is 900 ~ 1500 DEG C.
Preferably, described annealing temperature is 1000 ~ 1400 DEG C.
Better, described work in-process, in annealing process, rise to 1200 DEG C with 2-8 DEG C/min from room temperature and are incubated 1 ~ 10h.
S211, by the described work in-process sanding and polishing of annealed process, obtained Re:YAG laser transparent ceramic.
Concrete, step S211 comprises:
Polished through diamond wheel by the described work in-process of annealed process, described polishing comprises surface corase grind and fine grinding;
Described work in-process through polishing are carried out polished finish through diamond paste, obtained 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:
First, adopt hot pressing vibratory sintering technique, be sintered material while 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 superposition just produces vibration force.Material adds fast diffusion densification in hot pressing.
Secondly, material, when hot pressing vibratory sintering, is subject to two sizes identical, the power that direction is contrary.These two power moment are also in variation, moment reaches a kind of dynamic balance, the uniaxial pressure of the hot pressed sintering that such ratio is originally traditional has had more a thrust surface, material can be made to be issued to the densification of maximum possible in such two-way function, thus reach the optimum performance of this material.
Again, the stage of moving is climbed in the diffusion of phase after hot-pressing, and material internal is with shrinking, its most of pore is got rid of, the contraction speed of pore can significantly reduce, and pore major part becomes hole of holding one's breath, and hole of holding one's breath isolated is each other subject to spreading to be climbed the stress influence moved and still can constantly shrink.And along with the increase of sealed porosity internal pressure, get rid of these isolated pores further and just become more difficult.It is 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 applied vibration power of variable frequency and amplitude provides exitation factor, adds diffusion and climbs the speed of moving.Reach the last effect getting rid of pore.Therefore, hot pressing vibratory sintering mainly make use of vibration this, material is formed at high operating temperatures evenly internal structure, material can be made fine and close as much as possible.
In a word, hot pressing vibratory sintering technique is while material high temperature sintering, and to the additional pressure of material, material is sintered under pressure state, and like this, material easily obtains full densification.And, material can be made to be formed at high operating temperatures evenly internal structure, can shorten sintering period to 10 ~ about the 20h of laser transparent ceramic of the present invention like this, the sintering period is obviously faster than vacuum sintering, and heat-up rate is fast, soaking time is short, water-cooled fast cooling, effectively reduces costs.Meanwhile, also can reach better performance, higher index, obtained laser transparent ceramic density is high, and (density can reach 4.60g/cm
3), uniform crystal particles, pore is few, crystal boundary and lattice imperfection few, transmitance is high, at visible region transmittance >70%, infrared region transmittance >80%.
That is, the present invention can obtain that high densification, uniform crystal particles, pore are few at guarantee product, crystal boundary and lattice imperfection few, under transmitance height waits the prerequisite of excellent properties, still can shorten the sintering period, reduction sintering process is consuming time, reduces costs.
In addition, due to the present invention's employing is hot pressing vibratory sintering, can pressure be applied to powder and vibrate to make product Fast Sintering fine and close when sintering, therefore, the present invention only need adopt a kind of sintering aid tetraethoxy can reach corresponding effect, and its addition is 0 ~ 2wt%, avoid excessive use sintering aid, reduce the introducing of impurity, improve purity, the density of goods, simplify preparation technology.And when adopting vacuum sintering, owing to not having the effect of impressed pressure, sintering process is slow, and need multiple sintering aid as TEOS, MgO, CaO or SiO
2deng wherein one or more, just make product densified sintering product.
With specific embodiment, the present invention is further elaborated below, 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 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 DEG C, then cross 100 mesh sieves, then dry-pressing formed, pressure is 50T, obtains work in-process biscuit; (3) biscuit is heat-treated in 600 DEG C, insulation 0.5h; (4) biscuit after thermal treatment is sintered in vibration hot pressing furnace, concrete sin-tering mechanism is as follows: be first warming up to 1000 DEG C with the speed of 10 DEG C/min, be then warming up to 1760 DEG C with the speed of 6 DEG C/min, and be incubated 2h, pressure is 20T, then with stove nature water-cooled cooling.(5) vibrate sample anneal in Si-Mo rod stove of obtaining of hot pressed sintering, mechanism of anneal is for rising to 1200 DEG C with 5 DEG C/min from room temperature and being incubated 2h, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample finally crossed anneal 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 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 DEG C, then cross 100 mesh sieves, then dry-pressing formed, pressure is 50T, obtains work in-process biscuit; (3) biscuit is heat-treated in 800 DEG C, insulation 1h; (4) biscuit after thermal treatment is sintered in vibration hot pressing furnace, concrete sin-tering mechanism is as follows: be first warming up to 1000 DEG C with the speed of 8 DEG C/min, be then warming up to 1560 DEG C with the speed of 4 DEG C/min, and be incubated 3h, pressure is 10T, then with stove nature water-cooled cooling.(5) vibrate sample anneal in Si-Mo rod stove of obtaining of hot pressed sintering, mechanism of anneal is for rising to 1200 DEG C with 6 DEG C/min from room temperature and being incubated 5h, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample finally crossed anneal 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 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 DEG C, then cross 100 mesh sieves, then dry-pressing formed, pressure is 50T, obtains work in-process biscuit; (3) biscuit is heat-treated in 700 DEG C, insulation 2h; (4) biscuit after thermal treatment is sintered in vibration hot pressing furnace, concrete sin-tering mechanism is as follows: be first warming up to 1100 DEG C with the speed of 12 DEG C/min, be then warming up to 1900 DEG C with the speed of 7 DEG C/min, and be incubated 1h, pressure is 10T, then with stove nature water-cooled cooling.(5) vibrate sample anneal in Si-Mo rod stove of obtaining of hot pressed sintering, mechanism of anneal is for rising to 1200 DEG C with 4 DEG C/min from room temperature and being incubated 8h, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample finally crossed anneal 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) be titrated in metal salt solution by ammonium bicarbonate soln, while stirring titration, rate of titration is 40 droplets/minute; (3) titration complete after by throw out slaking 24h, then filter, wash, alcohol wash, then put into the oven dry of 60 DEG C, baking oven; (4) powder grinding is placed on silicon carbide rod furnace in 1100 DEG C of calcinings, insulation 3h; (5) burnt powder and 0.1g tetraethoxy are put 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 DEG C, then cross 150 mesh sieves, then dry-pressing formed, pressure is 50T, obtains work in-process biscuit; (3) biscuit is heat-treated in 600 DEG C, insulation 0.5h; (4) biscuit after thermal treatment is sintered in vibration hot pressing furnace, concrete sin-tering mechanism is as follows: be first warming up to 1000 DEG C with the speed of 10 DEG C/min, be then warming up to 1760 DEG C with the speed of 6 DEG C/min, and be incubated 2h, pressure is 20T, then with stove nature water-cooled cooling; (5) vibrate sample anneal in Si-Mo rod stove of obtaining of hot pressed sintering, mechanism of anneal is for rising to 1200 DEG C with 5 DEG C/min from room temperature and being incubated 2h, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample finally crossed anneal 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) be titrated in metal salt solution by ammonium bicarbonate soln, while stirring titration, rate of titration is 40 droplets/minute; (3) titration complete after by throw out slaking 24h, then filter, wash, alcohol wash, then put into the oven dry of 60 DEG C, baking oven; (4) powder grinding is placed on silicon carbide rod furnace in 1100 DEG C of calcinings, insulation 3h; (5) burnt powder and 0.1g tetraethoxy are put 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 DEG C, then cross 150 mesh sieves, then dry-pressing formed, pressure is 50T, obtains work in-process biscuit; (3) biscuit is heat-treated in 500 DEG C, insulation 1h; (4) biscuit after thermal treatment is sintered in vibration hot pressing furnace, concrete sin-tering mechanism is as follows: be first warming up to 900 DEG C with the speed of 9 DEG C/min, be then warming up to 1660 DEG C with the speed of 5 DEG C/min, and be incubated 3h, pressure is 25T, then with stove nature water-cooled cooling; (5) vibrate sample anneal in Si-Mo rod stove of obtaining of hot pressed sintering, mechanism of anneal is for rising to 1200 DEG C with 6 DEG C/min from room temperature and being incubated 2h, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample finally crossed anneal 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) be titrated in metal salt solution by ammonium bicarbonate soln, while stirring titration, rate of titration is 40 droplets/minute; (3) titration complete after by throw out slaking 24h, then filter, wash, alcohol wash, then put into the oven dry of 60 DEG C, baking oven; (4) powder grinding is placed on silicon carbide rod furnace in 1100 DEG C of calcinings, insulation 3h; (5) burnt powder and 0.1g tetraethoxy are put 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 DEG C, then cross 150 mesh sieves, then dry-pressing formed, pressure is 50T, obtains work in-process biscuit; (3) biscuit is heat-treated in 700 DEG C, insulation 1.5h; (4) biscuit after thermal treatment is sintered in vibration hot pressing furnace, concrete sin-tering mechanism is as follows: be first warming up to 1050 DEG C with the speed of 11 DEG C/min, be then warming up to 1800 DEG C with the speed of 5 DEG C/min, and be incubated 2.5h, pressure is 15T, then with stove nature water-cooled cooling; (5) vibrate sample anneal in Si-Mo rod stove of obtaining of hot pressed sintering, mechanism of anneal is for rising to 1200 DEG C with 5 DEG C/min from room temperature and being incubated 2h, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample finally crossed anneal is polished, polishing obtains high permeability.
Comparative example 1
(1) by 17g α-Al
2o
3powder, 22.374gY
2o
3powder, 0.35gNd
2o
3powder and 0.2gTEOS, 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 DEG C, then cross 100 mesh sieves, then dry-pressing formed, pressure is 50T, obtains work in-process biscuit; (3) biscuit is heat-treated in 600 DEG C, insulation 0.5h; (4) biscuit after thermal treatment is carried out 1750 DEG C of vacuum sinterings, insulation 10h.(5) sample anneal in Si-Mo rod stove of obtaining of vacuum sintering, mechanism of anneal is for rising to 1200 DEG C with 5 DEG C/min from room temperature and being incubated 2h, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample finally crossed anneal is polished, polishing obtains high permeability.
Comparative example 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) be titrated in metal salt solution by ammonium bicarbonate soln, while stirring titration, rate of titration is 40 droplets/minute; (3) titration complete after by throw out slaking 24h, then filter, wash, alcohol wash, then put into the oven dry of 60 DEG C, baking oven; (4) powder grinding is placed on silicon carbide rod furnace in 1100 DEG C of calcinings, insulation 3h; (5) by burnt powder and 0.2gCaO 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 DEG C, then cross 150 mesh sieves, then dry-pressing formed, pressure is 50T, obtains work in-process biscuit; (3) biscuit is heat-treated in 600 DEG C, insulation 0.5h; (4) biscuit after thermal treatment is carried out 1750 DEG C of vacuum sinterings, insulation 10h; (5) sample anneal in Si-Mo rod stove of obtaining of vacuum sintering, mechanism of anneal is for rising to 1200 DEG C with 5 DEG C/min from room temperature and being incubated 2h, then furnace cooling; (6) the Re:YAG laser transparent ceramic that the sample finally crossed anneal is polished, polishing obtains high permeability.
Laser transparent ceramic obtained by embodiment 1-6 is made following technology for detection, and compares with the crystalline ceramics that comparative example 1-2 adopts vacuum sintering obtained, record the technical parameter in each preparation process simultaneously, result as shown in Table 1:
As shown in Table 1, the density average out to 4.60g/cm of laser transparent ceramic that obtains of (1) the present invention
3, its density is high, and the density of the existing laser transparent ceramic obtained by vacuum sintering reaches 4.55g/cm
3, its density is also high;
(2) the pore quantity of laser transparent ceramic that obtains of the present invention is within 0 ~ 5, and its pore is few, and the pore quantity of the existing laser transparent ceramic obtained by vacuum sintering is within 3 ~ 5, and its pore is also few;
(3) laser transparent ceramic that obtains of the present invention is at visible region transmittance >70%, infrared region transmittance >80%, its transmitance is high, and the existing laser transparent ceramic obtained by vacuum sintering is at visible region transmittance >68%, infrared region transmittance >82%, its transmitance is also high;
(4) sintering period of laser transparent ceramic of obtaining of the present invention is at about 10 ~ 20h, and its cycle is short, and the sintering period of the existing laser transparent ceramic obtained by vacuum sintering is at about 48-72h, and its cycle is long;
(5), in the preparation process of laser transparent ceramic of the present invention, only needing to use a kind of sintering aid, is exactly tetraethoxy, and its addition is 0 ~ 2wt%, and in the preparation process of existing laser transparent ceramic, need the use coordinating 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%, avoids excessive use sintering aid, reduces the introducing of impurity, improves purity, the density of goods, simplifies preparation technology.And when adopting vacuum sintering, owing to not having the effect of impressed pressure, sintering process is slow, and need multiple sintering aid as TEOS, MgO, CaO or SiO
2deng wherein one or more, just make product densified sintering product.
It should be noted that other details of the vacuum sintering in comparative example 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 are also considered as protection scope of the present invention.
Claims (5)
1. a preparation method for laser transparent ceramic, is characterized in that, comprising:
Aluminum nitrate, Yttrium trinitrate and rare earth nitrate is adopted to be main raw material, by Re
xy
3-xal
5o
12stoichiometric ratio weigh, be configured to the metal salt solution that concentration is 0.08mol/L ~ 1.2mol/L;
Be that the ammonium bicarbonate soln of 0.08mol/L ~ 2.4mol/L is titrated to described metal salt solution, titration while stirring by concentration; After precipitated liquid at room temperature slaking 15-30h, carry out suction filtration, washing, alcohol wash, drying, grinding to it, obtain pre-powder, wherein, drying temperature is 50 ~ 100 DEG C;
Described pre-powder is calcined 2-4h at 900 ~ 1200 DEG C, obtained Re:YAG powder;
With described Re:YAG powder for base-material, add sintering aid and solvent ball milling 24 ~ 72h, obtain slurry;
Described slurry is put into oven drying, and drying temperature is 50 ~ 100 DEG C, and then ground 100 ~ 250 mesh sieves, obtain powder;
Described powder is carried out dry-pressing formed, obtains work in-process;
Described work in-process are carried out low-temperature heat treatment, and wherein, the temperature of described low-temperature heat treatment is 500 ~ 1100 DEG C;
Described work in-process through low-temperature heat treatment are carried out hot pressing vibratory sintering, and wherein, the sintering temperature of described hot pressing vibration is 1500 ~ 2000 DEG C, and pressure is 4 ~ 55MPa; The sin-tering mechanism of described hot pressing vibratory sintering is as follows: first, and described work in-process are warming up to 1000 DEG C with the speed of 10 DEG C/min; Then, described work in-process are warming up to 1760 DEG C with the speed of 6 DEG C/min, and are incubated 2h, pressure is 20T; Finally, by described work in-process furnace cooling;
Described work in-process through hot pressing vibratory sintering are carried out anneal, and annealing temperature is 900 ~ 1500 DEG C, and wherein, described work in-process, in annealing process, rise to 1200 DEG C with 2-8 DEG C/min from room temperature and are incubated 1 ~ 10h;
By the described work in-process sanding and polishing of annealed process, obtained Re:YAG laser transparent ceramic;
Wherein, described Re
xy
3-xal
5o
12in, x=0.03 ~ 3, Re is one or more in Nd, Yb, Er, Tb rare earth element.
2. the preparation method of laser transparent ceramic as claimed in claim 1, it is characterized in that, described sintering aid is tetraethoxy, and the addition of described sintering aid is 0 ~ 2wt% of described main raw material quality;
Described solvent is water or dehydrated alcohol, and the addition of described solvent and the mass ratio of described main raw material are 1:3 ~ 3:1.
3. the preparation method of laser transparent ceramic as claimed in claim 1, is characterized in that, described ball milling step adopts Al
2o
3ball and ZrO
2ball is ball-milling medium.
4. 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 process, the step of obtained Re:YAG laser transparent ceramic comprises:
Polished through diamond wheel by the described work in-process of annealed process, described polishing comprises surface corase grind and fine grinding;
Described work in-process through polishing are carried out polished finish through diamond paste, obtained Re:YAG laser transparent ceramic.
5. a laser transparent ceramic, is characterized in that, it adopts aluminum nitrate, Yttrium trinitrate and rare earth nitrate to be main raw material, and described main raw material is pressed Re
xy
3-xal
5o
12stoichiometric ratio weigh, and by as described in any one of claim 1-4 laser transparent ceramic preparation method obtain;
Wherein, x=0.03 ~ 3, Re is one or more in Nd, Yb, Er, Tb rare earth element.
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| CN101891477A (en) * | 2010-07-23 | 2010-11-24 | 中国科学院上海硅酸盐研究所 | Method for preparing circular rod-shaped RE:YAG laser transparent ceramics |
| CN102311258A (en) * | 2010-07-05 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Active ion controlled doping yttrium aluminum garnet base laser transparent ceramic material and preparation method thereof |
| CN103204678A (en) * | 2012-01-16 | 2013-07-17 | 佛山市陶瓷研究所有限公司 | Ceramic cutting tool with ultrahigh strength and ultrahigh toughness, and preparation method thereof |
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| CN102311258A (en) * | 2010-07-05 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Active ion controlled doping yttrium aluminum garnet base laser transparent ceramic material and preparation method thereof |
| CN101891477A (en) * | 2010-07-23 | 2010-11-24 | 中国科学院上海硅酸盐研究所 | Method for preparing circular rod-shaped RE:YAG laser transparent ceramics |
| CN103204678A (en) * | 2012-01-16 | 2013-07-17 | 佛山市陶瓷研究所有限公司 | Ceramic cutting tool with ultrahigh strength and ultrahigh toughness, and preparation method thereof |
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