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.
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.