CN109400158A

CN109400158A - Mix the preparation method of ytterbium luteium oxide laser ceramics

Info

Publication number: CN109400158A
Application number: CN201811637032.7A
Authority: CN
Inventors: 王肖戬; 李兴旺; 韩剑锋; 杨国利; 李洪峰; 王永国; 莫小刚
Original assignee: BEIJING OPTO-ELECTRONICS TECHNOLOGY Co Ltd
Current assignee: BEIJING OPTO-ELECTRONICS TECHNOLOGY Co Ltd
Priority date: 2018-12-29
Filing date: 2018-12-29
Publication date: 2019-03-01

Abstract

The invention discloses a kind of preparation methods for mixing ytterbium luteium oxide laser ceramics, belong to ceramic field.This method comprises: preparing ytterbium oxide powder；Prepare luteium oxide powder；Ytterbium oxide powder and luteium oxide powder are weighed according to the ytterbium concentration of mixing for mixing ytterbium luteium oxide laser ceramics；The mixture of ytterbium oxide powder and luteium oxide powder, sintering aid, organic solvent after weighing carries out ball-milling treatment, obtains the first slurry；First slurry is successively dried, the processing of forming processes, isostatic cool pressing, obtains ceramic body；Dumping processing, vacuum-sintering processing, hot pressing post-processing, annealing, polishing treatment are successively carried out to ceramic body, obtain mixing ytterbium luteium oxide laser ceramics.The laser ceramics that this method is prepared has good optical property, and is not in that doping concentration deviates, and is easy to control, is easy to large-scale production.

Description

Mix the preparation method of ytterbium luteium oxide laser ceramics

Technical field

The present invention relates to ceramic field, in particular to a kind of preparation method for mixing ytterbium luteium oxide laser ceramics.

Background technique

Laser ceramics is a kind of ceramic material that the energy such as extraneous electricity, light, ray can be converted into laser, because of tool Have the advantages that than laser glass good heat conductivity, is more easy to manufacture than monocrystalline laser material, being ground extensively convenient for large scale is made Study carefully and uses.In laser ceramics, ytterbium luteium oxide (Yb:Lu is mixed₂O₃) laser ceramics because during laser operation calorific value it is small, Laser operation is high-efficient, and has the performances such as good mechanical performance, chemical stability, hardness be low and be taken seriously.

The relevant technologies provide a kind of Yb:Lu₂O₃The preparation method of laser ceramics, comprising: by the soluble metal of Yb, Lu Salt is dissolved in the water, and forms the first mixed solution.Second mixed solution of ammonium hydrogen carbonate and hydrogen sulfate ammonia is added drop-wise to first to mix It closes in solution, Yb:Lu is obtained by coprecipitation method₂O₃Precursor.Yb:Lu₂O₃Precursor is through filtration treatment, carrying out washing treatment, dry After dry processing, calcination processing, Yb:Lu is obtained₂O₃Powder.By Yb:Lu₂O₃Powder is through ball-milling treatment, forming processes, vacuum-sintering After processing, annealing, polishing treatment, Yb:Lu is obtained₂O₃Laser ceramics.

In the preparation method that the relevant technologies provide, the Yb:Lu as made from coprecipitation method₂O₃Powder is easy to reunite, and burns Poor activity is tied, Yb:Lu obtained is caused₂O₃The transmitance of laser ceramics is poor.Moreover, because Yb³⁺、Lu³⁺Under the same conditions Solubility product is different, therefore the Yb:Lu as made from coprecipitation method₂O₃Ytterbium ion concentration cannot be controlled accurately in powder.In addition, This method complex process, operating difficulties, poor repeatability, it is difficult to accomplish scale production.

Summary of the invention

The embodiment of the invention provides a kind of preparation methods for mixing ytterbium luteium oxide laser ceramics, can solve above-mentioned technology and ask Topic.Specific technical solution is as follows:

The embodiment of the invention provides a kind of preparation methods for mixing ytterbium luteium oxide laser ceramics, which comprises

Prepare ytterbium oxide powder；

Prepare luteium oxide powder；

The ytterbium oxide powder and the luteium oxide powder are weighed according to the ytterbium concentration of mixing for mixing ytterbium luteium oxide laser ceramics；

By after weighing the ytterbium oxide powder and the luteium oxide powder with sintering aid, organic solvent mix and carry out Ball-milling treatment obtains the first slurry；

First slurry is successively dried, the processing of forming processes, isostatic cool pressing, obtains ceramic body；

Dumping processing, vacuum-sintering processing, hot pressing post-processing, annealing, polishing are successively carried out to the ceramic body Processing obtains described mixing ytterbium luteium oxide laser ceramics.

It is described to prepare ytterbium oxide powder in a kind of possible design, comprising:

Obtain the soluble-salt of ytterbium and the first mixed liquor of water, wherein the concentration of ytterbium ion is 0.1-2.5mol/L；

Obtain the second mixed liquor of ammonium hydrogen carbonate, dispersing agent, ethyl alcohol, water；

Under agitation, first mixed liquor is added dropwise in second mixed liquor, obtains the precipitating with ytterbium The third mixed liquor of object；

Ethyl orthosilicate is added dropwise into the third mixed liquor, obtains the 4th mixed liquor；

First aging process, the first filtration treatment, the first carrying out washing treatment, first are successively carried out very to the 4th mixed liquor Empty drying process, the first calcination processing, the first Screening Treatment, obtain the ytterbium oxide powder.

It is described to prepare luteium oxide powder in a kind of possible design, comprising:

Obtain the soluble-salt of lutetium and the 5th mixed liquor of water, wherein the concentration of lutetium ion is 0.1-2.5mol/L；

Obtain the 6th mixed liquor of ammonium hydrogen carbonate, dispersing agent, ethyl alcohol, water；

Under agitation, the 5th mixed liquor is added dropwise in the 6th mixed liquor, obtains the precipitating with lutetium 7th mixed liquor of object；

Ethyl orthosilicate is added dropwise into the 7th mixed liquor, obtains the 8th mixed liquor；

Second aging process, the second filtration treatment, the second carrying out washing treatment, second are successively carried out very to the 8th mixed liquor Empty drying process, the second calcination processing, the second Screening Treatment, obtain the luteium oxide powder.

In a kind of possible design, the dispersing agent is ammonium sulfate, polyethylene glycol, castor oil, ammonium polymethacrylate At least one of；

Molar concentration of the ammonium hydrogen carbonate in second mixed liquor and the 6th mixed liquor is 0.2-3mol/ L；

In second mixed liquor and the 6th mixed liquor, the volume ratio of water and ethyl alcohol is 1:2-3:1；

The time of first aging process and second aging process is 24-48h；

The temperature of first vacuum drying treatment and second vacuum drying treatment is 75-200 DEG C, and the time is 1-5 days；

The temperature of first calcination processing and second calcination processing is 800-1200 DEG C, and the time is 2-24h.

In a kind of possible design, the sintering aid is silica, in ethyl orthosilicate, magnesia, lithium fluoride At least one；

The mass percent that the sintering aid accounts for first slurry is 0.05%-1.5%；

The organic solvent is at least one of ethyl alcohol, ether, acetone；

The gross mass of the ytterbium oxide powder and the luteium oxide powder and the mass ratio of the organic solvent are 1:1- 1:4。

In a kind of possible design, the drying process includes: to be spray-dried to first slurry, described In spray drying, the inlet temperature of sprayer is 150-300 DEG C, and outlet temperature is 70-120 DEG C, and spray speed is 1-20mL/min；

In a kind of possible design, the forming processes include: to be placed in the first slurry after the drying process In the mold of nylon material, forming operation is carried out with the pressure of 5-30MPa；

The pressure of the isostatic cool pressing processing is 100-300MPa, time 1-10min.

In a kind of possible design, the temperature of the dumping processing is 800-1300 DEG C, time 1-24h；

The temperature of the annealing is 1200-1600 DEG C, and the heating rate of time 1-48h, the annealing are 1-5℃/min。

In a kind of possible design, the vacuum-sintering processing includes:

Will by the dumping, treated that ceramic body is placed in vacuum drying oven, and to the vacuum stove evacuation；

It controls the vacuum drying oven and is warming up to 1800-1850 DEG C with the speed of 1-10 DEG C/min；

Control the vacuum drying oven heat preservation 1-50h；

It controls the vacuum drying oven and is cooled to 18-28 DEG C with the speed of 3-10 DEG C/min.

In a kind of possible design, the hot pressing post-processing includes:

Will by the vacuum-sintering, treated that one or more ceramic bodies are placed in heating mould, and make one or It is wrapped up completely by boron nitride powder on the surface of multiple ceramic bodies；

Heating mould is placed in vacuum hotpressing stove, the vacuum hotpressing stove is controlled and is warming up to the speed of 1-10 DEG C/min 1600-1800 DEG C, pressure 1-50MPa, handle 0.5-5h；

It controls the vacuum hotpressing stove and is cooled to 18-28 DEG C.

Technical solution bring beneficial effect provided in an embodiment of the present invention includes at least:

The preparation method provided in an embodiment of the present invention for mixing ytterbium luteium oxide laser ceramics is prepared respectively by step-by-step precipitation method The ytterbium oxide powder and luteium oxide powder of sintering activity height, good dispersion are obtained, conducive to being prepared with favorable optical performance Laser ceramics.Then it makes pottery according to mix ytterbium concentration weighing ytterbium oxide powder and the luteium oxide powder of laser ceramics to prepare laser Porcelain is not in doping concentration deviation, is easy to control, is easy to large-scale production.

Detailed description of the invention

To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other Attached drawing.

Fig. 1 is the preparation method flow chart provided in an embodiment of the present invention for mixing ytterbium luteium oxide laser ceramics；

Fig. 2 is the schematic diagram that hot pressing provided in an embodiment of the present invention post-processes a ceramic body；

Fig. 3 is the schematic diagram that hot pressing provided in an embodiment of the present invention post-processes multiple ceramic bodies.

Wherein, appended drawing reference respectively indicates:

N- ceramic body,

M-BN powder,

P- hot pressing die.

Specific embodiment

Unless otherwise defined, all technical terms used in the embodiment of the present invention all have usual with those skilled in the art The identical meaning understood.

In embodiments of the present invention, Yb:Lu can be abbreviated as by mixing ytterbium luteium oxide laser ceramics₂O₃Laser ceramics.

To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention Formula is described in further detail.

The embodiment of the invention provides a kind of preparation methods for mixing ytterbium luteium oxide laser ceramics, as shown in Fig. 1, this method Include:

Step 1 prepares ytterbium oxide powder.

Specifically, step 1 includes but is not limited to following sub-step:

First mixed liquor of step 11, the soluble-salt for obtaining ytterbium and water, wherein the concentration of ytterbium ion is 0.1- 2.5mol/L。

For example, the concentration of ytterbium ion can be 0.1mol/L, 0.5mol/L, 0.9mol/L, 1mol/L, 1.3mol/ L, 1.5mol/L, 1.7mol/L, 1.9mol/L, 2mol/L, 2.1mol/L, 2.3mol/L, 2.5mol/L etc..

Wherein, the soluble-salt of ytterbium can be ytterbium nitrate and its hydrate, ytterbium chloride and its hydrate.

The purity of ytterbium has important influence to the translucency for improving obtained ceramics, is based on this, mixed in preparation first Before closing liquid, purification processes can be carried out to the soluble-salt of ytterbium.

The process of purification processes can be with are as follows: under conditions of 1300 DEG C, carries out at calcining to the soluble-salt of commercially available ytterbium 12h is managed, the soluble salt solutions of the ytterbium then dissolved using 2 microns of membrane filtration nitric acid, to remove indissoluble therein or not Molten impurity.

Step 12, the second mixed liquor for obtaining ammonium hydrogen carbonate, dispersing agent, ethyl alcohol, water.

Optionally, dispersing agent is at least one of ammonium sulfate, polyethylene glycol, castor oil, ammonium polymethacrylate.

Wherein, the molar concentration of ammonium hydrogen carbonate can be 0.2-3mol/L, such as can for 0.2mol/L, 0.5mol/L, 0.9mol/L、1mol/L、1.3mol/L、1.5mol/L、1.7mol/L、1.9mol/L、2mol/L、2.3mol/L、2.5mol/L、 2.7mol/L, 2.9mol/L, 3mol/L etc..The volume ratio of water and ethyl alcohol is 1:2-3:1, such as can be 1:2,2:1,3:1 Deng.

The molar ratio of ammonium sulfate and ytterbium ion can be 0.5:1-2:1, such as can be 0.5:1,0.7:1,1:1,1.5: 1,1.7:1,2:1 etc..

In the second mixed liquor, the mass percent of polyethylene glycol can be 0-1%, and the mass percent of castor oil can be with For 0-0.5%, the mass percent of ammonium polymethacrylate can be 0-1%.Wherein, polyethylene glycol can be polyethylene glycol 400(PEG400)。

By the mating reaction of above-mentioned ammonium hydrogen carbonate, dispersing agent, ethyl alcohol, water, the surface for the ytterbium oxide powder being prepared Tension is small, can reduce the agglomeration of ytterbium oxide powder, makes the good dispersion of ytterbium oxide powder obtained, and sintering activity is high.

Step 13, under agitation, the first mixed liquor is added dropwise in the second mixed liquor, the sediment with ytterbium is obtained Third mixed liquor.

First mixed liquor be added dropwise to the second mixed liquor speed can for 3-5mL/min, such as can for 3mL/min, 3.5mL/min, 4mL/min, 4.5mL/min, 5mL/min etc..

It so, it is possible that ytterbium ion is made sufficiently to react to obtain uniform precipitating with the bicarbonate radical in the second mixed liquor.

In titration process, needs to adjust the first mixed liquor and the mixed pH value of the second mixed liquor is 7-10, to promote The generation of the sediment of ytterbium avoids that side reaction occurs.Specifically, the pH value of pH meter monitoring third mixed liquor can be used, and with dense Nitric acid or concentrated ammonia liquor accurately adjust the pH value of third mixed liquor between 7-10.

Ethyl orthosilicate is added dropwise into third mixed liquor in step 14, obtains the 4th mixed liquor.

By the way that ethyl orthosilicate is added dropwise, so that it is wrapped in the surface of the sediment of ytterbium, form Si-CH₃Base wraps up shell structure, To eliminate the agglomeration traits of the sediment of ytterbium, the surface-active of the sediment of ytterbium is reduced, its dispersion performance is improved.

Specifically, 1-2mL ethyl orthosilicate can be added dropwise into third mixed liquor, continue to stir 2h, allow ethyl orthosilicate It is fully hydrolyzed, to be sufficiently wrapped in the surface of the sediment of ytterbium.

Step 15 successively carries out the first aging process, the first filtration treatment, the first carrying out washing treatment, to the 4th mixed liquor One vacuum drying treatment, the first calcination processing, the first Screening Treatment, obtain ytterbium oxide powder.

The time of first aging process can be 24-48h, such as can for for 24 hours, 27h, 30h, 33h, 35h, 37h, 39h, 40h, 43h, 48h etc..In this way, ytterbium ion is not only made to be sufficiently formed sediment, ethyl orthosilicate is also made sufficiently to be wrapped in the heavy of ytterbium The surface of starch, conducive to the dispersion performance for the sediment for improving ytterbium.

In the first carrying out washing treatment, sediment is washed several times with deionized water, until detecting washing lotion with barium chloride solution Until being generated without precipitating, then with washes of absolute alcohol 1-10 times.

The temperature of first vacuum drying treatment is 75-200 DEG C, such as can be 75 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 130 DEG C, 150 DEG C, 170 DEG C, 190 DEG C, 200 DEG C etc..The time of first vacuum drying treatment be 1-5 days, such as can be 1 day, 2 days, 3 days, 4 days, 5 days etc..

The temperature of first calcination processing be 800-1200 DEG C, such as can for 800 DEG C, 8500 DEG C, 900 DEG C, 9500 DEG C, 1000 DEG C, 1050 DEG C, 1100 DEG C, 1150 DEG C, 1200 DEG C etc..The time of first calcination processing be 2-24h, such as can for 2h, 5h, 8h, 10h, 12h, 16h, 18h, 20h, 22h, for 24 hours etc..

By above-mentioned processing, the high nanoscale ytterbium oxide powder of good dispersion, sintering activity can be made.

Step 2 prepares luteium oxide powder.

Step 2 includes but is not limited to following sub-step:

5th mixed liquor of step 21, the soluble-salt for obtaining lutetium and water, wherein the concentration of lutetium ion is 0.1- 2.5mol/L。

For example, the concentration of lutetium ion can be 0.1mol/L, 0.5mol/L, 0.9mol/L, 1mol/L, 1.3mol/ L, 1.5mol/L, 1.7mol/L, 1.9mol/L, 2mol/L, 2.1mol/L, 2.3mol/L, 2.5mol/L etc..

Wherein, the soluble-salt of lutetium can be lutecium nitrate and its hydrate, lutecium chloride and its hydrate.

The purity of lutetium has important influence to the translucency for improving obtained ceramics, is based on this, mixed in preparation first Before closing liquid, purification processes can be carried out to the soluble-salt of lutetium.

The process of purification processes can be with are as follows: under conditions of 1300 DEG C, carries out at calcining to the soluble-salt of commercially available lutetium 12h is managed, the soluble salt solutions of the lutetium then dissolved using 2 microns of membrane filtration nitric acid, to remove indissoluble therein or not Molten impurity.

Step 22, the 6th mixed liquor for obtaining ammonium hydrogen carbonate, dispersing agent, ethyl alcohol, water.

Wherein, the molar ratio of ammonium sulfate and lutetium ion can be 0.5:1-2:1, such as can for 0.5:1,0.7:1,1:1, 1.5:1,1.7:1,2:1 etc..

Restriction for other components, identical with step 12, details are not described herein again.

Step 23, under agitation, the 5th mixed liquor is added dropwise in the 6th mixed liquor, the sediment with lutetium is obtained The 7th mixed liquor.

5th mixed liquor be added dropwise to the 6th mixed liquor speed can for 3-5mL/min, such as can for 3mL/min, 3.5mL/min, 4mL/min, 4.5mL/min, 5mL/min etc..

It so, it is possible that lutetium ion is made sufficiently to react to obtain uniform precipitating with the bicarbonate radical in the 6th mixed liquor.

In titration process, needs to adjust the 5th mixed liquor and the 6th mixed pH value of mixed liquor is 7-10, to promote The generation of the sediment of lutetium avoids that side reaction occurs.Specifically, pH meter can be used to monitor the pH value of the 7th mixed liquor, and with dense Nitric acid or concentrated ammonia liquor accurately adjust the pH value of the 7th mixed liquor between 7-10.It so, it is possible to keep lutetium ion sufficiently mixed with the 6th The bicarbonate radical closed in liquid reacts to obtain uniform precipitating.

Ethyl orthosilicate is added dropwise into the 7th mixed liquor in step 24, obtains the 8th mixed liquor.

By the way that ethyl orthosilicate is added dropwise, so that it is wrapped in the surface of the sediment of lutetium, form Si-CH₃Base wraps up shell structure, To eliminate the agglomeration traits of the sediment of lutetium.

Specifically, 1-2mL ethyl orthosilicate can be added dropwise into the 7th mixed liquor, continue to stir 2h, allow ethyl orthosilicate It is fully hydrolyzed, to be wrapped in the surface of the sediment of lutetium.

Step 25 successively carries out the second aging process, the second filtration treatment, the second carrying out washing treatment, to the 8th mixed liquor Two vacuum drying treatments, the second calcination processing, the second Screening Treatment, obtain luteium oxide powder.

The time of second aging process can be 24-48h.

The temperature of second vacuum drying treatment can be 75-200 DEG C, and the time can be 1-5 days.

The temperature of second calcination processing can be 800-1200 DEG C, and the time can be 2-24h.

Specifically, step 15 can be found in for each processing.

Step 3 weighs ytterbium oxide powder and luteium oxide powder according to the ytterbium concentration of mixing for mixing ytterbium luteium oxide laser ceramics.

Specifically, according to chemical formula Yb_2xLu_2-2xO₃(0.001≤x≤0.2, x are mix ytterbium atomic fraction), use precision for The analytical precision balances of one thousandth gram weigh the quality of ytterbium oxide and luteium oxide respectively.Wherein, Yb³⁺The range of ion concentration is 0.1%-20% (atomic percent).

Step 4, by after weighing ytterbium oxide powder and luteium oxide powder mixed with sintering aid, organic solvent and carry out ball Mill processing, obtains the first slurry.

Optionally, sintering aid is at least one of silica, ethyl orthosilicate, magnesia, lithium fluoride.

Above-mentioned several sintering aids can promote ytterbium oxide and luteium oxide to sinter fine and close ceramic body into.

Sintering aid account for the first slurry mass percent can for 0.05%-1.5%, such as can for 0.05%, 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5% etc..

In this way, ytterbium oxide can not only effectively facilitate and luteium oxide sinters fine and close ceramic body into, it is additionally favorable for its structure Homogeneity, be not present bubble.

Organic solvent can be at least one of ethyl alcohol, ether, acetone.These types of organic solvent can make the first slurry In each component full and uniform dispersion, obtain the slurry of uniform particle diameter conducive to ball milling.

The mass ratio of the gross mass and organic solvent of ytterbium oxide powder and luteium oxide powder is 1:1-1:4, such as can be with For 1:1,1:2,1:3,1:4 etc..It so, it is possible to guarantee that ytterbium oxide powder and luteium oxide powder are well-dispersed in organic solvent.

Wherein, the material of ball grinder can be nylon, polytetrafluoroethylene (PTFE), agate, zirconium oxide etc..By adding in ball grinder Adding diameter is 3-5mm, and material is the abrading-ball progress ball-milling treatment of aluminum oxide, zirconium oxide, agate.

The time of ball milling can be 1-100h, such as can for 1h, 10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h, 100h etc..The revolving speed of ball mill can be 300-500rpm, such as can for 300rpm, 330rpm, 350rpm, 380rpm, 400rpm, 430rpm, 450rpm, 470rpm, 500rpm etc..

Step 5 is successively dried the first slurry, the processing of forming processes, isostatic cool pressing, obtains ceramic body.

Step 51, drying process include: to be spray-dried to the first slurry, in spray drying, the entrance of sprayer Temperature is 150-300 DEG C, such as can be 150 DEG C, 170 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 230 DEG C, 250 DEG C, 270 DEG C, 300 DEG C etc., outlet temperature is 70-120 DEG C, such as can be 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C etc., and spray speed is 1- 20mL/min, for example, can for 1mL/min, 3mL/min, 5mL/min, 7mL/min, 9mL/min, 10mL/min, 11mL/min, 13mL/min, 15mL/min, 17mL/min, 19mL/min, 20mL/min etc..

Step 52, forming processes include: that the first slurry after being dried is placed in the mold of nylon material, with 5- The pressure of 30MPa carries out forming operation.

It should be noted that just being carried out at molding after grinding to the first slurry after being dried and cross 200 meshes Reason.

In the prior art, forming operation is carried out using steel mold, frictional force effect when due to molding will lead to micro Iron filings adhere to ceramic body surface layer, during the sintering process, ferro element can diffuse into ceramic body, influence Yb: Lu₂O₃The laser activity of laser ceramics, it is difficult to synthesize the Yb:Lu of high quality₂O₃Laser ceramics.In embodiments of the present invention, pass through The mold of material is selected, introducing metal ion ceramic body is can avoid and pollutes.

Wherein, the nylon material of mold can be nylon 101, nylon MCPA, nylon66 fiber, nylon 610, nylon 1001 etc..

Step 53, in the processing of calm pressure, ceramic body after forming processes can be packed using latex, and be put in cold Calm pressure processing is carried out in isostatic pressing machine cylinder pressure.Wherein, the pressure of isostatic cool pressing processing is 100-300MPa, such as can be 100MPa, 150MPa, 200MPa, 250MPa, 300MPa etc., time 1-10min, such as can for 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min etc..

It is handled by isostatic cool pressing, the stomata through being pressed and molded in treated ceramic body can be further reduced, mentioned Fine and close Yb:Lu is made conducive to sintering in the density and density distribution uniformity of high green body₂O₃Laser ceramics.

Step 6 successively carries out dumping processing to ceramic body, vacuum-sintering processing, hot pressing post-processing, annealing, throws Light processing obtains mixing ytterbium luteium oxide laser ceramics.

Step 61, dumping processing in, organic matter remaining in ceramic body can be eliminated.Wherein, remaining organic Object can be carried out by way of burning.

Optionally, dumping processing temperature be 800-1300 DEG C, such as can for 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, 1050 DEG C, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C, 1300 DEG C etc..The time of dumping processing can be 1-24h, It such as can be 1h, 3h, 5h, 7h, 9h, 10h, 12h, 14h, 17h, 19h, 20h, 21h, 22h, 23h, for 24 hours etc..

Step 62, vacuum-sintering processing include but is not limited to following steps:

Step 621, will by dumping, treated that ceramic body is placed in vacuum drying oven, and to vacuum stove evacuation, make it Vacuum degree is better than 10^-2Pa。

Step 622, control vacuum drying oven are warming up to 1800-1850 DEG C with the speed of 1-10 DEG C/min.Wherein, heating rate can Think 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min, 10 DEG C/min etc..Temperature can be 1800 DEG C, 1810 DEG C, 1820 DEG C, 1830 DEG C, 1840 DEG C, 1850 DEG C etc..

Step 623, control vacuum drying oven keep the temperature 1-50h, such as can for 1h, 3h, 5h, 7h, 9h, 10h, 13h, 15h, 17h, 19h, 20h, 21h, 25h, 27h, 29h, 30h, 31h, 35h, 37h, 39h, 40h, 41h, 43,45,47h, 49h, 50h etc..

Step 624, control vacuum drying oven are cooled to 18-28 DEG C with the speed of 3-10 DEG C/min.Wherein, cooling rate can be 3 DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min, 10 DEG C/min etc., temperature can be 18 DEG C, 19 DEG C, 20 DEG C, 21 DEG C, 22 DEG C, 23 DEG C, 24 DEG C, 25 DEG C, 26 DEG C, 27 DEG C, 28 DEG C etc..

In this way, being conducive to obtain the excellent ceramic body of transmitance by vacuum-sintering processing.

Step 63, hot pressing post-processing include but is not limited to following steps:

Step 631, will by vacuum-sintering, treated that one or more ceramic bodies are placed in heating mould, and make one It is wrapped up completely by boron nitride powder on the surface of a or multiple ceramic bodies.

Wherein, heating mould is graphite jig, and multiple ceramic bodies can be placed in graphite jig, adjacent ceramic base It can be separated using boron nitride (BN) powder between body, and guarantee that every piece of ceramic body is sufficiently wrapped up by BN powder, BN powder Partial size be 0.1-500 μm.

As shown in Fig. 2, there is a ceramic body N in hot pressing die P, be BN powder M around ceramic body N.Such as Shown in attached drawing 3, there are multiple ceramic body N in hot pressing die P, be isolated between adjacent ceramic body N by BN powder M, often A ceramic body N is wrapped up by BN powder M.

Heating mould is placed in vacuum hotpressing stove by step 632, controls vacuum hotpressing stove with the speed liter of 1-10 DEG C/min Temperature handles 0.5-5h to 1600-1800 DEG C, pressure 1-50MPa.

Wherein, the heating rate of vacuum hotpressing stove can for 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/ Min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min, 10 DEG C/min etc..The temperature of heating can for 1600 DEG C, 1630 DEG C, 1650 DEG C, 1670 DEG C, 1700 DEG C, 1730 DEG C, 1750 DEG C, 1770 DEG C, 1800 DEG C etc..The time of processing can for 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h etc..

Step 633, control vacuum hotpressing stove are cooled to 18-28 DEG C.The temperature of cooling can be 18 DEG C, 19 DEG C, 20 DEG C, 21 DEG C, 22 DEG C, 23 DEG C, 24 DEG C, 25 DEG C, 26 DEG C, 27 DEG C, 28 DEG C etc..

In the hot pressing post-processing of the prior art, a ceramics sample, and the compression side of ceramics sample can only be once handled To two end faces must be smooth enough and parallel, be otherwise easily crushed.In embodiments of the present invention, by by ceramic body Be embedded under high temperature not with Yb:Lu₂O₃In the BN powder of crystal reaction, when ceramic body being made to be pressurized, BN powder can play good Buffer function can be filled into the concave surface of ceramics conducive to the mobility of powder, make up the fluctuating of ceramic body end face and the depth of parallelism Unbalance stress caused by difference, so that mechanical hot pressing processing be greatly lowered to the processing request of element, and can single treatment it is multiple Element improves production efficiency.The hot pressing post-processes hot isostatic apparatus that should not be expensive, reduces production cost, improves Security performance.

Step 634, in annealing, the ceramic body post-processed through hot pressing is placed in atmosphere high temperature furnace, is moved back Fire processing, the temperature of annealing can be 1200-1600 DEG C, for example, can for 1200 DEG C, 1250 DEG C, 1300 DEG C, 1350 DEG C, 1400 DEG C, 1450 DEG C, 1500 DEG C, 1550 DEG C, 1600 DEG C etc..The time of annealing can be 1-48h, such as can for 1h, 5h, 9h, 10h, 12h, 15h, 17h, 19h, 20h, 25h, 29h, 30,32,36h, 38h, 40h, 42h, 45h, 47h, 48h etc..It moves back Fiery heating rate can be 1-5 DEG C/min, such as can be 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/min Deng.

By above-mentioned annealing, the residual stress in ceramics obtained can be removed, and make uniform component.

Step 635 is processed by shot blasting the ceramics by annealing, obtains size, glossiness is all satisfied requirement Mix ytterbium luteium oxide laser ceramics.

In addition, carrying out forming processes in preparation method provided in an embodiment of the present invention using nylon mold, being effectively prevented from The pollution of other metal heteroions, and it is quiet can to can replace heat etc. with the multiple workpiece of single treatment in processing after hot-pressing Post-processing technology is pressed, and does not need expensive hot isostatic apparatus, reduces costs, improves safety.

Hereinafter the present invention will be further described through by specific embodiment.

In following specific embodiments, condition person is not specified in related operation, according to normal conditions or manufacturer It is recommended that condition carry out.It is raw materials used production firm is not specified and specification person be can be with conventional products that are commercially available.

Embodiment 1

A kind of preparation method for mixing ytterbium luteium oxide laser ceramics is present embodiments provided, this method comprises:

The 93.43g purity that weighs with scale is the Yb (NO of 5N₃)₃·6H₂O is dissolved in deionized water, forms 0.1mol L^-1Yb (NO₃)₃Solution (the first mixed liquor).79.05g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is In the deionized water and dehydrated alcohol of 1:1, forming concentration is 0.2molL^-1Ammonium bicarbonate soln, into ammonium bicarbonate soln 0.2mol (NH is added₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, Obtain the second mixed liquor.After mixing evenly, by Yb (NO₃)₃Solution is added drop-wise to the second mixed liquor with the speed of 2.5mL/min dropwise In, obtain the third mixed liquor of the sediment containing ytterbium.Period is continuously agitated third mixed liquor with blender, and is supervised with acidometer The pH value for surveying third mixed liquor adjusts third mixed liquor pH value between 7.0-7.5 with ammonium hydroxide and nitric acid.Into third mixed liquor 1mL ethyl orthosilicate is added dropwise, stirs 2h, obtains the 4th mixed liquor.After titration, aging process is put by the 4th mixed liquor is quiet 48h.Then sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Solution detects filtrate and produces without precipitating Until life, then washed three times with dehydrated alcohol.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, grinds After mill sieves with 100 mesh sieve (150 μm), in 1000 DEG C of temperature lower calcination 6h, then (74 μm) of ground 200 mesh sieves in Muffle furnace Net obtains the nanometer Yb of polymolecularity₂O₃Powder.

The 93.81g purity that weighs with scale is the Lu (NO of 5N₃)₃·6H₂O is dissolved in deionized water, forms 0.1mol L^-1Lu (NO₃)₃Solution (the 5th mixed liquor).79.05g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is In the deionized water and dehydrated alcohol of 1:1, forming concentration is 0.5molL^-1Ammonium bicarbonate soln, into ammonium bicarbonate soln 0.2mol (NH is added₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, Obtain the 6th mixed liquor.After mixing evenly, by Lu (NO₃)₃Solution is added drop-wise to the 6th mixed liquor with the speed of 2.5mL/min dropwise In, obtain the 7th mixed liquor with the sediment containing lutetium.Period is continuously agitated the 7th mixed liquor with blender, and uses acidity The pH value of meter monitoring mixed solution adjusts solution ph between 7.0-7.5 with ammonium hydroxide and nitric acid.It is added dropwise into the 7th mixed liquor 1mL ethyl orthosilicate stirs 2h, obtains the 8th mixed liquor.After titration, aging process 48h is put by the 8th mixed liquor is quiet.So Sediment is filtered out afterwards, is washed with deionized to 0.1molL^-1BaCl₂Until solution detects filtrate without precipitating generation, It is washed three times with dehydrated alcohol again.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, ground 100 After mesh (150 μm), in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, height is obtained The nanometer Lu of dispersibility₂O₃Powder.

With the nanometer Yb of above-mentioned preparation₂O₃Powder, Lu₂O₃Powder is raw material, and preparation 30g mixes ytterbium atom percentage concentration and is 0.1% Yb:Lu₂O₃Powder, i.e., according to chemical formula Yb_0.002Lu_1.998O₃Calculate a nanometer Yb₂O₃Powder and Lu₂O₃The matter of powder Amount, successively weighs 0.0297g Yb with precise electronic assay balance (accuracy 0.0001g)₂O₃、29.9703gLu₂O₃And it is put into In 500mL nylon ball grinder.72g dehydrated alcohol is added into nylon ball grinder, the high purity aluminium oxide ball that 150g diameter is 5mm, And the sintering aid ethyl orthosilicate (TEOS) of 0.5wt% is added.With the revolving speed of 500rpm, ball milling mixing for 24 hours after, take out first Slurry is spray-dried.Inlet temperature is 200 DEG C, and outlet temperature is 100 DEG C, and spray speed is 10mL/min.9g spray is weighed every time Powder after mist is dry, is put into mold made of 101 material of nylon, with the pressure of 20MPa, is pressed into the circle that diameter is 40mm Piece.After disk is encapsulated with latex rubber bag, with cold isostatic press at 280MPa pressure maintaining 10min.After taking-up, molding green body is existed In 800 DEG C of Muffle furnace, 6h is calcined, to remove remaining organic matter.Then green body is put in vacuum drying oven, opens vacuum system System, is evacuated to 1 × 10^-3After Pa, with the heating rate of 3-10 DEG C/min, rise to 1820 DEG C, after keeping the temperature 20h, then with 10 DEG C/ The rate of min is down to room temperature.

The BN powder that a certain amount of purity is 99.7% is put into graphite hot pressing die, it, then will be by true with a thickness of 1cm Yb:Lu after empty sintering processes₂O₃Ceramics sample is put into graphite hot pressing die.A pottery is often put into graphite hot pressing die After porcelain sample, it is put into the BN powder of 1cm, until all ceramics samples discharge, covers mold upper cover.Then by graphite hot-die Tool is put into vacuum hotpressing stove, and with pressure head by two end face tightenings above and below mold, gradually pressure arrives 20MPa.After closed furnace, open Vacuum system is opened, is evacuated to 1 × 10^-3Pa is then turned on power supply, rises to 1720 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 2h Afterwards, room temperature is down to the rate of 10 DEG C/min.

The ceramics sample post-processed through hot pressing is taken out, after 1400 DEG C of atmosphere anneal 10h, is polished, obtains this implementation What example provided mixes ytterbium luteium oxide laser ceramics.

Embodiment 2

The 77.49g purity that weighs with scale is the YbCl of 5N₃·6H₂O is dissolved in deionized water, forms 0.5molL^-1 YbCl₃Solution (the first mixed liquor).118.58g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is 2:1's In deionized water and dehydrated alcohol, forming concentration is 1molL^-1Ammonium bicarbonate soln, be added into ammonium bicarbonate soln 0.2mol(NH₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, obtain Second mixed liquor.After mixing evenly, by Yb (NO₃)₃Solution is added drop-wise in the second mixed liquor dropwise with the speed of 2.5mL/min, is obtained To the third mixed liquor of the sediment containing ytterbium.Period is continuously agitated third mixed liquor with blender, and monitors third with acidometer The pH value of mixed liquor adjusts solution ph between 7.5-8.0 with ammonium hydroxide and nitric acid.1.2mL is being added dropwise just into third mixed liquor Silester stirs 2h, obtains the 4th mixed liquor.After titration, aging process 48h is put by the 4th mixed liquor is quiet.Then it crosses Sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Until solution detects filtrate without precipitating generation, then use Dehydrated alcohol washs three times.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, grinding sieves with 100 mesh sieve After (150 μm), in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, high dispersive is obtained The nanometer Yb of property₂O₃Powder.

The 77.88g purity that weighs with scale is the LuCl of 5N₃·6H₂O is dissolved in deionized water, forms 0.5molL^-1 LuCl₃Solution (the 5th mixed liquor).118.58g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is 2:1's In deionized water and dehydrated alcohol, forming concentration is 1molL^-1Ammonium bicarbonate soln, be added into ammonium bicarbonate soln 0.2mol(NH₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, obtain 6th mixed liquor.After mixing evenly, by Lu (NO₃)₃Solution is added drop-wise in the 6th mixed liquor dropwise with the speed of 2.5mL/min, is obtained To the 7th mixed liquor of the sediment containing lutetium.Period is continuously agitated the 7th mixed liquor with blender, and is monitored and mixed with acidometer The pH value of solution adjusts solution ph between 7.5-8.0 with ammonium hydroxide and nitric acid.The positive silicon of 1.2mL is added dropwise into the 7th mixed liquor Acetoacetic ester stirs 2h, obtains the 8th mixed liquor.After titration, aging process 48h is put by the 8th mixed liquor is quiet.Then it filters Sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Until solution detects filtrate without precipitating generation, then use nothing Water-ethanol washs three times.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, grinding sieves with 100 mesh sieve After (150 μm), in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, high dispersive is obtained The nanometer Lu of property₂O₃Powder.

With the nanometer Yb of above-mentioned preparation₂O₃、Lu₂O₃Powder is raw material, and preparing 30g to mix ytterbium concentration be atomic percent is 1% Yb:Lu₂O₃Powder, i.e., according to chemical formula Yb_0.02Lu_1.98O₃Calculate a nanometer Yb₂O₃Powder and Lu₂O₃The quality of powder, with essence Close electronic analytical balance (accuracy 0.0001g) successively weighs 0.2971g Yb₂O₃、29.7029g Lu₂O₃And it is put into 500mL Buddhist nun In imperial ball grinder.72g dehydrated alcohol, 150g diameter is added into nylon ball grinder as the high purity aluminium oxide ball of 5mm, and is added The sintering aid TEOS of 0.5wt%.With the revolving speed of 500rpm, ball milling mixing for 24 hours after, take out the first slurry, be spray-dried. Inlet temperature is 200 DEG C, and outlet temperature is 100 DEG C, and spray speed is 10mL/min.Powder after weighing 9g spray drying every time, puts Enter in mold made of 101 material of nylon, with the pressure of 20MPa, is pressed into the disk that diameter is 40mm.By disk latex rubber bag After encapsulation, with cold isostatic press at 280MPa pressure maintaining 10min.After taking-up, by molding green body in 800 DEG C of Muffle furnace, 6h is calcined, to remove remaining organic matter.Then green body is put in vacuum drying oven, opens vacuum system, is evacuated to 1 × 10^- ³After Pa, with the heating rate of 3-10 DEG C/min, 1820 DEG C are risen to, after keeping the temperature 20h, then room temperature is down to the rate of 10 DEG C/min.

Embodiment 3

The 77.49g purity that weighs with scale is the YbCl of 5N₃·6H₂O is dissolved in deionized water, forms 1molL^-1's YbCl₃Solution (the first mixed liquor).118.58g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is going for 2:1 In ionized water and dehydrated alcohol, forming concentration is 2molL^-1Ammonium bicarbonate soln, be added into ammonium bicarbonate soln 0.2mol(NH₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, obtain Second mixed liquor.After mixing evenly, by Yb (NO₃)₃Solution is added drop-wise in the second mixed liquor dropwise with the speed of 2.5mL/min, is obtained To the third mixed liquor of the sediment containing ytterbium.Period is continuously agitated third mixed liquor with blender, and monitors third with acidometer The pH value of mixed liquor adjusts third mixed liquor pH value between 8.0-8.5 with ammonium hydroxide and nitric acid.It is added dropwise into third mixed liquor 1.4mL ethyl orthosilicate stirs 2h, obtains the 4th mixed liquor.After titration, aging process 48h is put by the 4th mixed liquor is quiet. Then sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Solution detection filtrate is produced as without precipitating Only, then with dehydrated alcohol it washs three times.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, it is ground After 100 meshes (150 μm), in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, obtain To the nanometer Yb of polymolecularity₂O₃Powder.

The 77.88g purity that weighs with scale is the LuCl of 5N₃·6H₂O is dissolved in deionized water, forms 1molL^-1's LuCl₃Solution.It takes 118.58g purity to be better than 99.9% ammonium hydrogen carbonate, is dissolved in by deionized water and dehydrated alcohol by volume It is 2molL than in the mixed solution that forms for 2:1, forming concentration^-1Ammonium bicarbonate soln, be added into ammonium bicarbonate soln 0.2mol(NH₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, obtain 6th mixed liquor.After mixing evenly, by Lu (NO₃)₃Solution is added drop-wise in the 6th mixed liquor dropwise with the speed of 2.5mL/min, is obtained To the 7th mixed liquor of the sediment containing lutetium.Period is continuously agitated the 7th mixed liquor with blender, and is monitored and mixed with acidometer The pH value of solution adjusts solution ph between 8.0-8.5 with ammonium hydroxide and nitric acid.The positive silicon of 1.4mL is added dropwise into the 7th mixed liquor Acetoacetic ester stirs 2h, obtains the 8th mixed liquor.After titration, aging process 48h is put by the 8th mixed liquor is quiet.Then it filters Sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Until solution detects filtrate without precipitating generation, then use nothing Water-ethanol washs three times.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, grinding sieves with 100 mesh sieve After (150 μm), in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, high dispersive is obtained The nanometer Lu of property₂O₃Powder.

With the nanometer Yb of above-mentioned preparation₂O₃、Lu₂O₃Powder is raw material, and preparing 30g to mix ytterbium atom percentage concentration is 5% Yb:Lu₂O₃Powder, i.e., according to chemical formula Yb_0.10Lu_1.90O₃Calculate a nanometer Yb₂O₃Powder and Lu₂O₃The quality of powder, with precision Electronic analytical balance (accuracy 0.0001g) successively weighs 1.4862g Yb₂O₃、28.5138g Lu₂O₃And it is put into 500mL nylon In ball grinder.72g dehydrated alcohol, 150g diameter is added into nylon ball grinder as the high purity aluminium oxide ball of 5mm, and is added The sintering aid TEOS of 0.5wt%.With the revolving speed of 500rpm, ball milling mixing for 24 hours after, take out the first slurry, be spray-dried. Inlet temperature is 150 DEG C, and outlet temperature is 70 DEG C, and spray speed is 1mL/min.Powder after weighing 9g spray drying every time, is put into In mold made of 101 material of nylon, with the pressure of 20MPa, it is pressed into the disk that diameter is 40mm.Disk is sealed with latex rubber bag After dress, with cold isostatic press at 280MPa pressure maintaining 10min.After taking-up, by molding green body in 800 DEG C of Muffle furnace, forge 6h is burnt, to remove remaining organic matter.Then green body is put in vacuum drying oven, opens vacuum system, is evacuated to 1 × 10^-3Pa Afterwards, with the heating rate of 3-10 DEG C/min, 1820 DEG C are risen to, after keeping the temperature 20h, then room temperature is down to the rate of 10 DEG C/min.

Embodiment 4

The 93.43g purity that weighs with scale is the Yb (NO of 5N₃)₃·6H₂O is dissolved in deionized water, forms 1.5mol L^-1Yb (NO₃)₃Solution (the first mixed liquor).79.05g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is In the deionized water and dehydrated alcohol of 2:1, forming concentration is 2.0molL^-1Ammonium bicarbonate soln, into ammonium bicarbonate soln 0.2mol (NH is added₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, Obtain the second mixed liquor.After mixing evenly, by Yb (NO₃)₃Solution is added drop-wise to the second mixed liquor with the speed of 2.5mL/min dropwise In, obtain the third mixed liquor of the sediment containing ytterbium.Period is continuously agitated third mixed liquor with blender, and is supervised with acidometer The pH value for surveying third mixed liquor adjusts third mixed liquor pH value between 8.0-8.5 with ammonium hydroxide and nitric acid.Into third mixed liquor 1.6mL ethyl orthosilicate is added dropwise, stirs 2h, obtains the 4th mixed liquor.After titration, aging process is put by the 4th mixed liquor is quiet 48h.Then sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Solution detects filtrate and produces without precipitating Until life, then washed three times with dehydrated alcohol.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, grinds After mill sieves with 100 mesh sieve (150 μm), in 1000 DEG C of temperature lower calcination 6h, then (74 μm) of ground 200 mesh sieves in Muffle furnace Net obtains the nanometer Yb of polymolecularity₂O₃Powder.

The 93.81g purity that weighs with scale is the Lu (NO of 5N₃)₃·6H₂O is dissolved in deionized water, forms 2.0mol L^-1Lu (NO₃)₃Solution (the 5th mixed liquor).79.05 purity are taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is 2: In 1 deionized water and dehydrated alcohol, forming concentration is 2.0molL^-1Ammonium bicarbonate soln, into ammonium bicarbonate soln plus Enter 0.2mol (NH₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, obtain To the 6th mixed liquor.After mixing evenly, by Lu (NO₃)₃Solution is added drop-wise in the 6th mixed liquor dropwise with the speed of 2.5mL/min, Obtain the 7th mixed liquor of the sediment containing lutetium.Period is continuously agitated the 7th mixed liquor with blender, and is monitored and mixed with acidometer The pH value for closing solution adjusts the 7th mixed liquor pH value between 8.0-8.5 with ammonium hydroxide and nitric acid.It is added dropwise into the 7th mixed liquor 1.6mL ethyl orthosilicate stirs 2h, obtains the 8th mixed liquor.After titration, aging process 48h is put by the 8th mixed liquor is quiet. Then sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Solution detection filtrate is produced as without precipitating Only, then with dehydrated alcohol it washs three times.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, it is ground After 100 meshes (150 μm), in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, obtain To the nanometer Lu of polymolecularity₂O₃Powder.

With the nanometer Yb of above-mentioned preparation₂O₃、Lu₂O₃Powder is raw material, and preparing 30g to mix ytterbium atom percentage concentration is 10% Yb:Lu₂O₃Powder, i.e., according to chemical formula Yb_0.2Lu_1.8O₃Calculate a nanometer Yb₂O₃Powder and Lu₂O₃The quality of powder, with essence Close electronic analytical balance (accuracy 0.0001g) successively weighs 2.9738g Yb₂O₃、27.0262g Lu₂O₃And it is put into 500mL Buddhist nun In imperial ball grinder.72g dehydrated alcohol, 150g diameter is added into nylon ball grinder as the high purity aluminium oxide ball of 5mm, and is added The sintering aid TEOS of 0.5wt%.With the revolving speed of 500rpm, ball milling mixing for 24 hours after, take out the first slurry, be spray-dried. Inlet temperature is 300 DEG C, and outlet temperature is 120 DEG C, and spray speed is 20mL/min.Powder after weighing 9g spray drying every time, puts Enter in mold made of 101 material of nylon, with the pressure of 20MPa, is pressed into the disk that diameter is 40mm.By disk latex rubber bag After encapsulation, with cold isostatic press at 280MPa pressure maintaining 10min.After taking-up, by molding green body in 800 DEG C of Muffle furnace, 6h is calcined, to remove remaining organic matter.Then green body is put in vacuum drying oven, opens vacuum system, is evacuated to 1 × 10^- ³After Pa, with the heating rate of 3-10 DEG C/min, 1820 DEG C are risen to, after keeping the temperature 20h, then room temperature is down to the rate of 10 DEG C/min.

Embodiment 5

The 93.43g purity that weighs with scale is the Yb (NO of 5N₃)₃·6H₂O is dissolved in deionized water, forms 2.5mol L^-1Yb (NO₃)₃Solution (the first mixed liquor).79.05g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is In 2:1 deionized water and dehydrated alcohol, forming concentration is 2.5molL^-1Ammonium bicarbonate soln, into ammonium bicarbonate soln plus Enter 0.2mol (NH₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, obtain To the second mixed liquor.After mixing evenly, by Yb (NO₃)₃Solution is added drop-wise in the second mixed liquor dropwise with the speed of 2.5mL/min, Obtain the third mixed liquor with the sediment containing ytterbium.Period is continuously agitated third mixed liquor with blender, and is supervised with acidometer The pH value for surveying third mixed liquor adjusts solution ph between 8.5-9.0 with ammonium hydroxide and nitric acid.It is added dropwise into third mixed liquor 1.8mL ethyl orthosilicate stirs 2h, obtains the 4th mixed liquor.After titration, aging process 48h is put by the 4th mixed liquor is quiet. Then sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Solution detection filtrate is produced as without precipitating Only, then with dehydrated alcohol it washs three times.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, it is ground After 100 meshes (150 μm), in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, obtain To the nanometer Yb of polymolecularity₂O₃Powder.

The 93.81g purity that weighs with scale is the Lu (NO of 5N₃)₃·6H₂O is dissolved in deionized water, forms 2.5mol L^-1Lu (NO₃)₃Solution (the 5th mixed liquor).79.05g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is In the deionized water and dehydrated alcohol of 2:1, forming concentration is 2.5molL^-1Ammonium bicarbonate soln, into ammonium bicarbonate soln 0.2mol (NH is added₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, Obtain the 6th mixed liquor.After mixing evenly, by Lu (NO₃)₃Solution is added drop-wise to the 6th mixed liquor with the speed of 2.5mL/min dropwise In, obtain the 7th mixed liquor of the sediment containing lutetium.Period is continuously agitated the 7th mixed liquor with blender, and is supervised with acidometer The pH value for surveying mixed solution adjusts solution ph between 8.5-9.0 with ammonium hydroxide and nitric acid.It is added dropwise into the 7th mixed liquor 1.8mL ethyl orthosilicate stirs 2h, obtains the 8th mixed liquor.After titration, aging process 48h is put by the 8th mixed liquor is quiet. Then sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Solution detection filtrate is produced as without precipitating Only, then with dehydrated alcohol it washs three times.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, it is ground After 100 meshes (150 μm), in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, obtain To the nanometer Lu of polymolecularity₂O₃Powder.

With the nanometer Yb of above-mentioned preparation₂O₃、Lu₂O₃Powder is raw material, and preparing 30g to mix ytterbium atom percentage concentration is 15% Yb:Lu₂O₃Powder, i.e., according to chemical formula Yb_0.30Lu_1.70O₃Calculate a nanometer Yb₂O₃Powder and Lu₂O₃The quality of powder, with essence Close electronic analytical balance (accuracy 0.0001g) successively weighs 4.4629g Yb₂O₃、25.5371g Lu₂O₃And it is put into 500mL Buddhist nun In imperial ball grinder.72g dehydrated alcohol, 150g diameter is added into nylon ball grinder as the high purity aluminium oxide ball of 5mm, and is added The sintering aid TEOS of 0.5wt%.With the revolving speed of 500rpm, ball milling mixing for 24 hours after, take out the first slurry, be spray-dried. Inlet temperature is 200 DEG C, and outlet temperature is 100 DEG C, and spray speed is 10mL/min.Powder after weighing 9g spray drying every time, puts Enter in mold made of 101 material of nylon, with the pressure of 20MPa, is pressed into the disk that diameter is 40mm.By disk latex rubber bag After encapsulation, with cold isostatic press at 280MPa pressure maintaining 10min.After taking-up, by molding green body in 800 DEG C of Muffle furnace, 6h is calcined, to remove remaining organic matter.Then green body is put in vacuum drying oven, opens vacuum system, is evacuated to 1 × 10^- ³After Pa, with the heating rate of 3-10 DEG C/min, 1820 DEG C are risen to, after keeping the temperature 20h, then room temperature is down to the rate of 10 DEG C/min.

Embodiment 6

The 93.43g purity that weighs with scale is the Yb (NO of 5N₃)₃·6H₂O is dissolved in deionized water, forms 2.5mol L^-1Yb (NO₃)₃Solution (the first mixed liquor).79.05g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is In the deionized water and dehydrated alcohol of 3:1, forming concentration is 3.0molL^-1Ammonium bicarbonate soln, into ammonium bicarbonate soln 0.2mol (NH is added₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, Obtain the second mixed liquor.After mixing evenly, by Yb (NO₃)₃Solution is added drop-wise to the second mixed liquor with the speed of 2.5mL/min dropwise In, obtain the third mixed liquor of the sediment containing ytterbium.Period is continuously agitated third mixed liquor with blender, and is supervised with acidometer The pH value for surveying third mixed liquor adjusts solution ph between 9.0-9.5 with ammonium hydroxide and nitric acid.It is added dropwise into third mixed liquor 1.9mL ethyl orthosilicate stirs 2h, obtains the 4th mixed liquor.After titration, aging process 48h is put by the 4th mixed liquor is quiet. Then sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Solution detection filtrate is produced as without precipitating Only, then with dehydrated alcohol it washs three times.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, it is ground After 100 meshes (150 μm), in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, obtain To the nanometer Yb of polymolecularity₂O₃Powder.

The 93.81g purity that weighs with scale is the Lu (NO of 5N₃)₃·6H₂O is dissolved in deionized water, forms 2.5mol L^-1Lu (NO₃)₃Solution (the 5th mixed liquor).79.05g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is In the deionized water and dehydrated alcohol of 3:1, forming concentration is 3.0molL^-1Ammonium bicarbonate soln, into ammonium bicarbonate soln 0.2mol (NH is added₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, Obtain the 6th mixed liquor.After mixing evenly, by Lu (NO₃)₃Solution is added drop-wise to the 6th mixed liquor with the speed of 2.5mL/min dropwise In, obtain the 7th mixed liquor of the sediment containing lutetium.Period is continuously agitated the 7th mixed liquor with blender, and is supervised with acidometer The pH value for surveying mixed solution adjusts solution ph between 9.0-9.5 with ammonium hydroxide and nitric acid.It is added dropwise into the 7th mixed liquor 1.9mL ethyl orthosilicate stirs 2h, obtains the 8th mixed liquor.After titration, aging process 48h is put by the 8th mixed liquor is quiet. Then sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Solution detection filtrate is produced as without precipitating Only, then with dehydrated alcohol it washs three times.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, it is ground After 100 meshes (150 μm), in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, obtain To the nanometer Lu of polymolecularity₂O₃Powder.

With the nanometer Yb of above-mentioned preparation₂O₃、Lu₂O₃Powder is raw material, and preparing 30g to mix ytterbium atom percentage concentration is 20% Yb:Lu₂O₃Powder, i.e., according to chemical formula Yb_0.40Lu_1.60O₃Calculate a nanometer Yb₂O₃Powder and Lu₂O₃The quality of powder, with essence Close electronic analytical balance (accuracy 0.0001g) successively weighs 5.9534g Yb₂O₃、24.0466g Lu₂O₃And it is put into 500mL Buddhist nun In imperial ball grinder.72g dehydrated alcohol, 150g diameter is added into nylon ball grinder as the high purity aluminium oxide ball of 5mm, and is added The sintering aid TEOS of 0.5wt%.With the revolving speed of 500rpm, ball milling mixing for 24 hours after, take out the first slurry, be spray-dried. Inlet temperature is 200 DEG C, and outlet temperature is 100 DEG C, and spray speed is 10mL/min.Powder after weighing 9g spray drying every time, puts Enter in mold made of 101 material of nylon, with the pressure of 20MPa, is pressed into the disk that diameter is 40mm.By disk latex rubber bag After encapsulation, with cold isostatic press at 280MPa pressure maintaining 10min.After taking-up, by molding green body in 800 DEG C of Muffle furnace, 6h is calcined, to remove remaining organic matter.Then green body is put in vacuum drying oven, opens vacuum system, is evacuated to 1 × 10^- ³After Pa, with the heating rate of 3-10 DEG C/min, 1820 DEG C are risen to, after keeping the temperature 20h, then room temperature is down to the rate of 10 DEG C/min.

The BN powder that a certain amount of purity is 99.7% is put into graphite hot pressing die, it, then will be by true with a thickness of 1cm Yb:Lu after empty sintering processes₂O₃Ceramics sample is put into graphite hot pressing die.A pottery is often put into graphite hot pressing die After porcelain sample, it is put into the BN powder of 1cm, until all ceramics samples discharge, covers mold upper cover.Then by graphite hot-die Tool is put into vacuum hotpressing stove, and with pressure head by two end face tightenings above and below mold, gradually pressure arrives 20MPa.After closed furnace, open Vacuum system is opened, is evacuated to 1 × 10^-3Pa is then turned on power supply, is warming up to 1720 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 2h Afterwards, room temperature is down to the rate of 10 DEG C/min.

Ceramics sample is taken out, after 1400 DEG C of atmosphere anneal 10h, is polished, obtains provided in this embodiment mixing ytterbium oxygen Change lutetium laser ceramics.

Embodiment 7

The 77.49g purity that weighs with scale is the YbCl of 5N₃·6H₂O is dissolved in deionized water, forms 2.50molL^-1YbCl₃Solution (the first mixed liquor).118.58g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is 3:1 Deionized water and dehydrated alcohol in, formed concentration be 3molL^-1Ammonium bicarbonate soln, be added into ammonium bicarbonate soln 0.2mol(NH₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, obtain Second mixed liquor.After mixing evenly, by Yb (NO₃)₃Solution is added drop-wise in the second mixed liquor dropwise with the speed of 2.5mL/min, is obtained To the third mixed liquor of the sediment containing ytterbium.Period is continuously agitated third mixed liquor with blender, and monitors third with acidometer The pH value of mixed liquor adjusts solution ph between 9.5-10.0 with ammonium hydroxide and nitric acid.The positive silicon of 2mL is added dropwise into third mixed liquor Acetoacetic ester stirs 2h, obtains the 4th mixed liquor.After titration, aging process 48h is put by the 4th mixed liquor is quiet.Then it filters Sediment is filtered out, is washed with deionized to 0.1molL^-1BaCl₂Until solution detects filtrate without precipitating generation, then use nothing Water-ethanol washs three times.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, grinding sieves with 100 mesh sieve After (150 μm), in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, high dispersive is obtained The nanometer Yb of property₂O₃Powder.

The 77.88g purity that weighs with scale is the LuCl of 5N₃·6H₂O is dissolved in deionized water, forms 2.50molL^-1LuCl₃Solution (the 5th mixed liquor).118.58g purity is taken to be better than 99.9% ammonium hydrogen carbonate, being dissolved in volume ratio is 3:1 Deionized water and dehydrated alcohol in, formed concentration be 3molL^-1Ammonium bicarbonate soln, be added into ammonium bicarbonate soln 0.2mol(NH₄)₂SO₄, 0.1wt% PEG400,0.1wt% castor oil and 0.2wt% ammonium polymethacrylate, obtain 6th mixed liquor.After mixing evenly, by Lu (NO₃)₃Solution is added drop-wise in the 6th mixed liquor dropwise with the speed of 2.5mL/min, is obtained To the 7th mixed liquor of the sediment containing lutetium.Period is continuously agitated the 7th mixed liquor with blender, and is monitored and mixed with acidometer The pH value of solution adjusts solution ph between 9.5-10.0 with ammonium hydroxide and nitric acid.The positive silicic acid of 2mL is added dropwise into the 7th mixed liquor Ethyl ester stirs 2h, obtains the 8th mixed liquor.After titration, aging process 48h is put by the 8th mixed liquor is quiet.Then filtering filter Sediment out is washed with deionized to 0.1molL^-1BaCl₂Solution detects until filtrate generates without precipitating, then with anhydrous Ethanol washing three times.Then be put in vacuum drying oven, 80 DEG C at a temperature of, it is dry for 24 hours.It takes out, grinding sieves with 100 mesh sieve (150 μm) after, in 1000 DEG C of temperature lower calcination 6h, then ground 200 mesh (74 μm) sieve in Muffle furnace, obtain polymolecularity Nanometer Lu₂O₃Powder.

Comparative example 1

This comparative example provides a kind of preparation method for mixing ytterbium luteium oxide laser ceramics, this method comprises:

With commercially available 5N nanometers of Yb₂O₃、Lu₂O₃(d₅₀=50nm) it is raw material, preparation 30g mixes ytterbium atom percentage concentration and is 5.0% Yb:Lu₂O₃Powder, i.e., according to chemical formula Yb_0.10Lu_1.90O₃Calculate a nanometer Yb₂O₃Powder and Lu₂O₃The matter of powder Amount weighs 1.4862g Yb with precise electronic assay balance (accuracy 0.0001g)₂O₃、28.5138g Lu₂O₃, and be put into In 500mL nylon ball grinder.90mL dehydrated alcohol is added into nylon ball grinder, the high purity aluminium oxide ball that 150g diameter is 5mm, And the sintering aid TEOS of 0.5wt% is added.With the revolving speed of 500rpm, ball milling mixing for 24 hours after, take out the first slurry, sprayed Mist is dry.Inlet temperature is 200 DEG C, and outlet temperature is 100 DEG C, and spray speed is 10mL/min.After weighing 9g spray drying every time Powder is put into mold made of 101 material of nylon, with the pressure of 20MPa, is pressed into the disk that diameter is 40mm.By disk After being encapsulated with latex rubber bag, with cold isostatic press at 280MPa pressure maintaining 10min.Horse after taking-up, by molding green body at 800 DEG C Not in furnace, 6h is calcined, to remove remaining organic matter.Then green body is put in vacuum drying oven, opens vacuum system, is evacuated to 1×10^-3After Pa, with the heating rate of 3-10 DEG C/min, 1820 DEG C are risen to, after keeping the temperature 20h, then is down to the rate of 10 DEG C/min Room temperature.

The ceramics sample after hot-pressing processing is taken out, after 1400 DEG C of atmosphere anneal 10h, is polished, obtains this comparison What example provided mixes ytterbium luteium oxide laser ceramics.

Comparative example 2

This comparative example provides a kind of preparation method for mixing ytterbium luteium oxide laser ceramics, what this method and embodiment 1 provided Method is essentially identical, difference are as follows: post-processes without hot pressing, directly through 1400 DEG C of atmosphere annealing 10h after vacuum-sintering Afterwards, it is polished, obtain the offer of this comparative example mixes ytterbium luteium oxide laser ceramics.

Application Example

The Yb for the method preparation that this application embodiment provides embodiment 1 to embodiment 7, comparative example 1, comparative example 2 respectively: Lu₂O₃The transmitance of ceramics is evaluated.Detailed process are as follows: through Lambda950 type spectrophotometer at wavelength is 1080nm The Yb:Lu for the method preparation that detection embodiment 1 to embodiment 7, comparative example 1, comparative example 2 provides respectively respectively₂O₃The transmission of ceramics Rate, see Table 1 for details for design parameter.

Table 1

The Yb:Lu that embodiment provides₂O₃Laser ceramics	Wavelength/nm	Transmitance
			Embodiment 1	1080	67.6%
Embodiment 2	1080	65.9%
			Embodiment 3	1080	68.2%
Embodiment 4	1080	66.8%
			Embodiment 5	1080	68.2%
Embodiment 6	1080	66.6%
			Embodiment 7	1080	64.2%
Comparative example 1	1080	34.0%
			Comparative example 2	1080	55.1%

As shown in Table 1, comparative example 1 uses commercially available Yb₂O₃Powder and Lu₂O₃The Yb:Lu of powder preparation₂O₃Laser ceramics Transmitance is 34.0%, far below the Yb:Lu for the method preparation that embodiment 1- embodiment 7 provides₂O₃Laser ceramics.Comparative example 2 mentions The Yb:Lu of confession₂O₃For laser ceramics due to not post-processing by hot pressing, transmitance only has 67.6%, lower than after hot pressing The Yb:Lu for the method preparation that the embodiment 1- embodiment 7 of reason provides₂O₃Laser ceramics.As it can be seen that side provided in an embodiment of the present invention Method prepares Yb by substep₂O₃Powder and Lu₂O₃Powder makes it have better sintering activity, and hot pressing is combined to post-process, The Yb:Lu being prepared₂O₃The transmitance of laser ceramics is high.

All the above alternatives can form the alternative embodiment of the disclosure, herein no longer using any combination It repeats one by one.

The foregoing is merely illustrative embodiments of the invention, the protection scope being not intended to limit the invention is all at this Within the spirit and principle of invention, any modification, equivalent replacement, improvement and so on should be included in protection model of the invention Within enclosing.

Claims

1. a kind of preparation method for mixing ytterbium luteium oxide laser ceramics, which is characterized in that the described method includes:

Prepare ytterbium oxide powder；

Prepare luteium oxide powder；

By after weighing the ytterbium oxide powder and the luteium oxide powder mixed with sintering aid, organic solvent and carry out ball milling Processing, obtains the first slurry；

Dumping processing, vacuum-sintering processing, hot pressing post-processing, annealing, polishing treatment are successively carried out to the ceramic body, Ytterbium luteium oxide laser ceramics is mixed described in obtaining.

2. the method according to claim 1, wherein described prepare ytterbium oxide powder, comprising:

Under agitation, first mixed liquor is added dropwise in second mixed liquor, obtains the sediment with ytterbium Third mixed liquor；

It is dry that first aging process, the first filtration treatment, the first carrying out washing treatment, the first vacuum are successively carried out to the 4th mixed liquor Dry processing, the first calcination processing, the first Screening Treatment, obtain the ytterbium oxide powder.

3. according to the method described in claim 2, it is characterized in that, described prepare luteium oxide powder, comprising:

Under agitation, the 5th mixed liquor is added dropwise in the 6th mixed liquor, obtains the sediment with lutetium 7th mixed liquor；

It is dry that second aging process, the second filtration treatment, the second carrying out washing treatment, the second vacuum are successively carried out to the 8th mixed liquor Dry processing, the second calcination processing, the second Screening Treatment, obtain the luteium oxide powder.

4. according to the method described in claim 3, it is characterized in that, the dispersing agent be ammonium sulfate, polyethylene glycol, castor oil, At least one of ammonium polymethacrylate；

Molar concentration of the ammonium hydrogen carbonate in second mixed liquor and the 6th mixed liquor is 0.2-3mol/L；

The time of first aging process and second aging process is 24-48h；

The temperature of first vacuum drying treatment and second vacuum drying treatment is 75-200 DEG C, and the time is 1-5 It；

5. the method according to claim 1, wherein the sintering aid is silica, ethyl orthosilicate, oxygen Change at least one of magnesium, lithium fluoride；

The organic solvent is at least one of ethyl alcohol, ether, acetone；

The gross mass of the ytterbium oxide powder and the luteium oxide powder and the mass ratio of the organic solvent are 1:1-1:4.

6. the method according to claim 1, wherein the drying process includes: to carry out to first slurry Spray drying, in the spray drying, the inlet temperature of sprayer is 150-300 DEG C, and outlet temperature is 70-120 DEG C, spray speed For 1-20mL/min.

7. the method according to claim 1, wherein the forming processes include: will be after the drying process The first slurry be placed in the mold of nylon material, forming operation is carried out with the pressure of 5-30MPa；

8. method according to claim 1-7, which is characterized in that the temperature of the dumping processing is 800-1300 DEG C, time 1-24h；

The temperature of the annealing is 1200-1600 DEG C, time 1-48h, and the heating rate of the annealing is 1-5 ℃/min。

9. method according to claim 1-7, which is characterized in that the vacuum-sintering, which is handled, includes:

Control the vacuum drying oven heat preservation 1-50h；

10. method according to claim 1-7, which is characterized in that the hot pressing, which post-processes, includes:

Will by the vacuum-sintering, treated that one or more ceramic bodies are placed in heating mould, and make one or more It is wrapped up completely by boron nitride powder on the surface of ceramic body；

It controls the vacuum hotpressing stove and is cooled to 18-28 DEG C.