CN107540367B - Method for preparing garnet-based transparent ceramic by non-aqueous gel injection molding - Google Patents
Method for preparing garnet-based transparent ceramic by non-aqueous gel injection molding Download PDFInfo
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Abstract
The invention relates toA method for preparing a garnet-based transparent ceramic by non-aqueous gel injection molding comprises the following steps: weighing Y in stoichiometric ratio2O3、Lu2O3、Gd2O3、Al2O3、Ga2O3And RE oxide, or (Y) synthesized by liquid phase chemical method1‑a‑b‑xLuaGdbREx)3(Al1‑c‑dSccGad)5O12The powder is raw material powder; adding a non-aqueous solvent, a curing agent and epoxy resin into the obtained raw material powder, and performing ball-milling mixing or ultrasonic dispersion mixing to obtain ceramic slurry, wherein the non-aqueous solvent is at least one of ethanol, methanol, propanol, ethylene glycol, acetone, butanone, cyclohexane and dodecane; and injecting the obtained ceramic slurry into a mold after vacuum degassing, and sintering for 5 minutes to 60 hours at 800-1900 ℃ after curing, drying, demolding and glue discharging treatment to obtain the garnet-based transparent ceramic.
Description
Technical Field
The invention provides a method for preparing garnet-based transparent ceramic by non-aqueous gel injection molding, which can be applied to the fields of laser, scintillation, LED, optical windows and the like and belongs to the technical field of special transparent ceramic molding and manufacturing processes.
Background
The transparent ceramic is a new emerging material, is widely used for optical parts of high-temperature instruments, high-pressure sodium lamp tubes, head covers and the like at present, and has increasing importance in the fields of laser, scintillation and the like as a light functional material. Wherein the garnet base (Y) belongs to a highly symmetric cubic system1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Due to the excellent physical and chemical comprehensive performance of the transparent ceramic, the transparent ceramic has a very important application position and application prospect in the industrial fields (lighting industry, up-conversion luminescence, LED, laser medical treatment, nuclear medical imaging, safety detection, high-energy physics and the like) and military neighborhoods (high-energy laser weapons, laser nuclear fusion ignition devices, infrared windows, fairings and the like). In 2009, YAG transparent ceramics have successfully achieved hundreds of kW laser output, which will move the output power towards the target of 600kW-1 MW. The Ce (Lu, Tb) from GE company is reported3Al5O12Scintillating ceramics (Gemstone) has been successfully used in medical CT detection. Multicomponent RE (Y)1-a-bLuaGdb)3(Al1-c-dSccGad)5O12The transparent ceramic can regulate and control laser wavelength, can regulate and control scintillation property and the like, and has important prospect in widening the application of materials in the aspect of optical functional characteristics.
From the prior transparent ceramic preparation process, the obtained green body with uniform components and high density is very important for sintering and preparing transparent ceramic with high quality, large size and controllable microstructure, and the forming process is at a key position of the material preparation process, which has great influence on obtaining high-quality green bodies.
The gel casting method is a technique for forming near net-size ceramics. The forming principle is that a macromolecular network structure is formed through the chemical reaction of a gel system in the slurry to solidify and form ceramic powder into a ceramic blank in situ, and in the forming process, the solvent does not move, so that the movement and rearrangement of powder particles can not be caused, and the component uniformity of the formed blank is further ensured, so that the forming method is particularly suitable for multi-component (Y)1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12And (5) preparing a ceramic blank.
Gel casting is divided into water-based gel casting and non-water-based gel castingAnd (5) molding. In the process of forming a ceramic blank by water-based gel injection molding, special drying conditions are needed in order to reduce the defects of the blank, and the problem of powder hydration and the like also need to be considered. Gel casting preparation of (Y) in the prior art1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12The maximum solids content of the water-based ceramic slurry in the transparent ceramic process is also only 75 wt.% ([1 ]]Qin X.,Zhou G.,Yang Y.,Zhang J.,Shu X.,Shimai S.,and Wang S.Gelcasting of transparent YAG ceramics by a new gellingsystem[J].Ceramics International.2014,40(8):12745-12750.[2]Sun Y.,Qin X.,ZhouG.,Zhang H.,Peng X.,and Wang S.Gelcasting and reactive sintering of sheet-like YAG transparent ceramics[J]Journal of Alloys and compounds.2015,65(2): 250-. No non-aqueous solution gel injection molding preparation (Y) has been adopted1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Report on transparent ceramics.
Disclosure of Invention
In view of the above problems, it is an object of the present invention to provide a non-aqueous gel injection molding preparation (Y) with simple operation1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12A method of making a transparent ceramic greenbody.
The invention provides a method for preparing garnet-based transparent ceramic by non-aqueous gel injection molding, wherein the garnet-based transparent ceramic comprises the following components of (Y)1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, a + b + x is less than or equal to 1, and RE is at least one of rare earth ions Nd, Yb, Ce, Er, Pr, Eu, Sm, Ho, Tm and Dy, wherein x is more than or equal to 0 and less than or equal to 0.08 when RE is at least one of Nd, Ce and Pr, and RE is Yb, Er, Eu, Sm, Ho, Tm and DyWhen at least one is selected, x is more than or equal to 0 and less than or equal to 1, the method comprises the following steps:
weighing Y in stoichiometric ratio2O3、Lu2O3、Gd2O3、Al2O3、Ga2O3And RE oxide, or (Y) synthesized by liquid phase chemical method1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12The powder is raw material powder;
adding a non-aqueous solvent, a curing agent and epoxy resin into the obtained raw material powder, and performing ball-milling mixing or ultrasonic dispersion mixing to obtain ceramic slurry, wherein the non-aqueous solvent is at least one of ethanol, methanol, propanol, ethylene glycol, acetone, butanone, cyclohexane and dodecane;
and injecting the obtained ceramic slurry into a mold after vacuum degassing, and sintering for 5 minutes to 60 hours at 800-1900 ℃ after curing, drying, demolding and glue discharging treatment to obtain the garnet-based transparent ceramic.
The implementation steps of the invention are as follows: mixing ceramic powder with a non-aqueous solvent, adding a proper amount of curing agent, dispersing agent and epoxy resin, mixing to prepare slurry, carrying out vacuum degassing on the slurry, directly injecting the slurry into moulds with different structural shapes, and carrying out in-situ solidification on the slurry to form a ceramic blank. The garnet-based transparent ceramic comprises the following components of (Y)1-a-b-xLuaGdbREx)3(Al1-c- dSccGad)5O12And may also be represented by RE (Y)1-a-bLuaGdb)3(Al1-c-dSccGad)5O12. Wherein, RE is used as doping ion, and the doping concentration of RE is different for different ions in consideration of lattice adaptation, ion radius and other factors. Wherein when RE comprises at least one of Nd, Ce and Pr, the doping concentration of the ions can be 0-8 at.%. When RE comprises at least one of Yb, Er, Eu, Sm, Ho, Tm and Dy, the doping concentration of the ions can be 0-100 at%;
the technical scheme has the advantages that: 1) can avoid the hydration of the powder easy to hydrate and the hydrosolvent; 2) according to the judgment of the gel reaction principle of the epoxy resin and the polyamine curing agent, the non-aqueous solvent with smaller polarity is more beneficial to the gel reaction relative to the aqueous solvent with larger polarity, so that the time for forming a network high molecular structure by the reaction of the epoxy resin and the curing agent is shorter, the component segregation phenomenon is avoided, the formed network high molecular structure is used for curing the ceramic particles in situ, the particles cannot migrate along with the directional movement of the non-aqueous solvent in the drying process, and the defects of a ceramic blank can be reduced; 3) the shrinkage stress of the ceramic blank body during drying can be reduced, and shrinkage cracks are avoided: because the organic solvent has lower surface tension than the aqueous solvent, the wetting property to the powder is better; 4) the solid content of the ceramic body can be effectively improved, because the Hamaker constant of the ceramic powder in an organic solvent is smaller than that in an aqueous solution, the van der Waals attraction of the powder is smaller, and meanwhile, according to the similar compatibility principle, the non-aqueous solvent is easier to dissolve organic additives, the organic matter content is effectively reduced, and the solid content of the slurry is increased;
by combining the effects, the technical scheme can finally improve the solid content by 85 wt% (equivalent to 54 vol%), while the traditional water-based ceramic reported in the literature has the highest solid content of only 75 wt%. Meanwhile, the formed green body has uniform components and structure, narrow pore distribution and high relative density, and is beneficial to removing pores in the green body in the sintering process, thereby improving the density of the sintered ceramic and obtaining the transparent ceramic with high optical quality.
Preferably, a sintering aid is further added into the raw material powder, and the sintering aid is Li2O、Na2O、K2O、MgO、CaO、B2O3、La2O3、GeO2、SiO2、LiF、NaF、MgF2、CaF2、AlF3、YF3And Tetraethoxysilane (TEOS) and H3BO3At least one of (1). Further, it is preferable that the sintering aid is not more than 1.5% by mass of the raw material powder.
Preferably, a proper amount of dispersant is also added into the raw material powder, and the dispersant is at least one of polyethyleneimine, herring oil, polyacrylamide, polyacrylate and the like. Preferably, the dispersant accounts for 3 to 8 wt% of the raw material powder.
Preferably, the mass of the nonaqueous solvent is 8 wt% to 25 wt% of the raw material powder.
Preferably, the epoxy resin is at least one of ethylene glycol diglycidyl ether (EGDGE), sorbitol glycidyl ether (SPGE), and glycerol glycidyl ether (GPGE).
Preferably, the mass of the epoxy resin is 8-40 wt% of the non-aqueous solvent.
Preferably, the curing agent is at least one of 3-3' -Diaminodipropylamine (DPTA), diethylenetriamine and ethylenediamine.
Preferably, the curing agent is used in an amount of 0.1 to 0.75 mol/epoxy equivalent. Wherein the epoxy equivalent is the mass of the epoxy resin containing one epoxy group.
Preferably, the curing is a reaction at room temperature to 90 ℃ for 10 minutes to 4 hours.
Preferably, the sintering method is one of vacuum sintering, atmosphere sintering, pressureless sintering, spark plasma sintering and hot isostatic pressing sintering; or adopting one of vacuum sintering, atmosphere sintering, pressureless sintering and spark plasma sintering to perform pre-sintering, and then adopting hot isostatic pressing sintering to perform secondary sintering.
Preferably, the prepared garnet-based transparent ceramic is subjected to heat preservation for 1-100 hours at 800-1600 ℃ in an annealing atmosphere.
Further, it is preferable that the annealing atmosphere is at least one of air, oxygen, hydrogen, argon, nitrogen, and vacuum.
The invention has the beneficial effects that:
1. compared with the reported water-based slurry (the solid content is 75 wt%), the non-aqueous solvent and the slurry preparation process adopted by the invention can prepare the ceramic slurry with low viscosity and good stability, the solid content of which is as high as 85 wt%, and the ceramic slurry is very suitable for gel injection molding, simple to operate and strong in practicability;
2. the invention canPreparing multi-component (Y) with uniform components and high density1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12The ceramic biscuit can also control the size, shape, strength and the like of the biscuit, and has positive effect on the subsequent processing process of the transparent ceramic;
3. the garnet-based transparent ceramic prepared by the invention can be applied to the fields of laser, scintillation, LED, optical windows and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a cross-section of a non-water-based Nd: YAG green body prepared in example 1;
FIG. 2 is a macrostructure of a non-aqueous Nd: YAG green body prepared in example 1;
FIG. 3 is a back-scattered scanning electron micrograph of a cross section of a non-water-based Nd: YAG green body prepared in example 1;
FIG. 4 is a pore distribution of a non-aqueous Nd: YAG green body prepared in example 1;
FIG. 5 is a transmittance curve of the non-water-based Nd: YAG ceramic prepared in example 1;
FIG. 6 is a pore distribution of a non-aqueous Nd: YAG green body prepared in example 2;
FIG. 7 is a DTA test analysis curve.
Detailed Description
The present invention is further illustrated below with reference to the following examples, which are intended to illustrate the invention only and are not to be construed as limiting the invention.
The invention adopts a non-water-based gel injection molding method to prepare the garnet-based transparent ceramic. Wherein the garnet-based transparent ceramic has a composition of (Y)1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, a + b + x is less than or equal to 1, and RE is at least one of rare earth ions such as Nd, Yb, Ce, Er, Pr, Eu, Sm, Ho, Tm and Dy. Wherein the doping concentration of Nd, Ce and Pr is 0-8 at.%, and the doping concentration of Yb, Er, Eu, Sm, Ho, Tm and Dy is highThe degree is 0-100 at.%, preferably 0-60 at.%.
The following is an exemplary description of a method for preparing a garnet-based transparent ceramic by non-aqueous gel injection molding according to the present invention.
In the invention, Y is2O3、Lu2O3、Gd2O3、Al2O3、Ga2O3And an oxide of RE as a raw material according to (Y)1-a-b- xLuaGdbREx)3(Al1-c-dSccGad)5O12The raw material powder is obtained after the stoichiometric ratio of (A) to (B) is weighed. Wherein RE is any one or combination of rare earth active ions Nd, Yb, Ce, Er, Pr, Eu, Sm, Ho, Tm and Dy. The powder used may be a commercial oxide powder, for example Y2O3、Lu2O3、Gd2O3、Al2O3、Ga2O3、Sc2O3、Nd2O3、Yb2O3、Ce2O3、Er2O3、Pr2O3、Eu2O3、Sm2O3、Ho2O3、Tm2O3And Dy2O3And the like.
The invention can also prepare (Y) by liquid phase chemical synthesis (such as coprecipitation method, sol-gel combustion method, homogeneous coprecipitation method and the like)1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12The powder is used as raw material powder to be directly weighed and mixed.
Adding a non-aqueous solvent, a sintering aid, a dispersing agent (such as polyethyleneimine, herring oil, polyacrylamide, polyacrylate and the like), a curing agent and epoxy resin into the raw material powder, and uniformly mixing to obtain ceramic slurry with the solid phase content of 30-60 vol%. The ceramic slurry prepared by the non-aqueous solvent can keep good performance at 30-54 vol%, and the solid phase content of the ceramic slurry reaches 54-60 vol%, and the ceramic slurry is stickyLow in fluidity, high in fluidity and good in stability. The non-aqueous solvent is used as a ball milling medium, and can be at least one of ethanol, methanol, propanol, ethylene glycol, acetone, butanone, cyclohexane, dodecane and the like, and the mass of the non-aqueous solvent can be 8-25% of that of the raw material powder. The mass of the dispersing agent can be 3-8% of the raw material powder. The sintering aid can be, but is not limited to, Li2O、Na2O、K2O、MgO、CaO、B2O3、La2O3、GeO2、SiO2、LiF、NaF、MgF2、CaF2、AlF3、YF3TEOS (tetraethylorthosilicate), H3BO3One or a combination of several or no sintering aid is added. The sintering aid can be 0-1.5% of the raw material powder by mass. The epoxy resin can be at least one of ethylene glycol diglycidyl ether (EGDGE), sorbitol glycidyl ether (SPGE), glycerol glycidyl ether (GPGE), and the like, and the dosage is in the range of 8-40 wt% of the solvent. The curing agent may be an amine group such as: at least one of 3-3' -Diaminodipropylamine (DPTA), diethylenetriamine, ethylenediamine, etc., in an amount within a range of 0.1 to 0.75mol/eq (mol/epoxy equivalent). Epoxy equivalent: corresponding to the mass of an epoxy resin containing one epoxy group. The mixing mode in the preparation process of the slurry can adopt a common or high-energy ball milling method to mix powder, and the powder is crushed through the collision effect among ball mills, so that the particle size and the particle morphology of the powder are improved, for example, the ball milling rotating speed can be 60-150rmp/min, and the ball milling time can be 10min-36 h. Or ultrasonic dispersion mixing is carried out for 10min to 36h, and uniformly dispersed ceramic slurry is obtained.
And injecting the ceramic slurry into a mold after vacuum degassing, sealing the mold, reacting for 10 minutes to 4 hours at the room temperature to 90 ℃, and inducing the slurry to be cured to form a blank. Specifically, the temperature is controlled to be between room temperature and 90 ℃ by using modes such as an oven, microwaves, a water bath and the like, and a gel system is induced to react for 10min-4h to promote the slurry gel in-situ curing powder to be formed.
And drying the solidified green body to naturally demould the green body to obtain the ceramic green body. In addition, the drying of the blank in the mould after the slurry is injected can be carried out synchronously with the forming of the blank, the blank is placed for 2 hours to 10 days, and the blank is automatically demoulded after being dried and can also be carried out under certain drying atmosphere and conditions.
And (3) guiding the rubber discharging process of the dried ceramic blank according to a DTA test analysis curve (see figure 7), and discharging rubber to obtain a ceramic biscuit. The glue removing treatment is specifically high-temperature degreasing, and the ceramic biscuit is obtained by heat preservation for 10 hours at the temperature of 600-700 ℃.
Sintering the ceramic biscuit after the rubber removal at 800-1900 ℃ for 5 minutes to 60 hours to obtain the garnet-based transparent ceramic. The sintering method comprises the following steps: vacuum sintering, atmosphere sintering, pressureless sintering, Spark Plasma Sintering (SPS), hot isostatic pressing sintering (HIP), and the like. And firstly adopting vacuum sintering or atmosphere sintering or pressureless sintering or SPS method for presintering, and then adopting HIP for secondary sintering.
To be prepared (Y)1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12And annealing the transparent ceramic to obtain the transparent ceramic with optimized performance. Specifically, the prepared garnet-based transparent ceramic is subjected to heat preservation for 1 to 100 hours at the temperature of 800 to 1600 ℃ in an annealing atmosphere. The annealing atmosphere may be at least one of air, oxygen, hydrogen, argon, nitrogen, and vacuum.
The ceramic biscuit prepared by the invention has the advantages of uniform components, uniform microstructure, narrow pore distribution, higher relative density, high strength of the biscuit and easy processing. After the biscuit is formed, the transmittance of the transparent ceramic prepared by combining the relevant sintering system is higher.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
33.5323g Y will be mixed2O3Powder 25.4903g Al2O3Powder 0.5047g Nd2O3Powder, 0.0476g MgO powder and 0.476g TEOS are added into a high-purity alumina ball milling tank (alumina ball mill 160-. After ball milling, the slurry was degassed for 5min under vacuum (-0.1 MPa). And after degassing, pouring the slurry into a plastic mold, sealing the mold, and then putting the mold into a 40 ℃ oven for reaction and drying. Taking out the dried and demoulded blank after 3 days, and carrying out a scanning electron microscope on the blank as shown in figure 1, wherein the condition that the organic matter reacts to fix and form the particles is shown, and the surface is relatively uniform and has no large holes. And then carrying out glue discharging treatment on the blank, wherein the glue discharging condition is that the temperature is raised to 350 ℃ at the speed of 1 ℃/min and is kept for 2h, then the temperature is raised to 600 ℃ at the speed of 1 ℃/min and is kept for 10h, and the Nd: YAG biscuit is obtained after furnace cooling, and the macroscopic structure of the Nd: YAG biscuit is as shown in figure 2, the surface is smooth, and no macroscopic defect exists. The microstructure scanning results (fig. 3) of the biscuit cross section show that the composition is uniformly distributed and the structure is uniform. The pore distribution of the biscuit was measured by mercury porosimetry, as shown in fig. 4, the unimodal pore distribution of the biscuit was about 180nm, and the relative density was about 55%. Directly carrying out vacuum sintering on a biscuit obtained after glue discharging, wherein the sintering conditions are as follows: 1775 deg.C, 20 h. The sintered sample is annealed for 10h at 1450 ℃ in air atmosphere, then the double-side polishing is carried out to obtain 1 at.% Nd: YAG transparent ceramic, and the transmittance of the transparent ceramic is up to 83% at 1064nm as shown in figure 5 measured by a Cary-5000 type ultraviolet-visible-near infrared spectrophotometer.
Example 2
33.1940g Y will be mixed2O3Powder 25.4903g Al2O3Powder, 1.0094g Nd2O3Adding 0.476g TEOS into a high-purity alumina ball mill pot (180 g alumina ball mill), adding 8.9ml absolute ethyl alcohol, 0.4ml dispersant (polyethyleneimine) and 0.32ml DPTA ballsAfter grinding and mixing for 12h, adding 1.5ml of EGDGE, continuing to perform ball milling for 40min to prepare ceramic slurry, wherein the solid content of the ceramic slurry is calculated to be 55 vol%. Pouring the slurry into a beaker after ball milling, putting the beaker into a vacuum drying oven, and vacuumizing (-0.1MPa) for 5 min. After degassing, the slurry was poured into a plastic mold, placed at room temperature for reaction for 2h, then dried at 40 ℃ for 2 days, and further dried at 70 ℃ for 2 days. And drying, taking out the green body, then carrying out glue discharging treatment on the green body, wherein the glue discharging condition is that the temperature is raised to 200 ℃ at the speed of 2 ℃/min and is kept for 2h, then the temperature is raised to 700 ℃ at the speed of 1 ℃/min and is kept for 10h, and furnace cooling is carried out to obtain the Nd: YAG biscuit which is smooth in surface and free of macroscopic defects. The microstructure scanning result of the biscuit section shows that the components are uniformly distributed and the structure is uniform. The pore distribution of the biscuit was measured by mercury porosimetry, and as shown in fig. 6, the unimodal pore distribution of the biscuit was about 141nm, and the relative density was about 54.7%. Directly carrying out vacuum sintering on a biscuit obtained after glue discharging, wherein the sintering conditions are as follows: 1800 ℃ for 20 h. The sintered sample is annealed for 10h at 1400 ℃ in an air atmosphere, and then double-sided polished to obtain 2 at.% Nd: YAG transparent ceramic.
Example 3
32.5166g Y will be mixed2O3Powder 25.4903g Al2O3Powder 2.3646g Yb2O3Adding 0.1811g TEOS into a high-purity alumina ball milling tank (180 g of alumina ball mill), adding 8.9ml of absolute ethyl alcohol, 0.4ml of dispersant (polyethyleneimine) and 1.1ml of EGDGE, carrying out ball milling and mixing for 12h, adding 0.56ml of DPTA, continuing ball milling for 40min, and preparing ceramic slurry, wherein the solid content of the ceramic slurry is 54 vol% according to calculation. And (4) vacuumizing the slurry after ball milling (-0.1MPa) for 5min by using a suction filtration device. After degassing, pouring the slurry into a plastic mold, sealing the mold, and then putting the mold into a 65 ℃ oven for reaction and drying. And taking out the dried and demoulded green body after 2 days, then carrying out glue removing treatment on the green body, wherein the glue removing condition is that the temperature is raised to 350 ℃ at the speed of 1 ℃/min and is kept for 2 hours, then the temperature is raised to 600 ℃ at the speed of 1 ℃/min and is kept for 8 hours, and the Yb: YAG green body is obtained after furnace cooling, the surface is smooth, no macroscopic defect is caused, the components are uniformly distributed, and the microstructure is uniform. Directly carrying out vacuum sintering on a biscuit obtained after glue discharging, wherein the sintering conditions are as follows: 1750 ℃ and 10 h. The sintered sample is removed under the air atmosphere of 1400 DEG CFire treatment for 10h, and then double-side polishing to obtain 4 at.% Yb: YAG transparent ceramic.
Example 4
41.0292g Lu2O3Powder 17.9579g Al2O3Powder 1.0412g Yb2O3Adding 0.0480g of MgO powder and 0.4800g of TEOS into a high-purity alumina ball mill pot (180 g of alumina ball mill), adding 7ml of absolute ethyl alcohol, 0.4ml of dispersant (polyethyleneimine) and 0.3ml of DPTA, carrying out ball milling for 18h, adding GPGE 1.3ml, continuing ball milling for 30min to prepare ceramic slurry, calculating that the solid content of the ceramic slurry is 52 vol%, pouring the slurry into a plastic mold after vacuum degassing of the slurry, placing the mold into a 30 ℃ oven for reaction for 3h, taking the mold into a 65 ℃ oven for drying for 20 h.20h, taking a dried and demoulded blank out, carrying out degumming treatment, wherein the process scheme is the same as the scheme 1, carrying out furnace cooling to obtain a Yb: LuAG blank, the surface is flat, has no macroscopic defects, the components are uniformly distributed, the microstructure is uniform, directly carrying out vacuum sintering on the blank obtained after degumming, and carrying out 1850 ℃ and 10h post-treatment on a sample (× 3h at 5 MPa), obtaining a 1821450 h sample with hot isostatic pressure of 200MPa, and℃annealing for 8h in air atmosphere, and then polishing the two sides to obtain 2.5 at.% Yb: LuAG transparent ceramic.
Example 5
41.7452g Lu2O3Powder 17.9706g Al2O3Powder 0.2846g Nd2O3Adding powder, 0.0480g of MgO powder and 0.4800g of TEOS into a high-purity alumina ball milling tank (180 g of alumina ball mill), adding 6ml of absolute ethyl alcohol, 0.3ml of dispersant (polyethyleneimine) and 1.5ml of GPGE, carrying out ball milling and mixing for 16h, adding 0.26ml of DPTA, and continuing ball milling for 30min to prepare ceramic slurry, wherein the solid content of the ceramic slurry is 51 vol% according to calculation. Performing vacuum degassing on the slurry after ball milling, pouring the slurry into a plastic mould after degassing, putting the plastic mould into a 60 ℃ oven (containing ethanol atmosphere) for reaction and drying for 36h, taking out a dried and demoulded blank after 36h, then performing glue discharging treatment, wherein the glue discharging process is the same as that of case column 2, obtaining an Nd: LuAG biscuit after furnace cooling, and then directly performing vacuum sintering under the sintering conditions: 1800 ℃ for 30 h. Then will beThe sample was subjected to post-hot isostatic pressing (1800 ℃ C. × 3h, 200MPa), the obtained sample was annealed at 1500 ℃ for 5h in an air atmosphere, and then double-side polished to obtain 0.8 at.% Nd: LuAG transparent ceramic.
Example 6
53.4223g Lu2O35.1616g of Gd powder2O3Powder 0.5047g Nd2O3Powder 25.4903g Al2O3Powder, 0.0507g of MgO powder, 0.5075g of TEOS are added into a high-purity alumina ball mill pot (180 g of alumina ball mill), 8.8ml of absolute ethyl alcohol, 0.5ml of dispersant (polyethyleneimine) and 1.7ml of EGDGE are added and ball-milled and mixed for 16 hours, then DPTA0.5ml is added, ball milling is continued for 10min to prepare ceramic slurry, and the solid content of the ceramic slurry is calculated to be 52 vol%. The rest of the procedure was the same as in example 2. Sample sintering conditions: 1725 deg.C, 10 h. Annealing the sintered sample at 1400 ℃ for 10h in air atmosphere, and then polishing the two sides to obtain 1 at.% Nd: Lu2.7Gd0.3Al5O12A transparent ceramic.
Example 7
23.3342g Lu2O3Powder 13.2414g Y2O3Powder 2.4332g Yb2O3Powder 20.9785g Al2O3Adding powder, 0.0480g of MgO powder and 0.4800g of TEOS into a high-purity alumina ball milling tank (180 g of alumina ball mill), adding 7ml of absolute ethyl alcohol, 0.4ml of dispersant (polyethyleneimine) and 0.5ml of DPTA, carrying out ball milling and mixing for 14h, adding EGDGE1.5ml, continuing ball milling for 5min to prepare ceramic slurry, wherein the solid content of the ceramic slurry is 52 vol% by calculation. The rest of the procedure was the same as in example 5. Biscuit sintering conditions: 1850 deg.C, 30 h. Annealing the sintered sample at 1500 ℃ in an air atmosphere for 10h, and then polishing the two sides to obtain 5 at.% Yb (Lu)0.5Y0.5)3Al5O12A transparent ceramic.
Claims (5)
1. The non-water-based gel injection molding method for preparing the garnet-based transparent ceramic is characterized in that the garnet-based transparent ceramic comprises the following components of (Y)1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, a + b + x is less than or equal to 1, and RE is at least one of rare earth ions Nd, Yb, Ce, Er, Pr, Eu, Sm, Ho, Tm and Dy, wherein x is more than or equal to 0 and less than or equal to 0.08 when RE is at least one of Nd, Ce and Pr, and x is more than or equal to 0 and less than or equal to 1 when RE is at least one of Yb, Er, Eu, Sm:
weighing Y in stoichiometric ratio2O3、Lu2O3、Gd2O3、Al2O3、Ga2O3And RE oxide, or (Y) synthesized by liquid phase chemical method1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12The powder is raw material powder;
adding a non-aqueous solvent, a curing agent and epoxy resin into the obtained raw material powder, and performing ball-milling mixing or ultrasonic dispersion mixing to obtain ceramic slurry, wherein the non-aqueous solvent is at least one of ethanol, methanol, propanol, ethylene glycol, acetone, butanone, cyclohexane and dodecane; the mass of the non-aqueous solvent is 8-25 wt% of the raw material powder, and the mass of the epoxy resin is 8-40 wt% of the non-aqueous solvent; the epoxy resin is at least one of ethylene glycol diglycidyl ether, sorbitol glycidyl ether and glycerol glycidyl ether, the curing agent is at least one of 3-3' -diaminodipropylamine, diethylenetriamine and ethylenediamine, and the using amount of the curing agent is 0.1-0.75 mol/epoxy equivalent;
and injecting the obtained ceramic slurry into a mold after vacuum degassing, and sintering for 5 minutes to 60 hours at 800-1900 ℃ after curing, drying, demolding and glue discharging treatment to obtain the garnet-based transparent ceramic.
2. The method according to claim 1, wherein a sintering aid is further added to the raw material powder, and the sintering aid is Li2O、Na2O、K2O、MgO、CaO、B2O3、La2O3、GeO2、SiO2、LiF、NaF、MgF2、CaF2、AlF3、YF3Tetraethoxysilane, H3BO3At least one of (1).
3. The method as claimed in claim 1, wherein a proper amount of dispersant is added into the raw powder, wherein the dispersant is at least one of polyethyleneimine, herring oil, polyacrylamide and polyacrylate.
4. The method of claim 1, wherein the sintering method is one of vacuum sintering, atmosphere sintering, pressureless sintering, spark plasma sintering, hot isostatic pressing sintering; or adopting one of vacuum sintering, atmosphere sintering, pressureless sintering and spark plasma sintering to perform pre-sintering, and then adopting hot isostatic pressing sintering to perform secondary sintering.
5. The method according to any one of claims 1 to 4, wherein the obtained garnet-based transparent ceramic is heat-preserved at 800 to 1600 ℃ for 1 to 100 hours in an annealing atmosphere.
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