CN107540367A - A kind of method that non-water-base gel casting prepares garnet-base transparent ceramic - Google Patents
A kind of method that non-water-base gel casting prepares garnet-base transparent ceramic Download PDFInfo
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Abstract
The present invention relates to a kind of method that non-water-base gel casting prepares garnet-base transparent ceramic, including：Y is weighed according to stoichiometric proportion2O3、Lu2O3、Gd2O3、Al2O3、Ga2O3And RE oxide, material powder, the or (Y synthesized with liquid chemical method are uniformly obtained after mixing1‑a‑b‑xLuaGdbREx)3(Al1‑c‑dSccGad)5O12Powder is material powder；Nonaqueous solvents, curing agent and epoxy resin are added in gained material powder, ceramic slurry is obtained after ball milling mixing or ultrasonic disperse mixing, wherein the nonaqueous solvents is at least one of ethanol, methanol, propyl alcohol, ethylene glycol, acetone, butanone, hexamethylene and dodecane；Mould will be injected after gained ceramic slurry vacuum degassing, is sintered 5 minutes~60 hours at 800 1900 DEG C after cured, the dry, demoulding, dumping processing, obtains the garnet-base transparent ceramic.
Description
Technical field
The present invention provides a kind of method that non-water-base gel casting prepares garnet-base transparent ceramic, can be applied to swash
The fields such as light, flicker, LED, optical window, belong to extraordinary crystalline ceramics shaping and manufacturing process technology field.
Background technology
Crystalline ceramics is a kind of emerging material, is now widely used in the optical element and high-pressure mercury lamp of high temperature instrument
Pipe, head-shield etc., while optical function material is used as, it has importance growing day by day in neighborhoods such as laser, flickers.Wherein, belong to
In the garnet-base (Y of high symmetrical cubic system1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Crystalline ceramics is excellent due to its
Physical chemistry combination property, in industrial circle (illuminating industry, up-conversion luminescence, LED, laser medicine, nuclear medicine, peace
Full inspection survey, high-energy physics etc.) and military neighborhood (high energy laser weapon, laser fusion igniter, infrared window, radome fairing
Deng) there are very important application status and application prospect.2009, Nd:YAG crystalline ceramics has successfully realized hundred kilowatts of laser
Output, its power output will advance towards 600kW-1MW target.It is reported that the Ce of GE companies:(Lu,Tb)3Al5O12Dodge
Bright ceramics (Gemstone) are successfully used for medical CT detections.Multicomponent RE:(Y1-a-bLuaGdb)3(Al1-c-dSccGad)5O12Thoroughly
Bright ceramics can regulate and control optical maser wavelength, can regulate and control scintillation properties etc., have to widening application of the material in terms of light functional characteristic
There is important prospect.
From the point of view of current crystalline ceramics preparation technology, the acquisition base substrate that composition is uniform, consistency is high prepares high-quality to sintering
The controllable crystalline ceramics of amount, large scale, microstructure is extremely important, and moulding process is in material preparation process and formed a connecting link
Key position, to obtain high-quality base substrate have significant impact.
Gel-casting method is a kind of forming technique of near net-shape ceramics.Its forming principle is by being coagulated in slurry
The chemical reaction of colloid system forms macromolecular network structure and ceramic powder in-situ solidifying is shaped into ceramic body, is being molded
Journey, solvent are not moved so the mobile rearrangement of powder granule will not be caused, and then ensure the homogeneity of ingredients of molding blank,
Particularly suitable for multi-component (Y1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12It is prepared by ceramic body.
Gel casting forming is divided into aqueous gel casting and non-aqueous gel casting.Water-base gel casting ceramic body
Process, in order to reduce body defect, it is necessary to special drying condition, while also need to consider powder hydration problem etc..It is existing
There is gel casting forming in technology to prepare (Y1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Water base pottery during crystalline ceramics
The solid content peak of porcelain slurry be also only 75wt% ([1] Qin X., Zhou G., Yang Y., Zhang J., Shu X.,
Shimai S.,and Wang S.Gelcasting of transparent YAG ceramics by a new gelling
system[J].Ceramics International.2014,40(8):12745-12750.[2]Sun Y.,Qin X.,Zhou
G.,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):
The mobility of slurry, stability etc. start to be deteriorated when 250-253.), higher than this solid content.It there have been no at present using non-aqueous solution
Gel casting forming prepares (Y1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12The report of crystalline ceramics.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of preparation of the non-water-base gel casting of ease of Use
(Y1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12The method of crystalline ceramics biscuit.
The invention provides a kind of method that non-water-base gel casting prepares garnet-base transparent ceramic, the pomegranate
The composition of ground mass crystalline ceramics is:(Y1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12, wherein 0≤a≤1,0≤b≤1,0≤
C≤1,0≤d≤1, a+b+x≤1, the RE be rare earth ion Nd, Yb, Ce, Er, Pr, Eu, Sm, Ho, Tm and Dy at least
One kind, wherein when RE is at least one of Nd, Ce and Pr, 0≤x≤0.08, when RE be Yb, Er, Eu, Sm, Ho, Tm and
During at least one of Dy, 0≤x≤1, including：
Y is weighed according to stoichiometric proportion2O3、Lu2O3、Gd2O3、Al2O3、Ga2O3And RE oxide, uniformly obtained after mixing former
Feed powder body, the or (Y synthesized with liquid chemical method1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Powder is material powder；
Nonaqueous solvents, curing agent and epoxy resin are added in gained material powder, after ball milling mixing or ultrasonic disperse mixing
Ceramic slurry is obtained, wherein the nonaqueous solvents is ethanol, methanol, propyl alcohol, ethylene glycol, acetone, butanone, hexamethylene and 12
At least one of alkane；
Mould will be injected after gained ceramic slurry vacuum degassing, at 800-1900 DEG C after cured, the dry, demoulding, dumping processing
Lower sintering 5 minutes~60 hours, obtains the garnet-base transparent ceramic.
The present invention implementation steps be：Ceramic powder is mixed with nonaqueous solvents, adds appropriate curing agent, dispersant
Slurry is mixed with epoxy resin, is directly injected into after slurry vacuum degassing in the mould of different structure shape, original position solidification slurry
Expect forming ceramic base substrate.The composition of heretofore described garnet-base transparent ceramic is:(Y1-a-b-xLuaGdbREx)3(Al1-c- dSccGad)5O12, it is also denoted as RE:(Y1-a-bLuaGdb)3(Al1-c-dSccGad)5O12.Wherein RE considers as Doped ions
It is adapted to lattice, factor, the RE doping concentration such as ionic radius size are because of different ions and different.Wherein RE includes Nd, Ce, Pr
At least one of when, the doping concentration of the ion can be 0~8at.%.When RE is included in Yb, Er, Eu, Sm, Ho, Tm, Dy
When at least one, the doping concentration of the ion can be 0~100at.%；
The advantage of the technical program is：1) hydration of easy aquation powder and aqueous solvent can be avoided；2) according to epoxy resin and
More amine curing agent gel reaction principles judge that the larger aqueous solvent of the less nonaqueous solvents relative polarity of polarity is more beneficial for coagulating
Glue reaction carry out, so epoxy resin reacted with curing agent to be formed network macromolecular structure time it is shorter, avoid generation composition
Segregation phenomena, the network macromolecular structure of formation is by ceramic particle in-situ solidifying, and particle will not be with non-aqueous in the drying process
The displacement of agent and migrate, the defects of ceramic body can be reduced；3) shrinkage stress during ceramic blank drying can be reduced, is avoided
Contraction crack：It is more preferable to powder wetability because organic solvent has lower surface tension than aqueous solvent；4) pottery can be effectively improved
The solid content of porcelain billet body, because the Hamaker constants of ceramic powder in organic solvent more in aqueous small, makes powder
Van der waals force is smaller, while according to similar compatibility principle, the more soluble organic additive of nonaqueous solvents, effectively reducing has
Machine thing content, increase slurry solid content；
In summary effect, the technical program finally can improve solid content to reach 85wt% (equivalent to 54vol%), and document report
Traditional aqueous-based ceramic solid content in road is only up to 75wt%.Meanwhile the composition and even structure of molding blank, gas cell distribution compared with
Narrow, relative density is higher, is advantageous to the stomata exclusion in base substrate in sintering process, and then improves the consistency of Low fire ceramic,
Obtain the crystalline ceramics of high optical quality.
It is preferred that being additionally added sintering aid in the material powder, the sintering aid is Li2O、Na2O、K2O、MgO、
CaO、B2O3、La2O3、GeO2、SiO2、LiF、NaF、MgF2、CaF2、AlF3、YF3With tetraethyl orthosilicate (TEOS) and H3BO3In
It is at least one.Also, it is preferred that the quality of described sintering aid is no more than the 1.5% of the material powder.
It is preferred that being additionally added appropriate dispersant in the material powder, the dispersant is polyethyleneimine, catfish
At least one of oil, polyacrylamide and polyacrylate etc..Also, it is preferred that the quality of the dispersant is the raw material
3wt%~8wt% of powder.
It is preferred that the quality of the nonaqueous solvents is 8wt%~25wt% of material powder.
It is preferred that the epoxy resin is ethylenediamine diglycidyl ether (EGDGE), D-sorbite glycidol ether
(SPGE), at least one of propanetriol-diglycidyl-ether (GPGE).
It is preferred that the quality of the epoxy resin is the 8-40wt% of nonaqueous solvents.
It is preferred that the curing agent be 3-3 '-ethylenediamine diaminourea (DPTA), diethylenetriamine and ethylenediamine at least
It is a kind of.
It is preferred that the dosage of the curing agent is in 0.1-0.75mol/ epoxide equivalents.Wherein epoxide equivalent is containing a ring
The quality of the epoxy resin of epoxide.
It is preferred that described be cured as reacting 10 minutes~4 hours at room temperature~90 DEG C.
It is preferred that the sintering method is vacuum-sintering, atmosphere sintering, pressureless sintering, discharge plasma sintering, heat etc.
One kind in static pressure sintering；Or first using one in vacuum-sintering, atmosphere sintering, pressureless sintering, discharge plasma sintering
Kind carries out pre-sintering, then carries out double sintering using HIP sintering again.
It is preferred that the garnet-base transparent ceramic of preparation at 800-1600 DEG C is incubated 1 hour in annealing atmosphere-
100 hours.
Also, it is preferred that the annealing atmosphere is at least one of air, oxygen, hydrogen, argon gas, nitrogen and vacuum.
The beneficial effects of the invention are as follows：
1st, the water-based slurry (solid content 75wt%) reported relatively, the nonaqueous solvents and slurry that the present invention uses prepare work
Skill, solid concentration can be prepared and be up to the 85wt% relatively low high fluidity of viscosity and the ceramic slurry having good stability, it is very suitable
Simple to operate together in gel casting, practicality is stronger；
2nd, the present invention can prepared composition uniformly, the multicomponent (Y of high-compactness1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Pottery
Porcelain biscuit, key can also control size, shape, intensity of biscuit etc., and the following process process used crystalline ceramics has product
Pole acts on；
3rd, garnet-base transparent ceramic prepared by the present invention can be applied to the fields such as laser, flicker, LED, optical window.
Brief description of the drawings
Fig. 1 is non-water base Nd prepared by embodiment 1:The electron scanning micrograph of YAG base substrate sections；
Fig. 2 is non-water base Nd prepared by embodiment 1:The macrostructure of YAG biscuits；
Fig. 3 is non-water base Nd prepared by embodiment 1:The back-scattered scanning electron microphotograph of YAG biscuit sections；
Fig. 4 is non-water base Nd prepared by embodiment 1:The gas cell distribution of YAG biscuits；
Fig. 5 is non-water base Nd prepared by embodiment 1:The transmittance curve of YAG ceramics；
Fig. 6 is non-water base Nd prepared by embodiment 2:The gas cell distribution of YAG biscuits；
Fig. 7 is DTA test analysis curves.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, it should be appreciated that following embodiments are merely to illustrate the present invention,
It is not intended to limit the present invention.
The present invention prepares garnet-base transparent ceramic using non-water-base gel casting method.Wherein, the garnet
The composition of base transparent ceramic is (Y1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12, wherein 0≤a≤1,0≤b≤1,0≤c
≤ 1,0≤d≤1, a+b+x≤1, the RE be in rare earth ion such as Nd, Yb, Ce, Er, Pr, Eu, Sm, Ho, Tm, Dy at least
It is a kind of.Wherein, Nd, Ce, Pr doping concentration are 0~8at.%, Yb, Er, Eu, Sm, Ho, Tm, Dy doping concentration for 0~
100at.%, preferably 0~60at.%.
Illustrate to following exemplary that non-water-base gel casting provided by the invention prepares garnet-base transparent ceramic
Method.
The present invention is with Y2O3、Lu2O3、Gd2O3、Al2O3、Ga2O3And RE oxide is raw material, according to (Y1-a-b- xLuaGdbREx)3(Al1-c-dSccGad)5O12Stoichiometric proportion weigh after material powder.Wherein RE is rare earth activation ion
Any one of Nd, Yb, Ce, Er, Pr, Eu, Sm, Ho, Tm, Dy or several combination.Powder used can be commercial oxidation thing powder
Body, such as Y2O3、Lu2O3、Gd2O3、Al2O3、Ga2O3、Sc2O3、Nd2O3、Yb2O3、Ce2O3、Er2O3、Pr2O3、Eu2O3、Sm2O3、
Ho2O3、Tm2O3And Dy2O3Deng.
The present invention can also synthesize (such as coprecipitation, sol-gel combustion method, homogeneous co-precipitation process by liquid chemical method
Deng) prepare (Y1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Powder, dispensing is directly weighed as material powder.
Nonaqueous solvents, sintering aid, dispersant are added in material powder (for example, polyethyleneimine, herring oil, poly- third
Acrylamide, polyacrylate etc.), curing agent and epoxy resin, solid concentration is uniformly obtained after mixing can be for 30~60vol%'s
Ceramic slurry.The ceramic slurry that the present invention is prepared using nonaqueous solvents can not only keep superperformance in 30~54vol, when
While its solid concentration is up to 54~60vol%, its viscosity is low, mobility is high and stability is still good.Wherein, it is described non-
Aqueous solvent as in ball-milling medium, such as ethanol, methanol, propyl alcohol, ethylene glycol, acetone, butanone, hexamethylene, dodecane etc. extremely
Few one kind, the quality of the nonaqueous solvents can be the 8%~25% of material powder.The quality of the dispersant can be material powder
3%~8%.Described sintering aid can be but be not limited only to Li2O、Na2O、K2O、MgO、CaO、B2O3、La2O3、GeO2、
SiO2、LiF、NaF、MgF2、CaF2、AlF3、YF3, TEOS (tetraethyl orthosilicate), H3BO3In one or several kinds of combinations or
Any sintering aid is not added.The quality of described sintering aid can be the 0~1.5% of material powder.The epoxy resin can
For ethylenediamine diglycidyl ether (EGDGE), D-sorbite glycidol ether (SPGE), propanetriol-diglycidyl-ether (GPGE) etc.
At least one of, dosage is in the range of the 8-40wt% of solvent quality.The curing agent can be for amido class such as：3-3 '-second two
At least one of amine diaminourea (DPTA), diethylenetriamine, ethylenediamine etc., dosage 0.1-0.75mol/eq (mole/epoxy
Equivalent) in the range of.Epoxide equivalent：Equivalent to the quality of the epoxy resin containing an epoxy radicals.Mixed in above-mentioned slurry preparation process
Conjunction mode can use common or high-energy ball milling method mixed powder, and crush powder by the collision effect between ball milling, change
The grain size and granule-morphology of kind powder, such as rotational speed of ball-mill can be 60-150rmp/min, Ball-milling Time can be 10min-
36h.Or ultrasonic disperse mixing 10min-36h is used, obtain dispersed ceramic slurry.
Ceramic slurry is injected into mould after vacuum degassing, 10 minutes~4 are reacted at room temperature~90 DEG C after sealed mold
Hour, induced paste is formed by curing base substrate.Specifically, temperature is controlled in inducing temperature using modes such as baking oven, microwave, water-baths
In room temperature between 90 DEG C, induction gel rubber system reaction 10min-4h promotes pulp gel in-situ solidifying powder to be molded.
Base substrate after solidification is dried again makes it be stripped naturally, obtains ceramic body.In addition slurry injection molding rear mold
The drying of middle base substrate can be carried out synchronously with the shaping of base substrate, be placed 2h to 10 days, automatic demoulding after body drying also can be one
Fixed drying atmosphere and under the conditions of carry out.
Dried ceramic body is instructed into binder removal (see Fig. 7) according to DTA test analysis curve, obtained after dumping
Biscuit of ceramics.Dumping processing is specially high temperature degreasing, and the time of 10 hours is incubated at a temperature of 600-700 DEG C, obtains ceramics
Biscuit.
The transparent pottery of garnet-base is obtained after biscuit of ceramics after dumping is sintered 5 minutes~60 hours at 800-1900 DEG C
Porcelain.Its sintering method is：Vacuum-sintering, atmosphere sintering, pressureless sintering, discharge plasma sintering (SPS), HIP sintering
(HIP) etc..And it is first pre-sintered using vacuum-sintering or atmosphere sintering or pressureless sintering or SPS methods, then carry out two using HIP
Secondary sintering.
By (the Y of preparation1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Crystalline ceramics is made annealing treatment, and obtains performance
The crystalline ceramics of optimization.Specifically, the garnet-base transparent ceramic of preparation is protected at 800~1600 DEG C in annealing atmosphere
Temperature 1 hour~100 hours.The annealing atmosphere can be at least one of air, oxygen, hydrogen, argon gas, nitrogen, vacuum.
Biscuit of ceramics composition that the present invention is prepared is uniformly, uniform microstructure, gas cell distribution be narrow, relative density compared with
Height, blank strength are high and easy to process.After forming of green body, with reference to related sintering schedule prepare the transmitance of crystalline ceramics all compared with
It is high.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
By 33.5323g Y2O3Powder, 25.4903g Al2O3Powder, 0.5047g Nd2O3Powder, 0.0476g MgO powders,
0.476g TEOS are added in high purity aluminium oxide ball grinder (alumina balls mill 160-200g), are added absolute ethyl alcohol 8.85ml, are divided
After powder (polyethyleneimine) 0.4ml, DPTA 0.4ml ball milling mixings 18h, EGDGE 1.3ml are added, continue ball milling 20min systems
Standby ceramic slurry, calculating understand that the solid content of ceramic slurry is 54vol%.Slurry is vacuumized into (- 0.1MPa) degasification after ball milling
5min.After degasification, slurry is poured into plastic mould, reacting drying in 40 DEG C of baking ovens is put into after sealed mold.Take out and done after 3 days
Dry, the demoulding base substrate, ESEM is done to base substrate as shown in figure 1, display organic matter reaction is fixed-type by particle, face is more uniform
There is no big hole.Then base substrate is subjected to dumping processing, dumping condition is that 1 DEG C/min is warming up to 350 DEG C and is incubated 2h, then
600 DEG C are warming up to 1 DEG C/min and is incubated 10h, and Nd is obtained after furnace cooling:YAG biscuits, its macrostructure is as shown in Fig. 2 table
Face is smooth, non-nuclear density gauge.The microstructure scanning result (Fig. 3) of biscuit section is shown, its distributed components, structure is equal
It is even.Using the gas cell distribution of mercury injection apparatus method test biscuit, as shown in figure 4, biscuit stomata Unimodal Distribution size is about 180nm, phase
It is about 55% to consistency.The biscuit obtained after dumping, directly carry out vacuum-sintering, sintering condition：1775 DEG C, 20h.After sintering
Sample 10h is made annealing treatment under 1450 DEG C of air atmospheres, then twin polishing obtains 1at.%Nd:YAG crystalline ceramics, warp
Cary-5000 types are ultraviolet-visible-and near infrared spectrometer measurement understands that its transmitance is up to 83% at 1064nm, such as
Shown in Fig. 5.
Embodiment 2
By 33.1940g Y2O3Powder, 25.4903g Al2O3Powder, 1.0094g Nd2O3Powder, 0.476g TEOS add high
In pure alumina ball grinder (alumina balls mill 180g), add absolute ethyl alcohol 8.9ml, dispersant (polyethyleneimine) 0.4ml,
After DPTA 0.32ml ball milling mixings 12h, EGDGE 1.5ml are added, continues ball milling 40min and prepares ceramic slurry, calculates and understands to make pottery
The solid content of porcelain slurry is 55vol%.Slurry is poured into beaker after ball milling, is put into vacuum drying chamber and vacuumizes (- 0.1MPa)
Degasification 5min.After degasification, slurry is poured into plastic mould, is put into room temperature and reacts 2h, then dried 2 days, continue at 40 DEG C
70 DEG C of dryings 2 days.Base substrate is taken out after drying, base substrate is then subjected to dumping processing, dumping condition is that 2 DEG C/min is warming up to 200
DEG C and be incubated 2h, be then warming up to 700 DEG C with 1 DEG C/min and be incubated 10h, Nd is obtained after furnace cooling:YAG biscuits, surface are put down
It is whole, non-nuclear density gauge.The microstructure scanning result of biscuit section is shown, its distributed components, even structure.Utilize pressure
Mercury instrument method tests the gas cell distribution of biscuit, as shown in fig. 6, biscuit stomata Unimodal Distribution size is about 141nm, relative density is about
For 54.7%.The biscuit obtained after dumping, directly carry out vacuum-sintering, sintering condition：1800 DEG C, 20h.Sample after sintering exists
10h is made annealing treatment under 1400 DEG C of air atmospheres, then twin polishing obtains 2at.%Nd:YAG crystalline ceramics.
Embodiment 3
By 32.5166g Y2O3Powder, 25.4903g Al2O3Powder, 2.3646g Yb2O3Powder, 0.1811g TEOS add high
In pure alumina ball grinder (alumina balls mill 180g), add absolute ethyl alcohol 8.9ml, dispersant (polyethyleneimine) 0.4ml,
After EGDGE 1.1ml ball milling mixings 12h, DPTA 0.56ml are added, continues ball milling 40min and prepares ceramic slurry, calculates and understands to make pottery
The solid content of porcelain slurry is 54vol%.Ball milling disposed slurry vacuumizes (- 0.1MPa) degasification 5min using Suction filtration device.After degasification,
Slurry is poured into plastic mould, reacting drying in 65 DEG C of baking ovens is put into after sealed mold.The base dried, be stripped is taken out after 2 days
Body, base substrate is then subjected to dumping processing, dumping condition is that 1 DEG C/min is warming up to 350 DEG C and is incubated 2h, then with 1 DEG C/min
It is warming up to 600 DEG C and is incubated 8h, Yb is obtained after furnace cooling:YAG biscuits, surfacing, non-nuclear density gauge, component distributing are equal
Even, microstructure is uniform.The biscuit obtained after dumping, directly carry out vacuum-sintering, sintering condition：1750 DEG C, 10h.After sintering
Sample 10h is made annealing treatment under 1400 DEG C of air atmospheres, then twin polishing obtains 4at.%Yb:YAG crystalline ceramics.
Embodiment 4
By 41.0292g Lu2O3Powder, 17.9579g Al2O3Powder, 1.0412g Yb2O3Powder, 0.0480g MgO powders,
0.4800g TEOS are added in high purity aluminium oxide ball grinder (alumina balls mill 180g), add absolute ethyl alcohol 7ml, dispersant
After (polyethyleneimine) 0.4ml, DPTA 0.3ml ball milling mixings 18h, GPGE 1.3ml are added, continues ball milling 30min and prepares pottery
Porcelain slurry, calculating understand that the solid content of ceramic slurry is 52vol%.After slurry vacuum degassing, slurry is poured into plastic mould, mould
Tool, which is put into 30 DEG C of baking ovens, reacts 3h, and then mould, which is taken, dries 20h in 65 DEG C of baking ovens.The base dried, be stripped is taken out after 20h
Body, dumping processing is then carried out, process program and case row 1 are identical, and Yb is obtained after furnace cooling:LuAG biscuits, surfacing, nothing
Gross imperfection, distributed components, microstructure are uniform.The biscuit obtained after dumping, directly carry out vacuum-sintering, sintered bar
Part：1850 DEG C, 10h.Then sample is subjected to post-hiped (1825 DEG C × 3h, 200MPa), the sample of acquisition exists
8h is made annealing treatment under 1450 DEG C of air atmospheres, then twin polishing obtains 2.5at.%Yb:LuAG crystalline ceramics.
Embodiment 5
By 41.7452g Lu2O3Powder, 17.9706g Al2O3Powder, 0.2846g Nd2O3Powder, 0.0480g MgO powders,
0.4800g TEOS are added in high purity aluminium oxide ball grinder (alumina balls mill 180g), add absolute ethyl alcohol 6ml, dispersant
After (polyethyleneimine) 0.3ml, GPGE 1.5ml ball milling mixings 16h, DPTA 0.26ml are added, continues ball milling 30min and prepares pottery
Porcelain slurry, calculating understand that the solid content of ceramic slurry is 51vol%.Ball milling disposed slurry does vacuum degassing, and after degasification, slurry is fallen
Enter plastic mould, the base dried, be stripped is taken out after being put into (include alcohol atmosphere) in 60 DEG C of baking ovens reacting drying 36h, 36h
Body, dumping processing is then carried out, binder removal process and case row 2 are identical, and Nd is obtained after furnace cooling:LuAG biscuits, Ran Houzhi
Tap into row vacuum-sintering, sintering condition：1800 DEG C, 30h.Then by sample carry out post-hiped (1800 DEG C × 3h,
200MPa), the sample of acquisition makes annealing treatment 5h under 1500 DEG C of air atmospheres, and then twin polishing obtains 0.8at.%Nd:LuAG
Crystalline ceramics.
Embodiment 6
By 53.4223g Lu2O3Powder, 5.1616g Gd2O3Powder, 0.5047g Nd2O3Powder, 25.4903g Al2O3Powder
Body, 0.0507g MgO powders, 0.5075g TEOS are added in high purity aluminium oxide ball grinder (alumina balls mill 180g), added
After absolute ethyl alcohol 8.8ml, dispersant (polyethyleneimine) 0.5ml, EGDGE 1.7ml ball milling mixings 16h, DPTA is added
0.5ml, continue ball milling 10min and prepare ceramic slurry, calculating understands that the solid content of ceramic slurry is 52vol%.Remaining steps and
Embodiment 2 is identical.Sample sintering condition：1725 DEG C, 10h.Sample after sintering makes annealing treatment 10h under 1400 DEG C of air atmospheres,
Then twin polishing obtains 1at.%Nd:Lu2.7Gd0.3Al5O12Crystalline ceramics.
Embodiment 7
By 23.3342g Lu2O3Powder, 13.2414g Y2O3Powder, 2.4332g Yb2O3Powder, 20.9785g Al2O3Powder
Body, 0.0480g MgO powders, 0.4800g TEOS are added in high purity aluminium oxide ball grinder (alumina balls mill 180g), added
After absolute ethyl alcohol 7ml, dispersant (polyethyleneimine) 0.4ml, DPTA 0.5ml ball milling mixings 14h, EGDGE 1.5ml are added,
Continue ball milling 5min and prepare ceramic slurry, calculating understands that the solid content of ceramic slurry is 52vol%.Remaining steps and embodiment 5
It is identical.Biscuit sintering condition：1850 DEG C, 30h.Sample after sintering makes annealing treatment 10h under 1500 DEG C of air atmospheres, then two-sided
Polishing obtains 5at.%Yb:(Lu0.5Y0.5)3Al5O12Crystalline ceramics.
Claims (10)
1. a kind of method that non-water-base gel casting prepares garnet-base transparent ceramic, it is characterised in that the garnet
The composition of base transparent ceramic is: (Y1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12, wherein 0≤a≤1,0≤b≤1,0≤c
≤ 1,0≤d≤1, a+b+x≤1, the RE be rare earth ion Nd, Yb, Ce, Er, Pr, Eu, Sm, Ho, Tm and Dy at least
One kind, wherein when RE is at least one of Nd, Ce and Pr, 0≤x≤0.08, when RE is Yb, Er, Eu, Sm, Ho, Tm,
During with least one of Dy, 0≤x≤1, including：
Y is weighed according to stoichiometric proportion2O3、Lu2O3、Gd2O3、Al2O3、Ga2O3And RE oxide, uniformly obtain raw material after mixing
Powder, the or (Y synthesized with liquid chemical method1-a-b-xLuaGdbREx)3(Al1-c-dSccGad)5O12Powder is material powder；
Nonaqueous solvents, curing agent and epoxy resin are added in gained material powder, after ball milling mixing or ultrasonic disperse mixing
Ceramic slurry is obtained, wherein the nonaqueous solvents is ethanol, methanol, propyl alcohol, ethylene glycol, acetone, butanone, hexamethylene and 12
At least one of alkane；
Mould will be injected after gained ceramic slurry vacuum degassing, at 800-1900 DEG C after cured, the dry, demoulding, dumping processing
Lower sintering 5 minutes~60 hours, obtains the garnet-base transparent ceramic.
2. according to the method for claim 1, it is characterised in that sintering aid, the burning are additionally added in the material powder
Knot auxiliary agent is Li2O、Na2O、K2O、MgO、CaO、B2O3、La2O3、GeO2、SiO2、LiF、NaF、MgF2、CaF2、AlF3、YF3, just
Silester, H3BO3At least one of.
3. method according to claim 1 or 2, it is characterised in that appropriate dispersant is additionally added in the material powder,
The dispersant is at least one of polyethyleneimine, herring oil polyacrylamide, polyacrylate etc..
4. according to the method any one of claim 1-3, it is characterised in that the quality of the nonaqueous solvents is raw material powder
8%~25 wt% of body.
5. according to the method any one of claim 1-5, it is characterised in that the epoxy resin is that ethylenediamine two shrinks
At least one of glycerin ether, D-sorbite glycidol ether, propanetriol-diglycidyl-ether.
6. according to the method for claim 5, it is characterised in that the quality of the epoxy resin is the 8~40 of nonaqueous solvents
wt%。
7. according to the method any one of claim 1-6, it is characterised in that the curing agent is 3-3 '-ethylenediamine two
At least one of amino, diethylenetriamine, ethylenediamine.
8. according to the method for claim 7, it is characterised in that the dosage of the curing agent is in 0.1~0.75 mol/ epoxies
Equivalent.
9. according to the method any one of claim 1-8, it is characterised in that the sintering method is vacuum-sintering, gas
One kind in atmosphere sintering, pressureless sintering, discharge plasma sintering, HIP sintering；Or first using vacuum-sintering, atmosphere
A kind of progress in sintering, pressureless sintering, discharge plasma sintering is pre-sintered, then carries out two using HIP sintering again
Secondary sintering.
10. according to the method any one of claim 1-9, it is characterised in that by any one of claim 1-8
Method prepare garnet-base transparent ceramic be incubated 1 hour~100 hours at 800~1600 DEG C in annealing atmosphere.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752008A (en) * | 2018-06-14 | 2018-11-06 | 哈尔滨工业大学 | A kind of porous Si2N2O high temperature resistant wave-permeable ceramics and preparation method thereof |
| CN109574671A (en) * | 2018-12-04 | 2019-04-05 | 信阳师范学院 | It is a kind of using sodium fluoride as the preparation method of the fluorite mineral polycrystalline transparent ceramic of auxiliary agent |
| CN114149265A (en) * | 2021-12-21 | 2022-03-08 | 厦门钜瓷科技有限公司 | Method for net forming of aluminium nitride ceramics |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396121A (en) * | 2013-08-13 | 2013-11-20 | 中国科学院宁波材料技术与工程研究所 | Novel transparent glitter ceramic with garnet structure and preparation method thereof |
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2016
- 2016-06-28 CN CN201610485929.7A patent/CN107540367B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103396121A (en) * | 2013-08-13 | 2013-11-20 | 中国科学院宁波材料技术与工程研究所 | Novel transparent glitter ceramic with garnet structure and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752008A (en) * | 2018-06-14 | 2018-11-06 | 哈尔滨工业大学 | A kind of porous Si2N2O high temperature resistant wave-permeable ceramics and preparation method thereof |
| CN108752008B (en) * | 2018-06-14 | 2020-07-21 | 哈尔滨工业大学 | Porous Si2N2O high-temperature-resistant wave-transparent ceramic and preparation method thereof |
| CN109574671A (en) * | 2018-12-04 | 2019-04-05 | 信阳师范学院 | It is a kind of using sodium fluoride as the preparation method of the fluorite mineral polycrystalline transparent ceramic of auxiliary agent |
| CN114149265A (en) * | 2021-12-21 | 2022-03-08 | 厦门钜瓷科技有限公司 | Method for net forming of aluminium nitride ceramics |
| CN114149265B (en) * | 2021-12-21 | 2023-02-10 | 厦门钜瓷科技有限公司 | Method for net forming of aluminium nitride ceramics |
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