CN102060539B - Method for preparing yttrium aluminum garnet based transparent ceramic by slip casting - Google Patents
Method for preparing yttrium aluminum garnet based transparent ceramic by slip casting Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000007569 slipcasting Methods 0.000 title abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 49
- 235000015895 biscuits Nutrition 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910052574 oxide ceramic Inorganic materials 0.000 claims abstract description 7
- 239000011224 oxide ceramic Substances 0.000 claims abstract description 7
- 238000002347 injection Methods 0.000 claims description 28
- 239000007924 injection Substances 0.000 claims description 28
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 7
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000013530 defoamer Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 241000273930 Brevoortia tyrannus Species 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004902 Softening Agent Substances 0.000 claims description 6
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- 235000021323 fish oil Nutrition 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 2
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 2
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000005908 glyceryl ester group Chemical group 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 239000011354 acetal resin Substances 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 229920006324 polyoxymethylene Polymers 0.000 claims 1
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- 239000002671 adjuvant Substances 0.000 abstract 2
- 239000002518 antifoaming agent Substances 0.000 abstract 2
- 239000002270 dispersing agent Substances 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 36
- 239000011222 crystalline ceramic Substances 0.000 description 26
- 229910002106 crystalline ceramic Inorganic materials 0.000 description 26
- 229910052799 carbon Inorganic materials 0.000 description 16
- 238000010792 warming Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 14
- 229910006295 Si—Mo Inorganic materials 0.000 description 7
- 229910003460 diamond Inorganic materials 0.000 description 7
- 239000010432 diamond Substances 0.000 description 7
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011858 nanopowder Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007704 wet chemistry method Methods 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000087 laser glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
Abstract
The invention discloses a method for preparing a yttrium aluminum garnet (YAG) based transparent ceramic by slip casting. The method comprises the following steps: performing ball-milling and mixing on oxide ceramic powder, a sintering adjuvant, a nonaqueous solvent and a dispersant; adding an adhesive, a plasticizer and a defoaming agent; and preparing a nonaqueous based slurry through ball-milling and mixing, wherein the slurry consists of the following components in percentage by mass: 40 to 70 percent of oxide ceramic powder, 0.01 to 1 percent of sintering adjuvant, 0.005 to 2.5 percent of dispersant, 0.01 to 5 percent of adhesive, 0.01 to 3 percent of plasticizer, 0.005 to 0.5 percent of defoaming agent, and the balance of the nonaqueous solvent; and preparing a ceramic block from the slurry through slip casting, preparing a ceramic biscuit by adopting a two-step drying method, and preparing the transparent ceramic through vacuum sintering. The method adopts the slip casting, is particularly suitable for preparing the ceramic sample with complicated shape, large size and composite structure, and greatly widens the preparation means of the transparent ceramic.
Description
Technical field
The present invention relates to crystalline ceramics preparing technical field, particularly a kind of novel method of utilizing injection forming to prepare yttrium aluminum garnet (YAG) base transparent ceramic.
Background technology
Neodymium doped yttrium aluminum garnet (Nd:YAG) monocrystalline is that current performance is best, and output is maximum, the laser host material that purposes is the widest, but the natural characteristics of Crystal Growth Technique is restricted its performance and range of application.Material supply section scholar rose and just attempts the operation material as solid statelaser with crystalline ceramics in the sixties in 20th century, but effect is all undesirable.Until patent JP05-286761, JP05-286762, JP05-294722, JP05-294723, JP05-294724, after JP05-235462 etc. issue, the ceramic laser operation material that the Nd:YAG crystalline ceramics of take is representative is because it has monocrystalline at aspects such as technology of preparing and material properties, the unrivaled advantage of glass laser material has received people's very big concern, and obtained development rapidly.
The method of preparing Nd:YAG crystalline ceramics mainly contains two kinds: a kind of employing solid state reaction-vacuum sintering technique; Another method is first with wet chemistry method, to synthesize the Nd:YAG nano-powder of high sintering activity, then adopts vacuum sintering technique to prepare Nd:YAG crystalline ceramics.Nineteen ninety-five, A.Ikesue reported first with the Y of the synthetic high sintering activity of wet chemistry method
2o
3, Al
2o
3and Nd
2o
3powder, then adopt solid state reaction and vacuum sintering technique to prepare Nd:YAG crystalline ceramics [A.Ikesue, T.Kinoshita, K.Kamata, et al, Fabrication and optical properties of high-performancepolycrystalline Nd:YAG ceramics for solid-state lasers, J.Am.Ceram.Soc., 1995,78 (4): 1033-1040], and first realized the continuous laser output of Nd:YAG crystalline ceramics.Wet chemistry method is prepared Nd:YAG laser ceramics and in 1999, is obtained important breakthrough, day Benshen island (Konoshima) chemical company adopt a kind of improved urea precipitator method prepare particle size evenly, Nd:YAG nano-powder [the patent JP10-101333 of good dispersity, JP10-101334, JP10-101411, JP10-114519], by vacuum sintering technique, prepare high-quality Nd:YAG crystalline ceramics, and realized powerful Laser output.
Nd:YAG crystalline ceramics not only has light transmission and the laser activity that can compare favourably with laser monocrystalline, and have similar to laser glass can large size preparation and realize high-concentration dopant, especially also there is the distinctive good mechanical behavior under high temperature of structural ceramics and easily realize the feature of composite structure, so laser ceramics is considered to one of the most promising laserable material of 21 century.2006, the Nd:YAG crystalline ceramics that U.S. Lao Lunsi livermore national laboratory utilizes day Benshen island chemical company to produce, realized the solid state heat capacity Laser output of 67kW, cause showing great attention to of various countries Department of Defense, made laser ceramic material substitute the important option that laser monocrystalline becomes US military Solid State Laser weapon.The material using under high-end laser weapon use and particular surroundings often needs to have the features such as large size, complicated shape and composite structure, adopts conventional dry-pressing formed very difficult realization.Therefore, explore exploring the novel forming method tool that is applicable to preparing yttrium aluminum garnet base transparent ceramic is of great significance.
That injection forming is particularly suitable for preparing is complex-shaped, the sample of large size and composite structure.Injection forming and nano-powder technology of preparing, solid state reaction sintering technology and vacuum sintering technique are combined and prepare yttrium aluminum garnet base transparent ceramic, are very promising approach.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing slip-casting shaping process to prepare yttrium aluminum garnet base transparent ceramic, it is characterized in that the concrete technology step of the method comprises:
(1) material choice
The raw material that the present invention uses can be:
(a) α-Al
2o
3and Y
2o
3press that YAG forms preparation or by α-Al
2o
3, Y
2o
3and RE
2o
3press RE:YAG and form preparation, wherein RE
2o
3for Nd
2o
3, Yb
2o
3, Cr
2o
3, Er
2o
3, Sc
2o
3, La
2o
3, Tm
2o
3, Ho
2o
3, Sm
2o
3, Lu
2o
3, Ce
2o
3and Pr
2o
3in any one or a few combination; Or (b) with wet chemical method, comprise that YAG prepared by the precipitator method, sol-gel method, combustion synthesis method or RE:YAG powder (wherein RE is any one or several combination in Nd, Yb, Cr, Er, Sc, La, Tm, Ho, Sm, Lu, Ce and Pr element) are as oxide ceramic powder body.
(2) sintering aid is selected
Sintering aid can be LiF, NaF, MgF
2, CaF
2, AlF
3, Li
2o, Na
2o, K
2o, CaO, MgO, B
2o
3, Ga
2o
3, SiO
2, GeO
2and any one or several combination in TEOS (tetraethoxy), the addition of sintering aid is 10
2～10
6ppm.
(3) slurry preparation
First oxide ceramic powder body, non-aqueous solvent, sintering aid and dispersion agent ball milling are mixed after 6～8h, add binding agent, softening agent and defoamer, ball milling mixes 2～4h and prepares non-water-based slurry.Wherein slurry is comprised of following mass percent: oxide ceramic powder body 40～70%, and sintering aid 0.01 ~ 1%, dispersion agent 0.005～1%, binding agent 0.01～5%, softening agent 0.01～3%, defoamer 0.005～0.5%, surplus is solvent.
(4) injection forming
Slurry prepared by step (3) after injection forming, adopts two step desiccating methods to prepare biscuit of ceramics the demoulding: the first step drying temperature is 20～40 ℃, and be 2～48h time of drying in mould; Second step drying temperature is 60～90 ℃, and drying temperature is 2～24h.
(5) ceramic post sintering
Biscuit of ceramics prepared by step (4) carries out preheating in retort furnace: temperature rise rate is 1～10 ℃/min, and calcined temperature is 500～1200 ℃, and soaking time is 1～10h, to get rid of the organism in biscuit.By the sintering in vacuum tungsten coil furnace of the biscuit after preheating, comprising: first the speed with 10～20 ℃/min is warming up to 1000 ℃ from room temperature, then with 0.5～10 ℃/min, be warming up to 1650～1850 ℃ and be incubated 1～200h, vacuum tightness during insulation is higher than 10
-3pa.The crystalline ceramics that vacuum sintering obtains carries out anneal in air or oxygen atmosphere, and annealing temperature is 1300～1600 ℃, and soaking time is 2～100h.
Described raw material and the purity of sintering aid are all higher than 99.9%.
Described non-aqueous solvent is any one or the wherein several combinations in methyl alcohol, ethanol, ethylene glycol, acetone, butanone and in dimethylbenzene.Because of biscuit rate of drying prepared by non-aqueous solvent fast, smooth surface, microtexture is even, good mechanical performance can make the quality of crystalline ceramics be well controlled.
Described dispersion agent is any one in menhaden fish oil (MFO) polyacrylic acid (PAA) and glyceryl ester, and these dispersion agents can be adsorbed on solid particles surface, and the space steric effect of generation can effectively stop between particle and mutually assemble.
Described binding agent is any one in polyvinyl butyral acetal (PVB) and acrylic resin, and these two kinds of binding agents, by enwrapped granule surface, self solidify to form three-dimensional resinous framework, give biscuit certain intensity.
Described softening agent is any one in polyoxyethylene glycol (PEG), phthalandione dibutylester (DBP) and butyl benzyl phthalate (BBP), plasticizer molecule can be inserted in binding agent molecular chain, thereby reduce the rigidity of binding agent molecule, improve the plasticity of biscuit of ceramics.
Described defoamer is organic silicon modified by polyether, and this defoamer is very easily adsorbed in liquid bubble surface, strongly reduces local surface tension and the surface viscosity of bubble, weakens the Ability of Resisting Disturbance of bubble, destroys its stability, impels bubble to discharge liquid level.
During ball milling described in step a, ball grinder and ball milling grinding ball material used is aluminum oxide or zirconia ceramics.
The moulding stock that in described step (b), injection forming is used is any one in glass, gypsum, pottery, metal or plastics.
Described injection forming be direct once shaped prepare the biscuit of one-component or repeatedly moulding preparation there is the biscuit of the composite structure of layered composite structure, nucleocapsid structure.(referring to embodiment 4,5)
The present invention adopts injection forming, is particularly suitable for preparing the ceramics sample of complex-shaped, large size and composite structure, has greatly widened the approach of preparing of crystalline ceramics.
Accompanying drawing explanation
Fig. 1 is the photo in kind of YAG crystalline ceramics in embodiment 1
Fig. 2 is the straight line transmittance curve of YAG crystalline ceramics in embodiment 1
Fig. 3 is the fracture apperance photo of YAG crystalline ceramics in embodiment 1
Fig. 4 is the photo in kind of 2.0at%Nd:YAG crystalline ceramics in embodiment 2
Fig. 5 is the straight line transmittance curve of 2.0at%Nd:YAG crystalline ceramics in embodiment 2
Embodiment
Embodiment 1
α-the Al that is 300nm by 25.4904g median size
2o
3powder, 33.8715g median size is the Y of 3 μ m
2o
3powder, 0.3562g tetraethoxy (TEOS) and 0.0594g menhaden fish oil (MFO) are put into high purity aluminium oxide ball grinder, add high purity aluminium oxide abrading-ball 200g, dehydrated alcohol 34ml, then after ball milling mixing 8h, add after 0.1188g polyvinyl butyral acetal (PVB), 0.1782g polyoxyethylene glycol (PEG) and 0.1484g organic silicon modified by polyether, continue ball milling 2h, obtain injection forming ceramic size.The slurry making is carried out to injection forming, and the biscuit after slip casting, first at 30 ℃ of dry 24h, then, at 70 ℃ of dry 12h, is peeled off from mould, obtains the biscuit of ceramics that thickness is about 4mm.The biscuit of ceramics of preparation carries out preheating in retort furnace: temperature rise rate is 5 ℃/min, and calcined temperature is 600 ℃, and soaking time is 4h, to get rid of the organism in biscuit.Sintering is to carry out in vacuum tungsten coil furnace, concrete sintering mechanism is as follows: the speed with 10 ℃/min is warming up to 1000 ℃, then the speed with 5 ℃/min heats up 1450 ℃, then with the speed of 2 ℃/min, be warming up to 1770 ℃ and be incubated 30 hours, then the speed with 10 ℃/min is cooled to 1000 ℃, 1000 ℃ of following furnace cooling from 1770 ℃.The YAG pottery that vacuum sintering obtains anneal in Si-Mo rod stove, mechanism of anneal is: with 5 ℃/min, from room temperature, rise to 1450 ℃ and be incubated 20h, then from 1450 ℃ of furnace cooling.Finally with surface grinding machine and diamond paste, pottery is carried out attenuate and is polished to 1.5mm thick, obtain the YAG crystalline ceramics sample of relative density > 99.9%.Fig. 1 is its photo in kind, and Fig. 2 is its straight line transmittance curve, and Fig. 3 is the microstructure appearance schematic diagram of its fracture.
Embodiment 2
α-the Al that is 300nm by 25.4904g median size
2o
3powder, 33.1955g median size is the Y of 3 μ m
2o
3powder, the Nd that 0.5047g median size is 250nm
2o
3powder, 0.3582g tetraethoxy (TEOS) and 0.0895g menhaden fish oil (MFO) are put into high purity aluminium oxide ball grinder, add high purity aluminium oxide abrading-ball 200g, dehydrated alcohol 36ml, then after ball milling mixing 10h, add after 0.2985g polyvinyl butyral acetal (PVB), 0.1194g butyl benzyl phthalate (BBP) and 0.0597g organic silicon modified by polyether, continue ball milling 2h, obtain injection forming ceramic size.The slurry making is carried out to injection forming, and the biscuit after slip casting, first at 25 ℃ of dry 24h, then, at 80 ℃ of dry 10h, is peeled off from mould, obtains the biscuit of ceramics that thickness is about 4mm.The biscuit of ceramics of preparation carries out preheating in retort furnace: temperature rise rate is 2.5 ℃/min, and calcined temperature is 800 ℃, and soaking time is 1h, to get rid of the organism in biscuit.Sintering is to carry out in vacuum oven, concrete sintering mechanism is as follows: the speed with 20 ℃/min is warming up to 1000 ℃, then the speed with 5 ℃/min heats up 1400 ℃, then with the speed of 2 ℃/min, be warming up to 1760 ℃ and be incubated 50 hours, then the speed with 20 ℃/min is cooled to 1000 ℃, 1000 ℃ of following furnace cooling from 1760 ℃.The YAG pottery that vacuum sintering obtains anneal in Si-Mo rod stove, mechanism of anneal is: with 5 ℃/min, from room temperature, rise to 1450 ℃ and be incubated 20h, then from 1450 ℃ of furnace cooling.Finally with surface grinding machine and diamond paste, pottery is carried out attenuate and is polished to 1.5mm thick, obtain the 2.0at%Nd:YAG crystalline ceramics sample of relative density > 99.9%.Fig. 4 is its photo in kind, and Fig. 5 is its straight line transmittance curve.
Embodiment 3
α-the Al that is 300nm by 25.4903g median size
2o
3powder, 33.5328g median size is the Y of 3 μ m
2o
3powder, 0.5047g median size is the Er of 7 μ m
2o
3powder, 0.4800g tetraethoxy (TEOS) and 0.1188g polyacrylic acid (PAA) are put into high purity aluminium oxide ball grinder, add high purity aluminium oxide abrading-ball 180g, dehydrated alcohol 30ml, after ball milling mixing 10h, add after 0.0594g polyvinyl butyral acetal (PVB), 0.0594g butyl benzyl phthalate (BBP) and 0.0297g organic silicon modified by polyether, continue ball milling 2h, obtain injection forming ceramic size.The slurry making is carried out to injection forming, and the biscuit after slip casting, at 25 ℃ of dry 24h, is peeled off from mould, obtains the biscuit of ceramics that thickness is about 3mm.The biscuit of ceramics of preparation carries out preheating in retort furnace: temperature rise rate is 2.5 ℃/min, and calcined temperature is 800 ℃, and soaking time is 2h, to get rid of the organism in biscuit.Sintering is to carry out in vacuum oven, concrete sintering mechanism is as follows: the speed with 20 ℃/min is warming up to 1000 ℃, then the speed with 5 ℃/min heats up 1400 ℃, then with the speed of 2 ℃/min, be warming up to 1780 ℃ and be incubated 10 hours, then the speed with 20 ℃/min is cooled to 1000 ℃, 1000 ℃ of following furnace cooling from 1780 ℃.The YAG pottery that vacuum sintering obtains anneal in Si-Mo rod stove, mechanism of anneal is: with 5 ℃/min, from room temperature, rise to 1450 ℃ and be incubated 20h, then from 1450 ℃ of furnace cooling.Finally with surface grinding machine and diamond paste, pottery is carried out attenuate and is polished to 1mm thick, obtain the 1at%Er:YAG crystalline ceramics sample of relative density > 99.9%.
Embodiment 4
Respectively according to embodiment 1 and two kinds of slurries of embodiment 2 preparations.The slurry that embodiment 1 is made carries out injection forming, 25 ℃ of not demouldings of dry 10h, make sizing material forming but not exclusively dry, the slurry of embodiment 2 preparations is cast in above also first at 25 ℃ of dry 24h, then at 65 ℃ of dry 10h, from mould, peel off the biscuit of ceramics that obtains layered composite structure.The biscuit of ceramics of preparation carries out preheating in retort furnace: temperature rise rate is 5 ℃/min, and calcined temperature is 700 ℃, and soaking time is 4h, to get rid of the organism in biscuit.Sintering is to carry out in vacuum oven, concrete sintering mechanism is as follows: the speed with 20 ℃/min is warming up to 1000 ℃, then with the speed of 5 ℃/min, be warming up to 1760 ℃ and be incubated 20 hours, then the speed with 20 ℃/min is cooled to 1000 ℃, 1000 ℃ of following furnace cooling from 1760 ℃.Composite structure YAG/Nd:YAG pottery anneal in Si-Mo rod stove that vacuum sintering obtains, mechanism of anneal is: with 5 ℃/min, from room temperature, rise to 1450 ℃ and be incubated 20h, then from 1450 ℃ of furnace cooling.Finally with surface grinding machine and diamond paste, pottery is carried out to attenuate polished finish, obtain fine and close layered composite structure YAG/Nd:YAG crystalline ceramics.
Embodiment 5
Respectively according to embodiment 1 and two kinds of slurries of embodiment 2 preparations.Injection forming in the cylindrical die that the slurry that embodiment 2 is made is 20mm at internal diameter first at 25 ℃ of dry 24h, then at 65 ℃ of dry 10h, is peeled off and is obtained columniform biscuit of ceramics from mould.This biscuit of ceramics is put in the middle of the cylindrical die that internal diameter is 50mm, the slurry that embodiment 1 is made injects columniform biscuit of ceramics around, first, at 25 ℃ of dry 24h, then, at 70 ℃ of dry 10h, from mould, peel off the biscuit of ceramics that obtains having nucleocapsid structure.Then according to the successively pre-treatment in retort furnace of the technique of embodiment 5, vacuum sintering, annealing and polished finish, finally obtain the fine and close YAG/Nd:YAG crystalline ceramics with nucleocapsid structure.
Embodiment 6
α-the Al that is 300nm by 25.3629g median size
2o
3powder, 33.8715g median size is the Y of 3 μ m
2o
3powder, 0.1900g median size is the Cr of approximately 1 μ m
2o
3powder, 0.4457g tetraethoxy (TEOS), 0.0475g calcium oxide (CaO) powder and 0.0895g polyacrylic acid (PAA) are put into high purity aluminium oxide ball grinder, add high purity aluminium oxide abrading-ball 200g, dehydrated alcohol 35ml, then after ball milling mixing 10h, add after 0.1188g acrylic resin, 0.0594g phthalandione dibutylester (DBP) and 0.0297g organic silicon modified by polyether, continue ball milling 2h, obtain injection forming ceramic size.The slurry making is carried out in glassware to injection forming, the biscuit after slip casting, first at 25 ℃ of dry 24h, then, at 65 ℃ of dry 10h, is peeled off from mould, obtains the biscuit of ceramics that thickness is about 4mm.The biscuit of ceramics of preparation carries out preheating in retort furnace: temperature rise rate is 5 ℃/min, and calcined temperature is 600 ℃, and soaking time is 4h, to get rid of the organism in biscuit.Sintering is to carry out in vacuum oven, concrete sintering mechanism is as follows: the speed with 20 ℃/min is warming up to 1000 ℃, then the speed with 5 ℃/min heats up 1400 ℃, then with the speed of 2 ℃/min, be warming up to 1760 ℃ and be incubated 50 hours, then the speed with 20 ℃/min is cooled to 1000 ℃, 1000 ℃ of following furnace cooling from 1760 ℃.The ceramics sample that vacuum sintering obtains is anneal in Si-Mo rod stove, and mechanism of anneal is: with 5 ℃/min, from room temperature, rise to 1450 ℃ and be incubated 20h, then from 1450 ℃ of furnace cooling.Finally with surface grinding machine with pottery is carried out to attenuate to diamond paste and polishing obtains 0.5at%Cr:YAG crystalline ceramics.
Embodiment 7
α-the Al that is 300nm by 25.3629g median size
2o
3powder, 33.5328g median size is the Y of 3 μ m
2o
3powder, 0.1900g median size is about the Cr of 1 μ m
2o
3powder, 0.5911g median size is about the Yb of 5 μ m
2o
3powder, 0.0298g calcium oxide (CaO) powder, 0.3581g tetraethoxy (TEOS) and 0.0597g menhaden fish oil (MFO) are put into high purity aluminium oxide ball grinder, add high purity aluminium oxide abrading-ball 200g, dehydrated alcohol 36ml, then, after ball milling mixing 10h, adds after 0.0597g polyvinyl butyral acetal (PVB), 0.0895g polyoxyethylene glycol (PEG) and 0.0298g organic silicon modified by polyether, continue ball milling 2h, obtain injection forming ceramic size.The slurry making is carried out in glassware to injection forming, the biscuit after slip casting, first at 25 ℃ of dry 24h, then, at 65 ℃ of dry 10h, is peeled off from mould, obtains the biscuit of ceramics that thickness is about 4mm.The biscuit of ceramics of preparation carries out preheating in retort furnace: temperature rise rate is 5 ℃/min, and calcined temperature is 600 ℃, and soaking time is 1h, to get rid of the organism in biscuit.Sintering is to carry out in vacuum oven, concrete sintering mechanism is as follows: the speed with 20 ℃/min is warming up to 1000 ℃, then the speed with 5 ℃/min heats up 1400 ℃, then with the speed of 2 ℃/min, be warming up to 1770 ℃ and be incubated 30 hours, then the speed with 20 ℃/min is cooled to 1000 ℃, 1000 ℃ of following furnace cooling from 1770 ℃.The ceramics sample that vacuum sintering obtains is anneal in Si-Mo rod stove, and mechanism of anneal is: with 5 ℃/min, from room temperature, rise to 1500 ℃ and be incubated 20h, then from 1500 ℃ of furnace cooling.Finally with surface grinding machine with pottery is carried out to attenuate to diamond paste and polishing obtains 0.5at%Cr, 1.0at%Yb:YAG crystalline ceramics.
Embodiment 8
Take YAG nano powder, 0.2250g tetraethoxy (TEOS) and the 0.0297g menhaden fish oil (MFO) that median size that 30g prepared by coprecipitation method is about 100nm and put into high purity aluminium oxide ball grinder, add high purity aluminium oxide abrading-ball 180g, dehydrated alcohol 45ml, then after ball milling mixing 10h, add after 0.1188g polyvinyl butyral acetal (PVB), 0.0594g butyl benzyl phthalate (BBP) and 0.0297g organic silicon modified by polyether, continue ball milling 2h, obtain injection forming ceramic size.The slurry making is carried out to injection forming, and the biscuit after slip casting, first at 30 ℃ of dry 24h, then, at 70 ℃ of dry 12h, is peeled off from mould, obtains the biscuit of ceramics that thickness is about 4mm.The biscuit of ceramics of preparation carries out preheating in retort furnace: temperature rise rate is 5 ℃/min, and calcined temperature is 600 ℃, and soaking time is 4h, to get rid of the organism in biscuit.Sintering is to carry out in vacuum oven, concrete sintering mechanism is as follows: the speed with 10 ℃/min is warming up to 1000 ℃, then with the speed of 2 ℃/min, be warming up to 1750 ℃ and be incubated 10 hours, then the speed with 20 ℃/min is cooled to 1000 ℃, 1000 ℃ of following furnace cooling from 1750 ℃.The YAG pottery that vacuum sintering obtains anneal in Si-Mo rod stove, mechanism of anneal is: with 5 ℃/min, from room temperature, rise to 1500 ℃ and be incubated 10h, then from 1450 ℃ of furnace cooling.Finally with surface grinding machine and diamond paste, pottery is carried out attenuate and is polished to 1mm thick, obtain fine and close YAG crystalline ceramics.
Claims (6)
1. a method of utilizing the yttrium aluminum garnet base transparent ceramic of injection forming preparation doping, comprises slurry preparation, injection forming, sintering and anneal, it is characterized in that:
(a) slurry preparation
Described slurry is non-water-based slurry, and its mass percent is: oxide ceramic powder body 40-70%, and sintering aid 0.01-1%, dispersion agent 0.005-1%, binding agent 0.01-5%, softening agent 0.01-3%, defoamer 0.005-0.5%, surplus is non-aqueous solvent; First, first by oxide ceramic powder body, non-aqueous solvent, sintering aid and the mixing of dispersion agent ball milling after 6-8 hour, then add binding agent, softening agent and defoamer, then ball milling mixing 2-4 hour;
Described non-aqueous solvent is any one or several in methyl alcohol, ethanol, ethylene glycol, acetone, butanone and dimethylbenzene;
Described dispersion agent is any in menhaden fish oil, polyacrylic acid and glyceryl ester;
Described binding agent is a kind of in polyvinyl butyral acetal and acrylic resin;
Described softening agent is any in polyoxyethylene glycol, phthalandione dibutylester and butyl benzyl phthalate;
Described defoamer is organic silicon modified by polyether;
(b) after the non-water-based slurry injection forming demoulding of being prepared by step a, adopt two steps to be dried and prepare biscuit of ceramics, the first step drying temperature is 20-40 ℃, and second step is 60-90 ℃;
(c) by the dried biscuit of ceramics of step b, first pre-treatment at 500-1200 ℃ of temperature, then at 1650-1850 ℃, vacuum sintering, vacuum tightness >10 during sintering
-3pa;
(d) goods after step c sintering are annealed in 1300-1600 ℃ of air or oxygen atmosphere.
2. by method claimed in claim 1, it is characterized in that described sintering aid is LiF, NaF, MgF
2, CaF
2, AlF
3, Li
2o, Na
2o, K
2o, CaO, MgO, B
2o
3, Ga
2o
3, Sc
2o
3, La
2o
3, SiO
2, GeO
2with in TEOS any or several.
3. by method claimed in claim 1, while it is characterized in that the ball milling described in step a, ball grinder and ball milling grinding ball material used is aluminum oxide or zirconia ceramics.
4. by method claimed in claim 1, it is characterized in that:
1. the first step time of drying is 2～48h in step (b); Second step time of drying is 2～24h;
2. in step (c), pre-treatment soaking time is 1～10h;
3. in step (c), the sintered heat insulating time is 1～200h;
4. in step (d), annealing soaking time is 2～100h.
5. by method claimed in claim 1, the moulding stock that in the step (b) described in it is characterized in that, injection forming is used is any one in glass, gypsum, pottery, metal or plastics.
6. by method claimed in claim 1, it is characterized in that described injection forming be direct once shaped prepare the biscuit of one-component or repeatedly moulding preparation there is the biscuit of the composite structure of layered composite structure, nucleocapsid structure.
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| CN103044035B (en) * | 2012-12-03 | 2017-03-15 | 云南云天化股份有限公司 | LTCC slurry and preparation method thereof |
| CN103626487A (en) * | 2013-11-26 | 2014-03-12 | 中国科学院福建物质结构研究所 | Method for preparing yttrium aluminium garnet transparent ceramic with composite structure |
| CN104557012B (en) * | 2014-12-18 | 2017-03-08 | 徐州市江苏师范大学激光科技有限公司 | A kind of Pr：The preparation method of LuAG scintillating ceramic |
| CN104844212B (en) * | 2015-05-26 | 2017-08-29 | 中国工程物理研究院化工材料研究所 | The preparation method of yttrium aluminum garnet transparent ceramic |
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| CN107473728A (en) * | 2017-09-08 | 2017-12-15 | 江苏师范大学 | The preparation method of vacuum-sintering YAG base transparent ceramics under a kind of non-silicon additive |
| CN108516818B (en) * | 2018-05-25 | 2021-03-26 | 江苏师范大学 | Method for preparing YAG transparent ceramic based on improved Isodam gel system |
| RU2705848C1 (en) * | 2018-08-07 | 2019-11-12 | Российская Федерация, от имени которой выступает ФОНД ПЕРСПЕКТИВНЫХ ИССЛЕДОВАНИЙ | Single-phase polycrystalline yttrium-aluminum garnet, activated with erbium, ytterbium, and a method for production 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 |
| CN109354497B (en) * | 2018-12-12 | 2021-06-22 | 中国工程物理研究院化工材料研究所 | Ho-doped transparent scandium oxide ceramic and preparation method thereof |
| CN110183223A (en) * | 2019-07-01 | 2019-08-30 | 深圳市丁鼎陶瓷科技有限公司 | A kind of preparation method of crystalline ceramics |
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