CN108249909A - A kind of novel method for preparing terbium aluminum garnet-base nano-powder and magneto-optic crystalline ceramics - Google Patents
A kind of novel method for preparing terbium aluminum garnet-base nano-powder and magneto-optic crystalline ceramics Download PDFInfo
- Publication number
- CN108249909A CN108249909A CN201611239053.4A CN201611239053A CN108249909A CN 108249909 A CN108249909 A CN 108249909A CN 201611239053 A CN201611239053 A CN 201611239053A CN 108249909 A CN108249909 A CN 108249909A
- Authority
- CN
- China
- Prior art keywords
- magneto
- powder
- optic
- sintering
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000011222 crystalline ceramic Substances 0.000 title claims abstract description 30
- 229910002106 crystalline ceramic Inorganic materials 0.000 title claims abstract description 30
- FNCIDSNKNZQJTJ-UHFFFAOYSA-N alumane;terbium Chemical compound [AlH3].[Tb] FNCIDSNKNZQJTJ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000011858 nanopowder Substances 0.000 title abstract description 25
- 239000000919 ceramic Substances 0.000 claims abstract description 58
- 239000000843 powder Substances 0.000 claims abstract description 58
- 239000000243 solution Substances 0.000 claims abstract description 51
- 239000002270 dispersing agent Substances 0.000 claims abstract description 25
- 150000001455 metallic ions Chemical class 0.000 claims abstract description 24
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims description 69
- 238000004448 titration Methods 0.000 claims description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 235000015895 biscuits Nutrition 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910052771 Terbium Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 239000002223 garnet Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- -1 alkene imines Chemical class 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 238000001513 hot isostatic pressing Methods 0.000 claims 1
- 238000007731 hot pressing Methods 0.000 claims 1
- 238000000975 co-precipitation Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- 238000002791 soaking Methods 0.000 description 14
- 238000003825 pressing Methods 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000013049 sediment Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012538 light obscuration Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3229—Cerium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
- C04B2235/9653—Translucent or transparent ceramics other than alumina
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Magnetic Ceramics (AREA)
Abstract
The present invention relates to a kind of novel method for preparing terbium aluminum garnet-base nano-powder and magneto-optic crystalline ceramics, the preparation method of the terbium aluminum garnet-base magneto-optic transparent ceramic powder includes：It is respectively configured containing metal ion Tb3+、Al3+、A3+、B3+Metal ion salt solution, then according to Tb3‑xAxAl5‑yByO12Stoichiometric weighs solution, uniformly obtains metallic ion mixed liquor after mixing；Metallic ion mixed liquor is added drop-wise to dropwise in the precipitant solution containing dispersant or precipitant solution is added drop-wise to dropwise in the metallic ion mixed liquor containing dispersant, be sufficiently stirred to obtain precipitated liquid；It by precipitated liquid after washing, drying, be sieved, is calcined 1~10 hour at 900~1300 DEG C, obtains the terbium aluminum garnet-base magneto-optic transparent ceramic powder.It is of low cost that the present invention uses coprecipitation also to have, and equipment is simple, is easy to more advantages such as large-scale production.
Description
Technical field
The present invention provides a kind of method for preparing terbium aluminum garnet-base nano-powder and magneto-optic crystalline ceramics, is related specifically to
Coprecipitation prepares Tb3-xAxAl5-yByO12Nano-powder, and be combined using being pre-sintered with HIP sintering as agglomerant
Skill belongs to magneto-optic crystalline ceramics preparing technical field.
Background technology
Magneto-optic memory technique has very important application in high-tech areas such as fiber optic communication, Laser Processing, computers.In recent years
Come, the development of superpower laser proposes the performance of magneto-optic memory technique higher requirement, including high Verdet constants, high optics
Quality, large scale, high heat conductance, high laser damage threshold etc..Common magneto-optic memory technique is mainly magneto-optic glass and magneto-optic in early days
Crystal.However, the thermal conductivity of magneto-optic glass is relatively low, thermal damage is easily formed, higher laser power can not be born, gradually
The requirement of magnetic-optic devices can not be met；Although magneto-optical crystal is with higher thermal conductivity, growth period is longer, ruler
It is very little to be restricted, can not meet the needs of superpower laser is to heavy caliber magneto-optic element.In recent years, the hair of ceramics processing
So that the transparence of ceramics has become reality, and continuously improving with technology, the optical quality of crystalline ceramics obtains for exhibition
Further to improve, optical property can even compare favourably with monocrystalline.Magneto-optic ceramics are based on such background and come into being,
As a kind of novel magneto-optic memory technique occurred in recent years.Magneto-optic ceramics have higher thermal conductivity, and fracture toughness is high, anti-thermal shock
Performance is good, while is easy to get larger size.Advantage in these performances meets superpower laser to magneto-optic memory technique
Performance requirement so that magneto-optic ceramics have good application prospect.
Terbium aluminium garnet (Tb3Al5O12, hereinafter referred to as TAG) and in visible ray and near infrared band there is higher optics
Transmitance and larger Verdet constants, be it is current it has been recognized that in the optimal magneto-optic memory technique of this wave band.But
Due to the non-uniform melting characteristic of TAG, crystal preparation is very difficult, so not being widely applied always.And the system of ceramics
Standby technology is it is possible to prevente effectively from non-uniform melting problem, but also the magneto-optical property that TAG monocrystalline can be kept excellent, therefore TAG
Magneto-optic crystalline ceramics has good application prospect.In addition, by the part such as Ce, Pr, Nd, Gd, Tm, Yb, Lu or Y substitution Tb,
Or with the part such as Sc, Ga substitution Al, it can equally obtain the Tb with high optical transmittance and high Verdet constants3- xAxAl5-yByO12(wherein, A Ce, Pr, Nd, Gd, Tm, Yb, Lu or Y；B is Sc or Ga；The value range of x and y is：0≤x ＜
3,0≤y ＜ 5) magneto-optic crystalline ceramics.
Tb at present3-xAxAl5-yByO12The preparation of magneto-optic crystalline ceramics is passed through mainly or using solid reaction process
Tb4O7、Al2O3, ball milling mixing is uniform, then passes through high temperature long-time solid phase reaction between the oxide of A and the oxide powder of B
It is prepared by sintering.This method is since material powder particle size used is big and particle diameter distribution is wide, so sintering activity is poor, simultaneously
Impurity is readily incorporated in mechanical milling process, ceramic optical quality is very restricted.
Invention content
For this purpose, prepare the preferable Tb of dispersion performance present invention firstly provides a kind of3-xAxAl5-yByO12The side of nano-powder
Method, the present invention also provides a kind of Tb3-xAxAl5-yByO12The preparation method of magneto-optic crystalline ceramics.
On the one hand, the present invention provides the method for preparing terbium aluminum garnet-base magneto-optic transparent ceramic powder, the terbium aluminium stones
The composition of garnet base magneto-optic transparent ceramic powder is:Tb3-xAxAl5-yByO12, wherein A for Ce, Pr, Nd, Gd, Tm, Yb, Lu or
Y, B be Sc or Ga, 0≤x ＜ 3,0≤y ＜ 5, including：
It is respectively configured containing metal ion Tb3+、Al3+、A3+、B3+Metal ion salt solution, then according to Tb3-xAxAl5-yByO12
Stoichiometric weighs solution, uniformly obtains metallic ion mixed liquor after mixing；
Metallic ion mixed liquor is added drop-wise to dropwise in the precipitant solution containing dispersant or drips precipitant solution dropwise
It is added in the metallic ion mixed liquor containing dispersant, is sufficiently stirred to obtain precipitated liquid；
By precipitated liquid after washing, drying, be sieved, calcined 1~10 hour at 900~1300 DEG C, obtain the terbium aluminium stone
Garnet base magneto-optic transparent ceramic powder.
The Tb that the present invention is prepared using coprecipitation3-xAxAl5-yByO12Powder is pure phase, and no second phase exists, and
Dispersion performance is preferable, and particle size is tiny, average particle size particle size 88nm, has preferable sintering activity, it is saturating to be conducive to the later stage
The sintering of bright ceramics.In addition, titration mode is different, then dispersant addition manner is different.If titration mode (will be precipitated using positive drop
Agent solution is added drop-wise to metallic ion mixed liquor dropwise), then dispersant is added in metallic ion mixed liquor, if titration side
Formula is anti-drop (metallic ion mixed liquor is added drop-wise to precipitant solution dropwise), then dispersant is added to precipitant solution
In.
Preferably, by metal oxide be dissolved in salpeter solution be prepared metal ion salt solution or by metal salt it is molten
Metal ion salt solution is prepared in deionized water in solution.Wherein metal oxide be Tb, Al, A, the oxide of B.Metal salt can
For Tb, Al, A, the metal salt of B, such as the nitrate of Tb, Al, A, B, hydrochloride, sulfate etc..
Preferably, Al in the metallic ion mixed liquor3+A concentration of 0.05~2mol/L.
The precipitating reagent is NH4HCO3, at least one of ammonium hydroxide and urea, a concentration of the 0.01 of the precipitant solution
~5mol/L.
Preferably, in titration process, the speed being added dropwise dropwise is 1~40ml/ minutes, the dosage and metal ion of precipitating reagent
(Tb3+, Al3+, A3+, B3+The sum of) molar ratio be (2~10)：1.In just drop coprecipitation process, with the raising of pH, Al from
Son precipitates first, forms aluminium core, and induction Tb ion attachment nucleation ultimately forms co-precipitation；In anti-drop coprecipitation process, body
It is pH relatively very high, can realizes that the two moment reaches hypersaturated state simultaneously and settled jointly from solution system.Cause
This, Tb, Al Elemental redistribution are more uniform in the anti-presoma for dripping co-precipitation mode and obtaining, and are a kind of preferred modes.Work as precipitation
When the molar ratio of agent and metal ion dosage is relatively low, may cause Al ions completely precipitation and Tb ions do not precipitate completely, most
Tb/Al is less than stoichiometric ratio 0.6 in whole powder constituents；And precipitating reagent and metal ion dosage it is mole higher when, precipitation
Al (OH) in product3It dissolves, and Tb/Al can be caused to be more than stoichiometric ratio 0.6, therefore precipitating reagent and metal ion dosage
Molar ratio value should control in a rational section ((2~10)：1) in.
Preferably, the dispersant is (NH4)2SO4, polyethyleneimine, ammonium polyacrylate, ammonium citrate and polyethylene glycol
At least one of, the dispersant and Al in metallic ion mixed liquor3+Molar ratio be (0.1~5)：1.Dispersant draws
Enter the reunion that can be reduced between powder granule, improve dispersion performance.When dispersant is relatively low, it is impossible to effectively weaken powder
Contact and collision between grain, reunion still have；When dispersant is higher, more impurity can be introduced, influence final powder
The purity of body.General Decentralized agent and Al3+Molar ratio close to 1 when, dispersion effect is preferable.
Preferably, after titration, precipitated liquid is aged at 5~30 DEG C no more than 30 hours.Without ageing in the present invention
Step can equally obtain precipitated liquid really.But it is also not merely to make reaction more abundant to use ageing, digestion time can be right
Ingredient, pattern, dispersion performance of final powder etc. have an impact.When digestion time is shorter, metal ion solution is anti-with precipitating reagent
Should be insufficient, cause the decline of yield；When digestion time is long, the segregation of component and the separation of phase can be caused, reduce presoma
Uniformity, therefore digestion time answers optimum selecting (be no more than 30 hours be advisable).
Preferably, sediment is washed using deionized water and absolute ethyl alcohol.
Preferably, by 10-120h dry at the sediment after washing in an oven 20-80 DEG C.
Preferably, dried powder is crossed into 100-250 mesh sieve.
On the other hand, the present invention also provides a kind of terbium aluminum garnet-base magneto-optic crystalline ceramics powder prepared according to the above method
Body.
In another aspect, the present invention also provides a kind of method for preparing terbium aluminum garnet-base magneto-optic crystalline ceramics, including：
Biscuit of ceramics is made in above-mentioned terbium aluminum garnet-base magneto-optic transparent ceramic powder；
After gained biscuit of ceramics is pre-sintered, HIP sintering is handled 1~50 hour at 1200~1700 DEG C, is obtained
To final ceramics sample.
Preferably, the mode of the pre-sintering is vacuum-sintering, one kind in hot pressed sintering, oxygen atmosphere sintering；
The temperature of the vacuum-sintering is 1400~1700 DEG C, and the time is 1~50 hour, and vacuum degree is better than 10-2Pa；
The temperature of the hot pressed sintering is 1200~1600 DEG C, and the time is 1~50 hour, and pressure is 50~200Mpa；
The temperature of the oxygen atmosphere sintering is 1200~1700 DEG C, and the time is 1~50 hour.
Preferably, the preparation method of the biscuit of ceramics includes dry-pressing formed rear isostatic cool pressing or direct moulding by casting.
Preferably, the pressure of the HIP sintering processing is 20~250MPa.
The present invention according to material stoichiometric ratio preparing metal Ar ion mixing solution, while prepare it is certain density heavy
Shallow lake agent solution.Metallic ion mixed liquor is added drop-wise to dropwise in precipitant solution or precipitant solution is added drop-wise to metal dropwise
It in Ar ion mixing solution, is sufficiently stirred, then ageing forms precipitated liquid.A certain amount of dispersant is added in before titration, in mother liquor；It is heavy
Shallow lake liquid obtains presoma powder after washing, drying, be sieved.Presoma powder is calcined in air to obtain Tb3-xAxAl5- yByO12Nano-powder.Biscuit of ceramics is made in powder after calcining, and is pre-sintered.Ceramics sample after pre-sintering carries out again
HIP sintering processing, obtains final ceramics sample.
Compared with solid phase method, it is of low cost that the present invention uses coprecipitation also to have, and equipment is simple, is suitble to prepare large scale
And it is easy to various advantages such as large-scale production.Meanwhile with reference to follow-up HIP sintering technique to the Ceramic Like of pre-sintering
Product carry out the discharge that post processing is conducive to ceramic internal residual stomata, so as to improve the optical quality of crystalline ceramics.
Description of the drawings
Fig. 1 is Tb prepared by embodiment 13Al5O12The XRD spectrum of nano-powder；
Fig. 2 is Tb prepared by embodiment 13Al5O12The SEM photograph of nano-powder；
Fig. 3 is Tb prepared by embodiment 13Al5O12The photo in kind of ceramics；
Fig. 4 is Tb prepared by embodiment 13Al5O12The transmittance curve of ceramic (thickness 1.9mm)；
Fig. 5 is with Tb4O7And Al2O3SEM photograph for mixed powder after raw material ball milling.
Specific embodiment
It is further illustrated the present invention below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
Present invention offer first passes through coprecipitation and the preferable Tb of dispersion performance is prepared3-xAxAl5-yByO12Nano-powder,
It is combined again using pre-sintering and HIP sintering and Tb is prepared as sintering process3-xAxAl5-yByO12Magneto-optic is transparent
Ceramics.This method can obtain the good material powder of sintering activity, with reference to follow-up HIP sintering process advan in ceramics
The discharge of portion's Residual Pores, so as to improve the optical quality of crystalline ceramics.The present invention have technological process simple, safety and environmental protection,
The advantages that being easy to large-scale production, the Tb prepared3-xAxAl5-yByO12Magneto-optic crystalline ceramics has in visible and near infrared band
Higher optical transmittance and higher Verdet constants.
Illustrate to following exemplary the preparation method of terbium aluminum garnet-base magneto-optic transparent ceramic powder provided by the invention.
Prepare certain density Tb3+, Al3+, A3+, B3+Metal ion salt solution using the method for chemical analysis, is marked respectively
Make the concentration of each metal ion.Wherein metal ion salt solution can be dissolved in the preparation of high pure nitric acid solution with metal oxide,
Also can commercial metals salt directly be dissolved in deionized water to prepare.
According to Tb3-xAxAl5-yByO12Stoichiometric measures a certain amount of metal ion salt solution and is uniformly mixed to get
Metallic ion mixed liquor.Al in the metallic ion mixed liquor3+A concentration of 0.05-2mol/L.Before titration in mother liquor
A certain amount of dispersant is added in, (NH can be selected in dispersant4)2SO4, polyethyleneimine, ammonium polyacrylate, ammonium citrate and poly- second
Glycol etc..The dispersant and Al in metallic ion mixed liquor3+Molar ratio can be 0.1-5.If positive drop, mother liquor is metal
Ar ion mixing solution；If anti-drop, mother liquor is precipitant solution.
Prepare certain density precipitant solution simultaneously.The precipitating reagent can be NH4HCO3, ammonium hydroxide and urea etc., in solution
The concentration of precipitating reagent can be 0.01-5mol/L.
Above-mentioned metallic ion mixed liquor is added drop-wise to certain drop speed in precipitant solution dropwise or precipitating reagent is molten
Liquid is added drop-wise in metallic ion mixed liquor and is sufficiently stirred with certain drop speed dropwise, obtains precipitated liquid.Wherein rate of titration
Can be 1-40ml/min.Further the reaction was complete by ageing 0-30h at 5-30 DEG C after titration.In titration process, precipitation
The molar ratio of agent and metal ion is defined as R values, and R values are used for representing the dosage of precipitating reagent, and R values are 2-10.
By precipitated liquid by washing, drying, sieving, calcining, the terbium aluminum garnet-base magneto-optic transparent ceramic powder is obtained.
It specifically includes：Sediment is washed using deionized water and absolute ethyl alcohol.By the 20-80 in an oven of the sediment after washing
DEG C dry 10-120h.Then dried powder is crossed 100-250 mesh to sieve to obtain presoma powder.By presoma powder in sky
900-1300 DEG C of heat preservation 1-10h calcines to obtain terbium aluminum garnet-base magneto-optic transparent ceramic powder (Tb in gas3-xAxAl5-yByO12It receives
Rice flour body).
The present invention prepares Tb using coprecipitation3-xAxAl5-yByO12Nano-powder, obtained powder dispersity can be preferable,
Particle size is tiny, large specific surface area, and with preferable sintering activity, is conducive to the sintering of later stage crystalline ceramics.This method
Also have of low cost, equipment is simple, is suitble to prepare large scale crystalline ceramics, it is easy to accomplish the advantages that large-scale production.
The terbium aluminum garnet-base magneto-optic crystalline ceramics that the present invention is prepared has higher light in Visible-to-Near InfaRed wave band
Transmitance and higher Verdet constants are learned, and there is simple technological process, safety and environmental protection, be easy to large-scale production.
Illustrate to following exemplary the preparation method of terbium aluminum garnet-base magneto-optic crystalline ceramics provided by the invention.
By gained Tb3-xAxAl5-yByO12Isostatic cool pressing or direct moulding by casting obtain ceramics after nano-powder is dry-pressing formed
Biscuit.
By gained biscuit of ceramics, then it is pre-sintered.Pre-sintering can obtain consistency height, even structure, exist less
The ceramics sample of Residual Pores is measured, is conducive to the compression and discharge of stomata during later stage HIP sintering, to improve ceramics
Optical quality.Pre-sintering mode can be one kind in vacuum-sintering, hot pressed sintering, oxygen atmosphere sintering.Wherein vacuum-sintering
Holding temperature can be 1400-1700 DEG C, and soaking time can be 1-50h, and vacuum degree is better than 10-2Pa.The holding temperature of hot pressed sintering
It can be 1200-1600 DEG C, soaking time can be 1-50h, and the pressure applied to ceramic body can be 50-200Mpa.Oxygen atmosphere is burnt
The holding temperature of knot can be 1200-1700 DEG C, and soaking time can be 1-50h.
Ceramics sample after pre-sintering is subjected to HIP sintering processing again, it is saturating to obtain the terbium aluminum garnet-base magneto-optic
Bright ceramics.Wherein the holding temperature of HIP sintering can be 1200-1700 DEG C, soaking time can be 1-50h, furnace gas pressure
Power can be 50-250MPa.
The example for preparing terbium aluminum garnet-base magneto-optic crystalline ceramics as one, is as follows：1) it prepares certain dense
The Tb of degree3+, Al3+, A3+, B3+Metal ion salt solution using the method for chemical analysis, calibrates the dense of each metal ion respectively
Degree.2) according to Tb3-xAxAl5-yByO12Stoichiometric measures a certain amount of metal ion salt solution and uniformly mixes.Match simultaneously
Make certain density precipitant solution.3) above-mentioned metallic ion mixed liquor is added drop-wise to dropwise with certain drop speed a certain amount of
It is added drop-wise in metallic ion mixed liquor, is sufficiently stirred dropwise in precipitant solution or by precipitant solution with certain drop speed,
The a period of time of ageing at a certain temperature forms precipitated liquid after titration.A certain amount of dispersion is added in mother liquor before titration
Agent.4) precipitated liquid obtains presoma powder after washing, drying, be sieved, and presoma powder is calcined to obtain in air
Tb3-xAxAl5-yByO12Nano-powder.5) by Tb3-xAxAl5-yByO12Biscuit of ceramics is made in nano-powder, then carries out biscuit pre-
Sintering, the ceramics sample after pre-sintering carry out HIP sintering processing, obtain final ceramics sample again.
The present invention carries out the ceramics sample of pre-sintering post processing by HIP sintering technique and is conducive to inside ceramics
The discharge of Residual Pores, so as to improve the optical quality of crystalline ceramics, the Tb being sintered3-xAxAl5-yByO12The transparent pottery of magneto-optic
Porcelain has higher optical transmittance and higher Verdet constants in visible and near infrared band.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, it is impossible to be 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 all belong to the scope of protection 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 the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.
Embodiment 1
By Tb3Al5O12Chemical composition measures the Tb (NO of a concentration of 1.0226mol/L of 88.01ml respectively3)3Solution and 75.70ml
Al (the NO of a concentration of 1.9816mol/L3)3Solution is poured into 800ml beakers and is uniformly mixed, and is eventually adding deionized water constant volume and is arrived
500ml, at this time Al in solution3+A concentration of 0.3mol/L.Prepare the NH of a concentration of 1.5mol/L of 640ml4HCO3Precipitating reagent is molten
Liquid (R=4), and add in the (NH of 19.8209g4)2SO4As dispersant, (NH at this time4)2SO4With Al3+Molar ratio be 1.It will be golden
Belong to mixed solution and NH is added drop-wise to the drop speed of 20ml/min dropwise4HCO3In precipitating reagent and it is sufficiently stirred.At 25 DEG C after titration
Lower ageing 1h.Slurry after ageing is washed with deionized 4 times, and absolute ethyl alcohol washs 2 times, and the sediment after washing is in an oven
For 24 hours, dried powder crosses 200 mesh sieve, obtains presoma powder for 70 DEG C of dryings.Presoma powder is protected for 1100 DEG C in air
Warm 4h calcines to obtain Tb3Al5O12Nano-powder.By Tb3Al5O12Isostatic cool pressing after nano-powder is dry-pressing formed, then in vacuum drying oven
Interior pre-sintering, the holding temperature of vacuum-sintering is 1700 DEG C, soaking time 20h, and vacuum degree is better than 1 × 10-3Pa.After pre-sintering
Ceramics sample carry out HIP sintering processing again, the holding temperature of HIP sintering is 1700 DEG C, soaking time 3h,
Furnace inner gas pressure is 200MPa.Most sample twin polishing obtains Tb at last3Al5O12Magneto-optic crystalline ceramics.Fig. 1 is of the invention real
Apply the Tb prepared in example 13Al5O12The XRD spectrum of nano-powder, it can be seen that TAG phases are contained only in powder, without the second phase
In the presence of.Fig. 2 is the Tb prepared in embodiment 13Al5O12The SEM photograph of nano-powder, it can be seen that the dispersion performance of powder compared with
It is good, without apparent agglomeration, average grain diameter 88nm.Its specific surface area is measured as 11.13m by BET test methods2/
g.Fig. 3 is the Tb prepared in embodiment 13Al5O12The photo in kind of magneto-optic crystalline ceramics, the English that can be clearly apparent under sample
Word is female, the Tb illustrated3Al5O12Ceramics have certain optical transmittance.Fig. 4 is the Tb prepared in embodiment 13Al5O12
The transmittance curve (thickness 1.9mm) of magneto-optic crystalline ceramics, wherein the absorption peak at 486nm corresponds to Tb3+Ion7F6→5D4Transition, 600-1600nm wave bands transmitance be more than 25%.Verdet using light extinction method test sample is normal
Number, selection light source are He-Ne laser (wavelength 632.8nm), and test carries out at room temperature, and magnetic field intensity 1.27T is final to calculate
Verdet constant of the ceramics sample at 632.8nm is obtained as -179.7radT-1·m-1。
Embodiment 2
By (Tb0.997Ce0.003)3Al5O12Chemical composition measures the Tb (NO of a concentration of 1.0226mol/L of 87.75ml respectively3)3It is molten
Ce (the NO of a concentration of 1.0120mol/L of liquid, 0.27ml3)3Al (the NO of solution and a concentration of 1.9816mol/L of 75.70ml3)3It is molten
Liquid is poured into 800ml beakers and is uniformly mixed, and is eventually adding deionized water constant volume to 500ml, at this time Al in solution3+It is a concentration of
0.3mol/L.The ammonia spirit (R=5) of a concentration of 1.5mol/L of 800ml is prepared, and adds in the ammonium citrate conduct of 47.0594g
Dispersant, at this time ammonium citrate and Al3+Molar ratio be 1.5.Metal mixed solution is added dropwise dropwise with the drop speed of 15ml/min
Into ammonia spirit and it is sufficiently stirred.After titration 1h is aged at 25 DEG C.Slurry after ageing is washed with deionized 4
Secondary, absolute ethyl alcohol washs 2 times, and for 24 hours, dried powder crosses 200 mesh sieve to the sediment after washing, obtains for 70 DEG C of dryings in an oven
To presoma powder.By presoma powder, 1100 DEG C of heat preservation 4h calcine to obtain (Tb in air0.997Ce0.003)3Al5O12Nano powder
Body.By (Tb0.997Ce0.003)3Al5O12Isostatic cool pressing after nano-powder is dry-pressing formed, then carries out hot pressed sintering, hot pressed sintering
Holding temperature is 1680 DEG C, soaking time 10h, applies the pressure of 100MPa to green body.Ceramics sample after pre-sintering again into
The processing of row HIP sintering, the holding temperature of HIP sintering is 1600 DEG C, soaking time 3h, and furnace inner gas pressure is
200MPa.Most sample twin polishing obtains (Tb at last0.997Ce0.003)3Al5O12Magneto-optic crystalline ceramics.
Embodiment 3
By (Tb0.95Y0.05)3Al5O12Chemical composition measures the Tb (NO of a concentration of 1.0226mol/L of 83.61ml respectively3)3It is molten
Y (the NO of a concentration of 1.0221mol/L of liquid, 4.40ml3)3Al (the NO of solution and a concentration of 1.9816mol/L of 75.70ml3)3It is molten
Liquid is poured into 2L beakers and is uniformly mixed, and adds in the (NH of 19.8209g4)2SO4As dispersant, (NH at this time4)2SO4With Al3+
Molar ratio for 1, be eventually adding deionized water constant volume and cause Al in solution to 500ml3+A concentration of 0.3mol/L.It prepares
The NH of a concentration of 1.5mol/L of 640ml4HCO3Precipitant solution (R=4).By NH4HCO3Precipitating reagent with the drop speed of 20ml/min by
It is added drop-wise in metal mixed solution and is sufficiently stirred.After titration 1h is aged at 25 DEG C.Slurry after ageing spend from
Sub- water washing 4 times, absolute ethyl alcohol wash 2 times, the sediment after washing in an oven 70 DEG C of dryings for 24 hours, dried powder mistake
200 mesh sieve, and obtain presoma powder.By presoma powder, 1100 DEG C of heat preservation 4h calcine to obtain (Tb in air0.95Y0.05)3Al5O12Nano-powder.By (Tb0.95Y0.05)3Al5O12Nano-powder moulding by casting obtains biscuit of ceramics, then in vacuum drying oven
It is pre-sintered, the holding temperature of vacuum-sintering is 1700 DEG C, soaking time 10h, and vacuum degree is better than 1 × 10-3Pa.After pre-sintering
Ceramics sample carries out HIP sintering processing again, and the holding temperature of HIP sintering is 1650 DEG C, soaking time 3h, stove
Interior gas pressure is 200MPa.Most sample twin polishing obtains (Tb at last0.95Y0.05)3Al5O12Magneto-optic crystalline ceramics.
Embodiment 4
By Tb3(Al0.9Ga0.1)5O12Chemical composition measures the Tb (NO of a concentration of 1.0226mol/L of 88.01ml respectively3)3Solution,
Ga (the NO of a concentration of 1.0218mol/L of 14.68ml3)3Al (the NO of solution and a concentration of 1.9816mol/L of 68.13ml3)3It is molten
Liquid is poured into 800ml beakers and is uniformly mixed, and is eventually adding deionized water constant volume to 500ml, at this time Al in solution3+It is a concentration of
0.27mol/L.Prepare the NH of a concentration of 1mol/L of 960ml4HCO3Precipitant solution (R=4), and add in 26.7582g's
(NH4)2SO4As dispersant, (NH at this time4)2SO4With Al3+Molar ratio be 1.5.By metal mixed solution with 20ml/min's
Drop speed is added drop-wise to NH dropwise4HCO3In precipitating reagent and it is sufficiently stirred.After titration 4h is aged at 25 DEG C.Slurry after ageing
It is washed with deionized 4 times, absolute ethyl alcohol washs 2 times, and 70 DEG C of dryings are for 24 hours, dried in an oven for the sediment after washing
Powder crosses 200 mesh sieve, obtains presoma powder.By presoma powder, 1200 DEG C of heat preservation 4h calcine to obtain Tb in air3
(Al0.9Ga0.1)5O12Nano-powder.By Tb3(Al0.9Ga0.1)5O12Isostatic cool pressing after nano-powder is dry-pressing formed, then in oxygen
It is sintered under atmosphere, holding temperature is 1670 DEG C, soaking time 5h.Ceramics sample after pre-sintering is carried out at HIP sintering again
Reason, the holding temperature of HIP sintering is 1600 DEG C, soaking time 3h, furnace inner gas pressure 200MPa.Most sample at last
Product twin polishing obtains Tb3(Al0.9Ga0.1)5O12Magneto-optic crystalline ceramics.
Embodiment 5
By (Tb0.95Lu0.05)3(Al0.6Sc0.4)5O12Chemical composition measures the Tb of a concentration of 1.0226mol/L of 83.61ml respectively
(NO3)3Lu (the NO of a concentration of 1.0216mol/L of solution, 4.40ml3)3The Sc of a concentration of 1.0215mol/L of solution, 58.74ml
(NO3)3Al (the NO of solution and a concentration of 1.9816mol/L of 45.42ml3)3Solution is poured into 800ml beakers and is uniformly mixed, most
Deionized water constant volume is added in afterwards to 500ml, at this time Al in solution3+A concentration of 0.18mol/L.It is a concentration of to prepare 640ml
The NH of 1.5mol/L4HCO3Precipitant solution (R=4), and add in the (NH of 14.2710g4)2SO4As dispersant, at this time
(NH4)2SO4With Al3+Molar ratio be 1.2.Metal mixed solution is added drop-wise to NH dropwise with the drop speed of 20ml/min4HCO3It is heavy
In the agent of shallow lake and it is sufficiently stirred.After titration 1h is aged at 25 DEG C.Slurry after ageing is washed with deionized 4 times, anhydrous
Ethyl alcohol washs 2 times, and for 24 hours, dried powder crosses 200 mesh sieve to the sediment after washing, obtains forerunner for 70 DEG C of dryings in an oven
Body powder.By presoma powder, 1100 DEG C of heat preservation 4h calcine to obtain (Tb in air0.95Lu0.05)3(Al0.6Sc0.4)5O12Nanometer
Powder.By (Tb0.95Lu0.05)3(Al0.6Sc0.4)5O12Isostatic cool pressing after nano-powder is dry-pressing formed, the then pre-burning in vacuum drying oven
Knot, the holding temperature of vacuum-sintering is 1700 DEG C, soaking time 15h, and vacuum degree is better than 1 × 10-3Pa.Ceramics after pre-sintering
Sample carries out HIP sintering processing again, and the holding temperature of HIP sintering is 1680 DEG C, soaking time 3h, gas in stove
Body pressure is 200MPa.Most sample twin polishing obtains (Tb at last0.95Lu0.05)3(Al0.6Sc0.4)5O12Magneto-optic crystalline ceramics.
Comparative example
By Tb3Al5O12Chemical composition weighs the Tb of 43.1795g respectively4O7(purity 99.99%, 1 μm of grain size) and 19.6275g
Al2O3(purity 99.99%, grain size 300nm) is mixed.Material powder：α-Al2O3, upper Haifeng county standing grain Ceramic Corporation, purity
99.99%；Tb4O7, Shanghai allosaurus new material company, purity 99.99%.Powder after mixing is added into 38ml alcohol ball milling 12h, is starched
Material is dry, crosses after 200 mesh sieve and calcines 4h organics removals at 600 DEG C, obtains final mixed powder.Fig. 5 is with Tb4O7And Al2O3
For the SEM photograph of mixed powder after raw material ball milling, there are apparent powder reuniting phenomenons for gained mixed powder as can be known from Fig. 5.
The specific surface area of gained mixed powder is 4.44m2/ g far below the powder that the present invention synthesizes, illustrates that its dispersion performance is poor, no
It is sintered conducive to the later stage.
The present invention can realize element uniformly mixing on atomic level using the powder of Co deposited synthesis while obtain
The powder granule that arrives is tiny, large specific surface area, good dispersion, has good sintering activity, therefore compare with solid reaction process
It is more advantageous.
Claims (10)
1. a kind of method for preparing terbium aluminum garnet-base magneto-optic transparent ceramic powder, the terbium aluminum garnet-base magneto-optic crystalline ceramics
The composition of powder is: Tb3-xAxAl5-yByO12, wherein A is Ce, Pr, Nd, Gd, Tm, Yb, Lu or Y, and B is Sc or Ga, 0≤x ＜
3,0≤y ＜ 5, which is characterized in that including：
It is respectively configured containing metal ion Tb3+、Al3+、A3+、B3+Metal ion salt solution, then according to Tb3-xAxAl5-yByO12
Stoichiometric weighs solution, uniformly obtains metallic ion mixed liquor after mixing；
Metallic ion mixed liquor is added drop-wise to dropwise in the precipitant solution containing dispersant or drips precipitant solution dropwise
It is added in the metallic ion mixed liquor containing dispersant, is sufficiently stirred to obtain precipitated liquid；
By precipitated liquid after washing, drying, be sieved, calcined 1~10 hour at 900~1300 DEG C, obtain the terbium aluminium stone
Garnet base magneto-optic transparent ceramic powder.
2. according to the method described in claim 1, it is characterized in that, metal oxide is dissolved in salpeter solution is prepared gold
Belong to ion salt solution or metal ion salt solution is prepared in deionized water in dissolving metal salts.
3. method according to claim 1 or 2, which is characterized in that Al in the metallic ion mixed liquor3+It is a concentration of
0.05~2 mol/L.
4. method according to any one of claim 1-3, which is characterized in that the precipitating reagent is NH4HCO3, ammonium hydroxide and
At least one of urea, a concentration of 0.01~5 mol/L of the precipitant solution.
5. according to the described method of any one of claim 1-4, which is characterized in that in titration process, the speed that is added dropwise dropwise
It it is 1~40 ml/ minutes, the dosage of precipitating reagent and the molar ratio of metal ion are（2~10）：1.
6. method according to any one of claims 1-5, which is characterized in that the dispersant is (NH4)2SO4, poly- second
At least one of alkene imines, ammonium polyacrylate, ammonium citrate and polyethylene glycol, the dispersant and metallic ion mixed liquor
Middle Al3+Molar ratio be（0.1~5）：1.
7. according to the method described in any one of claim 1-6, which is characterized in that after titration, by precipitated liquid 5~30
Ageing is no more than 30 hours at DEG C.
8. a kind of terbium aluminum garnet-base magneto-optic transparent ceramic powder prepared according to any one of claim 1-7 the methods.
A kind of 9. method for preparing terbium aluminum garnet-base magneto-optic crystalline ceramics, which is characterized in that including：
Biscuit of ceramics is made in terbium aluminum garnet-base magneto-optic transparent ceramic powder according to any one of claims 8；
After gained biscuit of ceramics is pre-sintered, then at hot isostatic pressing pressure at 1200~1700 DEG C to be burnt under 20~250MPa
Knot processing 1~50 hour, obtains final ceramics sample.
10. according to the method described in claim 9, it is characterized in that, the mode of the pre-sintering is vacuum-sintering, hot pressing is burnt
One kind in knot, oxygen atmosphere sintering；
The temperature of the vacuum-sintering is 1400~1700 DEG C, and the time is 1~50 hour, and vacuum degree is better than 10-2 Pa；
The temperature of the hot pressed sintering is 1200~1600 DEG C, and the time is 1~50 hour, and pressure is 50~200 Mpa；
The temperature of the oxygen atmosphere sintering is 1200~1700 DEG C, and the time is 1~50 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611239053.4A CN108249909A (en) | 2016-12-28 | 2016-12-28 | A kind of novel method for preparing terbium aluminum garnet-base nano-powder and magneto-optic crystalline ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611239053.4A CN108249909A (en) | 2016-12-28 | 2016-12-28 | A kind of novel method for preparing terbium aluminum garnet-base nano-powder and magneto-optic crystalline ceramics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108249909A true CN108249909A (en) | 2018-07-06 |
Family
ID=62718986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611239053.4A Pending CN108249909A (en) | 2016-12-28 | 2016-12-28 | A kind of novel method for preparing terbium aluminum garnet-base nano-powder and magneto-optic crystalline ceramics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108249909A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133922A (en) * | 2018-09-28 | 2019-01-04 | 东北大学 | Codope rare earth ion garnet structure light functional ceramic powder and preparation method thereof |
| CN111138192A (en) * | 2020-01-03 | 2020-05-12 | 上海应用技术大学 | Vacuum hot-pressing preparation method of lutetium terbium oxide magneto-optical transparent ceramic |
| CN111592347A (en) * | 2019-12-11 | 2020-08-28 | 中国科学院福建物质结构研究所 | Terbium scandium aluminum garnet, magneto-optical transparent ceramic doped with terbium scandium aluminum garnet and preparation method of magneto-optical transparent ceramic |
| CN112110485A (en) * | 2019-06-21 | 2020-12-22 | 中国科学院上海硅酸盐研究所 | Yttrium-stabilized zirconia ceramic nano powder and preparation method and application thereof |
| CN114685158A (en) * | 2022-05-05 | 2022-07-01 | 闽都创新实验室 | Magneto-optical ceramic and preparation method and application thereof |
| CN115180940A (en) * | 2022-07-06 | 2022-10-14 | 中国科学院上海硅酸盐研究所 | Dy, tb and LuAG transparent ceramic for yellow laser and preparation method thereof |
| CN115180945A (en) * | 2021-04-02 | 2022-10-14 | 中国科学院上海硅酸盐研究所 | Iron-based garnet magneto-optical transparent ceramic and preparation method thereof |
| CN115490518A (en) * | 2022-10-17 | 2022-12-20 | 闽都创新实验室 | Ce-excess-doped magneto-optical transparent ceramic and preparation method and application thereof |
| CN116161953A (en) * | 2023-02-10 | 2023-05-26 | 中国科学院上海硅酸盐研究所 | Al (aluminum) alloy 2 O 3 Preparation method of YAG (yttrium aluminum garnet) -Ce composite phase powder and composite phase fluorescent ceramic |
| CN116477937A (en) * | 2022-01-13 | 2023-07-25 | 中国科学院上海硅酸盐研究所 | Method for preparing fine-grain terbium-aluminum garnet-based magneto-optical ceramic |
| WO2023213032A1 (en) * | 2022-05-05 | 2023-11-09 | 闽都创新实验室 | Preparation method for composite ceramic material and application of composite ceramic material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040188655A1 (en) * | 2003-03-28 | 2004-09-30 | Jui-Kung Wu | Fluorescent material of terbium aluminum garnet and producing methods therefor |
| CN102093054A (en) * | 2010-12-01 | 2011-06-15 | 中国科学院上海光学精密机械研究所 | Faraday magnetic rotation transparent ceramic and preparation method thereof |
| CN102910899A (en) * | 2012-11-16 | 2013-02-06 | 北京雷生强式科技有限责任公司 | Preparation method of yttrium aluminium garnet doped transparent laser ceramics |
| CN102976716A (en) * | 2012-12-17 | 2013-03-20 | 福建福晶科技股份有限公司 | Method for preparing transparent terbium gallium garnet ceramic |
| 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 |
| CN103502180A (en) * | 2011-03-16 | 2014-01-08 | 信越化学工业株式会社 | Transparent ceramic, method for manufacturing same, and magneto-optical device |
| CN103864409A (en) * | 2014-01-28 | 2014-06-18 | 中国科学院上海光学精密机械研究所 | Preparation method of neodymium-doped yttrium aluminum garnet transparent ceramic |
| CN104609849A (en) * | 2015-02-10 | 2015-05-13 | 中国科学院上海光学精密机械研究所 | Si/Ti doped terbium aluminum garnet Faraday magneto-optical rotation transparent ceramic and preparation method thereof |
-
2016
- 2016-12-28 CN CN201611239053.4A patent/CN108249909A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040188655A1 (en) * | 2003-03-28 | 2004-09-30 | Jui-Kung Wu | Fluorescent material of terbium aluminum garnet and producing methods therefor |
| CN102093054A (en) * | 2010-12-01 | 2011-06-15 | 中国科学院上海光学精密机械研究所 | Faraday magnetic rotation transparent ceramic and preparation method thereof |
| CN103502180A (en) * | 2011-03-16 | 2014-01-08 | 信越化学工业株式会社 | Transparent ceramic, method for manufacturing same, and magneto-optical device |
| CN102910899A (en) * | 2012-11-16 | 2013-02-06 | 北京雷生强式科技有限责任公司 | Preparation method of yttrium aluminium garnet doped transparent laser ceramics |
| CN102976716A (en) * | 2012-12-17 | 2013-03-20 | 福建福晶科技股份有限公司 | Method for preparing transparent terbium gallium garnet ceramic |
| 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 |
| CN103864409A (en) * | 2014-01-28 | 2014-06-18 | 中国科学院上海光学精密机械研究所 | Preparation method of neodymium-doped yttrium aluminum garnet transparent ceramic |
| CN104609849A (en) * | 2015-02-10 | 2015-05-13 | 中国科学院上海光学精密机械研究所 | Si/Ti doped terbium aluminum garnet Faraday magneto-optical rotation transparent ceramic and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 尹邦跃: "《陶瓷核燃料工艺》", 31 January 2016, 哈尔滨：哈尔滨工程大学出版社 * |
| 徐甲强: "《材料合成化学与合成实例》", 28 February 2015, 哈尔滨：哈尔滨工业大学出版社 * |
| 戴遐明等: "《纳米陶瓷材料及其应用》", 30 June 2005, 国防工业出版社 * |
| 施剑林等: "热等静压烧结", 《无机光学透明材料：透明陶瓷》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109133922A (en) * | 2018-09-28 | 2019-01-04 | 东北大学 | Codope rare earth ion garnet structure light functional ceramic powder and preparation method thereof |
| CN112110485A (en) * | 2019-06-21 | 2020-12-22 | 中国科学院上海硅酸盐研究所 | Yttrium-stabilized zirconia ceramic nano powder and preparation method and application thereof |
| CN111592347A (en) * | 2019-12-11 | 2020-08-28 | 中国科学院福建物质结构研究所 | Terbium scandium aluminum garnet, magneto-optical transparent ceramic doped with terbium scandium aluminum garnet and preparation method of magneto-optical transparent ceramic |
| CN111592347B (en) * | 2019-12-11 | 2021-11-05 | 中国科学院福建物质结构研究所 | Terbium scandium aluminum garnet, magneto-optical transparent ceramic doped with terbium scandium aluminum garnet and preparation method of magneto-optical transparent ceramic |
| CN111138192A (en) * | 2020-01-03 | 2020-05-12 | 上海应用技术大学 | Vacuum hot-pressing preparation method of lutetium terbium oxide magneto-optical transparent ceramic |
| CN115180945A (en) * | 2021-04-02 | 2022-10-14 | 中国科学院上海硅酸盐研究所 | Iron-based garnet magneto-optical transparent ceramic and preparation method thereof |
| CN116477937A (en) * | 2022-01-13 | 2023-07-25 | 中国科学院上海硅酸盐研究所 | Method for preparing fine-grain terbium-aluminum garnet-based magneto-optical ceramic |
| CN114685158A (en) * | 2022-05-05 | 2022-07-01 | 闽都创新实验室 | Magneto-optical ceramic and preparation method and application thereof |
| WO2023213032A1 (en) * | 2022-05-05 | 2023-11-09 | 闽都创新实验室 | Preparation method for composite ceramic material and application of composite ceramic material |
| CN115180940A (en) * | 2022-07-06 | 2022-10-14 | 中国科学院上海硅酸盐研究所 | Dy, tb and LuAG transparent ceramic for yellow laser and preparation method thereof |
| CN115490518A (en) * | 2022-10-17 | 2022-12-20 | 闽都创新实验室 | Ce-excess-doped magneto-optical transparent ceramic and preparation method and application thereof |
| CN116161953A (en) * | 2023-02-10 | 2023-05-26 | 中国科学院上海硅酸盐研究所 | Al (aluminum) alloy 2 O 3 Preparation method of YAG (yttrium aluminum garnet) -Ce composite phase powder and composite phase fluorescent ceramic |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108249909A (en) | A kind of novel method for preparing terbium aluminum garnet-base nano-powder and magneto-optic crystalline ceramics | |
| JP6438588B2 (en) | Translucent rare earth aluminum garnet ceramics | |
| CN104557041B (en) | Preparation method of yttria-base transparent ceramic | |
| CN107285770B (en) | A kind of purity is high zirconic acid lanthanum gadolinium powder of uniform morphology and crystalline ceramics preparation method | |
| CN108689422B (en) | Preparation method of large-specific-surface-area nano gadolinium oxide powder | |
| CN105858706B (en) | The preparation method of yttrium oxide powder | |
| US11339057B2 (en) | Preparation of sinterable complex oxide powder and manufacturing of transparent ceramics | |
| CN102079975A (en) | Coprecipitation preparation method of rare earth doped yttrium aluminum garnet fluorescent powder | |
| CN107010654B (en) | A kind of preparation method of monodisperse gallium oxide powder and its high density ceramic target | |
| CN100383047C (en) | Method for preparing alumina powder with small particle diameter | |
| CN103214016B (en) | Preparation method of yttrium aluminum garnet (YAG) nano-powder | |
| Cheng et al. | Low-temperature solution synthesis and characterization of Ce-doped YAG nanoparticles | |
| CN110563010A (en) | preparation method of low-sodium regular hexagonal flaky alpha-alumina micro powder | |
| CN111019648A (en) | Molten salt method preparation method of oxysalt or oxynitride fluorescent powder | |
| Kafili et al. | A comparative approach to synthesis and sintering of alumina/yttria nanocomposite powders using different precipitants | |
| CN109678506A (en) | A kind of preparation method of erbium oxide crystalline ceramics | |
| CN108046794B (en) | Method for preparing yttrium titanate transparent ceramic by using coprecipitation method synthetic powder | |
| JP6988779B2 (en) | A method for producing a garnet-type composite oxide powder for sintering, and a method for producing transparent ceramics. | |
| CN111087235A (en) | Method for preparing YAG transparent ceramic by adopting yttrium/auxiliary agent/aluminum triple core-shell structure powder | |
| CN108358635A (en) | A kind of preparation method of magneto-optic holimium oxide crystalline ceramics | |
| CN108329907A (en) | Hard template sol-gal process prepares long-persistence luminous nano material | |
| CN110256074A (en) | A kind of yttrium stablizes terbium oxide powder, magneto-optic crystalline ceramics and preparation method thereof | |
| CN110550945B (en) | Preparation method of LuAG Ce transparent ceramic and LuAG Ce transparent ceramic | |
| CN100376508C (en) | Gel combustion synthesis method for preparing neodymium-doped gadolinium-gallium garnet nano powder | |
| CN102618279B (en) | Preparation method of shape-controllable aluminate luminous materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180706 |
|
| RJ01 | Rejection of invention patent application after publication |