CN102093054B - Faraday magnetic rotation transparent ceramic and preparation method thereof - Google Patents

Faraday magnetic rotation transparent ceramic and preparation method thereof Download PDF

Info

Publication number
CN102093054B
CN102093054B CN201010568755.3A CN201010568755A CN102093054B CN 102093054 B CN102093054 B CN 102093054B CN 201010568755 A CN201010568755 A CN 201010568755A CN 102093054 B CN102093054 B CN 102093054B
Authority
CN
China
Prior art keywords
magnetic rotation
sintering furnace
conditions
pottery
hot
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.)
Active
Application number
CN201010568755.3A
Other languages
Chinese (zh)
Other versions
CN102093054A (en
Inventor
林辉
周圣明
滕浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Optics and Fine Mechanics of CAS
Original Assignee
Shanghai Institute of Optics and Fine Mechanics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Optics and Fine Mechanics of CAS filed Critical Shanghai Institute of Optics and Fine Mechanics of CAS
Priority to CN201010568755.3A priority Critical patent/CN102093054B/en
Publication of CN102093054A publication Critical patent/CN102093054A/en
Application granted granted Critical
Publication of CN102093054B publication Critical patent/CN102093054B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention discloses faraday magnetic rotation transparent ceramic and a preparation method thereof. The structural formula of the transparent ceramic is shown as Tb3-xAxAl5-yByO12, wherein A is Tm, Lu, Y or Gd; B is Sc or Ga; x is more than or equal to 0 and less than or equal to 2.9; and y is more than or equal to 0 and less than or equal to 5. The preparation method comprises the following steps of: preparing raw materials according to the components of the transparent ceramic with the structural formula of Tb3-xAxAl5-yByO12; adding 0.3 to 0.7 weight percent of ethyl orthosilicate serving as an additive; performing ball-milling, drying and tableting on powder; pressing with cool isostatic pressure of over 200 Mpa to obtain a blank body; pre-sintering to remove organic components; and putting the blank body into a vacuum or hot-press sintering furnace for sintering to obtain the magnetic rotation transparent ceramic with the structural formula of Tb3-xAxAl5-yByO12. The ceramic has high optical transmittance and high Verdet constant in a visible-near infrared band. The preparation method has the advantages of simple preparation technology, low cost, nontoxic preparation process and the like.

Description

Faraday magnetic rotation transparent ceramic and preparation method thereof
Technical field
The present invention relates to Faraday magnetic rotation transparent ceramic material, particularly a kind of component is Tb 3-xa xal 5-yb yo 12(wherein, A is Tm, Lu, and Y, Gd etc., B is Sc, Ga etc.; 0≤x≤2.9,0≤y≤5) Faraday magnetic rotation transparent ceramic and preparation method thereof.
Background technology
Optoisolator based on faraday's magnetic rotation material is one of essential device of optical communication, high power laser light processing and other fields, its principle of work is based on faraday's magnetic rotation phenomenon, magnetic rotation material under the action of a magnetic field by 90 ° of backpropagation polarisation of light direction rotations, thereby (passing through polaroid) plays the effect that isolation backlight is propagated.Weighing material is Felder (Verdet is abbreviated as V) constant in the physical parameter of unit tenacity the action of a magnetic field By Rotatory capacity of water, and its expression formula can be written as:
V＝θ/LH
Wherein, θ is the deflection angle of light process material rear polarizer direction, and L is length of material, and H is magneticstrength.
Several magnetic rotation materials that use at present mainly contain:
(1) terbium gallium garnet (Tb 3ga 5o 12, be abbreviated as TGG) and monocrystalline, visible ray and near-infrared band be the most frequently used magnetic rotation material at present, and first its shortcoming is that Ga is very expensive, and crystal growth cost is high.Secondly, due to Tb 3ga 5o 12crystal easily produces Ga in Czochralski grown process 2o 3volatilization, cause crystal composition to depart from and the variation of melt fusing point, so high quality Tb 3ga 5o 12also there is certain technical difficulty in the growth of monocrystalline;
(2) terbium glass, its advantage is that size can be done greatly, and shortcoming is that its Verdet constant is relatively little, and device volume is larger, and in addition, the thermal conductivity of glass is also poor than crystalline material;
(3) yttrium iron garnet (Fe 3al 5o 12, be abbreviated as YIG) and film, within the scope of 1.1～5.5 μ m, there is higher transparency, but it sees through rate variance at Visible-to-Near InfaRed wave band, is not suitable for using within the scope of 400～1100nm.In addition, Fe 3al 5o 12monocrystal thin films is normally at Gd 3ga 5g 12(GGG) in single crystalline substrate, prepare, and high quality, large size Gd 3ga 5g 12the growing technology of monocrystalline itself acquires a certain degree of difficulty with regard to tool, and the Ga in raw material 2o 3very expensive, therefore, the price of yig single crystal film is also more expensive at present.The more important thing is, in yig single crystal film preparation process, sometimes need to add leaded fusing assistant, environment, human body are all had to murder by poisoning.
At present, people generally believe that the optimal magnetic rotation material at Visible-to-Near InfaRed wave band is terbium aluminium garnet (Tb 3al 5o 12, be abbreviated as TAG) and monocrystalline, it has high Verdet constant, and all has higher transmitance at visible ray-near infrared region.
But Tb 3al 5o 12for non-uniform melting compound, be difficult to by melt method for growing high quality, large size single crystal.
Fortunately, Tb 3al 5o 12all belong to garnet cubic structure, we find and have proved by experiment to pass through preparation large size, high-quality Tb recently 3al 5o 12transparent ceramic material is realized Tb 3al 5o 12the magnetic rotation performance that monocrystalline is good.In addition, by Tm, Lu, Y, Gd etc. partly replace Tb; Or with Ga, Sc etc. partly replace Al, can obtain equally the Tb with high optical transmittance and high Verdet constant 3-xa xal 5-yb yo 12(wherein, A is Tm, Lu, and Y, Gd etc., B is Sc, Ga etc.; 0≤x≤2.9,0≤y≤5) transparent magnetic rotation stupalith.Object of the present invention is exactly with Tb 3-xa xal 5-yb yo 12transparent magnetic rotation stupalith is realized and is difficult to obtain high quality, large size Tb 3al 5o 12the technical barrier of monocrystalline.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art or difficulty, a kind of Faraday magnetic rotation transparent ceramic and preparation method thereof is provided, this pottery has higher optical transmittance and higher Verdet constant at Visible-to-Near InfaRed wave band, and it is simple, low-cost to have preparation technology, the advantage such as toxicological harmless in preparation process.
Technical solution of the present invention is as follows:
A kind of transparent faraday's magnetic rotation pottery, feature is that its molecular formula is:
Tb 3-xA xAl 5-yB yO 12，
Wherein: A is Tm, Lu, Y or Gd; B is Sc or Ga; The span of x and y is: 0≤x≤2.9,0≤y≤5.
The preparation method of described transparent faraday's magnetic rotation pottery, its feature is that the concrete steps of the method are as follows:
1. initial feed adopts material purity to be not less than 99.9% terbium peroxide (Tb 4o 7), terbium sesquioxide (Tb 2o 3), aluminic acid terbium (TbAlO 3), aluminum oxide (Al 2o 3), yttrium oxide (Y 2o 3), trioxide (Tm 2o 3), lutecium oxide (Lu 2o 3), gadolinium sesquioxide (Gd 2o 3), Scium trioxide (Sc 2o 3), gallium oxide (Ga 2o 3);
2. the transparent faraday's magnetic rotation pottery Tb preparing as required 3-xa xal 5-yb yo 12, selected transparent faraday's magnetic rotation pottery forms, and determines x, the value of y, and weigh in molar ratio corresponding powder raw material, raw material adds the tetraethoxy of 0.3wt%～0.7wt% as additive, through ball milling by powder mix, refinement;
3. mix, the powder of refinement dries by granulation, compressing tablet, the cold isostatic pressure that it is imposed more than 200MPa is pressed into base substrate, then organic composition is removed in pre-burning;
4. finally put into vacuum sintering furnace or hot-pressed sintering furnace sintering, obtain Tb 3-xa xal 5-yb yo 12transparent faraday's magnetic rotation pottery:
Vacuum sintering furnace sintering: the holding temperature in vacuum sintering furnace is 1400～1650 ℃, soaking time is 0.5～50 hour; Vacuum tightness in vacuum sintering furnace is better than 3 * 10 -2pa;
Hot-pressed sintering furnace sintering: the holding temperature in hot-pressed sintering furnace is 900～1500 ℃, is 0.2～10MPa to ceramic body applied pressure, and soaking time is 0.5～50 hour.
The preparation method of described transparent faraday's magnetic rotation pottery, its feature is that the method comprises the following steps:
1. initial feed adopts material purity to be not less than 99.9% Terbium trinitrate Tb (NO 3) 3or terbium chloride (TbCl 3), aluminum nitrate Al (NO 3) 3or aluminum chloride (AlCl 3), thulium nitrate Tm (NO 3) 3or thulium chloride (TmCl 3), lutecium nitrate or lutecium chloride (LuCl 3), gallium nitrate Ga (NO 3) 3or gallium chloride (GaCl 3), Scium trinitrate Sc (NO 3) 3or Scium trichloride (ScCl 3);
2. the transparent faraday's magnetic rotation pottery Tb preparing as required 3-xa xal 5-yb yo 12, the composition of selected transparent faraday's magnetic rotation pottery, determines x, the value of y, weighs corresponding powder raw material in molar ratio;
3. adopt with urea (CO (NH 2) 2) or bicarbonate of ammonia (NH 4hCO 3) be the chemical coprecipitation of precipitation agent or with citric acid (C 6h 8o 7) for adopting sol-gel method, stablizer prepares Tb 3-xa xal 5-yb yo 12precursor, by calcining to obtain Tb 3-xa xal 5-yb yo 12powder, then add the tetraethoxy of 0.3～0.7wt% by described Tb 3-xa xal 5-yb yo 12powder carries out ball milling, by injection forming or cold isostatic compaction, makes base substrate, then organic composition is removed in pre-burning;
4. finally put into vacuum sintering furnace or hot-pressed sintering furnace, obtain Tb 3-xa xal 5-yb yo 12transparent faraday's magnetic rotation pottery:
Vacuum sintering furnace sintering: the holding temperature in vacuum sintering furnace is 1400～1650 ℃, soaking time is 0.5～50 hour; Vacuum tightness in vacuum sintering furnace is better than 3 * 10 -2pa;
Hot-pressed sintering furnace sintering: the holding temperature in hot-pressed sintering furnace is 900～1500 ℃, is 0.2～10MPa to ceramic body applied pressure, and soaking time is 0.5～50 hour.
Technique effect of the present invention:
Tb in the present invention 3-xa xal 5-yb yo 12magnetic rotation pottery is than current commercial Tb 3ga 5o 12monocrystalline has the Verdet constant of higher optical transmittance and Geng Gao at Visible-to-Near InfaRed wave band; Preparation technology is also fairly simple for this magnetic rotation pottery, and yield rate is high, and cost is low, easily preparation in batches, and its in preparation process without using the virulent fusing assistant of human body environment, there is good human body, environment friendly.
Accompanying drawing explanation
Fig. 1 is the Tb of the embodiment of the present invention 1 preparation 3al 5o 12the transmittance curve of crystalline ceramics (thickness is 2mm)
Fig. 2 is embodiment of the present invention 1Tb 3al 5o 12pottery Verdet constant with wavelength change curve,
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, but should not limit the scope of the invention with this.
Embodiment 1Tb 3al 5o 12the preparation of transparent faraday's magnetic rotation pottery
Tb 3al 5o 12the preparation method of transparent faraday's magnetic rotation pottery, concrete steps are as follows:
1. initial feed adopts material purity to be not less than the powder of 99.9% terbium peroxide, terbium sesquioxide, aluminic acid terbium, aluminum oxide, yttrium oxide, trioxide, lutecium oxide, gadolinium sesquioxide, Scium trioxide, gallium oxide;
The molecular formula Tb of transparent faraday's magnetic rotation pottery of 2. preparing as required 3al 5o 12composition definite x=0, the value of y=0, purity is not less than 99.9% terbium sesquioxide (Tb 4o 7), aluminum oxide (Al 2o 3) powder be raw material, by the good powder raw material of mol ratio corresponding configuration of each metal ion in forming 30g altogether, add the tetraethoxy of 0.3wt%～0.7wt% as additive, through ball milling by powder mix, refinement;
3. powder is dried by granulation, compressing tablet, it is imposed to the above cold isostatic pressure of 200MPa and be pressed into base substrate, then organic composition is removed in pre-burning;
4. finally put into vacuum sintering furnace, obtain Tb 3-xa xal 5-yb yo 12transparent faraday's magnetic rotation pottery:
Vacuum sintering furnace sintering: the holding temperature in vacuum sintering furnace is 1400 ℃, soaking time is 0.5 hour; Vacuum tightness in vacuum sintering furnace is better than 2.5 * 10 -3pa;
The present embodiment is tested, and Fig. 1 is Tb prepared in the embodiment of the present invention 1 3al 5o 12the transmittance curve of crystalline ceramics (thickness is 2mm), is wherein positioned at the absorption band at 486nm place corresponding to Tb 3+the transition of the 4F6 → 5D4 of ion.Except absorption band, this crystalline ceramics is at transmitance>=80% of ultraviolet-visible-near-infrared band 500～1600nm, and its transmitance at visible ray 400～700nm wave band will be apparently higher than Tb 3ga 5o 12the transmitance of the monocrystalline (document 1 that sees reference " Growth andcharacterization ofTb 3ga 5-xal xo 12single crystal " Wenjing Zhang, FeiyunGuo, Jianzhong Chen, Journal of Crystal Growth 306 (2007) 195-199.), be more suitable for the magnetic rotation material as visible light wave range.
Fig. 2 is for testing Tb in the embodiment of the present invention 1 recording 3al 5o 12pottery Verdet constant with wavelength change curve, by with reference 2 (referring to " Growth of terbium aluminum garnet (Tb 3al 5o 12; TAG) single crystals by the hybrid laser floatingzone machine " Mikio Geho; Takenori Sekijima; Takashi Fujii, Journal of Crystal Growth267 (2004) 188-193.) Tb that provides 3al 5o 12with Tb 3ga 5o 12the data of monocrystalline compare, Tb prepared by visible the inventive method 3al 5o 12pottery Verdet constant at each wavelength place almost with Tb 3al 5o 12the numerical value of monocrystalline is in full accord, with Tb 3ga 5o 12monocrystalline is compared, Tb 3al 5o 12the magnetic rotation performance of pottery (particularly at visible light wave range) is well a lot.
Embodiment 2
Sintered heat insulating temperature is 1650 ℃, and other conditions, with embodiment 1, can obtain Tb equally 3al 5o 12crystalline ceramics.
Embodiment 3
Sintered heat insulating temperature is 1500 ℃, and other conditions, with embodiment 1, can obtain Tb equally 3al 5o 12crystalline ceramics.
Embodiment 4
The sintered heat insulating time is 50 hours, and other conditions, with embodiment 1, can obtain Tb equally 3al 5o 12crystalline ceramics.
Embodiment 5
The sintered heat insulating time is 10 hours, and other conditions, with embodiment 1, can obtain Tb equally 3al 5o 12crystalline ceramics.
Embodiment 6
Material purity is 99.99%, and other conditions, with embodiment 1, can obtain Tb equally 3al 5o 12crystalline ceramics.
Embodiment 7
Material purity is 99.999%, and other conditions, with embodiment 1, can obtain the Tb that optical quality is higher 3al 5o 12crystalline ceramics.
Embodiment 8
The add-on of tetraethyl orthosilicate is 0.7wt%, and other conditions, with embodiment 1, can obtain Tb equally 3al 5o 12crystalline ceramics.
Embodiment 9
Press Tb 2.9tm 0.1al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, other conditions, with embodiment 1, can obtain Tb 2.9tm 0.1al 5o 12crystalline ceramics.
Embodiment 10
Press Tb 2.9tm 0.1al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, sintered heat insulating temperature is 1500 ℃, other conditions, with embodiment 1, can obtain Tb 2.9tm 0.1al 5o 12crystalline ceramics.
Embodiment 11
Press Tb 2.9tm 0.1al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, sintered heat insulating temperature is 1650 ℃, other conditions, with embodiment 1, can obtain Tb 2.9tm 0.1al 5o 12crystalline ceramics.
Embodiment 12
Press Tb 0.1tm 2.9al 5o 12in composition, good other conditions of powder raw material of the mol ratio corresponding configuration of each metal ion, with embodiment 1, can obtain Tb 0.1tm 2.9al 5o 12crystalline ceramics.
Embodiment 13
Press Tb 0.1tm 2.9sc 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, other conditions, with embodiment 1, can obtain Tb 0.1tm 2.9sc 5o 12crystalline ceramics.
Embodiment 14
Press Tb 0.1tm 2.9ga 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, other conditions, with embodiment 1, can obtain Tb 0.1tm 2.9ga 5o 12crystalline ceramics.
Embodiment 15
Press Tb 0.1lu 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, other conditions, with embodiment 1, can obtain Tb 0.1lu 2.9al 5o 12crystalline ceramics.
Embodiment 16
Press Tb 0.1lu 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, sintered heat insulating temperature is 1650 ℃, other conditions, with embodiment 15, can obtain Tb 0.1lu 2.9al 5o 12crystalline ceramics.
Embodiment 17
Press Tb 0.1lu 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, TEOS add-on is 0.5wt%, other conditions, with embodiment 15, can obtain Tb 0.1lU 2.9al 5o 12crystalline ceramics.
Embodiment 18
Press Tb 0.1lu 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, TEOS add-on is 0.7wt%, other conditions, with embodiment 15, can obtain Tb 0.1lu 2.9al 5o 12crystalline ceramics.
Embodiment 19
Material purity is, 99.999%, and by Tb 0.1lu 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, other conditions, with embodiment 15, can obtain Tb 0.1lu 2.9al 5o 12crystalline ceramics.
Embodiment 20
Press Tb 0.1lu 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, in holding stage stove, vacuum tightness is better than 3.0 * 10 -4other conditions of Pa, with embodiment 15, can obtain Tb 0.1lu 2.9al 5o 12crystalline ceramics.
Embodiment 21
Press Tb 0.1lu 2.9sc 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, other conditions, with embodiment 1, can obtain Tb 0.1lu 2.9sc 5o 12crystalline ceramics.
Embodiment 22
Press Tb 0.1lu 2.9sc 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, sintering temperature is 1650 ℃, other conditions, with embodiment 1, can obtain Tb 0.1lu 2.9sc 5o 12thoroughly. bright pottery.
Embodiment 23
Press Tb 0.1lu 2.9sc 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, the sintered heat insulating time is 50 hours, other conditions, with embodiment 1, can obtain Tb 0.1lu 2.9sc 5o 12crystalline ceramics.
Embodiment 24
Press Tb 0.1lu 2.9sc 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, the sintered heat insulating time is 10 hours, other conditions, with embodiment 1, can obtain Tb 0.1lu 2.9sc 5o 12crystalline ceramics.
Embodiment 25
Press Tb 0.1lu 2.9sc 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, in holding stage stove, vacuum tightness is better than 3.0 * 10 -4pa, other conditions, with embodiment 1, can obtain Tb 0.1lu 2.9sc 5o 12crystalline ceramics.
Embodiment 26
Press Tb 0.1gd 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, other conditions, with embodiment 1, can obtain Tb 0.1gd 2.9al 5o 12crystalline ceramics.
Embodiment 27
Press Tb 0.1gd 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, sintered heat insulating temperature is 1650 ℃, other conditions, with embodiment 1, can obtain Tb 0.1gd 2.9al 5o 12crystalline ceramics.
Embodiment 28
Press Tb 0.1gd 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, sintered heat insulating temperature is 1500 ℃, other conditions, with embodiment 1, can obtain Tb 0.1gd 2.9al 5o 12crystalline ceramics.
Embodiment 29
Press Tb 0.1gd 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, TEOS add-on is 0.5wt%, other conditions, with embodiment 1, can obtain Tb 0.1gd 2.9al 5o 12crystalline ceramics.
Embodiment 30
Press Tb 0.1gd 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, TEOS add-on is 0.7wt%, other conditions, with embodiment 1, can obtain Tb 0.1gd 2.9al 5o 12crystalline ceramics.
Embodiment 31
Press Tb 0.1gd 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, in holding stage stove, vacuum tightness is better than 2 * 10 -4pa, other conditions, with embodiment 1, can obtain Tb 0.1gd 2.9al 5o 12crystalline ceramics.
Embodiment 32
Material purity is 99.999%, by Tb 0.1gd 2.9al 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, TEOS add-on is 0.7wt%, other conditions, with embodiment 1, can obtain Tb 0.1gd 2.9al 5o 12crystalline ceramics.
Embodiment 33
Press Tb 0.1gd 2.9sc 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, other conditions, with embodiment 1, can obtain Tb 0.1gd 2.9sc 5o 12crystalline ceramics.
Embodiment 34
Press Tb 0.1gd 2.9ga 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, other conditions, with embodiment 1, can obtain Tb 0.1gd 2.9ga 5o 12crystalline ceramics.
Embodiment 35
Press Tb 0.1y 2.9ga 5o 12the good powder raw material of the mol ratio corresponding configuration of each metal ion in composition, other conditions, with embodiment 1, can obtain Tb 0.1y 2.9al 5o 12crystalline ceramics.
Embodiment 36
By Tb 3al 5o 12base substrate is put into hot pressed sintering sintering, and holding temperature is 900 ℃, base substrate is applied to the pressure of 0.2MPa, and soaking time is 0.5 hour, and other conditions, with embodiment 1, can obtain Tb 3al 5o 12crystalline ceramics.
Embodiment 37
By Tb 3al 5o 12base substrate is put into hot pressed sintering sintering, and holding temperature is 1500 ℃, base substrate is applied to the pressure of 0.2MPa, and soaking time is 0.5 hour, and other conditions, with embodiment 36, can obtain Tb 3al 5o 12crystalline ceramics.
Embodiment 38
By Tb 3al 5o 12base substrate is put into hot pressed sintering sintering, and holding temperature is 1100 ℃, base substrate is applied to the pressure of 0.2MPa, and soaking time is 50 hours, and other conditions, with embodiment 36, can obtain Tb 3al 5o 12crystalline ceramics.
Embodiment 39
By Tb 3al 5o 12base substrate is put into hot pressed sintering sintering, and holding temperature is 900 ℃, base substrate is applied to the pressure of 10MPa, and soaking time is 0.5 hour, and other conditions, with embodiment 36, can obtain Tb 3al 5o 12crystalline ceramics.
Embodiment 40
By Tb 3al 5o 12base substrate is put into hot pressed sintering sintering, and holding temperature is 900 ℃, base substrate is applied to the pressure of 10MPa, and soaking time is 20 hours, and other conditions, with embodiment 36, can obtain Tb 3al 5o 12crystalline ceramics.
Embodiment 41
By Tb 3al 5o 12base substrate is put into hot pressed sintering sintering, and holding temperature is 1050 ℃, base substrate is applied to the pressure of 10MPa, and soaking time is 20 hours, and other conditions, with embodiment 36, can obtain Tb 3al 5o 12crystalline ceramics.
Embodiment 42
By Tb 3al 5o 12base substrate is put into hot pressed sintering sintering, and holding temperature is 1200 ℃, base substrate is applied to the pressure of 5MPa, and soaking time is 20 hours, and other conditions, with embodiment 36, can obtain Tb 3al 5o 12crystalline ceramics.
Embodiment 43
Press Tb 3al 5o 12chemical constitution, takes Terbium trinitrate (Tb (NO 3) 3), aluminum nitrate (Al (NO 3) 3) initial feed 50g altogether, by its molten 1000 ml water solution of making, after dropwise splash into urea (CO (NH 2) 2) in precipitant solution, obtain containing Tb (OH) 3, Tb 2(CO 3) 3, Al (OH) 3, Tb 2(CO 3) 3tb 3al 5o 12precursor throw out, by calcining to obtain Tb 3al 5o 12powder, adds the TEOS of 0.5wt% that this powder is carried out to ball milling, by injection forming or cold isostatic compaction, makes base substrate, then organic composition is removed in pre-burning; Finally put into vacuum sintering furnace sintering 0.5 hour at 1400 ℃ of temperature, obtain Tb 3al 5o 12transparent magnetic rotation pottery.
Embodiment 44
Sintered heat insulating temperature is 1650 ℃ of temperature, and other conditions, with embodiment 43, obtain Tb 3al 5o 12transparent magnetic rotation pottery.
Embodiment 45
Sintered heat insulating temperature is 1500 ℃ of temperature, and other conditions, with embodiment 43, obtain Tb 3al 5o 12transparent magnetic rotation pottery.
Embodiment 46
The sintered heat insulating time is 50 hours, and other conditions, with embodiment 43, obtain Tb 3al 5o 12transparent magnetic rotation pottery.
Embodiment 47
The sintered heat insulating time is 10 hours, and other conditions, with embodiment 43, obtain Tb 3al 5o 12transparent magnetic rotation pottery.
Embodiment 48
TEOS add-on is 0.3wt%, and other conditions, with embodiment 43, obtain Tb 3al 5o 12transparent magnetic rotation pottery.
Embodiment 49
TEOS add-on is 0.7wt%, and other conditions, with embodiment 43, obtain Tb 3al 5o 12transparent magnetic rotation pottery.
Embodiment 50
During insulation, in stove, vacuum tightness is better than 2 * 10 -4pa, other conditions, with embodiment 43, obtain Tb 3al 5o 12transparent magnetic rotation pottery.
Embodiment 51
By Tb 3al 5o 12base substrate is put into hot-pressed sintering furnace sintering, and holding temperature is 900～1500 ℃, base substrate is applied to the pressure of 0.2～10MPa, and soaking time is 0.5 hour, and other conditions, with embodiment 43, can obtain Tb 3al 5o 12crystalline ceramics.
Embodiment 52
Press Tb 1.5gd 1.5al 3ga 2o 12chemical constitution, takes Terbium trinitrate (Tb (NO 3) 3), aluminum nitrate (Al (NO 3) 3), Gadolinium trinitrate (Gd (NO 3) 3), gallium nitrate (Ga (NO 3) 3) initial feed 50g altogether, by its molten 1000 ml water solution of making, after dropwise splash into bicarbonate of ammonia (NH 4hCO 3) in precipitant solution, obtain containing Tb (OH) 3, Tb 2(CO 3) 3, Al (OH) 3, Tb 2(CO 3) 3tb 3al 5o 12precursor throw out, by calcining to obtain Tb 1.5gd 1.5al 3ga 2o 12powder, adds the TEOS of 0.3wt% that this powder is carried out to ball milling, by injection forming or cold isostatic compaction, makes base substrate, then organic composition is removed in pre-burning; Finally put into hot-pressed sintering furnace and base substrate is applied to the pressure of 0.2MPa, at 900 ℃ of temperature, sintering is 0.5～50 hour, obtains Tb 1.5gd 1.5al 3ga 2o 12transparent magnetic rotation pottery.
Embodiment 53
By Tb 1.5gd 1.5al 3ga 2o 12ceramic body is put into the pressure that hot-pressed sintering furnace applies 10MPa, and other conditions, with embodiment 52, can obtain Tb equally 1.5gd 1.5al 3ga 2o 12magnetic rotation crystalline ceramics.
Embodiment 54
By Tb 1.5gd 1.5al 3ga 2o 12ceramic body is put into the pressure that hot-pressed sintering furnace applies 5MPa, and other conditions, with embodiment 52, can obtain Tb equally 1.5gd 1.5al 3ga 2o 12magnetic rotation crystalline ceramics.
Embodiment 55
Sintered heat insulating temperature is 1500 ℃, and other conditions, with embodiment 52, can obtain Tb equally 1.5gd 1.5al 3ga 2o 12magnetic rotation crystalline ceramics.
Embodiment 56
Sintered heat insulating temperature is 1000 ℃, and other conditions, with embodiment 52, can obtain Tb equally 1.5gd 1.5al 3ga 2o 12magnetic rotation crystalline ceramics.
Embodiment 57
Press Tb 2.9lu 0.1al 3sc 2o 12form, take terbium chloride (TbCl 3), aluminum chloride (AlCl 3), lutecium chloride (LuCl 3), Scium trichloride (ScCl 3) etc. initial feed 50g altogether, by its molten 1000 ml water solution of making, adding 1wt% citric acid is stablizer, uses magnetic stirring apparatus stir and be heated to 60 ℃, obtains Tb 2.9lu 0.1al 3sc 2o 12precursor colloidal sol, by this colloidal sol ageing 24 hours, obtains Tb by thermal treatment 2.9lu 0.1al 3sc 2o 12powder, adds the TEOS of 0.7wt% that this powder is carried out to ball milling, by injection forming or cold isostatic compaction, makes base substrate, then organic composition is removed in pre-burning; Finally put into vacuum sintering furnace sintering 0.5 hour at 1400 ℃, obtain Tb 2.9lu 0.1al 3sc 2o 12magnetic rotation crystalline ceramics.
Embodiment 58
Holding temperature is 1650 ℃, and other conditions are with embodiment 57, and other conditions, with embodiment 57, obtain Tb 2.9lu 0.1al 3sc 2o 12magnetic rotation crystalline ceramics.
Embodiment 59
Holding temperature is 1500 ℃, and other conditions are with embodiment 57, and other conditions, with embodiment 57, obtain Tb 2.9lu 0.1al 3sc 2o 12magnetic rotation crystalline ceramics.
Embodiment 60
The sintered heat insulating time is 50 hours, and other conditions, with embodiment 57, can obtain Tb equally 2.9lu 0.1al 3sc 2o 12magnetic rotation crystalline ceramics.
Embodiment 61
The sintered heat insulating time is 20 hours, and other conditions, with embodiment 57, can obtain Tb equally 2.9lu 0.1al 3sc 2o 12magnetic rotation crystalline ceramics.
Embodiment 62
During insulation, in stove, vacuum tightness is better than 1 * 10 -4pa, other conditions, with 57, can obtain Tb equally 2.9lu 0.1al 3sc 2o 12magnetic rotation crystalline ceramics.
Embodiment 63
Press Tb 2.9lu 0.1al 3sc 2o 12form, take terbium chloride (TbCl 3), aluminum chloride (AlCl 3), lutecium chloride (LuCl 3), Scium trichloride (ScCl 3) etc. initial feed 50g altogether, by its molten 1000 ml water solution of making, adding 1wt% citric acid is stablizer, uses magnetic stirring apparatus stir and be heated to 60 ℃, obtains Tb 2.9lu 0.1al 3sc 2o 12precursor colloidal sol, by this colloidal sol ageing 24 as a child, obtained Tb by thermal treatment 2.9lu 0.1al 3sc 2o 12powder, adds the TEOS of 0.3wt～0.7wt% that this powder is carried out to ball milling, by injection forming or cold isostatic compaction, makes base substrate, then organic composition is removed in pre-burning; Finally put into hot-pressed sintering furnace and base substrate is applied to the pressure of 0.2MPa, at 1500 ℃ of temperature, sintering is 0.5 hour, obtains Tb 2.9lu 0.1al 3sc 2o 12magnetic rotation pottery.
Embodiment 64
The sintered heat insulating time is 50 hours, and other conditions, with embodiment 63, can obtain Tb equally 2.9lu 0.1al 3sc 2o 12magnetic rotation pottery.
Embodiment 65
The sintered heat insulating time is 10 hours, and other conditions, with embodiment 63, can obtain Tb equally 2.9lu 0.1al 3sc 2o 12magnetic rotation pottery.
Embodiment 66
By Tb 2.9lU 0.1al 3sc 2o 12ceramic body is put into hot-pressed sintering furnace and is applied 10MPa pressure, and sintered heat insulating temperature is 900 ℃, and other conditions, with embodiment 63, obtain Tb 2.9lu 0.1al 3sc 2o 12magnetic rotation pottery.
Embodiment 67
By Tb 2.9lu 0.1al 3sc 2o 12ceramic body is put into hot-pressed sintering furnace and is applied 5MPa pressure, and other conditions, with embodiment 66, obtain Tb 2.9lu 0.1al 3sc 2o 12magnetic rotation pottery.
Embodiment 68
Holding temperature is 1400 ℃, and other conditions, with embodiment 63, obtain Tb 2.9lu 0.1al 3sc 2o 12magnetic rotation pottery.
Embodiment 69
Holding temperature is 1050 ℃, and other conditions, with embodiment 63, obtain Tb 2.9lu 0.1al 3sc 2o 12magnetic rotation pottery.
By other conditions of stating in the claims in the present invention book, can obtain equally the magnetic rotation crystalline ceramics of respective components, at this, do not enumerate, but do not affect the protection domain of the claims in the present invention.

Claims (2)

1. a preparation method for transparent faraday's magnetic rotation pottery, the structural formula of this transparent faraday's magnetic rotation pottery is: Tb 3-xa xal 5-yb yo 12, wherein: A is Tm, Lu, Y or Gd; B is Sc or Ga; The span of x and y is: 0≤x≤2.9, and 0≤y < 5, is characterized in that the concrete steps of the method are as follows:
1. initial feed adopts material purity to be not less than the powder of 99.9% terbium peroxide, terbium sesquioxide, aluminic acid terbium, aluminum oxide, yttrium oxide, trioxide, lutecium oxide, gadolinium sesquioxide, Scium trioxide, gallium oxide;
The molecular formula Tb of transparent faraday's magnetic rotation pottery of 2. preparing as required 3-xa xal 5-yb yo 12composition definite x, the value of y, and weigh in molar ratio corresponding powder raw material, adds the tetraethoxy of 0.3wt%～0.7wt% as additive, through ball milling by powder mix, refinement;
3. powder is dried by granulation, compressing tablet, it is imposed to the above cold isostatic pressure of 200MPa and be pressed into base substrate, then organic composition is removed in pre-burning;
4. finally put into vacuum sintering furnace or hot-pressed sintering furnace sintering, obtain Tb 3-xa xal 5-yb yo 12transparent faraday's magnetic rotation pottery:
Vacuum sintering furnace sintering: the holding temperature in vacuum sintering furnace is 1400～1650 ℃, soaking time is 0.5～50 hour; Vacuum tightness in vacuum sintering furnace is better than 3 * 10 -2pa;
Hot-pressed sintering furnace sintering: the holding temperature in hot-pressed sintering furnace is 900～1500 ℃, is 0.2～10MPa to ceramic body applied pressure, and soaking time is 0.5～50 hour.
2. a preparation method for transparent faraday's magnetic rotation pottery, the structural formula of this transparent faraday's magnetic rotation pottery is: Tb 3-xa xal 5-yb yo 12, wherein: A is Tm or Lu; B is Sc or Ga; The span of x and y is: 0≤x≤2.9,0≤y < 5, is characterized in that the method comprises the following steps:
1. initial feed adopts material purity to be not less than 99.9% Terbium trinitrate or terbium chloride, aluminum nitrate or aluminum chloride, thulium nitrate or thulium chloride, lutecium nitrate or lutecium chloride, gallium nitrate or gallium chloride, Scium trinitrate or Scium trichloride;
The molecular formula Tb of transparent faraday's magnetic rotation pottery of 2. preparing as required 3-xa xal 5-yb yo 12composition and definite x, the value of y, weighs corresponding powder raw material in molar ratio;
3. adopt and take chemical coprecipitation or the citric acid of take that urea or bicarbonate of ammonia is precipitation agent and prepare Tb as stablizer adopts sol-gel method 3-xa xal 5-yb yo 12presoma, by calcining to obtain Tb 3-xa xal 5-yb yo 12powder, then add the tetraethoxy of 0.3～0.7wt% by described Tb 3-xa xal 5-yb yo 12powder carries out ball milling, by injection forming or cold isostatic compaction, makes base substrate, then organic composition is removed in pre-burning;
4. finally put into vacuum sintering furnace or hot-pressed sintering furnace, obtain Tb 3-xa xal 5-yb yo 12transparent faraday's magnetic rotation pottery:
Vacuum sintering furnace sintering: the holding temperature in vacuum sintering furnace is 1400～1650 ℃, soaking time is 0.5～50 hour; Vacuum tightness in vacuum sintering furnace is better than 3 * 10 -2pa;
Hot-pressed sintering furnace sintering: the holding temperature in hot-pressed sintering furnace is 900～1500 ℃, is 0.2～10MPa to ceramic body applied pressure, and soaking time is 0.5～50 hour.
CN201010568755.3A 2010-12-01 2010-12-01 Faraday magnetic rotation transparent ceramic and preparation method thereof Active CN102093054B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201010568755.3A CN102093054B (en) 2010-12-01 2010-12-01 Faraday magnetic rotation transparent ceramic and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201010568755.3A CN102093054B (en) 2010-12-01 2010-12-01 Faraday magnetic rotation transparent ceramic and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102093054A CN102093054A (en) 2011-06-15
CN102093054B true CN102093054B (en) 2014-04-09

Family

ID=44126343

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201010568755.3A Active CN102093054B (en) 2010-12-01 2010-12-01 Faraday magnetic rotation transparent ceramic and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102093054B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102850047A (en) * 2011-06-29 2013-01-02 圣戈本陶瓷及塑料股份有限公司 Manufacturing method of transparent ceramic scintillator based on doped lutecium-aluminum garnet (LuAG) or other lutecium-aluminum oxides
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
JP6465202B2 (en) * 2015-03-11 2019-02-06 信越化学工業株式会社 Magneto-optical material, manufacturing method thereof, and magneto-optical device
CN106431401A (en) * 2016-09-07 2017-02-22 吉林建筑大学 Magnetic-optical material and preparation method thereof
CN108249909A (en) * 2016-12-28 2018-07-06 中国科学院上海硅酸盐研究所 A kind of novel method for preparing terbium aluminum garnet-base nano-powder and magneto-optic crystalline ceramics
JP6743970B2 (en) * 2017-04-17 2020-08-19 信越化学工業株式会社 Paramagnetic garnet type transparent ceramics, magneto-optical material and magneto-optical device
US20190345072A1 (en) * 2018-05-11 2019-11-14 Shin-Etsu Chemical Co., Ltd. Method for preparing ceramic molded body for sintering and method for producing ceramic sintered body
JP6879264B2 (en) * 2018-05-18 2021-06-02 信越化学工業株式会社 Paramagnetic garnet type transparent ceramics, magneto-optical materials and magneto-optical devices
JP6911811B2 (en) * 2018-05-30 2021-07-28 信越化学工業株式会社 Manufacturing method of transparent ceramics for Faraday rotator
CN108751991B (en) * 2018-08-17 2020-03-13 徐州华焰特种陶瓷有限公司 Preparation of Tb: Lu by laser sintering2O3Method for producing ceramic

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1393422A (en) * 2001-07-01 2003-01-29 中国科学院福建物质结构研究所 Process for preparing finally formed transparent ceramics as laser medium
US20030174380A1 (en) * 2002-03-18 2003-09-18 Rongfu Xiao Faraday rotator with improved magnetooptic property
CN101514100A (en) * 2009-03-10 2009-08-26 中国科学院上海硅酸盐研究所 Twinkling transparent ceramics system with garnet structure and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008007385A (en) * 2006-06-30 2008-01-17 Murata Mfg Co Ltd Manufacturing method of ceramics comprising terbium/aluminum oxide and ceramics comprising terbium/aluminum oxide manufactured by the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1393422A (en) * 2001-07-01 2003-01-29 中国科学院福建物质结构研究所 Process for preparing finally formed transparent ceramics as laser medium
US20030174380A1 (en) * 2002-03-18 2003-09-18 Rongfu Xiao Faraday rotator with improved magnetooptic property
CN101514100A (en) * 2009-03-10 2009-08-26 中国科学院上海硅酸盐研究所 Twinkling transparent ceramics system with garnet structure and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Growth of {Tb3}[Sc2-xLux](Al3)O12 Single Crystals for Visible-Infrared Optical Isolators;Kiyoshi Shimamura et al.;《Crystal Growth & Design》;20100625;第10卷;第3466页至第3470页 *
Paramagnetic acoustic Faraday rotation in Tb3Ga5O12;Peter Thalmeier;《Physical Review B》;20091231;第80卷(第21期);第214421-1页至214421-9页 *

Also Published As

Publication number Publication date
CN102093054A (en) 2011-06-15

Similar Documents

Publication Publication Date Title
CN102093054B (en) Faraday magnetic rotation transparent ceramic and preparation method thereof
CN100455536C (en) Luetcium aluminum garnet -base transparent ceramic and process for preparing same
EP3342764B1 (en) Translucent rare earth element aluminum garnet ceramic
CN103189549B (en) Magneto-optic memory technique, Faraday rotor and optoisolator
CN111592347B (en) Terbium scandium aluminum garnet, magneto-optical transparent ceramic doped with terbium scandium aluminum garnet and preparation method of magneto-optical transparent ceramic
CN100551868C (en) The preparation method of mixed garnet base ceramic material
CN103502180A (en) Transparent ceramic, method for manufacturing same, and magneto-optical device
CN107285770B (en) A kind of purity is high zirconic acid lanthanum gadolinium powder of uniform morphology and crystalline ceramics preparation method
CN105378542B (en) Magneto-optic memory technique and its manufacture method and magnetic-optic devices
CN102924073A (en) Method for preparing rare earth ion-doped yttrium aluminum garnet (Re: YAG) transparent laser ceramic by using hot-pressing post treatment
CN104609849B (en) Terbium aluminium garnet Faraday magnetic rotation transparent ceramic of Si/Ti doping and preparation method thereof
CN102575382A (en) Single crystal, process for producing same, optical isolator, and optical processor using same
WO2018193848A1 (en) Paramagnetic garnet-type transparent ceramic, magneto-optical material, and magneto-optical device
JP6881391B2 (en) Manufacturing method of composite oxide powder for sintering and manufacturing method of transparent ceramics
CN103422172B (en) A kind of High-performance photoelectric functional calcium borate thulium oxide crystal and growth thereof with apply
Wang et al. Synthesis of nanosize powders and thin films of Yb-doped YAG by Sol− Gel methods
CN104364223B (en) Transparent rare-earth class Ga garnet pottery and manufacture method and Faraday polarization apparatus
Dong et al. Synthesis of highly sinterable Yb: Lu2O3 nanopowders via spray co-precipitation for transparent ceramics
CN104876587B (en) It is a kind of to substitute preparation method of the sapphire with anti-purple dizzy crystalline ceramics panel
Sun et al. Effect of Zn2+ and Li+ ions doped on microstructure and upconversion luminescence of Y2O3: Er3+-Yb3+ thin films
JP6988779B2 (en) A method for producing a garnet-type composite oxide powder for sintering, and a method for producing transparent ceramics.
CN110079861A (en) Yttrium phosphate strontium crystal and the preparation method and application thereof
Lai et al. Optical properties and Faraday magneto-optical effects of highly transparent novel Tb2Zr2O7 fluorite ceramics
CN109652856B (en) Tb3+Self-activated laser crystal, preparation method thereof and application thereof in visible-band solid-state laser
WO2020248987A1 (en) Photoelectric functional crystal m3re(po4)3, preparation method therefor, and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant