CN102815941A - Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof - Google Patents
Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof Download PDFInfo
- Publication number
- CN102815941A CN102815941A CN2012103375202A CN201210337520A CN102815941A CN 102815941 A CN102815941 A CN 102815941A CN 2012103375202 A CN2012103375202 A CN 2012103375202A CN 201210337520 A CN201210337520 A CN 201210337520A CN 102815941 A CN102815941 A CN 102815941A
- Authority
- CN
- China
- Prior art keywords
- zirconic acid
- acid lanthanum
- powder
- ceramic material
- gadolinium
- 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.)
- Granted
Links
Images
Landscapes
- Luminescent Compositions (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and a preparation method thereof. The chemical composition of the rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material is La0.4-yREyGd1.6Zr2O7, wherein 0.02<=y<=0.04, and RE is Pr, Tb or Sm. The rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material provided by the invention has the advantages of high visible light transmittance and high sintering density, and can satisfy the requirements for application in the fields of information detection, laser media, high-temperature windows, high-refractivity camera lenses, scintillators and the like.
Description
Technical field
The present invention relates to a kind of zirconic acid lanthanum gadolinium transparent ceramic material, specifically is rare earth ion doped zirconic acid lanthanum gadolinium transparent ceramic material and preparation method thereof, belongs to technical field of ceramic material.
Background technology
Crystalline ceramics has HS, high firmness, high insulation, stupalith inherent characteristic such as high temperature resistant, corrosion-resistant, also has the optical property of glass material concurrently, and its Application Areas is very extensive.
Compare with monocrystalline, the preparation temperature of crystalline ceramics especially has practical significance far below the preparation temperature of monocrystalline for some dystectic materials.Crystalline ceramics can also require to realize easily the even doping of high concentration ion according to device application, avoids because low, the pockety situation of doping content that the crystal growth technique restriction is caused.In addition, utilize the preparation method of pottery can obtain large size and complex-shaped material.Research shows that the performance of some crystalline ceramics has has met or exceeded monocrystal material, and is expected in some specific occasions progressively substitute the monocrystalline optical material.In addition, compare with glass material, high temperature resistant, advantages such as thermal conductivity is high, hardness is high, strong shock resistance that crystalline ceramics has have its unique using value at some special occasions.
From 1962, reported first was prepared since the translucent alumina ceramics in the U.S. Pat 3026210, and transparent ceramic material is all obtained very big progress in kind with using.Prepared YAG:Nd laser ceramicses such as [A.Ikesue, T.Kinoshita, K.Yoshida, J.Am.Ceram.Soc., 1995,78 (4): 1033-1037] at present, and (Y, Gd)
2O
3: Eu [U.S.P.4421671], Gd
2O
2S:Pr, Ce, F [Ito H, Yamada H, Yoshida M, et al, Jpn.J.Appl.Phys., 1988,27 (8): L1371-1373], Gd
3Ga
5O
12: Cr, Ce scintillating ceramics such as [U.S.P.5318722] also is successfully applied to industry and commercial X-CT.
Chinese patent CN1587187A adopts combustion method powder process, and methods such as high temperature hot pressing or hot isostatic pressing have been prepared hafnium acid lanthanum base transparent ceramic, but because sintering condition is harsh, the crystalline ceramics transmitance of preparing is not high.
In addition, Chinese patent CN102515752A discloses a kind of zirconic acid lanthanum yttrium stupalith and preparation method thereof recently, and it adopts glycocoll-nitrate salt combustion method to prepare zirconic acid lanthanum yttrium stupalith.
Summary of the invention
The purpose of this invention is to provide a kind of novel transparent stupalith than high visible light transmissivity and preparation method thereof that has; For the crystalline ceramics field increases a kind of product innovation, to satisfy the performance requriements of fields such as information detection, laser medium, high temperature form, high refractive index camera lens, scintillator to transparent ceramic material.
On the basis of above-mentioned prior art, the inventor recognizes that zirconic acid lanthanum gadolinium not only has high-density, high effective atomic number, can satisfy the requirement of scintillator to material, and its crystalline structure is stable cube pyrochlore constitution, does not have birefringent phenomenon.Therefore, zirconic acid lanthanum gadolinium is expected to be prepared into crystalline ceramics, and is expected to the substrate material as ceramic scintillator.The powder sintering activity of conventional solid-state method preparation is low, sintering temperature is high, is difficult to prepare the crystalline ceramics of single phase.It is that incendiary material prepares the active zirconic acid lanthanum of high sintering gadolinium powder with the glycocoll that the present invention also adopts combustion method, and the powder that makes can vacuum sintering prepare crystalline ceramics under the condition of no sintering aid.
At first, the present invention provides a kind of rare earth ion doped zirconic acid lanthanum gadolinium transparent ceramic material, and wherein, the chemical constitution of said zirconic acid lanthanum gadolinium transparent ceramic material is La
0.4-yRE
yGd
1.6Zr
2O
7, 0.002≤y≤0.04 wherein, RE is Pr, Tb or Sm.
Compared with prior art; The visible light transmissivity of rare earth ion doped zirconic acid lanthanum gadolinium transparent ceramic material provided by the invention is high; The thick sample of 1mm through twin polishing can reach more than 70% in the straight line transmitance of visible light wave range; Sintered density is high simultaneously, and specific refractory power can satisfy the application requiring in fields such as information detection, laser medium, high temperature form and high refractive index camera lens, scintillators near 2.1.
On the other hand, the present invention also provides the method for the above-mentioned rare earth ion doped zirconic acid lanthanum gadolinium transparent ceramic material of preparation, comprising: powder preparing operation, molding procedure, sintering circuit and annealing operation; Wherein, said powder preparing operation adopts glycocoll-nitrate salt combustion method to make zirconic acid lanthanum gadolinium powder, and said molding procedure adopts dry-pressing to combine cold isostatic compaction technology.
Method of the present invention adopts glycocoll-nitrate salt combustion method to prepare rare earth ion doped zirconic acid lanthanum gadolinium powder, and low, easy to operate to the preparation condition requirement, combustion reaction time is short, adopts dry-pressing to combine cold isostatic compaction technology can make fine and close biscuit of ceramics.
In the present invention, said powder preparing operation can comprise: according to La
0.4-yRE
yGd
1.6Zr
2O
7Atomic molar score another name get zirconium nitrate, Lanthanum trinitrate, Gadolinium trinitrate and rare earth ion nitrate salt and be configured to nitrate aqueous solution; Add glycocoll as incendiary material, regulator solution pH value is 2～6; Combustion reactions takes place in heating, to obtain the presoma powder; And said presoma powder heat-treated.
In the method for the invention, the precursor solution of wide range pH value all can be prepared the presoma powder, compares with other liquid phase method to have remarkable advantages.
Again, preferably, the nitrate ion in the said nitrate aqueous solution and the mol ratio of said glycocoll can be 2:1.
Said heat treated condition can be 800～1200 ℃ of insulations 2～4 hours.
Said powder preparing operation also can comprise, the powder after the thermal treatment is carried out ball milling, drying and screening handle to obtain the powder that median size is 50～100nm.
The processing condition of described ball milling can be with 250 changeed the per minute ball milling 20 hours; Said exsiccant condition is following dry 24 hours at 60 ℃.
Again, in the present invention, said molding procedure can comprise: under 2.5～5MPa pressure, said rare earth ion doped zirconic acid lanthanum gadolinium powder was carried out two-sided pressurization and pressurize 1 minute, make it dry-pressing formedly be biscuit; And the dry-pressing formed biscuit that makes is carried out isostatic cool pressing handle and to make rare earth ion doped zirconic acid lanthanum gadolinium biscuit of ceramics in 1～3 minute under 180～230MPa pressure.
Said sintering circuit can comprise: said rare earth ion doped zirconic acid lanthanum gadolinium biscuit of ceramics is first 800～1400 ℃ of pre-burnings 2～4 hours; And be 10 in vacuum tightness
-2Pa～10
-4Under the vacuum condition of Pa in 1800～1900 ℃ of sintering 4～10 hours.
Said annealing operation can comprise: the sample behind the sintering is incubated 4～10 hours down in 1400～1600 ℃ in air atmosphere.
Advantages such as preparation method of the present invention has that technology is simple, controllability good, need not sintering aid, sintering condition is relatively simple, easy handling and production.
Description of drawings
Fig. 1 illustrates the X ray diffracting spectrum of praseodymium doping zirconic acid lanthanum gadolinium transparent ceramic material of the present invention;
Fig. 2 illustrates the X ray diffracting spectrum of terbium doped zirconic acid lanthanum gadolinium transparent ceramic material of the present invention;
Fig. 3 illustrates the X ray diffracting spectrum of samarium doping zirconic acid lanthanum gadolinium transparent ceramic material of the present invention;
Fig. 4 illustrates the transmittance curve of praseodymium doping zirconic acid lanthanum gadolinium transparent ceramic material of the present invention zirconic acid lanthanum gadolinium ceramic plate of thickness 1mm after twin polishing;
Fig. 5 illustrates the transmittance curve of terbium doped zirconic acid lanthanum gadolinium transparent ceramic material of the present invention zirconic acid lanthanum gadolinium ceramic plate of thickness 1mm after twin polishing;
Fig. 6 illustrates the transmittance curve of samarium doping zirconic acid lanthanum gadolinium transparent ceramic material of the present invention zirconic acid lanthanum gadolinium ceramic plate of thickness 1mm after twin polishing;
Fig. 7 illustrates the fluorescence spectrum of praseodymium doping zirconic acid lanthanum gadolinium transparent ceramic material of the present invention;
Fig. 8 illustrates the fluorescence spectrum of terbium doped zirconic acid lanthanum gadolinium transparent ceramic material of the present invention;
Fig. 9 illustrates the fluorescence spectrum of samarium doping zirconic acid lanthanum gadolinium transparent ceramic material of the present invention.
Embodiment
Further specify the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment and/or accompanying drawing only are used to explain the present invention, and unrestricted the present invention.
Zirconic acid lanthanum gadolinium transparent ceramic material (La of the present invention
0.4-yRE
yGd
1.6Zr
2O
7, 0.002≤y≤0.04, RE is Pr, Tb or Sm) preparation comprise: powder preparing, moulding, sintering and annealing heat treatment step.
Described powder preparing adopts glycocoll-nitrate salt combustion method; Particularly with nitrate salt; Promptly, rare, the rare earth ion nitrate salt (praseodymium nitrate, Terbium trinitrate, samaric nitrate) of zirconium nitrate, Lanthanum trinitrate, Gadolinium trinitrate is raw material, as incendiary material, adopts combustion method to prepare zirconic acid lanthanum gadolinium powder with glycocoll.The raw material that the present invention adopts preferably adopts high pure raw material, for example more than 99.9%, more preferably more than 99.99%; Will also be understood that; The nitrate salt that adopts can be aqueous hydrate forms, promptly, in the above-mentioned nitrate salt one or more are hydrate forms, for example adopt Zr (NO
3)
43H
2O.In addition, should also be understood that can adopt oxide compound and nitric acid to dispose above-mentioned nitrate salt directly is used for following preparation process, for example with Gd
2O
3Be dissolved in excessive nitric acid preparation Gadolinium trinitrate solution.
Press La
0.4-yRE
yGd
1.6Zr
2O
7The mol ratio of each atom (promptly, 2: (0.4-y): y:1.60.002≤y≤0.04)) takes by weighing zirconium nitrate, Lanthanum trinitrate, Gadolinium trinitrate and rare earth ion nitrate salt, is dissolved in an amount of water, and preferred deionized water makes nitrate aqueous solution.Here, the volumetric molar concentration of nitrate ion can be 0.1～3mol/L in the nitrate aqueous solution that makes.
In above-mentioned nitrate aqueous solution, add an amount of incendiary material glycocoll, stirring is dissolved it fully.Here to be preferably be that the mol ratio of the nitrate ion in itself and the nitrate aqueous solution is 1:2 to the add-on of glycocoll.
The pH value of regulator solution is 2～6; Heating makes the generation combustion reactions, obtains the presoma powder., can adopt ammoniacal liquor to come regulator solution pH here, also be suitable for, for example triethylamine etc. but should understand other suitable pH value regulators.Heating can be carried out in heat-stable vessel, preferably has the vessel of big water surface of evaporation, and for example quartz crucible heats the moisture evaporation and the final generation combustion reactions that make solution earlier.Can be 2 minutes combustion time here.
Then, the presoma powder is heat-treated.Said heat-treat condition was preferably: 800～1200 ℃ of insulations 2～4 hours.
Can handle carry out ball milling, drying and screening through heat treated powder, to obtain the rare earth ion doped zirconic acid lanthanum gadolinium powder of appropriate particle size and homogeneous, for example median size is preferably the powder of 50～100nm.
Adopt dry-pressing to combine cold isostatic compaction technology to make the rare earth ion doped zirconic acid lanthanum gadolinium powder moulding that makes then.Described dry-pressing combines cold isostatic compaction technology can comprise the steps: under 2.5～5MPa pressure, and said rare earth ion doped zirconic acid lanthanum gadolinium powder was carried out two-sided pressurization and pressurize 1 minute, makes it dry-pressing formedly be biscuit; Then the dry-pressing formed biscuit that makes is carried out the isostatic cool pressing processing under 180～230MPa pressure and made rare earth ion doped zirconic acid lanthanum gadolinium biscuit of ceramics in 1～3 minute.Said dry-pressing formed the processing with isostatic cool pressing all preferably at room temperature carried out.
Then carry out sintering, said sintering can comprise: the rare earth ion doped zirconic acid lanthanum gadolinium biscuit of ceramics that will make is earlier 800～1400 ℃ of pre-burnings 2～4 hours, then under vacuum condition in 1800～1900 ℃ of sintering 4～10 hours.Said vacuum condition can be: vacuum tightness 10
-2Pa～10
-4Pa.
Carry out anneal at last: the sample behind the sintering is incubated 4～10 hours down in 1400～1600 ℃ in air atmosphere.
Rare earth ion doped zirconic acid lanthanum gadolinium transparent ceramic material provided by the invention can reach more than 70% through the thick sample of 1mm of twin polishing in the straight line transmitance of visible light wave range; Sintered density is high simultaneously; Specific refractory power can satisfy the application requiring in fields such as information detection, laser medium, high temperature form and high refractive index camera lens, scintillators near 2.1.Advantages such as in addition, preparation method of the present invention has that technology is simple, controllability good, need not sintering aid, sintering condition is relatively simple, easy handling and production.
Embodiment further give an example below to specify the present invention.Should understand equally; Following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The temperature of reaction that following example is concrete, time charging capacity etc. also only are examples in the OK range, promptly, those skilled in the art can do through the explanation of this paper and select in the suitable scope, and do not really want to be defined in the concrete numerical value of hereinafter example.
A) powder preparing: with zirconium nitrate (Zr (NO
3)
43H
2O, 99.9%), Lanthanum trinitrate (La (NO
3)
3, 99.99%), praseodymium nitrate (Pr (NO
3)
3, 99.99%) and Gadolinium trinitrate (Gd (NO
3)
399.995%) be 2 according to Zr, La, Pr, Gd mol ratio: (0.4-y): y:1.6 (y=0.002; Promptly, the doping of praseodymium is 0.1at%) weighing is dissolved in and is mixed with nitrate aqueous solution in the deionized water; Chemical equation according to the perfect combustion reaction need add an amount of fuel glycocoll then, stirs it is dissolved fully, and the pH value of using the ammoniacal liquor regulator solution afterwards is 4.Precursor solution is transferred to quartz crucible, and heating makes moisture evaporation and final generation combustion reactions on electric furnace, places retort furnace to carry out powder thermal treatment in 2 hours 1200 ℃ of insulations the precursor powder that obtains afterwards.Make ceramic powder and sieve through ball milling, obtaining median size is the praseodymium doping zirconic acid lanthanum gadolinium nano-powder of 50～100nm;
B) moulding: adopt dry-pressing (2.5MPa, pressurize 1 minute) to combine isostatic cool pressing (200MPa, pressurize 2 minutes) moulding process, obtain praseodymium doping zirconic acid lanthanum gadolinium biscuit of ceramics;
C) sintering: the zirconic acid lanthanum gadolinium biscuit of ceramics that makes is first 1400 ℃ of pre-burnings 3 hours, then in vacuum tightness 10
-2Pa～10
-4Under the vacuum condition of Pa in 1850 ℃ of sintering 6 hours;
D) annealing thermal treatment: the sample behind the sintering is incubated 5 hours down in 1500 ℃ in air atmosphere, promptly gets praseodymium doping zirconic acid lanthanum gadolinium (La
0.398Pr
0.002Gd
1.6Zr
2O
7) transparent ceramic material.
The basic process that repeats embodiment 1, difference are y=0.01 (promptly, the doping of praseodymium be 0.5at%), make praseodymium doping zirconic acid lanthanum gadolinium (La
0.39Pr
0.01Gd
1.6Zr
2O
7) transparent ceramic material.
The basic process that repeats embodiment 1, difference are y=0.02 (promptly, the doping of praseodymium be 1.0at%), make praseodymium doping zirconic acid lanthanum gadolinium (La
0.38Pr
0.02Gd
1.6Zr
2O
7) transparent ceramic material.
Embodiment 4
The basic process that repeats embodiment 1, difference are y=0.04 (promptly, the doping of praseodymium be 2.0at%), make praseodymium doping zirconic acid lanthanum gadolinium (La
0.36Pr
0.04Gd
1.6Zr
2O
7) transparent ceramic material.
Fig. 1 illustrates the X ray diffracting spectrum of the praseodymium doping zirconic acid lanthanum gadolinium transparent ceramic material that embodiment 1～4 makes, and visible by Fig. 1: prepared praseodymium doping zirconic acid lanthanum gadolinium crystalline ceramics is single pyrochlore constitution.
It is the transmittance curve of the crystalline ceramics photo of 1mm through thickness after the twin polishing that Fig. 4 illustrates the praseodymium doping zirconic acid lanthanum gadolinium transparent ceramic material that embodiment 1～4 makes, and visible by Fig. 4: prepared praseodymium doping zirconic acid lanthanum gadolinium transparent ceramic material has the good optical transparency at visible light and the equal scope of near-infrared band.
Fig. 7 illustrates the fluorescence spectrum of the praseodymium doping zirconic acid lanthanum gadolinium transparent ceramic material that embodiment 1～4 makes, and visible by Fig. 7: prepared praseodymium doping zirconic acid lanthanum gadolinium transparent ceramic material all shows the characteristics of luminescence at visible-range.
Embodiment 5
A) powder preparing: with zirconium nitrate (Zr (NO
3)
43H
2O, 99.9%), Lanthanum trinitrate (La (NO
3)
3, 99.99%), Terbium trinitrate (Tb (NO
3)
3, 99.99%) and Gadolinium trinitrate (Gd (NO
3)
399.995%) be 2 according to Zr, La, Tb, Gd mol ratio: (0.4-y): y:1.6 (y=0.002; Promptly, the doping of terbium is 0.1at%) weighing is dissolved in and is mixed with nitrate aqueous solution in the deionized water; Chemical equation according to the perfect combustion reaction need add an amount of fuel glycocoll then, stirs it is dissolved fully, and the pH value of using the ammoniacal liquor regulator solution afterwards is 2.Precursor solution is transferred to quartz crucible, and heating makes moisture evaporation and final generation combustion reactions on electric furnace, places retort furnace to carry out powder thermal treatment in 2 hours 1200 ℃ of insulations the precursor powder that obtains afterwards.Make ceramic powder and sieve through ball milling, obtaining median size is the terbium doped zirconic acid lanthanum gadolinium nano-powder of 50～100nm;
B) moulding: adopt dry-pressing (2.5MPa, pressurize 1 minute) to combine isostatic cool pressing (200MPa, pressurize 2 minutes) moulding process, obtain terbium doped zirconic acid lanthanum gadolinium biscuit of ceramics;
C) sintering: the terbium doped zirconic acid lanthanum gadolinium biscuit of ceramics that will make is earlier 1400 ℃ of pre-burnings 3 hours, then in vacuum tightness 10
-2Pa～10
-4Under the vacuum condition of Pa in 1850 ℃ of sintering 6 hours;
D) annealing thermal treatment: the sample behind the sintering is incubated 5 hours down in 1500 ℃ in air atmosphere, promptly gets terbium doped zirconic acid lanthanum gadolinium (La
0.398Tb
0.002Gd
1.6Zr
2O
7) transparent ceramic material.
Embodiment 6
The basic process that repeats embodiment 5, difference are y=0.01 (promptly, the doping of terbium be 0.5at%), make terbium doped zirconic acid lanthanum gadolinium (La
0.39Tb
0.01Gd
1.6Zr
2O
7) transparent ceramic material.
Embodiment 7
The basic process that repeats embodiment 5, difference are y=0.02 (promptly, the doping of terbium be 1.0at%), make terbium doped zirconic acid lanthanum gadolinium (La
0.38Tb
0.02Gd
1.6Zr
2O
7) transparent ceramic material.
Embodiment 8
The basic process that repeats embodiment 5, difference are y=0.04 (promptly, the doping of terbium be 2.0at%), make terbium doped zirconic acid lanthanum gadolinium (La
0.36Tb
0.04Gd
1.6Zr
2O
7) transparent ceramic material.
Fig. 2 illustrates the X ray diffracting spectrum of the terbium doped zirconic acid lanthanum gadolinium transparent ceramic material that embodiment 7～8 makes, and visible by Fig. 2: prepared terbium doped zirconic acid lanthanum gadolinium crystalline ceramics is single pyrochlore constitution.
It is the transmittance curve of the crystalline ceramics photo of 1mm through thickness after the twin polishing that Fig. 5 illustrates the terbium doped zirconic acid lanthanum gadolinium transparent ceramic material that embodiment 7～8 makes; Visible by Fig. 5: prepared terbium doped zirconic acid lanthanum gadolinium transparent ceramic material has the good optical transparency at visible light and the equal scope of near-infrared band, and wherein the adulterated zirconic acid lanthanum of 0.1at%Tb gadolinium can reach 95.8% of theoretical value in the transmitance at 633nm place.
Fig. 8 illustrates the fluorescence spectrum of the terbium doped zirconic acid lanthanum gadolinium transparent ceramic material that embodiment 7～8 makes, and visible by Fig. 8: prepared terbium doped zirconic acid lanthanum gadolinium transparent ceramic material all shows the characteristics of luminescence at visible-range.
Embodiment 9
A) powder preparing: with zirconium nitrate (Zr (NO
3)
43H
2O, 99.9%), Lanthanum trinitrate (La (NO
3)
3, 99.99%), samaric nitrate (Sm (NO
3)
3, 99.99%) and Gadolinium trinitrate (Gd (NO
3)
399.995%) be 2 according to Zr, La, Sm, Gd mol ratio: (0.4-y): y:1.6 (y=0.002; Promptly, the doping of samarium is 0.1at%) weighing is dissolved in and is mixed with nitrate aqueous solution in the deionized water; Chemical equation according to the perfect combustion reaction need add an amount of fuel glycocoll then, stirs it is dissolved fully, and the pH value of using the ammoniacal liquor regulator solution afterwards is 6.Precursor solution is transferred to quartz crucible, and heating makes moisture evaporation and final generation combustion reactions on electric furnace, places retort furnace to carry out powder thermal treatment in 2 hours 1200 ℃ of insulations the precursor powder that obtains afterwards.Make ceramic powder and sieve through ball milling, obtaining median size is the samarium doping zirconic acid lanthanum gadolinium nano-powder of 50～100nm;
B) moulding: adopt dry-pressing (2.5MPa, pressurize 1 minute) to combine isostatic cool pressing (200MPa, pressurize 2 minutes) moulding process, obtain samarium doping zirconic acid lanthanum gadolinium biscuit of ceramics;
C) sintering: the samarium doping zirconic acid lanthanum gadolinium biscuit of ceramics that makes is first 1400 ℃ of pre-burnings 3 hours, then in vacuum tightness 10
-2Pa～10
-4Under the vacuum condition of Pa in 1850 ℃ of sintering 6 hours;
D) annealing thermal treatment: the sample behind the sintering is incubated 5 hours down in 1500 ℃ in air atmosphere, promptly gets samarium doping zirconic acid lanthanum gadolinium (La
0.398Sm
0.002Gd
1.6Zr
2O
7) transparent ceramic material.
The basic process that repeats embodiment 9, difference are y=0.01 (promptly, the doping of samarium be 0.5at%), make samarium doping zirconic acid lanthanum gadolinium (La
0.39Sm
0.01Gd
1.6Zr
2O
7) transparent ceramic material.
Embodiment 11
The basic process that repeats embodiment 9, difference are y=0.02 (promptly, the doping of samarium be 1.0at%), make samarium doping zirconic acid lanthanum gadolinium (La
0.38Sm
0.02Gd
1.6Zr
2O
7) transparent ceramic material.
Embodiment 12
The basic process that repeats embodiment 9, difference are y=0.04 (promptly, the doping of samarium be 2.0at%), make samarium doping zirconic acid lanthanum gadolinium (La
0.36Sm
0.04Gd
1.6Zr
2O
7) transparent ceramic material.
Fig. 3 illustrates the X ray diffracting spectrum of the samarium doping zirconic acid lanthanum gadolinium transparent ceramic material that embodiment 9～12 makes, and visible by Fig. 3: prepared samarium doping zirconic acid lanthanum gadolinium crystalline ceramics is single pyrochlore constitution.
It is the transmittance curve of the crystalline ceramics photo of 1mm through thickness after the twin polishing that Fig. 6 illustrates the samarium doping zirconic acid lanthanum gadolinium transparent ceramic material that embodiment 9～12 makes, and visible by Fig. 6: prepared terbium doped zirconic acid lanthanum gadolinium transparent ceramic material has the good optical transparency at visible light and the equal scope of near-infrared band.
Fig. 9 illustrates the fluorescence spectrum of the samarium doping zirconic acid lanthanum gadolinium transparent ceramic material that embodiment 9～12 makes, and visible by Fig. 9: prepared samarium doping zirconic acid lanthanum gadolinium transparent ceramic material all shows the characteristics of luminescence at visible-range.
Industrial applicability: rare earth ion doped zirconic acid lanthanum gadolinium transparent ceramic material visible light transmissivity provided by the invention is high; Sintered density is high; Specific refractory power is near 2.1; Can satisfy application requiring, have broad application prospects in fields such as information detection, laser medium, high temperature form and high refractive index camera lens, scintillators.
Claims (10)
1. a rare earth ion doped zirconic acid lanthanum gadolinium transparent ceramic material is characterized in that the chemical constitution of said zirconic acid lanthanum gadolinium transparent ceramic material is La
0.4-yRE
yGd
1.6Zr
2O
7, 0.002≤y≤0.04 wherein, RE is Pr, Tb or Sm.
2. a method for preparing the described rare earth ion doped zirconic acid lanthanum gadolinium transparent ceramic material of claim 1 comprises: powder preparing operation, molding procedure, sintering circuit and annealing operation; It is characterized in that said powder preparing operation adopts glycocoll-nitrate salt combustion method to make rare earth ion doped zirconic acid lanthanum gadolinium powder, said molding procedure adopts dry-pressing to combine cold isostatic compaction technology.
3. method according to claim 2 is characterized in that, said powder preparing operation comprises:
According to La
0.4-yRE
yGd
1.6Zr
2O
7Atomic molar score another name get zirconium nitrate, Lanthanum trinitrate, Gadolinium trinitrate and rare earth ion nitrate salt and be configured to nitrate aqueous solution;
Add glycocoll as incendiary material, regulator solution pH value is 2～6;
Combustion reactions takes place in heating, to obtain the presoma powder; And said presoma powder heat-treated.
4. method according to claim 3 is characterized in that, the nitrate ion in the said nitrate aqueous solution and the mol ratio of said glycocoll are 2:1.
5. according to claim 3 or 4 described methods, it is characterized in that said heat treated condition is 800～1200 ℃ of insulations 2～4 hours.
6. according to each described method in the claim 3～4, it is characterized in that said powder preparing operation also comprises, the powder after the thermal treatment is carried out ball milling, drying and screening handle to obtain the powder that median size is 50～100 nm.
7. method according to claim 6 is characterized in that, the processing condition of described ball milling are to change the per minute ball milling 20 hours with 250; Said exsiccant condition is following dry 24 hours at 60 ℃.
8. according to each described method in the claim 3～4, it is characterized in that said molding procedure comprises:
Under 2.5～5 MPa pressure, said rare earth ion doped zirconic acid lanthanum gadolinium powder was carried out two-sided pressurization and pressurize 1 minute, make it dry-pressing formedly be biscuit; And the dry-pressing formed biscuit that makes is carried out isostatic cool pressing handle and to make rare earth ion doped zirconic acid lanthanum gadolinium biscuit of ceramics in 1～3 minute under 180～230 MPa pressure.
9. according to each described method in the claim 3～4, it is characterized in that said sintering circuit comprises:
Said rare earth ion doped zirconic acid lanthanum gadolinium biscuit of ceramics is first 800～1400 ℃ of pre-burnings 2～4 hours; And
In vacuum tightness is 10
-2Pa～10
-4Under the vacuum condition of Pa in 1800～1900 ℃ of sintering 4～10 hours.
10. according to each described method in the claim 3～5, it is characterized in that said annealing operation comprises: the sample behind the sintering is incubated 4～10 hours down in 1400～1600 ℃ in air atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210337520.2A CN102815941B (en) | 2012-09-13 | 2012-09-13 | Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210337520.2A CN102815941B (en) | 2012-09-13 | 2012-09-13 | Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102815941A true CN102815941A (en) | 2012-12-12 |
| CN102815941B CN102815941B (en) | 2014-04-02 |
Family
ID=47300446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210337520.2A Active CN102815941B (en) | 2012-09-13 | 2012-09-13 | Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102815941B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107267148A (en) * | 2017-07-26 | 2017-10-20 | 齐齐哈尔大学 | A kind of terbium ion doping zirconic acid lanthanum fluorescent material and preparation method thereof |
| CN109503164A (en) * | 2018-12-13 | 2019-03-22 | 云南大学 | The method that combustion method prepares ceramic powder |
| CN111099909A (en) * | 2019-12-30 | 2020-05-05 | 浙江大学 | High-performance ceramic with surface modified polycrystalline mullite fiber compounded with rare earth lanthanum zirconate and preparation method thereof |
| CN111646504A (en) * | 2020-05-29 | 2020-09-11 | 厦门理工学院 | Nano lanthanum zirconate and preparation method thereof |
| CN112279639A (en) * | 2020-11-04 | 2021-01-29 | 西南科技大学 | Preparation method of strontium titanate energy storage dielectric ceramic material with high breakdown and high energy storage density |
| CN116514548A (en) * | 2023-04-27 | 2023-08-01 | 四川大学 | Method for preparing high-transmittance lanthanum gadolinium zirconate transparent ceramic by solid phase method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007011409A2 (en) * | 2004-11-09 | 2007-01-25 | General Electric Company | Transparent multi-cation ceramic and method of making |
| CN101312926A (en) * | 2005-11-25 | 2008-11-26 | 株式会社村田制作所 | Transparent ceramic and its manufacture method and optical parts and optical device |
| CN102167587A (en) * | 2010-12-21 | 2011-08-31 | 中国科学院上海光学精密机械研究所 | Lanthanum-zirconium codoped rare earth sesquioxide transparent ceramic and preparation method thereof |
| CN102515752A (en) * | 2011-12-20 | 2012-06-27 | 中国科学院上海硅酸盐研究所 | Transparent ceramic material and preparation method thereof |
-
2012
- 2012-09-13 CN CN201210337520.2A patent/CN102815941B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007011409A2 (en) * | 2004-11-09 | 2007-01-25 | General Electric Company | Transparent multi-cation ceramic and method of making |
| CN101312926A (en) * | 2005-11-25 | 2008-11-26 | 株式会社村田制作所 | Transparent ceramic and its manufacture method and optical parts and optical device |
| CN102167587A (en) * | 2010-12-21 | 2011-08-31 | 中国科学院上海光学精密机械研究所 | Lanthanum-zirconium codoped rare earth sesquioxide transparent ceramic and preparation method thereof |
| CN102515752A (en) * | 2011-12-20 | 2012-06-27 | 中国科学院上海硅酸盐研究所 | Transparent ceramic material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107267148A (en) * | 2017-07-26 | 2017-10-20 | 齐齐哈尔大学 | A kind of terbium ion doping zirconic acid lanthanum fluorescent material and preparation method thereof |
| CN109503164A (en) * | 2018-12-13 | 2019-03-22 | 云南大学 | The method that combustion method prepares ceramic powder |
| CN111099909A (en) * | 2019-12-30 | 2020-05-05 | 浙江大学 | High-performance ceramic with surface modified polycrystalline mullite fiber compounded with rare earth lanthanum zirconate and preparation method thereof |
| CN111646504A (en) * | 2020-05-29 | 2020-09-11 | 厦门理工学院 | Nano lanthanum zirconate and preparation method thereof |
| CN112279639A (en) * | 2020-11-04 | 2021-01-29 | 西南科技大学 | Preparation method of strontium titanate energy storage dielectric ceramic material with high breakdown and high energy storage density |
| CN116514548A (en) * | 2023-04-27 | 2023-08-01 | 四川大学 | Method for preparing high-transmittance lanthanum gadolinium zirconate transparent ceramic by solid phase method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102815941B (en) | 2014-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wen et al. | Synthesis of nanocrystalline yttria powder and fabrication of transparent YAG ceramics | |
| CN100455536C (en) | Luetcium aluminum garnet -base transparent ceramic and process for preparing same | |
| CN102815941B (en) | Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof | |
| Tachiwaki et al. | Novel synthesis of Y3Al5O12 (YAG) leading to transparent ceramics | |
| Liu et al. | Influence of pH values on (Nd+ Y): Al molar ratio of Nd: YAG nanopowders and preparation of transparent ceramics | |
| Yu et al. | Fabrication of Nd: YAG transparent ceramics using powders synthesized by citrate sol-gel method | |
| CN102515752A (en) | Transparent ceramic material and preparation method thereof | |
| CN111925202B (en) | Yttrium aluminum garnet powder without sintering aid, yttrium aluminum garnet ceramic, and preparation method and application thereof | |
| Chen et al. | Systematic optimization of ball milling for highly transparent Yb: YAG ceramic using co-precipitated raw powders | |
| Sun et al. | Production and optical properties of Ce3+‐activated and Lu3+‐stabilized transparent gadolinium aluminate garnet ceramics | |
| CN101985398A (en) | Method for preparing transparent polycrystalline Re:YAG ceramic | |
| CN108751991B (en) | Preparation of Tb: Lu by laser sintering2O3Method for producing ceramic | |
| CN102690113A (en) | Method for preparing Ce:Lu3Al5O12 transparent ceramic scintillator by low-temperature vacuum sintering | |
| CN101580393B (en) | Preparation method of transparent yttrium hafnate ceramics | |
| CN102815945B (en) | Lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof | |
| CN1275903C (en) | Textured columbate leadless piezoelectric materials and method for making same | |
| CN1256300C (en) | Process for preparing yttrium oxide based transparent ceramic material | |
| Luo et al. | Fabrication and spectral properties of hot-pressed Co: MgAl2O4 transparent ceramics for saturable absorber | |
| Liu et al. | Transmittance, photoluminescence and electrical properties in Er-DOPED 0.98 K0. 5Na0. 5NbO3-0.02 Sr (Yb0. 5Ta0. 5) O3 ferroelectric ceramics | |
| Bettes et al. | Synthesis and processing of transparent polycrystalline doped yttrium aluminum garnet: a review | |
| Wang et al. | Preparation of YAG powders and ceramics through mixed precipitation method | |
| CN107473730A (en) | It is a kind of to prepare fine grain, the method for high-strength light-weight magnesite-alumina spinel refractories | |
| Fu et al. | Ce3+: Lu3Al5O12–Al2O3 optical nanoceramic scintillators elaborated via a low-temperature glass crystallization route | |
| CN102557624B (en) | Preparation method of zirconic acid yttrium transparent ceramics | |
| Ni et al. | Synthesis of yttria nanopowder with poly acrylic acid as dispersant for highly transparent yttria ceramics |
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 |