CN102815941B - 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
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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 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 high strength, high rigidity, high insulation, the intrinsic characteristic of stupalith 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, far below the preparation temperature of monocrystalline, especially has practical significance for some dystectic materials.Crystalline ceramics can also require to realize easily the Uniform Doped of high concentration ion according to device application, avoid low, the pockety situation of doping content causing due to crystal growth technique restriction.In addition, utilize ceramic preparation method can obtain large size and complex-shaped material.Research shows, the performance of some crystalline ceramics has has met or exceeded monocrystal material, and is expected in some specific occasions progressively substitute monocrystalline optical material.In addition, compare with glass material, high temperature resistant, the advantage such as thermal conductivity is high, hardness is high, strong shock resistance that crystalline ceramics has, has its unique using value at some special occasions.
From 1962, since in US Patent No. 3026210, reported first is prepared translucent alumina ceramics, transparent ceramic material was all obtained very large progress in kind and application.Prepared at present YAG:Nd[A.Ikesue, T.Kinoshita, K.Yoshida, J.Am.Ceram.Soc., 1995,78 (4): 1033-1037] etc. laser ceramics, 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[U.S.P.5318722] etc. scintillating ceramic and be successfully applied to industry and business X-CT.
Chinese patent CN1587187A adopts combustion method powder process, and the 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 glycine-nitrate process to prepare zirconic acid lanthanum yttrium stupalith.
Summary of the invention
The object of this invention is to provide a kind of novel transparent stupalith compared with high visible light transmissivity and preparation method thereof that has, for crystalline ceramics field increases a kind of product innovation, to meet the performance requriementss of field to transparent ceramic material such as information detection, laser medium, high-temperature window, high refractive index camera lens, scintillator.
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 meet 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.Powder sintering activity prepared by conventional solid-state method is low, sintering temperature is high, is difficult to prepare the crystalline ceramics of single-phase.The present invention also adopts combustion method to take glycine to prepare the zirconic acid lanthanum gadolinium powder of high sintering activity as incendiary material, and the powder making can vacuum sintering be prepared crystalline ceramics under the condition without sintering aid.
First, the invention provides a kind of rare earth ion doped zirconic acid lanthanum gadolinium transparent ceramic material, wherein, the chemical constitution of described 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, specific refractory power approaches 2.1, can meet the application requiring in fields such as information detection, laser medium, high-temperature window and high refractive index camera lens, scintillators.
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 preparation section, molding procedure, sintering circuit and annealing operation; Wherein, described powder preparation section adopts glycine-nitrate process to make zirconic acid lanthanum gadolinium powder, and described molding procedure adopts dry-pressing in conjunction with cold isostatic compaction technique.
Method of the present invention adopts glycine-nitrate process to prepare rare earth ion doped zirconic acid lanthanum gadolinium powder, and low, easy to operate to preparation condition requirement, combustion reaction time is short, adopts dry-pressing can make fine and close biscuit of ceramics in conjunction with cold isostatic compaction technique.
In the present invention, described powder preparation section can comprise: according to La
0.4-yrE
ygd
1.6zr
2o
7atomic molar score another name get zirconium nitrate, lanthanum nitrate, Gadolinium trinitrate and rare earth ion nitrate and be configured to nitrate aqueous solution; Add glycine as incendiary material, regulator solution pH value is 2～6; There is combustion reactions in heating, to obtain presoma powder; And described presoma powder is heat-treated.
In the method for the invention, the precursor solution of wide range pH value all can be prepared presoma powder, compares and has obvious advantage with other liquid phase method.
Again, preferably, the nitrate ion in described nitrate aqueous solution and the mol ratio of described glycine can be 2:1.
Described heat treated condition can be 800～1200 ℃ of insulations 2～4 hours.
Described powder preparation section also can comprise, to the powder after thermal treatment carry out ball milling, dry and screening is processed take and is obtained the powder that median size is 50～100nm.
The processing condition of described ball milling can be with 250 and turn per minute ball milling 20 hours; Described dry condition is to be dried 24 hours at 60 ℃.
Again, in the present invention, described molding procedure can comprise: under 2.5～5MPa pressure, described rare earth ion doped zirconic acid lanthanum gadolinium powder is carried out to two-sided pressurization pressurize 1 minute, making it dry-pressing formed is biscuit; And the dry-pressing formed biscuit making is carried out to isostatic cool pressing under 180～230MPa pressure and process and within 1～3 minute, to make rare earth ion doped zirconic acid lanthanum gadolinium biscuit of ceramics.
Described sintering circuit can comprise: described 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.
Described annealing operation can comprise: the sample after sintering is incubated to 4～10 hours in air atmosphere at 1400～1600 ℃.
The advantages such as preparation method of the present invention has that technique is simple, controllability good,, easy handling relatively simple without sintering aid, sintering condition and production.
Accompanying drawing explanation
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
Below in conjunction with accompanying drawing and following embodiment, further illustrate the present invention, should be understood that following embodiment and/or accompanying drawing are only for the present invention is described, 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 preparation, moulding, sintering and annealing heat treatment step.
Described powder preparation adopts glycine-nitrate process, particularly with nitrate,, rare, the rare earth ion nitrate (praseodymium nitrate, Terbium trinitrate, samaric nitrate) of zirconium nitrate, lanthanum nitrate, Gadolinium trinitrate is raw material, usings glycine as incendiary material, adopts combustion method to prepare zirconic acid lanthanum gadolinium powder.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 adopting can be moisture hydrate forms, and one or more, in above-mentioned nitrate 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 configure above-mentioned nitrate is directly used in following preparation process, for example, by 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 (, 2:(0.4-y): y:1.60.002≤y≤0.04)) take zirconium nitrate, lanthanum nitrate, Gadolinium trinitrate and rare earth ion nitrate, be dissolved in appropriate water, preferably deionized water makes nitrate aqueous solution.Here, in the nitrate aqueous solution making, the volumetric molar concentration of nitrate ion can be 0.1～3mol/L.
In above-mentioned nitrate aqueous solution, add appropriate incendiary material glycine, stir it is dissolved completely.Here to be preferably be that the mol ratio of the nitrate ion in itself and nitrate aqueous solution is 1:2 to the add-on of glycine.
The pH value of regulator solution is 2～6; Heating makes to occur combustion reactions, obtains presoma powder., can adopt ammoniacal liquor to carry out regulator solution pH here, but should understand other suitable pH value conditioning agents, also be suitable for, such as triethylamine etc.Heating can be carried out in heat-resisting vessel, preferably has the vessel of large water surface of evaporation, and for example quartz crucible, heats the moisture evaporation the final generation combustion reactions that first make solution.Can be 2 minutes combustion time here.
Then, presoma powder is heat-treated.Described heat-treat condition was preferably: 800～1200 ℃ of insulations 2～4 hours.
Can be to carry out ball milling, dry and screening processing 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.
Then adopt dry-pressing in conjunction with cold isostatic compaction technique, to make the rare earth ion doped zirconic acid lanthanum gadolinium powder moulding making.Described dry-pressing can comprise the steps: under 2.5～5MPa pressure in conjunction with cold isostatic compaction technique, and described rare earth ion doped zirconic acid lanthanum gadolinium powder is carried out to two-sided pressurization pressurize 1 minute, and making it dry-pressing formed is biscuit; Then the dry-pressing formed biscuit making is carried out under 180～230MPa pressure to isostatic cool pressing processing and within 1～3 minute, make rare earth ion doped zirconic acid lanthanum gadolinium biscuit of ceramics.Described dry-pressing formed and isostatic cool pressing is processed and is all preferably at room temperature carried out.
Then carry out sintering, described sintering can comprise: by the rare earth ion doped zirconic acid lanthanum gadolinium biscuit of ceramics making first 800～1400 ℃ of pre-burnings 2～4 hours, then under vacuum condition in 1800～1900 ℃ of sintering 4～10 hours.Described vacuum condition can be: vacuum tightness 10
-2pa～10
-4pa.
Finally carry out anneal: the sample after sintering is incubated to 4～10 hours in air atmosphere at 1400～1600 ℃.
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 approaches 2.1, can meet the application requiring in fields such as information detection, laser medium, high-temperature window and high refractive index camera lens, scintillators.The advantages such as in addition, preparation method of the present invention has that technique is simple, controllability good,, easy handling relatively simple without sintering aid, sintering condition and production.
Further exemplify embodiment below to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the 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., those skilled in the art can do in suitable scope and be selected by explanation herein the temperature of reaction that following example is concrete, time charging capacity etc. are only also examples in OK range,, and do not really want to be defined in the below concrete numerical value of example.
A) powder preparation: by zirconium nitrate (Zr (NO
3)
43H
2o, 99.9%), lanthanum nitrate (La (NO
3)
3, 99.99%), praseodymium nitrate (Pr (NO
3)
3, 99.99%) and Gadolinium trinitrate (Gd (NO
3)
399.995%) according to Zr, La, Pr, Gd mol ratio, be 2:(0.4-y): y:1.6(y=0.002,, the doping of praseodymium is 0.1at%) weigh to be dissolved in and in deionized water, be mixed with nitrate aqueous solution, then according to the chemical equation of perfect combustion reaction, need to add appropriate fuel glycine, stirring is dissolved it completely, is 4 afterwards by the pH value of ammoniacal liquor regulator solution.Precursor solution is transferred to quartz crucible, and on electric furnace, heating makes moisture evaporation final generation combustion reactions, afterwards the precursor powder obtaining is placed in to retort furnace and within 2 hours, carries out powder thermal treatment 1200 ℃ of insulations.Make ceramic powder and sieve through ball milling, the praseodymium doping zirconic acid lanthanum gadolinium nano-powder that acquisition median size is 50～100nm;
B) moulding: adopt dry-pressing (2.5MPa, pressurize 1 minute) in conjunction with 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 making 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 after sintering is incubated to 5 hours in air atmosphere at 1500 ℃, obtains 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 be y=0.01(, the doping of praseodymium is 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 be y=0.02(, the doping of praseodymium is 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 be y=0.04(, the doping of praseodymium is 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, as seen from Figure 1: prepared praseodymium doping zirconic acid lanthanum gadolinium crystalline ceramics is single pyrochlore constitution.
Fig. 4 illustrates the transmittance curve of the praseodymium doping zirconic acid lanthanum gadolinium transparent ceramic material crystalline ceramics photo that thickness is 1mm after twin polishing that embodiment 1～4 makes, as seen from Figure 4: prepared praseodymium doping zirconic acid lanthanum gadolinium transparent ceramic material has good optical transparence at visible ray 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, as seen from Figure 7: prepared praseodymium doping zirconic acid lanthanum gadolinium transparent ceramic material all shows the characteristics of luminescence at visible-range.
Embodiment 5
A) powder preparation: by zirconium nitrate (Zr (NO
3)
43H
2o, 99.9%), lanthanum nitrate (La (NO
3)
3, 99.99%), Terbium trinitrate (Tb (NO
3)
3, 99.99%) and Gadolinium trinitrate (Gd (NO
3)
399.995%) according to Zr, La, Tb, Gd mol ratio, be 2:(0.4-y): y:1.6(y=0.002,, the doping of terbium is 0.1at%) weigh to be dissolved in and in deionized water, be mixed with nitrate aqueous solution, then according to the chemical equation of perfect combustion reaction, need to add appropriate fuel glycine, stirring is dissolved it completely, is 2 afterwards by the pH value of ammoniacal liquor regulator solution.Precursor solution is transferred to quartz crucible, and on electric furnace, heating makes moisture evaporation final generation combustion reactions, afterwards the precursor powder obtaining is placed in to retort furnace and within 2 hours, carries out powder thermal treatment 1200 ℃ of insulations.Make ceramic powder and sieve through ball milling, the terbium doped zirconic acid lanthanum gadolinium nano-powder that acquisition median size is 50～100nm;
B) moulding: adopt dry-pressing (2.5MPa, pressurize 1 minute) in conjunction with 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 making 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 after sintering is incubated to 5 hours in air atmosphere at 1500 ℃, obtains 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 be y=0.01(, the doping of terbium is 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 be y=0.02(, the doping of terbium is 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 be y=0.04(, the doping of terbium is 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, as seen from Figure 2: prepared terbium doped zirconic acid lanthanum gadolinium crystalline ceramics is single pyrochlore constitution.
Fig. 5 illustrates the transmittance curve of the terbium doped zirconic acid lanthanum gadolinium transparent ceramic material crystalline ceramics photo that thickness is 1mm after twin polishing that embodiment 7～8 makes, as seen from Figure 5: prepared terbium doped zirconic acid lanthanum gadolinium transparent ceramic material has good optical transparence at visible ray and the equal scope of near-infrared band, wherein the transmitance of the zirconic acid lanthanum gadolinium of 0.1at%Tb doping at 633nm place can reach 95.8% of theoretical value.
Fig. 8 illustrates the fluorescence spectrum of the terbium doped zirconic acid lanthanum gadolinium transparent ceramic material that embodiment 7～8 makes, as seen from Figure 8: prepared terbium doped zirconic acid lanthanum gadolinium transparent ceramic material all shows the characteristics of luminescence at visible-range.
Embodiment 9
A) powder preparation: by zirconium nitrate (Zr (NO
3)
43H
2o, 99.9%), lanthanum nitrate (La (NO
3)
3, 99.99%), samaric nitrate (Sm (NO
3)
3, 99.99%) and Gadolinium trinitrate (Gd (NO
3)
399.995%) according to Zr, La, Sm, Gd mol ratio, be 2:(0.4-y): y:1.6(y=0.002,, the doping of samarium is 0.1at%) weigh to be dissolved in and in deionized water, be mixed with nitrate aqueous solution, then according to the chemical equation of perfect combustion reaction, need to add appropriate fuel glycine, stirring is dissolved it completely, is 6 afterwards by the pH value of ammoniacal liquor regulator solution.Precursor solution is transferred to quartz crucible, and on electric furnace, heating makes moisture evaporation final generation combustion reactions, afterwards the precursor powder obtaining is placed in to retort furnace and within 2 hours, carries out powder thermal treatment 1200 ℃ of insulations.Make ceramic powder and sieve through ball milling, the samarium doping zirconic acid lanthanum gadolinium nano-powder that acquisition median size is 50～100nm;
B) moulding: adopt dry-pressing (2.5MPa, pressurize 1 minute) in conjunction with 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 making 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 after sintering is incubated to 5 hours in air atmosphere at 1500 ℃, obtains 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 be y=0.01(, the doping of samarium is 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 be y=0.02(, the doping of samarium is 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 be y=0.04(, the doping of samarium is 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, as seen from Figure 3: prepared samarium doping zirconic acid lanthanum gadolinium crystalline ceramics is single pyrochlore constitution.
Fig. 6 illustrates the transmittance curve of the samarium doping zirconic acid lanthanum gadolinium transparent ceramic material crystalline ceramics photo that thickness is 1mm after twin polishing that embodiment 9～12 makes, as seen from Figure 6: prepared terbium doped zirconic acid lanthanum gadolinium transparent ceramic material has good optical transparence at visible ray 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, as seen from Figure 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 approaches 2.1, can meet the application requiring in fields such as information detection, laser medium, high-temperature window and high refractive index camera lens, scintillators, have broad application prospects.
Claims (10)
1. a rare earth ion doped zirconic acid lanthanum gadolinium transparent ceramic material, is characterized in that, the chemical constitution of described 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, described zirconic acid lanthanum gadolinium transparent ceramic material shows the characteristics of luminescence at visible-range.
2. a method of preparing rare earth ion doped zirconic acid lanthanum gadolinium transparent ceramic material claimed in claim 1, comprising: powder preparation section, molding procedure, sintering circuit and annealing operation; It is characterized in that, described powder preparation section adopts glycine-nitrate process to make rare earth ion doped zirconic acid lanthanum gadolinium powder, and described molding procedure adopts dry-pressing in conjunction with cold isostatic compaction technique.
3. method according to claim 2, is characterized in that, described powder preparation section comprises:
According to La
0.4-yrE
ygd
1.6zr
2o
7atomic molar score another name get zirconium nitrate, lanthanum nitrate, Gadolinium trinitrate and rare earth ion nitrate and be configured to nitrate aqueous solution, described rare earth ion nitrate is praseodymium nitrate, Terbium trinitrate or samaric nitrate;
Add glycine as incendiary material, regulator solution pH value is 2～6;
There is combustion reactions in heating, to obtain presoma powder; And described presoma powder is heat-treated.
4. method according to claim 3, is characterized in that, the nitrate ion in described nitrate aqueous solution and the mol ratio of described glycine are 2:1.
5. according to the method described in claim 3 or 4, it is characterized in that, described heat treated condition is 800～1200 ℃ of insulations 2～4 hours.
6. according to the method described in claim 3 or 4, it is characterized in that, described powder preparation section also comprises, to the powder after thermal treatment carry out ball milling, dry and screening is processed take and is obtained median size as the powder of 50～100 nm.
7. method according to claim 6, is characterized in that, the processing condition of described ball milling are for to turn per minute ball milling 20 hours with 250; Described dry condition is to be dried 24 hours at 60 ℃.
8. according to the method described in claim 3 or 4, it is characterized in that, described molding procedure comprises:
Under 2.5～5 MPa pressure, described rare earth ion doped zirconic acid lanthanum gadolinium powder is carried out to two-sided pressurization pressurize 1 minute, making it dry-pressing formed is biscuit; And the dry-pressing formed biscuit making is carried out under 180～230 MPa pressure to isostatic cool pressing and process and within 1～3 minute, to make rare earth ion doped zirconic acid lanthanum gadolinium biscuit of ceramics.
9. method according to claim 8, is characterized in that, described sintering circuit comprises:
Described 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, be 10
-2pa～10
-4under the vacuum condition of Pa in 1800～1900 ℃ of sintering 4～10 hours.
10. according to the method described in claim 3 or 4, it is characterized in that, described annealing operation comprises: the sample after sintering is incubated to 4～10 hours in air atmosphere at 1400～1600 ℃.
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