CN109879305A - It is a kind of to prepare micron size LaAlO3:xMm+The method of spheric granules - Google Patents
It is a kind of to prepare micron size LaAlO3:xMm+The method of spheric granules Download PDFInfo
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- CN109879305A CN109879305A CN201910235484.0A CN201910235484A CN109879305A CN 109879305 A CN109879305 A CN 109879305A CN 201910235484 A CN201910235484 A CN 201910235484A CN 109879305 A CN109879305 A CN 109879305A
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- lanthanum aluminate
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- 239000008187 granular material Substances 0.000 title claims abstract description 32
- 229910002244 LaAlO3 Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 44
- -1 lanthanum aluminate Chemical class 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 9
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 9
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 81
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 14
- 239000012798 spherical particle Substances 0.000 description 13
- 150000001298 alcohols Chemical class 0.000 description 7
- 230000002349 favourable effect Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000013049 sediment Substances 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021117 Sm(NO3)3 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(III) nitrate Inorganic materials [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention belongs to materials science field, proposes and a kind of prepare micron size LaAlO3:xMm+The new method of spheric granules.Wherein, M is one of Mn, Yb, Dy, Nd, Eu, Ce, Tb, Er, Tm, Ho, Pr, Sm, using hydro-thermal method, add certain additive, the super large monodisperse lanthanum aluminate spheric granules of rare earth doped element or transition metal element is prepared, size can reach micron order (1 μm -20 μm).Spheric granules has high light emitting efficiency, photocatalysis, in terms of have indispensable role.The spheric granules obtained in this experiment is other in the micron-scale, particle surface is smooth, and the technical solution of invention is simple and easy, good theoretical basis (Commercial optical powder particles size is in the micron-scale) is illustrated for the preparation of novel Commercial optical powder, with high directive significance and application prospect.
Description
Technical field
The invention belongs to materials science fields, in particular to a kind of to prepare micron size LaAlO3:xMm+(M=Mn,
Yb, Dy, Nd, Eu, Ce, Tb, Er, Tm, Ho, Pr, Sm) spheric granules new method.
Background technique
Lanthanum aluminate due to the advantages that chemical stability is good, thermal stability is high, electronic device, catalysis, high-temperature fuel cell,
Ceramics, sewage treatment and substrate material etc. have a wide range of applications.Lanthanum aluminate is typical perovskite structure, for a cube knot
Structure, La and Al other metal ions similar in radius replace but its crystal structure remains unchanged, in substituted process
In may generate number of drawbacks, such as the vacancy La, the vacancy Al, the vacancy O and charge compensation defect, so as to improve its photoelectricity
Performance, preparation transient state fluorescent material, long-afterglow material or up-conversion luminescent material.
The preferable lanthanum aluminate phosphor of fluorescence property to be synthesized need to reduce reflections from phosphor particles rate, refractive index, improve absorptivity
And conversion ratio, size, granule-morphology, particle surface form of fluorescent powder grain etc. determine the luminescent properties of fluorescent powder grain.?
Grain is learned research and is had shown that, particle whether loosely-packed or tightly packed, the sphericity (sphericity is defined as: spherome surface of particle
Product is to same volume irregular particle surface area ratio) it is lower, accumulation voidage is higher.Spherical light-emitting particles can get higher
Bulk density, to reduce the scattering of illuminator, since spherical luminescent particle bulk density high porosity reduces, transmitted light
Loss is also few, and for illuminator, optimal particle shape is exactly spherical.The existing method for preparing aluminate lanthanum powder is solid
The particle of Xiang Fa, molte-salt synthesis etc., formation is more serious without pattern reunion, and calcination temperature is higher, and preparation process is more complex.Hydro-thermal
Method is a kind of test method for being chemically reacted in a fluid under certain temperature, pressure condition.Using hydro-thermal method can gram
It takes certain high temperature and prepares inevitable hard aggregation etc., there is purity is high, good dispersion, uniform, narrowly distributing, soilless sticking, crystalline substance
Type is good, controlled shape and the features such as be conducive to the depollution of environment.Therefore using hydro-thermal method prepare doping with rare-earth ions (Yb, Dy, Nd, Eu,
Ce, Tb, Er, Tm, Ho, Pr, Sm) or transition metal ions (Mn) lanthanum aluminate particle, can get luminous efficiency it is high size it is micro-
The spherical phosphor particle of meter level.
Summary of the invention
In view of the problems of the existing technology, the present invention, which provides, a kind of prepares monodisperse LaAlO3:xMm+Spheric granules it is new
Method.
Technical solution of the present invention:
It is a kind of to prepare micron size LaAlO3:xMm+The method of spheric granules, comprises the following steps that
Step 1: by quantitative Al (NO3)3·9H2O、La(NO3)3And M (NO3)mDeionized water and ethylene glycol is added in solution
Solution in stir, while citric acid solid is added；Stirring evenly, until citric acid is completely dissolved, mixed solution is transparent；
Wherein, when M is one kind of Yb, Dy, Nd, Eu, Ce, Tb, Er, Tm, Ho, Pr, Sm in rare earth element, then Al:La:M molar ratio is
1:(1-x): x, x=0~1；When M be Mn when, then Al:La:M molar ratio be (1-x): 1:x, x=0~1, citric acid with mix it is molten
The molar ratio of total metal ion is 0.5~3:1 in liquid；
Step 2: the mixed solution for the transparence that step 1 is obtained moves in hydrothermal reaction kettle, carries out hydro-thermal reaction, to
After reaction, cooled to room temperature removes supernatant in reaction kettle, is cleaned, is dried to get aluminium is arrived to precipitated product
Sour lanthanum presoma；The hydrothermal reaction condition are as follows: 100~200 DEG C of temperature, time 1h~168h；
Step 3: the lanthanum aluminate presoma that step 2 reaction obtains being calcined to get micron-sized monodisperse spherical is arrived
Lanthanum aluminate particle；The calcination condition: oxygen atmosphere, 900~1300 DEG C of temperature, calcination time 2-8h.
Above-mentioned steps 2: the stirring evenly time is 10-60min.
Above-mentioned steps 2: it cleans as deionized water three times, the eccentric cleaning of dehydrated alcohol twice.
Above-mentioned steps 2: drying condition is 40~80 DEG C of temperature, time -72h for 24 hours.
Above-mentioned steps 3: the partial size for obtaining micron-sized monodisperse spherical lanthanum aluminate particle is 1 μm~20 μm.
Compared with prior art, the features of the present invention and beneficial effect are:
The present invention uses hydro-thermal method, adds certain additive, has prepared rare earth doped element or transition metal element
Super large monodisperse lanthanum aluminate spheric granules, size can reach micron order (1 μm -20 μm).Spheric granules has high light emitting effect
Rate, photocatalysis, in terms of have indispensable role.The spheric granules obtained in this experiment is in the micron-scale
Not, particle surface is smooth, and the technical solution invented is simple and easy, illustrates good reason for the preparation of novel Commercial optical powder
By basic (Commercial optical powder particles size is in the micron-scale), with high directive significance and application prospect.
Detailed description of the invention
Fig. 1 (a) is the LaAlO prepared in the embodiment of the present invention 13: 0.1%Mn4+Presoma SEM scanned photograph.
It (b) is the LaAlO prepared in the embodiment of the present invention 13: 0.1%Mn4+SEM scanned photograph.
Fig. 2 (a) is the spheric granules LaAlO prepared in the embodiment of the present invention 13: 0.1%Mn4+XRD spectrum.
It (b) is the spheric granules LaAlO prepared in the embodiment of the present invention 23: 0.5%Mn4+XRD spectrum.
It (c) is the spheric granules LaAlO prepared in the embodiment of the present invention 33: 1%Mn4+XRD spectrum.
It (d) is the spheric granules LaAlO prepared in the embodiment of the present invention 43: 1%Eu3+XRD spectrum.
It (e) is the spheric granules LaAlO prepared in the embodiment of the present invention 53: 2.5%Tb3+XRD spectrum.
It (f) is the spheric granules LaAlO prepared in the embodiment of the present invention 63: 5%Sm3+XRD spectrum.
It (g) is the spheric granules LaAlO prepared in the embodiment of the present invention 73: 0.1%Mn4+XRD spectrum.
Fig. 3 (a) is the LaAlO prepared in the embodiment of the present invention 23: 0.5%Mn4+Presoma SEM scanned photograph.
Fig. 3 (b) is the LaAlO prepared in the embodiment of the present invention 23: 0.5%Mn4+SEM scanned photograph.
Fig. 4 (a) is the LaAlO prepared in the embodiment of the present invention 33: 1%Mn4+The SEM scanned photograph of presoma.
Fig. 4 (b) is the LaAlO prepared in the embodiment of the present invention 33: 1%Mn4+SEM scanned photograph.
Fig. 5 (a) is the LaAlO prepared in the embodiment of the present invention 43: 1%Eu3+The SEM scanned photograph of presoma.
Fig. 5 (b) is the LaAlO prepared in the embodiment of the present invention 43: 1%Eu3+SEM scanned photograph.
Fig. 6 (a) is the LaAlO prepared in the embodiment of the present invention 53: 2.5%Tb3+Presoma SEM scanned photograph.
Fig. 6 (b) is the LaAlO prepared in the embodiment of the present invention 53: 2.5%Tb3+SEM scanned photograph.
Fig. 7 (a) is the LaAlO prepared in the embodiment of the present invention 63: 5%Sm3+The SEM scanned photograph of presoma.
Fig. 7 (b) is the LaAlO prepared in the embodiment of the present invention 63: 5%Sm3+SEM scanned photograph.
Fig. 8 (a) is the LaAlO prepared in the embodiment of the present invention 73: 0.1%Mn4+Presoma SEM scanned photograph.
Fig. 8 (b) is the LaAlO prepared in the embodiment of the present invention 73: 0.1%Mn4+SEM scanned photograph.
Specific embodiment
Specific embodiments of the present invention are described in detail below in conjunction with technical solution and attached drawing.
Chemical reagent employed in present example is the pure grade product of analysis；Using the X ' of model PW3040/60
Pert Pro X-ray diffractometer carries out XRD material phase analysis；Pattern is carried out using JSM-7001F type JEOL field emission scanning electron microscope
Observation and analysis.
Embodiment 1
Measure Al (NO3)3·9H2O、La(NO3)3And Mn (NO3)2Solution is in the beaker of 100ml, Al:La:Mn=
0.999:1:0.001 is uniformly mixed, while citric acid is added, and the ratio of citric acid and metal ion is 1:1, is added simultaneously
Enter deionized water 20mL and ethylene glycol 40mL (ratio 1:2), stir 30min, until citric acid is completely dissolved, and mixes equal
It is even, clear solution is transferred in 100mL hydrothermal reaction kettle, 8h is reacted, hydrothermal temperature is 180 DEG C, to the end of reacting, makes to react
Kettle cooled to room temperature removes supernatant, carries out eccentric cleaning (3 deionized waters, 2 dehydrated alcohols) to sediment, in
After 70 DEG C of drying for 24 hours, the presoma of lanthanum aluminate is obtained.Presoma is subjected to calcining 4h for 1000 DEG C under oxygen atmosphere, is obtained straight
The lanthanum aluminate super large monodisperse spherical particle that diameter is about 2 μm.
LaAlO3: 0.1%Mn4+Presoma is amorphous phase, is monodisperse spherical particle, diameter is about 2-3 μm, such as Fig. 1
(a) shown in.After calcining, favorable dispersibility spheric granules is obtained, size is micro- reduction, and diameter is about 2 μm, such as Fig. 1 (b) institute
Show, shown in XRD spectrum such as Fig. 2 (a), it was demonstrated that it is lanthanum aluminate pure phase.
Embodiment 2
Measure Al (NO3)3·9H2O、La(NO3)3And Mn (NO3)2Solution is in the beaker of 100ml, Al:La:Mn=
0.995:1:0.005 is uniformly mixed, while citric acid is added, and the ratio of citric acid and metal ion is 1:1, is added simultaneously
Enter deionized water 60mL and ethylene glycol 0mL, stir 40min, until citric acid is completely dissolved, and is uniformly mixed, by clear solution
It is transferred in 100mL hydrothermal reaction kettle, reacts 18h, hydrothermal temperature is 180 DEG C, to the end of reacting, naturally cools to reaction kettle
Room temperature removes supernatant, carries out eccentric cleaning (3 deionized waters, 2 dehydrated alcohols) to sediment, for 24 hours in 70 DEG C of drying
Afterwards, the presoma of lanthanum aluminate is obtained.Presoma is subjected to calcining 4h for 1100 DEG C under oxygen atmosphere, obtains single point of super large lanthanum aluminate
Dissipate spheric granules.
LaAlO3: 0.5%Mn4+Presoma is amorphous phase, is monodisperse spherical particle, and diameter is about 10-13 μm, is such as schemed
Shown in 3 (a).After calcining, the lanthanum aluminate spheric granules of favorable dispersibility is obtained, diameter is micro- reduction, and diameter is about 8-10 μm,
As shown in Fig. 3 (b), shown in XRD spectrum such as Fig. 2 (b), it was demonstrated that it is lanthanum aluminate pure phase.
Embodiment 3
Measure Al (NO3)3·9H2O、La(NO3)3And Mn (NO3)2Solution is in the beaker of 100ml, Al:La:Mn=
0.99:1:0.01 is uniformly mixed, while citric acid is added, and the ratio of citric acid and metal ion is 1:1, is added simultaneously
Deionized water 50mL and ethylene glycol 10mL (ratio 5:1) stirs 40min, until citric acid is completely dissolved, and is uniformly mixed,
Clear solution is transferred in 100mL hydrothermal reaction kettle, 4h is reacted, 160 DEG C of reaction temperature, to the end of reacting, makes reaction kettle certainly
It is so cooled to room temperature, removes supernatant, eccentric cleaning (3 deionized waters, 2 dehydrated alcohols) are carried out to sediment, in 80 DEG C
After drying 72h, the presoma of lanthanum aluminate is obtained.Presoma is subjected to calcining 4h for 1000 DEG C under oxygen atmosphere, obtains diameter about
For 2 μm of lanthanum aluminate super large monodisperse spherical particle.
LaAlO3: 1%Mn4+Presoma is amorphous phase, is monodisperse spherical particle, diameter is about 3-5 μm, such as Fig. 4 (a)
It is shown.After calcining, the lanthanum aluminate spheric granules of favorable dispersibility is obtained, size is micro- reduction, and diameter is about 3 μm, such as Fig. 4
(b) shown in, shown in XRD spectrum such as Fig. 2 (c), it was demonstrated that it is lanthanum aluminate pure phase.
Embodiment 4
Measure Al (NO3)3·9H2O、La(NO3)3、Eu(NO3)3Solution is in the beaker of 100ml, Al:La:Eu=1:
0.99:0.01 is uniformly mixed, while citric acid is added, and the ratio of citric acid and metal ion is 1:1, while being added and being gone
Ionized water 40mL and ethylene glycol 20mL (ratio 2:1) stirs 40min, until citric acid is completely dissolved, and is uniformly mixed, it will
Clear solution is transferred in 100mL hydrothermal reaction kettle, is reacted 4h, 180 DEG C of reaction temperature, to the end of reacting, is kept reaction kettle natural
It is cooled to room temperature, removes supernatant, eccentric cleaning (3 deionized waters, 2 dehydrated alcohols) are carried out to sediment, are dried in 60 DEG C
After dry 36h, the presoma of lanthanum aluminate is obtained.Presoma is subjected to calcining 4h for 1100 DEG C under oxygen atmosphere, obtaining diameter is about
2.5 μm of lanthanum aluminate super large monodisperse spherical particle.
LaAlO3: 1%Eu3+Presoma is amorphous phase, is monodisperse spherical particle, diameter is about 3-5 μm, such as Fig. 5 (a)
It is shown.After calcining, the lanthanum aluminate spheric granules of favorable dispersibility is obtained, diameter is micro- reduction, and diameter is about 2.5 μm, such as Fig. 5
(b) shown in, shown in XRD spectrum such as Fig. 2 (d), it was demonstrated that it is lanthanum aluminate pure phase.
Embodiment 5
Measure Al (NO3)3·9H2O、La(NO3)3、Tb(NO3)3Solution is in the beaker of 100ml, Al:La:Tb=1:
0.975:0.025 is uniformly mixed, while citric acid is added, and the ratio of citric acid and metal ion is 1.5:1, is added simultaneously
Enter deionized water 30mL and ethylene glycol 30mL (ratio 1:1), stir 30min, until citric acid is completely dissolved, and mixes equal
It is even, clear solution is transferred in 100mL hydrothermal reaction kettle, 6h is reacted, 200 DEG C of reaction temperature, to the end of reacting, makes reaction kettle
Cooled to room temperature removes supernatant, eccentric cleaning (3 deionized waters, 2 dehydrated alcohols) is carried out to sediment, in 60
DEG C drying for 24 hours after, obtain the presoma of lanthanum aluminate.Presoma is subjected to calcining 4h for 1200 DEG C under oxygen atmosphere, obtains diameter
About 3 μm of lanthanum aluminate super large monodisperse spherical particle.
LaAlO3: 2.5%Tb3+Presoma is amorphous phase, is monodisperse spherical particle, diameter is about 3-5 μm, such as Fig. 6
(a) shown in.After calcining, the lanthanum aluminate spheric granules of favorable dispersibility is obtained, size is micro- reduction, and diameter is about 3 μm, such as schemes
Shown in 6 (b), shown in XRD spectrum such as Fig. 2 (e), it was demonstrated that it is as doping Tb3+It is afterwards still lanthanum aluminate pure phase.
Embodiment 6
Measure Al (NO3)3·9H2O、La(NO3)3、Sm(NO3)3Solution is in the beaker of 100ml, Al:La:Sm=1:
0.95:0.05 is uniformly mixed, while citric acid is added, and the ratio of citric acid and metal ion is 2:1, while being added and being gone
Ionized water 10mL and ethylene glycol 50mL (ratio 1:5) stirs 25min, until citric acid is completely dissolved, and is uniformly mixed, it will
Clear solution is transferred in 100mL hydrothermal reaction kettle, is reacted 9h, 140 DEG C of reaction temperature, to the end of reacting, is kept reaction kettle natural
It is cooled to room temperature, removes supernatant, eccentric cleaning (3 deionized waters, 2 dehydrated alcohols) are carried out to sediment, are dried in 60 DEG C
After doing for 24 hours, the presoma of lanthanum aluminate is obtained.Presoma is subjected to calcining 4h for 1300 DEG C under oxygen atmosphere, obtaining diameter is about 3
μm lanthanum aluminate super large monodisperse spherical particle.
LaAlO3: 5%Sm3+Presoma is amorphous phase, is monodisperse spherical particle, diameter is about 3 μm, such as Fig. 7 (a) institute
Show.After calcining, the lanthanum aluminate spheric granules of favorable dispersibility is obtained, size is micro- reduction, and diameter is about 2 μm, such as Fig. 7 (b)
It is shown, shown in XRD spectrum such as Fig. 2 (f), it was demonstrated that it is as doping Sm3+It is afterwards still lanthanum aluminate pure phase.
Embodiment 7
Measure Al (NO3)3·9H2O、La(NO3)3And Eu (NO3)3Solution is in the beaker of 100ml, Al:La:Eu=
0.999:1:0.001 is uniformly mixed, while citric acid is added, and the ratio of citric acid and metal ion is 1:1, is added simultaneously
Enter deionized water 20mL and ethylene glycol 40mL (ratio 1:2), stir 40min, until citric acid is completely dissolved, and mixes equal
It is even, clear solution is transferred in 100mL hydrothermal reaction kettle, reaction 4h makes reaction kettle naturally cool to room to the end of reacting
Temperature removes supernatant, carries out eccentric cleaning (3 deionized waters, 2 dehydrated alcohols) to sediment, after 70 DEG C of drying for 24 hours,
Obtain the presoma of lanthanum aluminate.By presoma under oxygen atmosphere 1000 DEG C of calcining 4h, it is super to obtain lanthanum aluminate that diameter is about 2 μm
Big monodisperse spherical particle.
Lanthanum aluminate presoma is amorphous phase, is monodisperse spherical particle, diameter is about 2-3 μm, as shown in Fig. 8 (a).Through
After calcining, the lanthanum aluminate spheric granules of favorable dispersibility is obtained, size is micro- reduction, and diameter is about 2 μm, as shown in Fig. 8 (b),
Shown in XRD spectrum such as Fig. 2 (g), it was demonstrated that when it adulterates Mn4+Still it is lanthanum aluminate pure phase, does not contain other miscellaneous phases.
Claims (5)
1. a kind of prepare micron size LaAlO3:xMm+The method of spheric granules, which is characterized in that comprise the following steps that
Step 1: by quantitative Al (NO3)3·9H2O、La(NO3)3And M (NO3)mThe solution of solution addition deionized water and ethylene glycol
Middle stirring, while citric acid solid is added；Stirring evenly, until citric acid is completely dissolved, mixed solution is transparent；Wherein,
When one kind that M is Yb, Dy, Nd, Eu, Ce, Tb, Er, Tm, Ho, Pr, Sm in rare earth element, then Al:La:M molar ratio is 1:(1-
X): x, x=0~1；When M is Mn, then Al:La:M molar ratio is (1-x): 1:x, x=0~1, in citric acid and mixed solution
The molar ratio of total metal ion is 0.5~3:1；
Step 2: the mixed solution for the transparence that step 1 is obtained moves in hydrothermal reaction kettle, hydro-thermal reaction is carried out, wait react
After, cooled to room temperature removes supernatant in reaction kettle, is cleaned, is dried to get lanthanum aluminate is arrived to precipitated product
Presoma；The hydrothermal reaction condition are as follows: 100~200 DEG C of temperature, time 1h~168h；
Step 3: the lanthanum aluminate presoma that step 2 reaction obtains being calcined to get micron-sized monodisperse spherical aluminic acid is arrived
Lanthanum particle；The calcination condition: oxygen atmosphere, 900~1300 DEG C of temperature, calcination time 2-8h.
2. preparing micron size LaAlO according to claim 13:xMm+The method of spheric granules, which is characterized in that step
Rapid 2: the stirring evenly time is 10-60min.
3. according to claim 1 or claim 2 prepare micron size LaAlO3:xMm+The method of spheric granules, feature exist
In step 2: cleaning as deionized water three times, the eccentric cleaning of dehydrated alcohol twice.
4. according to claim 1 or claim 2 prepare micron size LaAlO3:xMm+The method of spheric granules, feature exist
In step 2: drying condition is 40~80 DEG C of temperature, time -72h for 24 hours.
5. according to claim 1 or claim 2 prepare micron size LaAlO3:xMm+The method of spheric granules, feature exist
In step 3: the partial size for obtaining micron-sized monodisperse spherical lanthanum aluminate particle is 1 μm~20 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910235484.0A CN109879305B (en) | 2019-03-27 | 2019-03-27 | Preparation of micron-sized monodisperse LaAlO3:xMm+Method for producing spherical particles |
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