CN103923652B - hollow structure calcium titanate luminescent material and preparation method thereof - Google Patents

hollow structure calcium titanate luminescent material and preparation method thereof Download PDF

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CN103923652B
CN103923652B CN201310014469.6A CN201310014469A CN103923652B CN 103923652 B CN103923652 B CN 103923652B CN 201310014469 A CN201310014469 A CN 201310014469A CN 103923652 B CN103923652 B CN 103923652B
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luminescent material
hollow structure
preparation
calcium titanate
tio
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CN103923652A (en
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周明杰
王荣
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention belongs to field of light emitting materials, it discloses a kind of hollow structure calcium titanate luminescent material and preparation method thereof; The general structure of this luminescent material is Ca 1-xtiO 3: Pr x; Wherein, the span of x is 0 < x≤0.01.The present invention obtains hollow structure calcium titanate luminescent material, and the carbon bead adopting dispersion is template, and the calcium titanate obtained is spherical hollow structure, not only morphology controllable, and effectively can reduce the consumption of rare earth metal, reduce product cost, a large amount of rare earth resources saving preciousness.

Description

Hollow structure calcium titanate luminescent material and preparation method thereof
Technical field
The present invention relates to field of light emitting materials, particularly relate to a kind of hollow structure calcium titanate luminescent material and preparation method thereof.
Background technology
Red fluorescence powder comprises sulfide-based, oxide-based, several large class material such as oxysulfide class and metatitanic acid salt, wherein, metatitanic acid salt type material has the advantages such as higher stability, color developing be good, can be used for the occasion higher to the requirement of fluorescent material job stability, as the field emission display screen used under low voltage and high current density.The Typical Representative material C aTiO of metatitanic acid salt 3: the cie color coordinate of Pr is x=0.680 and y=0.311, with desirable ruddiness closely, be a kind of more satisfactory fluorescent material, have larger application prospect.
But mostly prepare with high temperature solid-state method at present, the pattern of gained fluorescent material is uneven, need repetitious ball milling thus obtain suitable granularity (5-10 μm), the impurity of the defect that mechanical milling process produces and introducing damages the luminous intensity of luminescent powder sometimes.
Summary of the invention
Problem to be solved by this invention is to provide that a kind of pattern is even, the good hollow structure calcium titanate luminescent material of luminous intensity.
Technical scheme of the present invention is as follows:
A kind of hollow structure calcium titanate luminescent material, its general structure is Ca 1-xtiO 3: Pr x; Wherein, the span of x is 0 < x≤0.01.
Described hollow structure calcium titanate luminescent material, preferably, the span of x is 0.001≤x≤0.005.
The present invention obtains hollow structure calcium titanate luminescent material, and the carbon bead adopting dispersion is template, and the calcium titanate obtained is spherical hollow structure, not only morphology controllable, and effectively can reduce the consumption of rare earth metal, reduce product cost, a large amount of rare earth resources saving preciousness.
The present invention also provides the preparation method of above-mentioned hollow structure calcium titanate luminescent material, comprises the steps:
Be that the sucrose of 0.00075 ~ 0.15g/ml or the ethanolic soln of glucose are placed in reactor by concentration, at 120 ~ 200 DEG C, 5 ~ 36h is reacted after sealed reactor, be cooled to centrifugation after room temperature, and the solid phase obtained is washed, obtain carbon bead template after drying;
Be Ca according to general structure 1-xtiO 3: Pr xin each element chemistry metering ratio, be in the ethanolic soln of the tetrabutyl titanate of 1mol/L, add the Pr (NO that concentration is 0.005 ~ 0.1mol/L toward concentration 3) 3ca (the NO of solution and 0.1 ~ 1mol/L 3) 2solution, obtains mixing solutions; The pH value of mixing solutions is regulated to be 2 ~ 3 subsequently; Then add carbon bead template again, stir 0.5-6h, more then slowly add oxalic acid sinking agent when stirring, produce precipitation, then stirring reaction 2-8h, then suction filtration is also dry, obtains Ca 1-xtiO (C 2o 4) 2: Pr x@C presoma; Wherein, described carbon bead template and Ca 1-xtiO 3: Pr xmol ratio be 0.025:1 ~ 10:1; @represents Ca 1-xtiO (C 2o 4) 2: Pr xcoated C (carbon), C are also carbon bead template;
Described presoma is ground, and powder pre-burning 1 ~ 6 hour at 500 ~ 800 DEG C will be ground, grinding after cooling, and then in 800 ~ 1200 DEG C of calcining 1 ~ 10h, obtain Ca 1-xtiO 3: Pr xluminescent material; Wherein, pre-burning and the calcining of described grinding powder are all in air atmosphere, carry out in high temperature box furnace.
In above-mentioned steps, the span of x is 0 < x≤0.01.
The preparation method of described hollow structure calcium titanate luminescent material, preferably, the reactor in described carbon bead template preparation process is teflon-lined reactor.
The preparation method of described hollow structure calcium titanate luminescent material preferably, is use deionized water and dehydrated alcohol repetitive scrubbing successively repeatedly to the washing of described separation solid phase.
The preparation method of described hollow structure calcium titanate luminescent material, preferably, carries out at 60 ~ 80 DEG C the drying of the solid phase after described washing.
The preparation method of described hollow structure calcium titanate luminescent material, preferably, when regulating the pH value of described mixing solutions, adopts HNO 3carry out.
The preparation method of described hollow structure calcium titanate luminescent material, preferably, the relative Ca of mole dosage of described sinking agent 2+and TiO 2+mole dosage excessive 25%; Sinking agent utilizes the TiO of hydrolysis in the butyl (tetra) titanate aqueous solution 2+with C 2o 4 2-form TiO (C 2o 4) 2 2-the feature of complex ion, first forms complex ion, then it and Ca is reacted generate CaTi O (C 2o 4) 2presoma.
The preparation method of described hollow structure calcium titanate luminescent material, preferably, the span of x is 0.001≤x≤0.005.
The preparation method of hollow structure calcium titanate luminescent material of the present invention, first adopts hydrothermal method to prepare carbon bead, and then with carbon bead for template adopts oxalate precipitation method to prepare Ca 1-xtiO (C 2o 4) 2: Pr x@C precursor powder, and then through calcining, in calcination process, carbon bead will be converted into CO 2effusion, finally obtains hollow structure Ca 1-xtiO 3: Pr xluminescent material.
The preparation method of hollow structure calcium titanate luminescent material of the present invention, processing step is few, relatively simply; Processing condition are not harsh, easily reach, and cost is low; Do not introduce other impurity, the luminescent material quality obtained is high, can be widely used in the preparation of luminescent material.
Accompanying drawing explanation
Fig. 1 is the embodiment 2 hollow structure calcium titanate luminescent material prepared and the luminescent spectrum comparison diagram contrasted under the cathode-ray exciting of luminescent material under acceleration voltage is 1.5KV; Wherein, curve 1 is the hollow structure calcium titanate luminescent material Ca of the hollow structure that embodiment 3 obtains 0.998tiO 3: Pr 0.002luminescent spectrum, curve 2 is contrast luminescent material Ca 0.998tiO 3: Pr 0.002luminescent spectrum.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The precipitator method prepare Ca 0.999tiO 3: Pr 0.001
Take 4g glucose and be dissolved in the sorbitol solution that dehydrated alcohol obtains 40mL, this solution being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 120 DEG C of reaction 36h, prepare the solution of carbon bead, this solution of centrifugation obtains solid formation, washs 2 times respectively with deionized water and dehydrated alcohol, and dry at 60 DEG C, namely obtain carbon bead template.
Under magnetic stirring tetrabutyl titanate is dissolved in ethanol and obtains 1mol/L clear solution, then according to stoichiometric ratio, pipette 4mL1mol/L tetrabutyl titanate, then add 0.4mL0.01mol/L Pr (NO 3) 3with 39.96mL0.1mol/L Ca (NO 3) 2, adopt HNO 3regulator solution pH value is 2, adds carbon bead template 480mg, stirs 0.5h, then slowly adds 20mL0.5mol/L sinking agent oxalic acid when stirring, and produces precipitation, then stirring reaction 8h.Then suction filtration is also dry, obtains Ca 0.999tiO (C 2o 4) 2: Pr 0.001@C presoma;
Presoma is ground, is put in atmosphere in 500 DEG C of pre-burnings 6 hours in high temperature box furnace, grinding after cooling, and then in 700 DEG C of calcining 10h, obtain Ca 0.999tiO 3: Pr 0.001luminescent material.
Embodiment 2
The precipitator method prepare Ca 0.998tiO 3: Pr 0.002
Take 0.05g sucrose dissolved obtains 40mL sucrose alcohol solution in dehydrated alcohol, this solution being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 160 DEG C of reaction 20h, prepare the solution of carbon bead, this solution of centrifugation obtains solid formation, washs 3 times respectively with deionized water and dehydrated alcohol, and dry at 80 DEG C, namely obtain carbon bead template.
Under magnetic stirring tetrabutyl titanate is dissolved in ethanol and obtains 1mol/L clear solution, then according to stoichiometric ratio, pipette 4mL1mol/L tetrabutyl titanate, then add 0.4mL0.02mol/L Pr (NO 3) 3with 19.96mL0.2mol/L Ca (NO 3) 2, adopt HNO 3regulator solution pH value is 3, adds carbon bead template 200mg, stirs 2h, then slowly adds 20mL0.5mol/L sinking agent oxalic acid when stirring, and produces precipitation, then stirring reaction 4h.Then suction filtration is also dry, obtains Ca 0.998tiO (C 2o 4) 2: Pr 0.002@C presoma;
Presoma is ground, is put in high temperature box furnace calcining at constant temperature 4h at 700 DEG C, grinding after cooling, and then in 1000 DEG C of calcining 4h, obtain Ca 0.998tiO 3: Pr 0.002luminescent material.
Fig. 1 is the embodiment 3 hollow structure calcium titanate luminescent material prepared and the luminescent spectrum comparison diagram contrasted under the cathode-ray exciting of luminescent material under acceleration voltage is 1.5KV; Wherein, curve 1 is the hollow structure calcium titanate luminescent material Ca of the hollow structure that embodiment 3 obtains 0.998tiO 3: Pr 0.002luminescent spectrum, curve 2 is contrast luminescent material Ca 0.998tiO 3: Pr 0.002luminescent spectrum.
As can be seen from Figure 1, at the emission peak at 612nm place, the luminous intensity of luminescent material prepared by the present embodiment enhances 17%.
Embodiment 3
The precipitator method prepare Ca 0.995tiO 3: Pr 0.005
Take 0.003g glucose and be dissolved in the sorbitol solution that dehydrated alcohol obtains 40mL, this solution being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 150 DEG C of reaction 10h, prepare the solution of carbon bead, this solution of centrifugation obtains solid formation, washs 2 times respectively with deionized water and dehydrated alcohol, and dry at 70 DEG C, namely obtain carbon bead template.
Under magnetic stirring tetrabutyl titanate is dissolved in ethanol and obtains 1mol/L clear solution, then according to stoichiometric ratio, pipette 4mL1mol/L tetrabutyl titanate, then add 2mL0.01mol/L Pr (NO 3) 3with 7.96mL0.5mol/L Ca (NO 3) 2, adopt HNO 3regulator solution pH value is 3, adds carbon bead template 4.8mg, stirs 0.5h, then slowly adds sinking agent oxalic acid when stirring, and produces precipitation, then stirring reaction 8h.Then suction filtration is also dry, obtains Ca 0.995tiO (C 2o 4) 2: Pr 0.005@C presoma;
Presoma is ground, is put in high temperature box furnace calcining at constant temperature 6h at 500 DEG C, grinding after cooling, and then in 1200 DEG C of calcining 1h, obtain Ca 0.995tiO 3: Pr 0.005luminescent material.
Embodiment 4
The precipitator method prepare Ca 0.99tiO 3: Pr 0.01
Take 5g glucose and be dissolved in the sorbitol solution that dehydrated alcohol obtains 40mL, this solution being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 180 DEG C of reaction 24h, prepare the solution of carbon bead, this solution of centrifugation obtains solid formation, washs 2 times respectively with deionized water and dehydrated alcohol, and dry at 60 DEG C, namely obtain carbon bead template.
Under magnetic stirring tetrabutyl titanate is dissolved in ethanol and obtains 1mol/L clear solution, then according to stoichiometric ratio, pipette 4mL1mol/L tetrabutyl titanate, then add 0.8mL0.005mol/LPr (NO 3) 3with 3.96mL1mol/L Ca (NO 3) 2, adopt HNO 3regulator solution pH value is 3, adds carbon bead template 1.2mg, stirs 0.5-6h, then slowly adds 10mL1mol/L sinking agent oxalic acid when stirring, and produces precipitation, then stirring reaction 2-8h.Then suction filtration is also dry, obtains Ca 0.99tiO (C 2o 4) 2: Pr 0.01@C presoma;
Presoma is ground, is put in high temperature box furnace calcining at constant temperature 1h at 700 DEG C, grinding after cooling, and then in 900 DEG C of calcining 10h, obtain Ca 0.99tiO 3: Pr 0.01luminescent material.
Embodiment 5
The precipitator method prepare Ca 0.996tiO 3: Pr 0.004
Take 6g sucrose dissolved obtains 40mL sucrose alcohol solution in dehydrated alcohol, this solution being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 200 DEG C of reaction 5h, prepare the solution of carbon bead, this solution of centrifugation obtains solid formation, washs 2 times respectively with deionized water and dehydrated alcohol, and dry at 75 DEG C, namely obtain carbon bead template.
Under magnetic stirring tetrabutyl titanate is dissolved in ethanol and obtains 1mol/L clear solution, then according to stoichiometric ratio, pipette 4mL1mol/L tetrabutyl titanate, then add 0.32mL0.05mol/LPr (NO 3) 3with 19.92mL0.2mol/L Ca (NO 3) 2, adopt HNO 3regulator solution pH value is 2.5, adds carbon bead template 100mg, stirs 4h, then slowly adds 20mL0.5mol/L sinking agent oxalic acid when stirring, and produces precipitation, then stirring reaction 5h.Then suction filtration is also dry, obtains Ca 0.996tiO (C 2o 4) 2: Pr 0.004@C presoma;
Presoma is ground, is put in high temperature box furnace calcining at constant temperature 3h at 600 DEG C, grinding after cooling, and then in 700 DEG C of calcining 5h, obtain Ca 0.996tiO 3: Pr 0.004luminescent material.
Embodiment 6
The precipitator method prepare Ca 0.994tiO 3: Pr 0.006
Take 5.705g sucrose dissolved obtains 40mL sucrose alcohol solution in dehydrated alcohol, this solution being proceeded to 50mL is with in teflon-lined reactor, add a cover after screwing, in 140 DEG C of reaction 15h, prepare the solution of carbon bead, this solution of centrifugation obtains solid formation, washs 2 times respectively with deionized water and dehydrated alcohol, and dry at 80 DEG C, namely obtain carbon bead template.
Under magnetic stirring tetrabutyl titanate is dissolved in ethanol and obtains 1mol/L clear solution, then according to stoichiometric ratio, pipette 4mL1mol/L tetrabutyl titanate, then add 0.24mL0.1mol/L Pr (NO 3) 3with 19.88mL0.2mol/L Ca (NO 3) 2, adopt HNO 3regulator solution pH value is 2, adds carbon bead template 150mg, stirs 3h, then slowly adds 10mL1mol/L sinking agent oxalic acid when stirring, and produces precipitation, then stirring reaction 6h.Then suction filtration is also dry, obtains Ca 0.994tiO (C 2o 4) 2: Pr 0.006@C presoma;
Presoma is ground, is put in high temperature box furnace calcining at constant temperature 2h at 550 DEG C, grinding after cooling, and then in 800 DEG C of calcining 8h, obtain Ca 0.994tiO 3: Pr 0.006luminescent material.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.

Claims (8)

1. a preparation method for hollow structure calcium titanate luminescent material, is characterized in that, comprises the steps:
Be that the sucrose of 0.00075 ~ 0.15g/ml or the ethanolic soln of glucose are placed in reactor by concentration, at 120 ~ 200 DEG C, 5 ~ 36h is reacted after sealed reactor, be cooled to centrifugation after room temperature, and the solid phase obtained is washed, obtain carbon bead template after drying;
Be Ca according to general structure 1-xtiO 3: Pr xin each element chemistry metering ratio, be in the ethanolic soln of the tetrabutyl titanate of 1mol/L, add the Pr (NO that concentration is 0.005 ~ 0.1mol/L toward concentration 3) 3ca (the NO of solution and 0.1 ~ 1mol/L 3) 2solution, obtains mixing solutions; The pH value of mixing solutions is regulated to be 2 ~ 3 subsequently; Then add carbon bead template again, stir 0.5-6h, more then slowly add oxalic acid sinking agent when stirring, produce precipitation, then stirring reaction 2-8h, then suction filtration is also dry, obtains Ca 1-xtiO (C 2o 4) 2: Pr x@C presoma; Wherein, described carbon bead template and Ca 1-xtiO 3: Pr xmol ratio be 10:1;
Described presoma is ground, and powder pre-burning 1 ~ 6 hour at 500 ~ 800 DEG C will be ground, grinding after cooling, and then in 800 ~ 1200 DEG C of calcining 1 ~ 10h, obtain Ca 1-xtiO 3: Pr xluminescent material;
In above-mentioned steps, the span of x is 0 < x≤0.01.
2. the preparation method of hollow structure calcium titanate luminescent material according to claim 1, is characterized in that, the reactor in described carbon bead template preparation process is teflon-lined reactor.
3. the preparation method of hollow structure calcium titanate luminescent material according to claim 1, is characterized in that, is use deionized water and dehydrated alcohol repetitive scrubbing successively repeatedly to the washing of described separation solid phase.
4. the preparation method of hollow structure calcium titanate luminescent material according to claim 1, is characterized in that, carries out at 60 ~ 80 DEG C the drying of the solid phase after described washing.
5. the preparation method of hollow structure calcium titanate luminescent material according to claim 1, is characterized in that, when regulating the pH value of described mixing solutions, adopts HNO 3carry out.
6. the preparation method of hollow structure calcium titanate luminescent material according to claim 1, is characterized in that, the relative Ca of mole dosage of described sinking agent 2+and TiO 2+mole dosage excessive 25%.
7. the preparation method of hollow structure calcium titanate luminescent material according to claim 1, is characterized in that, pre-burning and the calcining of described grinding powder are carried out all in air atmosphere, in high temperature box furnace.
8. the preparation method of hollow structure calcium titanate luminescent material according to claim 1, is characterized in that, the span of x is 0.001≤x≤0.005.
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Publication number Priority date Publication date Assignee Title
CN102337136A (en) * 2010-07-21 2012-02-01 海洋王照明科技股份有限公司 Metal-nanoparticle-doped oxide luminescent material with hollow structure and preparation method thereof
CN102477294A (en) * 2010-11-25 2012-05-30 海洋王照明科技股份有限公司 Calcium titanate luminescent material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102337136A (en) * 2010-07-21 2012-02-01 海洋王照明科技股份有限公司 Metal-nanoparticle-doped oxide luminescent material with hollow structure and preparation method thereof
CN102477294A (en) * 2010-11-25 2012-05-30 海洋王照明科技股份有限公司 Calcium titanate luminescent material and preparation method thereof

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草酸盐共沉淀法制备CaTiO3:Pr3+长余辉发光材料的性能研究;尚用甲等;《功能材料》;20090120;第40卷;第17页右栏第1-11行 *

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