CN104059660A - Gadolinium acid calcium luminescent material with hollow structure and preparation method thereof - Google Patents

Gadolinium acid calcium luminescent material with hollow structure and preparation method thereof Download PDF

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CN104059660A
CN104059660A CN201310091428.7A CN201310091428A CN104059660A CN 104059660 A CN104059660 A CN 104059660A CN 201310091428 A CN201310091428 A CN 201310091428A CN 104059660 A CN104059660 A CN 104059660A
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luminescent material
hollow structure
acid calcium
gadolinium
preparation
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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 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 the luminescent material field, and discloses a gadolinium acid calcium luminescent material with a hollow structure and a preparation method thereof. A general chemical formula of the luminescent material is CaGd4-xO7: Tbx, and the value range of x is greater than 0 and is less than or equal to 0.3. In the gadolinium acid calcium luminescent material with the hollow structure, a dispersed small carbon ball C is employed as a template, so that the gadolinium acid calcium luminescent material with the spherical hollow structure is obtained, the morphology is controllable, so that amount of rare earth metal can be effectively reduced, product cost is reduced, and precious rare earth resource can be saved.

Description

Gadolinium acid calcium luminescent material and the preparation method of hollow structure
Technical field
The present invention relates to field of light emitting materials, relate in particular to a kind of gadolinium acid calcium luminescent material and preparation method of hollow structure.
Background technology
Present commercial luminescent material is prepared with high temperature solid-state method mostly, pyroreaction big energy-consuming and size distribution inequality, and powder pattern is different, need by the method for ball milling to obtain the fluorescent material of 2-8 micron grain size, and make powder granule size inconsistent, pattern is imperfect, causes coating inequality.People pass through to use sol-gel method, hydrothermal synthesis method, and the methods such as complexing gel method are prepared fluorescent material, and these methods can make up the deficiency of high temperature solid phase synthesis, but the luminous intensity of the fluorescent material of these method gained is not as high temperature solid phase synthesis.The target that to obtain size, pattern luminescent material controlled and good luminous performance be researchist's effort always.
Summary of the invention
Problem to be solved by this invention is to provide the gadolinium acid calcium luminescent material of the hollow structure that a kind of luminous efficiency is higher, pattern is controlled.
Technical scheme of the present invention is as follows:
A gadolinium acid calcium luminescent material for hollow structure, its chemical general formula is CaGd 4-xo 7: Tb x, wherein, x is the mole number that Tb atom replaces Gd atom, the span of x is 0 < x≤0.3.
The gadolinium acid calcium luminescent material of described hollow structure, preferably, the span of x is 0.001≤x≤0.15.
The present invention also provides a kind of preparation method of gadolinium acid calcium luminescent material of hollow structure, comprises the steps:
The sucrose that is 0.000075 ~ 0.15g/ml by concentration or glucose ethanolic soln move in reactor, sealed state reacts 5 ~ 36h at 120 ~ 200 DEG C, be cooled to subsequently centrifugation after room temperature, obtain solid formation, and solid formation is washed, obtains carbon bead C after dry; Wherein, C represents carbon;
According to CaGd 4-xo 7: Tb xin each element chemistry metering ratio, measure the each self-corresponding salts solution of Ca, Gd and Tb, put into beaker, then add described carbon bead C, stir; And then slowly add oxalic acid precipitation agent, and obtain mixing solutions, and to regulate the pH value of mixing solutions be 10 ~ 12 rear reaction 2 ~ 8h, stopped reaction, reaction solution after filtration, be precipitated thing after washing, drying treatment, is CaGd 4-x(C 2o 4) 7: Tb x@C presoma; Wherein, CaGd 4-x(C 2o 4) 7: Tb xin@C, CaGd 4-x(C 2o 4) 7: Tb xrepresent shell, C represents writing a Chinese character in simplified form of carbon bead C, and@represents CaGd 4-x(C 2o 4) 7: Tb xcarbon coated bead C, colon ": " represents the doping of Tb; Carbon bead C and CaGd 4-xo 7: Tb xmol ratio be 0.025:1 ~ 10:1,
Described presoma is ground, grind powder and be put in air atmosphere in 600 ~ 1000 DEG C of pre-burning 1 ~ 8h, at 1300 ~ 1600 DEG C, 2 ~ 12h is processed in reduction more subsequently, and furnace cooling is cooled to room temperature, and obtaining chemical general formula is CaGd 4-xo 7: Tb xthe gadolinium acid calcium luminescent material of hollow structure;
In above-mentioned steps, x is the mole number that Tb atom replaces Gd atom, and the span of x is 0 < x≤0.3.
The preparation method of the gadolinium acid calcium luminescent material of described hollow structure, preferably, reactor is band teflon-lined reactor.
The preparation method of the gadolinium acid calcium luminescent material of described hollow structure, preferably, to using successively deionized water and dehydrated alcohol repetitive scrubbing repeatedly comprising of described centrifugal gained solid formation; The drying treatment of solid formation after described washing is comprised at 60 ~ 80 DEG C, carrying out 2 ~ 12h is dried.
The preparation method of the gadolinium acid calcium luminescent material of described hollow structure, preferably, comprises that to the dry of described washing postprecipitation thing at 60 ~ 100 DEG C, carrying out 2 ~ 10h is catching up with.
The preparation method of the gadolinium acid calcium luminescent material of described hollow structure, preferably, described oxalic acid precipitation agent mole dosage be ensure Ca, Gd and Tb precipitation completely and excessive 25%, its effect is:
While reaction according to chemical equation, complete to ensure the precipitation of Ca, Gd and Tb ion, excessive effect all precipitates completely in order to ensure all metal ions exactly, and unreacted oxalic acid is solution, in the time filtering, can wash away.
The preparation method of the gadolinium acid calcium luminescent material of described hollow structure, wherein, the each self-corresponding salts solution of Ca, Gd and Tb is respectively nitrate solution or acetate solution.
The preparation method of the gadolinium acid calcium luminescent material of described hollow structure, preferably, regulates and adopts ammoniacal liquor to carry out the pH value of mixing solutions.
The preparation method of the gadolinium acid calcium luminescent material of described hollow structure, preferably, presoma grinds the pre-burning of powder and reduces to process and carry out in retort furnace.
The preparation method of the gadolinium acid calcium luminescent material of described hollow structure, preferably, preferably, it is that volume ratio is the N of 95:5 that the reducing gas adopting is processed in described reduction 2with H 2mixed gas (is 95v%N 2with 5v%H 2), CO, H 2in at least one.
The preparation method of the gadolinium acid calcium luminescent material of described hollow structure, preferably, the span of x is 0.001≤x≤0.15.
The gadolinium acid calcium luminescent material of hollow structure provided by the invention, adopting the carbon bead C disperseing is template, the gadolinium acid calcium luminescent material obtaining is spherical hollow structure, not only pattern is controlled, and can effectively reduce the consumption of rare earth metal, reduce product cost, saved in a large number precious rare earth resources.
The invention provides preparation method, first adopt hydrothermal method to prepare carbon bead C, and then taking carbon bead C as template, adopt oxalate precipitation method to prepare CaGd 4-x(C 2o 4) 7: Tb x@C precursor powder, and then through calcining, in calcination process, carbon bead C and oxalate will be converted into CO 2overflow, finally obtaining chemical general formula is CaGd 4-xo 7: Tb xthe gadolinium acid calcium luminescent material of hollow structure.
The preparation method of the gadolinium acid calcium luminescent material of hollow structure of the present invention, processing step is few, relatively simple; Processing condition are not harsh, easily reach, and cost is low; Do not introduce other impurity, the luminescent material quality obtaining is high, can be widely used in the preparation of luminescent material.
Brief description of the drawings
Fig. 1 is that luminescent material and the comparative example luminescent material that the embodiment of the present invention 2 makes is the luminescent spectrum comparison diagram under the cathode-ray exciting under 1.5KV at acceleration voltage; Wherein, curve 1 is hollow structure CaGd prepared by the present embodiment 2 3.92o 7: Tb 0.08the luminescent spectrum of luminescent material, curve 2 is the non-hollow structure CaGd of comparative example 3.92o 7: Tb 0.08the luminescent spectrum of luminescent material.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The precipitator method are prepared CaGd 3.7o 7: Tb 0.3:
The glucose that takes 4g is dissolved in dehydrated alcohol, making liquor capacity is 40mL, then solution is proceeded in 50mL band teflon-lined reactor, add a cover and screw, at 120 DEG C of reaction 36h, prepare the carbon bead C solution of clad metal nano particle, with deionized water and absolute ethanol washing repeatedly, centrifugation, 60 DEG C of dry carbon bead C that obtain clad metal nano particle, in order to stand-by;
Take the Ca (NO that 5.6080gCaO is dissolved in nitric acid and obtains 100mL1mol/L 3) 3solution; Take 18.1250g Gd 2o 3be dissolved in the Gd (NO that nitric acid obtains 100mL1mol/L 3) 3solution; Take 9.3400g Tb 4o 7be dissolved in the Tb (NO that nitric acid obtains 100mL0.5mol/L 3) 3solution.
According to CaGd 3.7o 7: Tb 0.3stoichiometric ratio pipette 4mL1mol/L Ca (NO 3) 2, 14.8mL1mol/LGd (NO 3) 3and 2.4mL0.5mol/L Tb (NO 3) 3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes carbon bead C4.8mg and adds in mixed solution, stirs.Under magnetic agitation, add 17.5mL precipitation agent oxalic acid solution (2mol/L), then to regulate pH by ammoniacal liquor be 10, after reaction 4h, after filtration, deionized water and washing with alcohol, 100 DEG C of vacuum-drying 2h, be precipitated thing, i.e. CaGd 3.7(C 2o 4) 7: Tb 0.3@C precursor powder;
Presoma is ground, be put in retort furnace in air in 1000 DEG C of pre-burning 1h, grind, and then in the lower 1600 DEG C of calcining 2h of CO reducing atmosphere, be cooled to room temperature and obtain CaGd 3.7o 7: Tb 0.3the gadolinium acid calcium luminescent material of hollow ball structure.
Embodiment 2
The precipitator method are prepared CaGd 3.92o 7: Tb 0.08:
Take the sorbitol solution that 0.003g glucose is dissolved in dehydrated alcohol and obtains 40mL, this solution is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 150 DEG C of reaction 10h, prepare the solution of carbon bead C, this solution of centrifugation obtains solid formation, washs respectively 2 times with deionized water and dehydrated alcohol, and dry at 70 DEG C, obtain carbon bead C.
According to CaGd 3.92o 7: Tb 0.08stoichiometric ratio pipette 2mL2mol/L Ca (NO 3) 2solution, 15.68mL1mol/L Gd (NO 3) 3solution and 3.2mL0.1mol/L Tb (NO 3) 3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes carbon bead C200mg and adds in mixed solution, stirs.Under magnetic agitation, add 35mL1mol/L precipitation agent oxalic acid solution, then to regulate pH by ammoniacal liquor be 10, after reaction 6h, after filtration, deionized water and washing with alcohol, 80 DEG C of vacuum-drying 4h, be precipitated thing, i.e. CaGd 3.92(C 2o 4) 7: Tb 0.08@C precursor powder;
Presoma is ground, is put in retort furnace in air in 800 DEG C of pre-burning 4h, grind, then in tube furnace at 95v%N 2add 5v%H 2the lower 1450 DEG C of calcining 5h of weakly reducing atmosphere, furnace cooling is cooled to room temperature, and obtained sample is ground to powder, obtains the CaGd of hollow structure 3.92o 7: Tb 0.08the gadolinium acid calcium luminescent material of hollow ball structure.
Fig. 1 is that luminescent material and the comparative example luminescent material that the embodiment of the present invention 2 makes is the luminescent spectrum comparison diagram under the cathode-ray exciting under 1.5KV at acceleration voltage; Wherein, curve 1 is hollow structure CaGd prepared by the present embodiment 2 3.92o 7: Tb 0.08the luminescent spectrum of luminescent material, curve 2 is the non-hollow structure CaGd of comparative example 3.92o 7: Tb 0.08the luminescent spectrum of luminescent material.
As can be seen from Figure 1,, at the emission peak at 544nm place, the luminous intensity of luminescent material prepared by the present embodiment has strengthened 18%.
Embodiment 3
The precipitator method are prepared CaGd 3.999o 7: Tb 0.001:
Take the sorbitol solution that 4g glucose is dissolved in dehydrated alcohol and obtains 40mL, this solution is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 120 DEG C of reaction 36h, prepare the solution of carbon bead C, this solution of centrifugation obtains solid formation, washs respectively 2 times with deionized water and dehydrated alcohol, and dry at 60 DEG C, obtain carbon bead C.
According to CaGd 3.999o 7: Tb 0.001stoichiometric ratio pipette 8mL0.5mol/L Ca (CH 3cOO) 2solution, 31.992mL0.5mol/L Gd (CH 3cOO) 3solution and 4mL0.001mol/L Tb (CH 3cOO) 3solution, is placed in 100mL beaker and forms mixed solution, then takes carbon bead C480mg and adds in mixed solution, stirs.Under magnetic agitation, add 14mL2.5mol/L precipitation agent oxalic acid solution, then to regulate pH by ammoniacal liquor be 12, after reaction 2h, after filtration, deionized water and washing with alcohol, 60 DEG C of vacuum-drying 8h, be precipitated thing, i.e. CaGd 3.999(C 2o 4) 7: Tb 0.001@C precursor powder;
Presoma is ground, is put in retort furnace in air in 700 DEG C of pre-burnings 6 hours, grind, and then in tube furnace at pure H 2the lower 1300 DEG C of calcining 12h of reducing atmosphere, are cooled to room temperature and obtain CaGd 3.999o 7: Tb 0.001the gadolinium acid calcium luminescent material of hollow ball structure.
Embodiment 4
The precipitator method are prepared CaGd 3.9o 7: Tb 0.1:
Take the sorbitol solution that 5g glucose is dissolved in dehydrated alcohol and obtains 40mL, this solution is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 180 DEG C of reaction 24h, prepare the solution of carbon bead C, this solution of centrifugation obtains solid formation, washs respectively 2 times with deionized water and dehydrated alcohol, and dry at 60 DEG C, obtain carbon bead C.
According to CaGd 3.9o 7: Tb 0.1stoichiometric ratio pipette 4mL1mol/L Ca (NO 3) 2solution, 7.8mL2mol/L Gd (NO 3) 3solution and 8mL0.05mol/L Tb (NO 3) 3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes carbon bead C1.2mg and adds in mixed solution, stirs.Under magnetic agitation, add 35mL precipitation agent oxalic acid solution (1mol/L), then to regulate pH by ammoniacal liquor be 11, after reaction 3h, after filtration, deionized water and washing with alcohol, 70 DEG C of vacuum-drying 6h, be precipitated thing, i.e. CaGd 3.92(C 2o 4) 7: Tb 0.1@C precursor powder;
Presoma is ground, be put in retort furnace in air in 600 DEG C of pre-burnings 8 hours, grind, and then in the lower 1400 DEG C of calcining 10h of CO reducing atmosphere, be cooled to room temperature and obtain CaGd 3.9o 7: Tb 0.1the gadolinium acid calcium luminescent material of hollow ball structure.
Embodiment 5
The precipitator method are prepared CaGd 3.88o 7: Tb 0.12:
Take 6g sucrose dissolved obtains 40mL sucrose alcohol solution in dehydrated alcohol, this solution is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 200 DEG C of reaction 5h, prepare the solution of carbon bead C, this solution of centrifugation obtains solid formation, washs respectively 2 times with deionized water and dehydrated alcohol, and dry at 75 DEG C, obtain carbon bead C.
Take 10.0090g CaCO 3be dissolved in the Ca (NO that nitric acid obtains 100mL1mol/L 3) 2solution; Take 49.4524g Gd 2(CO 3) 3be dissolved in the Gd (NO that nitric acid obtains 100mL2mol/L 3) 3solution; Take 4.9786gTb 2(CO 3) 3be dissolved in the Tb (NO that nitric acid obtains 100mL0.2mol/L 3) 3solution.
According to CaGd 3.88o 7: Tb 0.12stoichiometric ratio pipette 4mL1mol/L Ca (NO 3) 2solution, 7.66mL2mol/L Ga (NO 3) 3solution and 2.4mL0.2mol/L Tb (NO 3) 3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes carbon bead C100mg and adds in mixed solution, stirs.Under magnetic agitation, add 35mL precipitation agent oxalic acid solution (1mol/L), then to regulate pH by ammoniacal liquor be 10, after reaction 3h, after filtration, deionized water and washing with alcohol, 70 DEG C of vacuum-drying 5h, be precipitated thing, i.e. CaGd 3.88(C 2o 4) 7: Tb 0.12@C precursor powder;
Presoma is ground, is put in retort furnace in air in 750 DEG C of pre-burnings 4 hours, grind, and then in tube furnace at 95v%N 2add 5v%H 2the lower 1300 DEG C of calcining 12h of weakly reducing atmosphere, are cooled to room temperature and obtain CaGd 3.88o 7: Tb 0.12the gadolinium acid calcium luminescent material of hollow ball structure.
Embodiment 6
The precipitator method are prepared CaGd 3.85o 7: Tb 0.15:
Take 5.705g sucrose dissolved obtains 40mL sucrose alcohol solution in dehydrated alcohol, this solution is proceeded in 50mL band teflon-lined reactor, after adding a cover and screwing, in 140 DEG C of reaction 15h, prepare the solution of carbon bead C, this solution of centrifugation obtains solid formation, washs respectively 2 times with deionized water and dehydrated alcohol, and dry at 80 DEG C, obtain carbon bead C.
According to CaGd 3.85o 7: Tb 0.15stoichiometric ratio pipette 4mL1mol/L Ca (NO 3) 2solution, 15.4mL1mol/L Gd (NO 3) 3solution and 6mL0.1mol/L Tb (NO 3) 3solution, is placed in 100mL beaker and forms nitric acid mixed solution, then takes carbon bead C150mg and adds in mixed solution, stirs.Under magnetic agitation, add 35mL precipitation agent oxalic acid solution (1mol/L), then to regulate pH by ammoniacal liquor be 11, after reaction 8h, after filtration, deionized water and washing with alcohol, 90 DEG C of vacuum-drying 3h, be precipitated thing, i.e. CaGd 3.85(C 2o 4) 7: Tb 015@C precursor powder;
Presoma is ground, is put in retort furnace in air in 900 DEG C of pre-burnings 2 hours, grind, and then in tube furnace at 95v%N 2add 5v%H 2the lower 1450 DEG C of calcining 6h of weakly reducing atmosphere, are cooled to room temperature and obtain CaGd 3.85o 7: Tb 0.15the gadolinium acid calcium luminescent material of hollow ball structure.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. the gadolinium of a hollow structure acid calcium luminescent material, is characterized in that, its chemical general formula is: CaGd 4-xo 7: Tb x, wherein, x is the mole number that Tb atom replaces Gd atom, the span of x is 0<x≤0.3.
2. the gadolinium of hollow structure according to claim 1 acid calcium luminescent material, is characterized in that, the span of x is 0.001≤x≤0.15.
3. a preparation method for the gadolinium of hollow structure acid calcium luminescent material, is characterized in that, comprises the steps:
The sucrose that is 0.000075 ~ 0.15g/ml by concentration or glucose ethanolic soln move in reactor, sealed state reacts 5 ~ 36h at 120 ~ 200 DEG C, be cooled to subsequently centrifugation after room temperature, obtain solid formation, and solid formation is washed, obtains carbon bead C after dry;
According to CaGd 4-xo 7: Tb xin each element chemistry metering ratio, measure the each self-corresponding salts solution of Ca, Gd and Tb, put into beaker, then add described carbon bead C, stir; And then slowly add oxalic acid precipitation agent, and obtain mixing solutions, and to regulate the pH value of mixing solutions be 10 ~ 12 rear reaction 2 ~ 8h, stopped reaction, reaction solution after filtration, be precipitated thing after washing, drying treatment, is CaGd 4-x(C 2o 4) 7: Tb x@C presoma; Wherein, carbon bead C and CaGd 4-xo 7: Tb xmol ratio be 0.025:1 ~ 10:1;
Described presoma is ground, grind powder and be put in air atmosphere in 600 ~ 1000 DEG C of pre-burning 1 ~ 8h, at 1300 ~ 1600 DEG C, 2 ~ 12h is processed in reduction more subsequently, and furnace cooling is cooled to room temperature, and obtaining chemical general formula is CaGd 4-xo 7: Tb xthe gadolinium acid calcium luminescent material of hollow structure;
In above-mentioned steps, x is the mole number that Tb atom replaces Gd atom, and the span of x is 0<x≤0.3.
4. the preparation method of the gadolinium of hollow structure according to claim 3 acid calcium luminescent material, is characterized in that, to using successively deionized water and dehydrated alcohol repetitive scrubbing repeatedly comprising of described centrifugal gained solid formation; The drying treatment of solid formation after described washing is comprised at 60 ~ 80 DEG C, carrying out 2 ~ 12h is dried.
5. the preparation method of the gadolinium of hollow structure according to claim 3 acid calcium luminescent material, is characterized in that, described sedimentary being dried comprised at 60 ~ 100 DEG C, carrying out 2 ~ 10h is dried.
6. the preparation method of the gadolinium of hollow structure according to claim 3 acid calcium luminescent material, is characterized in that, the mole dosage of described oxalic acid precipitation agent be ensure Ca, Gd and Tb ion precipitation completely and excessive 25%.
7. the preparation method of the gadolinium of hollow structure according to claim 3 acid calcium luminescent material, is characterized in that, the each self-corresponding salts solution of Ca, Gd and Tb is respectively nitrate solution or acetate solution.
8. the preparation method of the gadolinium of hollow structure according to claim 3 acid calcium luminescent material, is characterized in that, the pH value of mixing solutions is regulated and adopts ammoniacal liquor to carry out.
9. the preparation method of the gadolinium of hollow structure according to claim 3 acid calcium luminescent material, is characterized in that, it is that volume ratio is the N of 95:5 that the reducing gas adopting is processed in described reduction 2with H 2mixed gas, CO, H 2in at least one.
10. the preparation method of the gadolinium of hollow structure according to claim 3 acid calcium luminescent material, is characterized in that, the span of x is 0.001≤x≤0.15.
CN201310091428.7A 2013-03-20 2013-03-20 Gadolinium acid calcium luminescent material with hollow structure and preparation method thereof Pending CN104059660A (en)

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Application publication date: 20140924