CN104927851A - Green long-afterglow light emitting material and preparation method therefor - Google Patents

Green long-afterglow light emitting material and preparation method therefor Download PDF

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CN104927851A
CN104927851A CN201510235097.9A CN201510235097A CN104927851A CN 104927851 A CN104927851 A CN 104927851A CN 201510235097 A CN201510235097 A CN 201510235097A CN 104927851 A CN104927851 A CN 104927851A
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green long
long afterglow
green
afterglow
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常程康
石明明
章冬云
李南
郭芸芸
邓玲
孙怡雯
郭倩
王永强
蔡元元
陈雪平
钟国兵
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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Abstract

The invention relates to a green long-afterglow light emitting material, the molecular formula of which is Ca(2-x)SnO4: Erx, B0.05, wherein x is equal to 0.005-0.05. The invention further provides a preparation method of the green long-afterglow light emitting material. The preparation method comprises the following steps: weighing CaCO3, SnO2, Er2O3 and H3BO3 in percentage by mass; fully grinding and uniformly mixing the mixture and screening the mixture by a 180-220-mesh sieve; tabletting the obtained mixed powder and calculating the powder; naturally cooling the powder to room temperature; and grinding and screening the powder by the 180-220-mesh screen to obtain the green long-afterglow light emitting material. Through ultraviolet excitation, a sample gives out bright green afterglow, and through emission spectrum determination, the main emission peaks are positioned near 552 nm. After ultraviolet light is removed, the sample has an obvious green long-afterglow characteristic and the afterglow can be seen by naked eyes. The green long-afterglow light emitting material provided by the invention is simple in preparation method, free of pollution and radioactivity and low in cost, does not need atmosphere protection, and is suitable for being produced on a large scale.

Description

A kind of green long afterglow luminescent material and preparation method thereof
Technical field
The invention belongs to materialogy field, particularly relate to a kind of luminescent material, specifically a kind of green long afterglow luminescent material and preparation method thereof.
Background technology
Long after glow luminous material is a kind of New Photoinduced energy storage material, it produces light when extraneous light source activation, simultaneously stability luminous energy also stores, again stored energy is outwards discharged slowly in the form of light after exciting stopping, have energy-conservation, the feature such as can be recycled, be widely used in noctilucent material, safety instruction, the aspects such as low light level Emergency Light and military science field.
Research major part at present for long after glow luminous material all concentrates on alkaline earth metal aluminosilicate aspect, as: SrAl 2o 4: Eu 2+, Dy 3+and Sr 2mgSi 2o 7: Eu 2+, Dy 3+deng.Long-persistence luminous pottery is also the hot topic of research long after glow luminous material, as disclosed a kind of preparation method of calcium aluminosilicate blue long afterflow pottery in Chinese patent Authorization Notice No. CN 101935204.And in patent CN 101805609, Sm is disclosed to people such as the representational Lei Ping Fu of being of report most of stannate long-afterglow material 3+the orange long afterglow material of the stronitum stannate system composite oxide activated.China Patent Publication No. is the preparation method disclosing a kind of europium-doped calcium stannate luminescent material in CN 101696354.Chinese patent Authorization Notice No. is the preparation method disclosing a kind of manganese ion activated green long afterglow luminescent material in CN 100463950C.
The defects such as in sum, from published literature, the kind in this field is not still enriched at present, and particularly stannic acid salt long-afterglow material exists glow color and do not enrich, and the strong and stability of after-glow brightness is not good enough.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of green long afterglow luminescent material and preparation method thereof, described this green long afterglow luminescent material and preparation method thereof solves stannic acid salt long-afterglow material of the prior art and there is the technical problem that glow color is not abundant, after-glow brightness is not strong and stability is not good enough.
A kind of green long afterglow luminescent material of the present invention, its chemical formula is: Ca 2-xsnO 4: Er x, B 0.05, x=0.005 ~ 0.05 in formula, x is the mol ratio coefficient of Er Ion Phase for Ca2SnO4.
Further, the matrix of described material is Ca 2snO 4, activator is trivalent erbium ion Er 3+, fusing assistant is boric acid.
Present invention also offers the preparation method of above-mentioned a kind of green long afterglow luminescent material, comprise the following steps:
(1) CaCO is taken by mass percentage 3, SnO 2, Er 2o 3and H 3bO 3, in the feed, CaCO 3mass percent be 54.43 ~ 56.33%, SnO 2mass percent be 42.07 ~ 42.52%, E r2O 3mass percent be 0.27 ~ 2.67%, H 3bO 3mass percent be 0.83 ~ 0.88%;
(2) raw material weighed up is put into mortar, grind;
(3) raw material mixed after grinding is crossed 180 ~ 220 mesh sieves;
(4) carry out compressing tablet to the raw material after sieving, pressure is 8 ~ 12MPa;
(5) sample after compressing tablet is put into porcelain boat, be warming up to 1200 ~ 1350 DEG C in air atmosphere, calcining 4 ~ 10h, naturally cools to room temperature with stove, obtained described green long afterglow luminescent material after pulverizing 180 ~ 220 mesh sieves.
Further, the time of grinding is 1.5 ~ 2h.
Preferably, be warming up to 1350 DEG C in air atmosphere, calcining 4h, naturally cools to room temperature with stove.
A kind of green long afterglow stannate material of the present invention, the substrate material selected is the Ca of stable chemical nature, high temperature resistant, high pure phase 2snO 4, use single Er 3+ion is activator, calcine 4 ~ 10 hours in 1200 ~ 1350 DEG C of High Temperature Furnaces Heating Apparatuss in air atmosphere, furnace cooling takes out the technical scheme of product, the kind which overcoming existing long-afterglow material is few, the defects such as particularly stannic acid salt long-afterglow material exists glow color and do not enrich, and the strong and stability of after-glow brightness is not good enough.
The method preparing stannate green long afterglow material of the present invention, it adopts traditional high temperature solid-state method synthesis in air atmosphere, and its synthesis technique is simple, and synthesis cost is low, environmentally friendly, is convenient to large-scale industrial and produces.In addition, can also add in the feed relative to substrate material Ca when grinding in this preparation method 2snO 4mol ratio coefficient is that the boric acid of 0.05 is as fusing assistant.Its role is to reduce crystalline phase nucleation temperature of reaction and grain growing reaction energy barrier adding of boric acid, thus accelerate surface reaction speed, and fusing assistant boric acid add the degree of depth and density that very likely increase electronic defects trap level, so fusing assistant add the luminescent properties not only contributing to sintering but also can improve material.
The present invention compared with prior art has the following advantages and beneficial effect:
(1) rare earth Er 3+ion is often used in up-conversion luminescence field due to its special level structure, and rarely has report in steady persistence field.But in the present invention, use calcium stannate as luminescent ceramic matrix, use trivalent erbium ion Er 3+as luminescence center and Trapping Centers, excellent green long afterglow behavior just can be produced through simple solid state reaction;
(2) the present invention adopts Alkaline earth stannates to be the stable chemical nature of matrix, its product, water-tolerant;
(3) the present invention adopts traditional high temperature solid-state technique, synthesizes in air atmosphere, and synthesis technique is simple, easily operates, and is applicable to large-scale industrial and produces;
(4) moiety of the present invention is simple, low production cost, and fluffy easy grinding is "dead", to environment, can not be convenient to penetration and promotion.
The present invention compares with prior art, and its technical progress is significant.Stannate green long afterglow material of the present invention, is be matrix with calcium stannate, uses single rare earth Er 3+produce stable chemical nature for ion-activated dose, not facile hydrolysis, have the material of longer time of persistence.Stannate green long afterglow material of the present invention is applicable to passive display and the energy-saving illumination of making traffic, display equipment etc.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the long after glow luminous material that embodiment 1 obtains.
Fig. 2 is the transmitting spectrogram of the long after glow luminous material that embodiment 1 obtains.
Fig. 3 is the decay of afterglow graphic representation of the long after glow luminous material that embodiment 1 obtains.
Embodiment
Also by reference to the accompanying drawings the present invention is set forth further below by specific embodiment, but do not limit the present invention.
Embodiment 1
A kind of green long afterglow luminescent material, its chemical formula is Ca 1.995snO 4: Er 0.005, B 0.05.
The preparation method of above-mentioned a kind of green long afterglow luminescent material, specifically comprises the steps:
1) calculate by mass percentage, i.e. CaCO 3: SnO 2: Dy 2o 3: H 3bO 3for the ratio of 56.33%:42.52%:0.27%:0.88%, take chemical pure CaCO 3, SnO 2, H 3bO 3, Er 2o 3raw material,
2) raw material weighed up is put into mortar, carry out grinding 1 hour, powder is mixed;
3) raw material mixed after grinding is crossed 200 mesh sieves;
4) carry out compressing tablet to the raw material after sieving, pressure is 10MPa;
5) sample after compressing tablet is put into porcelain boat, in 1200 DEG C of High Temperature Furnaces Heating Apparatuss, calcination 4 hours, takes out after naturally cooling to room temperature, pulverizes 200 mesh sieves, obtains green long afterglow material.
The green long afterglow material appearance of above-mentioned gained is in white.
X-ray diffractometer (TD-3000, Dandong is sensible) is adopted to be Ca to above-mentioned gained molecular formula 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, as shown in Figure 1, as can be seen from Figure 1, its structure is rhombic system to its XRD figure, compares with standard P DF card (#04-008-291), and its phase composite is Ca 2snO 4, there is no impurity peaks.Show that above-mentioned molecular formula is Ca 1.995snO 4: Er 0.005, B 0.05green long afterglow material be Ca 2snO 4pure phase.
Fluorescence spectrophotometer (FLS8900, Edinburgh, Britain Instruments company) is adopted to be Ca to the molecular formula of above-mentioned gained 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, as shown in Figure 2, under 263nm optical excitation, its emission wavelength is positioned at 523 to the transmitting spectrogram of gained, 563 and 656nm, correspond respectively to Er 3+'s 2h 11/2→ 4i 15/2, 4s 3/2→ 4i 15/2with 4f 9/2→ 4i 15/2.
The molecular formula of microcomputer thermoluminescent dosimeter (FJ-27A1, Beijing center instrument plant) to appeal gained is adopted to be Ca 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, the decay of afterglow matched curve of gained as shown in Figure 3, the after-glow brightness of show sample over time and obviously exponentially rule in figure.After ultra violet lamp, in the dark present green afterglow; After light source is removed, this material can also continuous illumination the discernmible luminosity (more than 0.32mcd/m2) of human eye.
Embodiment 2
A kind of green long afterglow luminescent material, its chemical formula is Ca 1.995snO 4: Er 0.005, B 0.05
The preparation method of above-mentioned a kind of green long afterglow luminescent material, specifically comprises the steps:
1) calculate by mass percentage, i.e. CaCO 3: SnO 2: Dy 2o 3: H 3bO 3for the ratio of 56.33%:42.52%:0.27%:0.88%, take chemical pure CaCO 3, SnO 2, H 3bO 3, Er 2o 3raw material,
2) raw material weighed up is put into mortar, carry out grinding 1 hour, powder is mixed;
3) raw material mixed after grinding is crossed 200 mesh sieves;
4) carry out compressing tablet to the raw material after sieving, pressure is 10MPa;
5) sample after compressing tablet is put into porcelain boat, in 1200 DEG C of High Temperature Furnaces Heating Apparatuss, calcination 10 hours, takes out after naturally cooling to room temperature, pulverizes 200 mesh sieves, obtains green long afterglow material.
The green long afterglow material appearance of above-mentioned gained is in white.
X-ray diffractometer (TD-3000, Dandong is sensible) is adopted to be Ca to above-mentioned gained molecular formula 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, its XRD figure is similar to Fig. 1, and its structure is rhombic system, compares with standard P DF card (#04-008-291), and its phase composite is Ca 2snO 4, there is no impurity peaks.Show that above-mentioned molecular formula is Ca 1.995snO 4: Er 0.005, B 0.05green long afterglow material be Ca 2snO 4pure phase.
Fluorescence spectrophotometer (FLS8900, Edinburgh, Britain Instruments company) is adopted to be Ca to the molecular formula of above-mentioned gained 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, the transmitting spectrogram of gained is similar to Fig. 2, and under 263nm optical excitation, its emission wavelength is positioned at 523,563 and 656nm, correspond respectively to Er 3+'s 2h 11/2→ 4i 15/2, 4s 3/2→ 4i 15/2with 4f 9/2→ 4i 15/2.Interpret sample, under the exciting of UV-light, can produce good green emission, and brightness is higher than embodiment 1.
The molecular formula of microcomputer thermoluminescent dosimeter (FJ-27A1, Beijing center instrument plant) to appeal gained is adopted to be Ca 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, the decay of afterglow matched curve of gained is similar to Fig. 3, the after-glow brightness of sample over time and obviously exponentially rule.After ultra violet lamp, in the dark present green afterglow; After light source is removed, this material can also continuous illumination the discernmible luminosity (more than 0.32mcd/m2) of human eye.
Embodiment 3
A kind of green long afterglow luminescent material, its chemical formula is Ca 1.995snO 4: Er 0.005, B 0.05
The preparation method of above-mentioned a kind of green long afterglow luminescent material, specifically comprises the steps:
6) calculate by mass percentage, i.e. CaCO 3: SnO 2: Dy 2o 3: H 3bO 3for the ratio of 56.33%:42.52%:0.27%:0.88%, take chemical pure CaCO 3, SnO 2, H 3bO 3, Er 2o 3raw material,
7) raw material weighed up is put into mortar, carry out grinding 1 hour, powder is mixed;
8) raw material mixed after grinding is crossed 200 mesh sieves;
9) carry out compressing tablet to the raw material after sieving, pressure is 10MPa;
10) sample after compressing tablet is put into porcelain boat, in 1300 DEG C of High Temperature Furnaces Heating Apparatuss, calcination 4 hours, takes out after naturally cooling to room temperature, pulverizes 200 mesh sieves, obtains green long afterglow material.
The green long afterglow material appearance of above-mentioned gained is in white.
X-ray diffractometer (TD-3000, Dandong is sensible) is adopted to be Ca to above-mentioned gained molecular formula 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, its XRD figure is similar to Fig. 1, and its structure is rhombic system, compares with standard P DF card (#04-008-291), and its phase composite is Ca 2snO 4, there is no impurity peaks.Show that above-mentioned molecular formula is Ca 1.995snO 4: Er 0.005, B 0.05green long afterglow material be Ca 2snO 4pure phase.
Fluorescence spectrophotometer (FLS8900, Edinburgh, Britain Instruments company) is adopted to be Ca to the molecular formula of above-mentioned gained 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, the transmitting spectrogram of gained is similar to Fig. 2, and under 263nm optical excitation, its emission wavelength is positioned at 523,563 and 656nm, correspond respectively to Er 3+'s 2h 11/2→ 4i 15/2, 4s 3/2→ 4i 15/2with 4f 9/2→ 4i 15/2.Interpret sample, under the exciting of UV-light, can produce good green emission, and brightness is higher than embodiment 1 and 2.
The molecular formula of microcomputer thermoluminescent dosimeter (FJ-27A1, Beijing center instrument plant) to appeal gained is adopted to be Ca 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, the decay of afterglow matched curve of gained is similar to Fig. 3, the after-glow brightness of sample over time and obviously exponentially rule.After ultra violet lamp, in the dark present green afterglow; After light source is removed, this material can also continuous illumination the discernmible luminosity (more than 0.32mcd/m2) of human eye.
Embodiment 4
A kind of green long afterglow luminescent material, its chemical formula is Ca 1.995snO 4: Er 0.005, B 0.05.
The preparation method of above-mentioned a kind of green long afterglow luminescent material, specifically comprises the steps:
11) calculate by mass percentage, i.e. CaCO 3: SnO 2: Dy 2o 3: H 3bO 3for the ratio of 56.33%:42.52%:0.27%:0.88%, take chemical pure CaCO 3, SnO 2, H 3bO 3, Er 2o 3raw material,
12) raw material weighed up is put into mortar, carry out grinding 1 hour, powder is mixed;
13) raw material mixed after grinding is crossed 200 mesh sieves;
14) carry out compressing tablet to the raw material after sieving, pressure is 10MPa;
15) sample after compressing tablet is put into porcelain boat, in 1350 DEG C of High Temperature Furnaces Heating Apparatuss, calcination 4 hours, takes out after naturally cooling to room temperature, pulverizes 200 mesh sieves, obtains green long afterglow material.
The green long afterglow material appearance of above-mentioned gained is in white.
X-ray diffractometer (TD-3000, Dandong is sensible) is adopted to be Ca to above-mentioned gained molecular formula 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, its XRD figure is similar to Fig. 1, and its structure is rhombic system, compares with standard P DF card (#04-008-291), and its phase composite is Ca 2snO 4, there is no impurity peaks.Show that above-mentioned molecular formula is Ca 1.995snO 4: Er 0.005, B 0.05green long afterglow material be Ca 2snO 4pure phase.
Fluorescence spectrophotometer (FLS8900, Edinburgh, Britain Instruments company) is adopted to be Ca to the molecular formula of above-mentioned gained 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, the transmitting spectrogram of gained is similar to Fig. 2, and under 263nm optical excitation, its emission wavelength is positioned at 523,563 and 656nm, correspond respectively to Er 3+'s 2h 11/2→ 4i 15/2, 4s 3/2→ 4i 15/2with 4f 9/2→ 4i 15/2.Interpret sample, under the exciting of UV-light, can produce good green emission, and brightness is higher than embodiment 1,2 and 3.
The molecular formula of microcomputer thermoluminescent dosimeter (FJ-27A1, Beijing center instrument plant) to appeal gained is adopted to be Ca 1.995snO 4: Er 0.005, B 0.05green long afterglow material measure, the decay of afterglow matched curve of gained is similar to Fig. 3, the after-glow brightness of sample over time and obviously exponentially rule.After ultra violet lamp, in the dark present green afterglow; After light source is removed, this material can also continuous illumination the discernmible luminosity (more than 0.32mcd/m2) of human eye.
Embodiment 5
A kind of green long afterglow luminescent material, its chemical formula is Ca 1.99snO 4: Er 0.01, B 0.05.
The preparation method of above-mentioned a kind of green long afterglow luminescent material, specifically comprises the steps:
1) calculate by mass percentage, i.e. CaCO 3: SnO 2: Dy 2o 3: H 3bO 3for the ratio of 56.12%:42.47%:0.55%:0.87%, take chemical pure CaCO 3, SnO 2, H 3bO 3, Er 2o 3raw material;
2) raw material weighed up is put into mortar, carry out grinding 1 hour, powder is mixed;
3) raw material mixed after grinding is crossed 200 mesh sieves;
4) carry out compressing tablet to the raw material after sieving, pressure is 10MPa;
5) sample after compressing tablet is put into porcelain boat, in 1350 DEG C of High Temperature Furnaces Heating Apparatuss, calcination 4 hours, takes out after naturally cooling to room temperature, pulverizes 200 mesh sieves, obtains green long afterglow material.
X-ray diffractometer (TD-3000, Dandong is sensible) is adopted to be Ca to above-mentioned gained molecular formula 1.99snO 4: Er 0.01, B 0.05green long afterglow material measure, its XRD figure is similar to Fig. 1, and its structure is rhombic system, compares with standard P DF card (#04-008-291), and its phase composite is Ca 2snO 4, there is no impurity peaks.Show that above-mentioned molecular formula is Ca 1.99snO 4: Er 0.01, B 0.05green long afterglow material be Ca 2snO 4pure phase.
Fluorescence spectrophotometer (FLS8900, Edinburgh, Britain Instruments company) is adopted to be Ca to the molecular formula of above-mentioned gained 1.99snO 4: Er 0.01, B 0.05green long afterglow material measure, the transmitting spectrogram of gained is similar to Fig. 2, and under 263nm optical excitation, its emission wavelength is positioned at 523,563 and 656nm, correspond respectively to Er 3+'s 2h 11/2→ 4i 15/2, 4s 3/2→ 4i 15/2with 4f 9/2→ 4i 15/2.Interpret sample, under the exciting of UV-light, can produce good green emission, and brightness is higher than embodiment 1,2,3 and 4.
The molecular formula of microcomputer thermoluminescent dosimeter (FJ-27A1, Beijing center instrument plant) to appeal gained is adopted to be Ca 1.99snO 4: Er 0.01, B 0.05green long afterglow material measure, the decay of afterglow matched curve of gained is similar to Fig. 3, the after-glow brightness of sample obvious exponentially rule over time.After ultra violet lamp, in the dark present green afterglow; After light source is removed, this material can also continuous illumination the discernmible luminosity (more than 0.32mcd/m2) of human eye.
Embodiment 6
A kind of green long afterglow luminescent material, its chemical formula is Ca 1.98snO 4: Er 0.02, B 0.05.
The preparation method of above-mentioned a kind of green long afterglow luminescent material, specifically comprises the steps:
1) calculate by mass percentage, i.e. CaCO 3: SnO 2: Dy 2o 3: H 3bO 3for the ratio of 55.69%:42.35%:1.08%:0.86%, take chemical pure CaCO 3, SnO 2, H 3bO 3, Er 2o 3raw material;
2) raw material weighed up is put into mortar, carry out grinding 1 hour, powder is mixed;
3) raw material mixed after grinding is crossed 200 mesh sieves;
4) carry out compressing tablet to the raw material after sieving, pressure is 10MPa;
5) sample after compressing tablet is put into porcelain boat, in 1350 DEG C of High Temperature Furnaces Heating Apparatuss, calcination 4 hours, takes out after naturally cooling to room temperature, pulverizes 200 mesh sieves, obtains green long afterglow material
The green long afterglow material appearance of above-mentioned gained is in white.
X-ray diffractometer (TD-3000, Dandong is sensible) is adopted to be Ca to above-mentioned gained molecular formula 1.98snO 4: Er 0.02, B 0.05.Green long afterglow material measure, its XRD figure is similar to Fig. 1, and its structure is rhombic system, compares with standard P DF card (#04-008-291), and its phase composite is Ca 2snO 4, there is no impurity peaks.Show that above-mentioned molecular formula is Ca 1.98snO 4: Er 0.02, B 0.05green long afterglow material be Ca 2snO 4pure phase.
Fluorescence spectrophotometer (FLS8900, Edinburgh, Britain Instruments company) is adopted to be Ca to the molecular formula of above-mentioned gained 1.98snO 4: Er 0.02, B 0.05green long afterglow material measure, the transmitting spectrogram of gained is similar to Fig. 2, and under 263nm optical excitation, its emission wavelength is positioned at 523,563 and 656nm, correspond respectively to Er 3+'s 2h 11/2→ 4i 15/2, 4s 3/2→ 4i 15/2with 4f 9/2→ 4i 15/2, interpret sample, under the exciting of UV-light, can produce good green emission, and brightness is higher than embodiment 1,2,3,4 and 5.
Microcomputer thermoluminescent dosimeter (FJ-27A1, Beijing center instrument plant) is adopted to be Ca to the molecular formula of gained 1.98snO 4: Er 0.02, B 0.05green long afterglow material measure, the decay of afterglow matched curve of gained is similar to Fig. 3, the after-glow brightness of sample obvious exponentially rule over time.After ultra violet lamp, in the dark present green afterglow; After light source is removed, this material can also continuous illumination the discernmible luminosity (more than 0.32mcd/m2) of human eye.
Embodiment 7
A kind of green long afterglow luminescent material, its chemical formula is Ca 1.97snO 4: Er 0.03, B 0.05.
The preparation method of above-mentioned a kind of green long afterglow luminescent material, specifically comprises the steps:
1) calculate by mass percentage, i.e. CaCO 3: SnO 2: Dy 2o 3: H 3bO 3for the ratio of 55.27%:42.27%:1.61%:0.85%, take chemical pure CaCO 3, SnO 2, H 3bO 3, Er 2o 3raw material;
2) raw material weighed up is put into mortar, carry out grinding 1 hour, powder is mixed;
3) raw material mixed after grinding is crossed 200 mesh sieves;
4) carry out compressing tablet to the raw material after sieving, pressure is 10MPa;
5) sample after compressing tablet is put into porcelain boat, in 1350 DEG C of High Temperature Furnaces Heating Apparatuss, calcination 4 hours, takes out after naturally cooling to room temperature, pulverizes 200 mesh sieves, obtains green long afterglow material.
The green long afterglow material appearance of above-mentioned gained is in white.
X-ray diffractometer (TD-3000, Dandong is sensible) is adopted to be Ca to above-mentioned gained molecular formula 1.97snO 4: Er 0.03, B 0.05green long afterglow material measure, its XRD figure is similar to Fig. 1, and its structure is rhombic system, compares with standard P DF card (#04-008-291), and its phase composite is Ca 2snO 4, there is no impurity peaks.Show that above-mentioned molecular formula is Ca 1.97snO 4: Er 0.03, B 0.05green long afterglow material be Ca 2snO 4pure phase.
Fluorescence spectrophotometer (FLS8900, Edinburgh, Britain Instruments company) is adopted to be Ca to the molecular formula of above-mentioned gained 1.97snO 4: Er 0.03, B 0.05green long afterglow material measure, the transmitting spectrogram of gained is similar to Fig. 2, and under 263nm optical excitation, its emission wavelength is positioned at 523,563 and 656nm, correspond respectively to Er 3+'s 2h 11/2→ 4i 15/2, 4s 3/2→ 4i 15/2with 4f 9/2→ 4i 15/2, interpret sample, under the exciting of UV-light, can produce good green emission, brightness higher than embodiment 1,2,3,4 and 5, but lower than embodiment 6.
Microcomputer thermoluminescent dosimeter (FJ-27A1, Beijing center instrument plant) is adopted to be Ca to the molecular formula of gained 1.97snO 4: Er 0.03, B 0.05green long afterglow material measure, the decay of afterglow matched curve of gained is similar to Fig. 3, the after-glow brightness of sample obvious exponentially rule over time.After ultra violet lamp, in the dark present green afterglow; After light source is removed, this material can also continuous illumination the discernmible luminosity (more than 0.32mcd/m2) of human eye.
Embodiment 8
A kind of green long afterglow luminescent material, its chemical formula is Ca 1.96snO 4: Er 0.04, B 0.05.
The preparation method of above-mentioned a kind of green long afterglow luminescent material, specifically comprises the steps:
1) calculate by mass percentage, i.e. CaCO 3: SnO 2: Dy 2o 3: H 3bO 3for the ratio of 54.85%:42.17%:2.14%:0.84%, take chemical pure CaCO 3, SnO 2, H 3bO 3, Er 2o 3raw material;
2) raw material weighed up is put into mortar, carry out grinding 1 hour, powder is mixed;
3) raw material mixed after grinding is crossed 200 mesh sieves;
4) carry out compressing tablet to the raw material after sieving, pressure is 10MPa;
5) sample after compressing tablet is put into porcelain boat, in 1350 DEG C of High Temperature Furnaces Heating Apparatuss, calcination 4 hours, takes out after naturally cooling to room temperature, pulverizes 200 mesh sieves, obtains green long afterglow material.
The green long afterglow material appearance of above-mentioned gained is in white.
X-ray diffractometer (TD-3000, Dandong is sensible) is adopted to be Ca to above-mentioned gained molecular formula 1.96snO 4: Er 0.04, B 0.05green long afterglow material measure, its XRD figure is similar to Fig. 1, and its structure is rhombic system, compares with standard P DF card (#04-008-291), and its phase composite is Ca 2snO 4, there is no impurity peaks.Show that above-mentioned molecular formula is Ca 1.96snO 4: Er 0.04, B 0.05green long afterglow material be Ca 2snO 4pure phase.
Fluorescence spectrophotometer (FLS8900, Edinburgh, Britain Instruments company) is adopted to be Ca to the molecular formula of above-mentioned gained 1.96snO 4: Er 0.04, B 0.05green long afterglow material measure, the transmitting spectrogram of gained is similar to Fig. 2, and under 263nm optical excitation, its emission wavelength is positioned at 523,563 and 656nm, correspond respectively to Er 3+'s 2h 11/2→ 4i 15/2, 4s 3/2→ 4i 15/2with 4f 9/2→ 4i 15/2, interpret sample, under the exciting of UV-light, can produce good green emission, brightness higher than embodiment 1,2,3 and 4, but lower than embodiment 5,6 and 7.
Microcomputer thermoluminescent dosimeter (FJ-27A1, Beijing center instrument plant) is adopted to be Ca to the molecular formula of gained 1.96snO 4: Er 0.04, B 0.05green long afterglow material measure, the decay of afterglow matched curve of gained is similar to Fig. 3, the after-glow brightness of sample obvious exponentially rule over time.After ultra violet lamp, in the dark present green afterglow; After light source is removed, this material can also continuous illumination the discernmible luminosity (more than 0.32mcd/m2) of human eye.
Embodiment 9
A kind of green long afterglow luminescent material, its chemical formula is Ca 1.95snO 4: Er 0.05, B 0.05.
The preparation method of above-mentioned a kind of green long afterglow luminescent material, specifically comprises the steps:
1) calculate by mass percentage, i.e. CaCO 3: SnO 2: Dy 2o 3: H 3bO 3for the ratio of 54.43%:42.07%:2.67%:0.83%, take chemical pure CaCO 3, SnO 2, H 3bO 3, Er 2o 3raw material;
2) raw material weighed up is put into mortar, carry out grinding 1 hour, powder is mixed;
3) raw material mixed after grinding is crossed 200 mesh sieves;
4) carry out compressing tablet to the raw material after sieving, pressure is 10MPa;
5) sample after compressing tablet is put into porcelain boat, in 1350 DEG C of High Temperature Furnaces Heating Apparatuss, calcination 4 hours, takes out after naturally cooling to room temperature, pulverizes 200 mesh sieves, obtains green long afterglow material.
The green long afterglow material appearance of above-mentioned gained is in white.
X-ray diffractometer (TD-3000, Dandong is sensible) is adopted to be Ca to above-mentioned gained molecular formula 1.95snO 4: Er 0.05, B 0.05green long afterglow material measure, its XRD figure is similar to Fig. 1, and its structure is rhombic system, compares with standard P DF card (#04-008-291), and its phase composite is Ca 2snO 4, there is no impurity peaks.Show that above-mentioned molecular formula is Ca 1.95snO 4: Er 0.05, B 0.05green long afterglow material be Ca 2snO 4pure phase.
Fluorescence spectrophotometer (FLS8900, Edinburgh, Britain Instruments company) is adopted to be Ca to the molecular formula of above-mentioned gained 1.95snO 4: Er 0.05, B 0.05green long afterglow material measure, the transmitting spectrogram of gained is similar to Fig. 2, and under 263nm optical excitation, its emission wavelength is positioned at 523,563 and 656nm, correspond respectively to Er 3+'s 2h 11/2→ 4i 15/2, 4s 3/2→ 4i 15/2with 4f 9/2→ 4i 15/2, interpret sample, under the exciting of UV-light, can produce good green emission, brightness higher than embodiment 1,2 and 3, but lower than embodiment 4,5,6,7 and 8.
Microcomputer thermoluminescent dosimeter (FJ-27A1, Beijing center instrument plant) is adopted to be Ca to the molecular formula of gained 1.95snO 4: Er 0.05, B 0.05green long afterglow material measure, the after-glow brightness of sample obvious exponentially rule over time.After ultra violet lamp, in the dark present green afterglow; After light source is removed, this material is at the discernmible luminosity (0.32mcd/m of human eye 2above) can also continuous illumination.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not by the restriction of embodiment; the change done under other any does not deviate from spirit of the present invention and principle, modification, combination, to substitute; be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (5)

1. a green long afterglow luminescent material, is characterized in that: chemical formula is: Ca 2-xsnO 4: Er x, B 0.05, x=0.005 ~ 0.05 in formula, x is that Er Ion Phase is for Ca 2snO 4mol ratio coefficient.
2. a kind of green long afterglow luminescent material as claimed in claim 1, is characterized in that: the matrix of described material is Ca 2snO 4, activator is trivalent erbium ion Er 3+, fusing assistant is boric acid.
3. the preparation method of a kind of green long afterglow luminescent material described in claims 1, is characterized in that comprising the following steps:
(1) CaCO is taken by mass percentage 3, SnO 2, Er 2o 3and H 3bO 3, in the feed, CaCO 3mass percent be 54.43 ~ 56.33%, SnO 2mass percent be 42.07 ~ 42.52%, Er 2o 3mass percent be 0.27 ~ 2.67%, H 3bO 3mass percent be 0.83 ~ 0.88%;
(2) raw material weighed up is put into mortar, grind;
(3) raw material mixed after grinding is crossed 180 ~ 220 mesh sieves;
(4) carry out compressing tablet to the raw material after sieving, pressure is 8 ~ 12MPa;
(5) sample after compressing tablet is put into porcelain boat, be warming up to 1200 ~ 1350 DEG C in air atmosphere, calcining 4 ~ 10h, naturally cools to room temperature with stove, obtained described green long afterglow luminescent material after pulverizing 180 ~ 220 mesh sieves.
4. the preparation method of a kind of green long afterglow luminescent material according to claims 3, is characterized in that: the time of grinding is 1.5 ~ 2h.
5. the preparation method of a kind of green long afterglow luminescent material according to claims 3, is characterized in that: in air atmosphere, be warming up to 1350 DEG C, and calcining 4h, naturally cools to room temperature with stove.
CN201510235097.9A 2015-05-11 2015-05-11 Green long-afterglow light emitting material and preparation method therefor Pending CN104927851A (en)

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CN109370579A (en) * 2018-12-04 2019-02-22 华北电力大学 A kind of green light long after glow luminous material and preparation method thereof

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* Cited by examiner, † Cited by third party
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CN109370579A (en) * 2018-12-04 2019-02-22 华北电力大学 A kind of green light long after glow luminous material and preparation method thereof
CN109370579B (en) * 2018-12-04 2020-05-15 华北电力大学 Green light long afterglow luminescent material and preparation method thereof

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