TWI712672B - Long afterglow material and preparation method thereof - Google Patents

Abstract

The present invention discloses a long afterglow material and a preparation method thereof. By adding a tin ion to the long afterglow material, the long afterglow material doped tin (blue-ray) is formed to improve the problems (weak luminous intensity and too short luminous time, etc.) of the long afterglow material, and further prepare the long afterglow material with high stability.

Description

Long afterglow material and preparation method thereof

The present invention relates to a long afterglow material, especially a long afterglow material and a preparation method thereof.

Long afterglow materials, also known as non-radioactive energy storage luminescent materials, self-luminous materials, self-luminous powders, new energy storage luminescent powders, solar energy storage luminescent materials or long-lasting energy storage luminescent materials.

Long afterglow material is a kind of energy storage effect after being irradiated by sunlight, light or other light sources. It can emit light for a long time at night or in the dark. Generally, it can effectively emit light for more than 6 hours, and it can be repeated to store light and Luminous material.

Since the long afterglow material can store the absorbed light and continuously emit bright and identifiable visible light at night or in a darker environment, it can be made into luminous paint, luminous ink, luminous fiber, luminous plastic, luminous glass, Luminous ceramics, luminous marking... and other products.

The above-mentioned luminous products can often be used for low-light indications in many aspects such as safety emergency, transportation, building decoration, meters, electrical switches, and public equipment. Therefore, the business opportunities for its long afterglow materials are huge.

The development of this luminous material is divided into 3 periods. The first period: the early self-luminous materials can be traced back to the radium element proposed by Madame Curie from the uranium radium pitch mine. The self-luminous materials in this period can be called the first A generation of self-luminous materials. However, this kind of luminous material has strong radiation and poison, and is not practical.

Furthermore, the second period: The second generation of self-luminous materials is ZnS (zinc sulfide) in the 1930s and 1940s, that is, the traditional sulfide fluorescent materials. Due to its certain toxicity and radioactivity to the human body, Coupled with its shortcomings such as low luminous brightness and short duration, its application field is greatly limited, and it is mostly used for clock surfaces.

Nowadays, the long afterglow materials used belong to the third period and came out in the 1990s. Strontium aluminate is the most representative. Compared with the self-luminous materials of the previous two periods, this long afterglow material has significant advantages such as non-toxic and non-radioactive.

The outstanding feature of long afterglow material is: it absorbs and stores all kinds of visible light during the day, such as sunlight, fluorescent light, lamp, ultraviolet light and other stray light. After 10 to 20 minutes, it can self-illuminate, and it can continue to emit light for more than several hours in the dark. The luminous intensity and luminous duration are dozens of times that of traditional luminescent materials, and its stability is excellent.

Generally speaking, the preparation of long afterglow materials often uses high temperature solid phase method or sol-gel method. As the name implies, the high-temperature solid-phase method requires a relatively high temperature for the reaction, and the reaction time is very long, so its manufacturing cost is also high. Another method for manufacturing long afterglow materials is the sol-gel method. The sol-gel method does not require the high reaction temperature of the high-temperature solid phase method, and the reaction time is also shorter than the higher temperature solid phase method.

However, whether it is a long afterglow material synthesized by a high-temperature solid-phase method or a sol-gel method, its luminous intensity is not strong enough, and the luminous time is not long enough. Therefore, the shortcomings of luminous intensity and luminous time will limit the application of long afterglow materials and reduce the practicality at all levels.

To this end, improve the luminous intensity and luminous time of long afterglow materials, so that long afterglow materials are applicable and practical at all levels (safety emergency, transportation, architectural decoration, instrumentation, electrical switches, and public equipment). Sexual improvement is a problem that those skilled in the art want to solve.

The main purpose of the present invention is to provide a long afterglow material and a preparation method thereof, by adding tin-containing compounds in the preparation method to form a long afterglow material containing tin ions (light emitting blue light) to increase its luminous intensity and luminous time .

In order to achieve the above objectives and effects, the present invention discloses a long afterglow material, the composition of which includes: a calcium ion; a europium ion; a neodymium ion; an aluminum ion; and a tin ion; wherein the long afterglow material The chemical formula is Ca _x Eu _y Nd _z Al _α Sn _β O ₄ , with 0＜x＜1, 0＜y＜0.05, 0＜z＜0.05, 0＜α＜1, 0＜β＜0.05.

In addition, the present invention also discloses a method for preparing a long afterglow material. The steps include: taking a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound, and a solvent in a grinding In the device, grinding to form a mixed slurry; the mixed slurry is subjected to a drying treatment to form a precursor powder; and the precursor powder is subjected to a calcination treatment at 800°C to 1500°C to react to form a long afterglow Material; wherein the chemical formula of the long afterglow material is Ca _x Eu _y Nd _z Al _α Sn _β O ₄ , with 0＜x＜1, 0＜y＜0.05, 0＜z＜0.05, 0＜α＜1 0<β<0.05.

The present invention provides an embodiment, the content of which is a preparation method of a long afterglow material, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound, and a solvent are taken in a In the step of the grinding device, a boron-containing compound is further added.

The present invention provides an embodiment, the content of which is a preparation method of a long afterglow material, wherein the boron-containing compound is selected from one of the group consisting of boron monoxide, boron hydroxide and boron nitride or combination.

The present invention provides an embodiment, the content of which is a preparation method of a long afterglow material, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound, and a solvent are taken in a In the step in the grinding device, the solvent is an organic solvent.

The present invention provides an embodiment, the content of which is a preparation method of a long afterglow material, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound, and a solvent are taken in a In the step in the grinding device, the calcium-containing compound is selected from one of the group consisting of calcium chloride, calcium sulfate, calcium acetate, calcium nitrate, calcium hydroxide, and calcium carbonate, or combination.

The present invention provides an embodiment, the content of which is a preparation method of a long afterglow material, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound, and a solvent are taken in a In the step of the grinding device, the europium-containing compound is selected from one or a combination of europium fluoride, europium halide, europium nitrate, europium oxalate, and europium monoxide.

The present invention provides an embodiment, the content of which is a preparation method of a long afterglow material, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound, and a solvent are taken in a In the step of the grinding device, the neodymium-containing compound is selected from one or a combination of neodymium carbonate, neodymium hydroxide, neodymium nitrate, neodymium chloride, and neodymium oxide.

The present invention provides an embodiment, the content of which is a preparation method of a long afterglow material, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound, and a solvent are taken in a In the step of the grinding device, the aluminum-containing compound is selected from one of the group consisting of aluminum sulfate, aluminum acetate, aluminum hydroxide, aluminum nitrate, aluminum chloride, and aluminum oxide, or combination.

The present invention provides an embodiment, the content of which is a preparation method of a long afterglow material, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound, and a solvent are taken in a In the step in the grinding device, the tin-containing compound is selected from one of the group consisting of tin sulfate, tin nitrate, tin fluoride, tin chloride, tin sulfide and tin oxide or combination.

The present invention provides an embodiment, the content of which is a preparation method of a long afterglow material, wherein in the step of performing a drying treatment on the mixed slurry, the temperature of the drying treatment is between 50°C and 100°C.

The present invention provides an embodiment, the content of which is a preparation method of a long afterglow material, wherein in the step of performing a calcination treatment on the precursor powder at 800°C to 1500°C, the calcination treatment is performed under a mixed gas Treatment, wherein the mixed gas system is one helium and one hydrogen.

In order to enable your reviewer to have a further understanding and understanding of the features of the present invention and the effects achieved, I would like to provide examples and accompanying explanations. The description is as follows:

In view of the shortcomings of insufficient luminous intensity and insufficient luminescence time of the past long-lasting materials, the application of long-lasting materials will be limited. Accordingly, the present invention proposes a long afterglow material and a preparation method thereof to solve the problems caused by the conventional technology.

The following will further explain one of the features of the present invention, its matched structure and method:

First, the long afterglow material of the present invention includes: a calcium ion; a europium ion; a neodymium ion; an aluminum ion; and a tin ion; wherein the chemical formula of a long afterglow material is Ca _x Eu _y Nd _z Al _α Sn _β O ₄ has 0<x<1, 0<y<0.05, 0<z<0.05, 0<α<1, 0<β<0.05. In addition, the first embodiment of the long afterglow material (blue-emitting) of the present invention is Ca _0.98 Eu _0.01 Nd _0.01 Al _0.965 Sn _0.035 O ₄ .

Please also refer to Figure 1, which is a flowchart of the steps of the first embodiment of the present invention. As shown in the figure, the method for preparing a long afterglow material of the present invention includes:

S1: Take a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound, and a solvent in a grinding device to form a mixed slurry;

S2: Drying the mixed slurry to form a precursor powder; and

S3: The precursor powder is calcined at 800°C~1500°C to react to form a long afterglow material.

Among them, the chemical formula of the long afterglow material of the present invention is Ca _x Eu _y Nd _z Al _α Sn _β O ₄ , with 0＜x＜1, 0＜y＜0.05, 0＜z＜0.05, 0＜α＜1 , 0<β<0.05, the first embodiment of the long afterglow material (blue light) of the present invention is Ca _0.98 Eu _0.01 Nd _0.01 Al _0.965 Sn _0.035 O ₄ .

Next, as shown in step S1, take a calcium-containing compound (a calcium carbonate), a europium-containing compound (europium monoxide), a neodymium-containing compound (neodymium monoxide), an aluminum-containing compound (a alumina), and a The tin-containing compound (tin monoxide) is placed in a polishing device according to the chemical formula (Ca _0.98 Eu _0.01 Nd _0.01 Al _0.965 Sn _0.035 O ₄ ), and a boron-containing compound is further added (a boron hydroxide ( 2wt%)) mixing and adding a solvent (as a medium, an organic solvent (such as ethanol) or water) in the grinding device, and grinding (about 2-12 hours) to form a mixed slurry. Wherein, in addition to using the boron hydroxide alone, the boron-containing compound is selected from one or a combination of the group consisting of boron monoxide, the boron hydroxide and the boron nitride.

Moreover, in addition to using the calcium carbonate alone, the calcium-containing compound of the present invention is selected from the group consisting of calcium chloride, calcium sulfate, calcium acetate, calcium nitrate, calcium hydroxide and the calcium carbonate One or a combination of them. Similarly, in addition to using the europium oxide alone, the europium-containing compound of the present invention is selected from one of the group consisting of a europium fluoride, a europium halide, a europium nitrate, a europium oxalate, and the europium oxide Or a combination. Moreover, in addition to using the neodymium oxide alone, the neodymium-containing compound of the present invention is selected from one of the group consisting of neodymium carbonate, neodymium hydroxide, neodymium nitrate, neodymium chloride and the neodymium oxide Or a combination.

Furthermore, in addition to using the alumina alone, the aluminum-containing compound of the present invention is selected from the group consisting of aluminum sulfate, aluminum acetate, aluminum hydroxide, aluminum nitrate, aluminum chloride and the alumina One or a combination of groups. Moreover, in addition to using the tin oxide alone, the tin-containing compound of the present invention is selected from the group consisting of tin sulfate, tin nitrate, tin fluoride, tin chloride, tin sulfide and the tin oxide One or a combination of them.

Next, as shown in step S2, the mixed slurry is dried at 50°C to 100°C (the preferred temperature in the first embodiment is 80°C) to form a precursor powder; and as shown in step S3, The precursor powder is subjected to a calcination treatment (the calcination treatment is performed under a mixed gas at 800°C to 1500°C (the preferred holding temperature in the first embodiment is 1350°C), wherein the mixed gas system is a Helium and hydrogen, the time is about 9-15 hours, the first embodiment is 10 hours), react to form the long afterglow material (Ca _0.98 Eu _0.01 Nd _0.01 Al _0.965 Sn _0.035 O ₄ ).

Furthermore, please refer to FIG. 2, which is a graph of the experimental results of the first embodiment of the present invention. To measure the luminous intensity of the long afterglow material, sample A (the first embodiment of the present invention is Ca _0.98 Eu _0.01 Nd _0.01 Al _0.965 Sn _0.035 O ₄ ) and sample B (the control group is Ca _0.98 Eu _0.01 Nd _0.01 AlO ₄ , which is also prepared by the above steps S1 to S3) is analyzed by a fluorescence spectrometer, and the excitation light wavelength is 340 nm. And as shown in Figure 2, the long afterglow material of the first embodiment (the solid line sample A) and the control group (the dashed line sample B) have a luminous peak near 450 nm, which is blue light. And it can be seen from Figure 2 that the first embodiment (the solid line sample A) has a higher luminous intensity than the control group (the dotted line sample B). It is shown that after further adding the tin ion, the luminous intensity of the long afterglow material will increase. In order to improve the problem that the long afterglow material (light emitting blue) light intensity is too weak in the past.

In addition, the second embodiment of the long afterglow material of the present invention has the same composition as the first embodiment, and both include: the calcium ion; the europium ion; the neodymium ion; the aluminum ion; and the tin ion; , The chemical formula of the long afterglow material is also Ca _x Eu _y Nd _z Al _α Sn _β O ₄ , with 0＜x＜1, 0＜y＜0.05, 0＜z＜0.05, 0＜α＜1, 0＜ β<0.05. However, the chemical formula of the second embodiment of the long-lasting material (blue light) of the present invention is Ca _0.96 Eu _0.02 Nd _0.02 Al _0.96 Sn _0.04 O ₄ .

Furthermore, in the second embodiment of the long afterglow material of the present invention, the selection of components and the preferably selected components (the calcium carbonate, the europium oxide, the neodymium oxide, the aluminum oxide and the tin oxide) and The first embodiment is the same. Moreover, the experimental procedure is also the same as the first embodiment.

However, the second embodiment and the first embodiment have different experimental conditions in the experimental steps. The concentration of the boron hydroxide added during the grinding (about 2-12 hours) is 1 wt%. Moreover, the preferred temperature of the drying treatment is changed to 60°C. The final calcination treatment (the same is the mixed gas of the nitrogen and the hydrogen) is carried out at a temperature holding temperature of 1400°C for about 8 hours to form the long afterglow material (blue light) (Ca _0.96 Eu _0.02 Nd _0.02 Al _0.96 Sn _0.04 O ₄ ).

Finally, in order to measure the afterglow intensity (that is, the emission time) of the long afterglow material (light emitting blue), sample C (the second embodiment of the present invention is Ca _0.96 Eu _0.02 Nd _0.02 Al _0.96 Sn _0.04 O ₄ ) And sample D (the control group is Ca _0.96 Eu _0.02 Nd _0.02 AlO ₄ , which is also prepared according to the above steps S1~S3 and experimental conditions (second embodiment)) After 30 minutes of UV light irradiation, the light source is turned off, and then afterglow Strength test.

The afterglow intensity of the long afterglow material (blue light) of the second embodiment of the present invention (sample C) is 0.025 cd/m ² , while the afterglow intensity of the control group (sample D) is 0.02 cd/m ² , It can be seen that sample C has a higher afterglow intensity than sample D. It is shown that after further adding the tin ion, the afterglow intensity (luminescence time) of the long afterglow material will increase. In order to improve the problem of the long afterglow material (light emitting blue) that the afterglow intensity (light emitting time) is too short.

Therefore, the present invention is really novel, progressive, and available for industrial use. It should meet the patent application requirements of my country's patent law. Undoubtedly, I filed an invention patent application in accordance with the law. I pray that the Bureau will grant the patent as soon as possible.

However, the above are only the preferred embodiments of the present invention, and are not used to limit the scope of implementation of the present invention. For example, the shapes, structures, features and spirits described in the scope of the patent application of the present invention are equally changed and modified. , Should be included in the scope of patent application of the present invention.

S1~S3: step flow

Figure 1: It is a flowchart of the steps of the first embodiment of the present invention; and

Figure 2: It is a graph of experimental results of the first embodiment of the present invention.

S1~S3: step flow

Claims (12)

A long afterglow material, which is composed of: a calcium ion; a europium ion; a neodymium ion; an aluminum ion; and a tin ion; wherein the chemical formula of the long afterglow material is Ca _x Eu _y Nd _z Al _α Sn _β O ₄ , with 0<x<1, 0<y<0.05, 0<z<0.05, 0<α<1, 0<β<0.05. A method for preparing a long afterglow material, including the steps of: taking a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound, and a solvent in a grinding device to form a Mixed slurry; the mixed slurry is subjected to a drying treatment to form a precursor powder; and the precursor powder is subjected to a calcination treatment at 800°C to 1500°C to react to form a long afterglow material; wherein, the long afterglow material The chemical formula of the afterglow material is Ca _x Eu _y Nd _z Al _α Sn _β O ₄ , with 0<x<1, 0<y<0.05, 0<z<0.05, 0<α<1, 0<β<0.05. The method for preparing a long afterglow material according to claim 2, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound and a solvent are taken in a grinding device In the step, a boron-containing compound is further added. The method for preparing a long afterglow material according to claim 3, wherein the boron-containing compound is selected from one or a combination of boron monoxide, boron hydroxide and boron nitride. The method for preparing a long afterglow material according to claim 2, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound and a solvent are taken in a grinding device In the step, the solvent is an organic solvent. The method for preparing a long afterglow material according to claim 2, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound and a solvent are taken in a grinding device In the step, the calcium-containing compound is selected from one or a combination of calcium chloride, calcium sulfate, calcium acetate, calcium nitrate, calcium hydroxide, and calcium carbonate. The method for preparing a long afterglow material according to claim 2, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound and a solvent are taken in a grinding device In the step, the europium-containing compound is selected from one or a combination of europium halide, europium nitrate, europium oxalate, and europium monoxide. The method for preparing a long afterglow material according to claim 2, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound and a solvent are taken in a grinding device In the step, the neodymium-containing compound is selected from one or a combination of neodymium carbonate, neodymium hydroxide, neodymium nitrate, neodymium chloride, and neodymium oxide. The method for preparing a long afterglow material according to claim 2, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound and a solvent are taken in a grinding device In the step, the aluminum-containing compound is selected from one or a combination of aluminum sulfate, aluminum acetate, aluminum hydroxide, aluminum nitrate, aluminum chloride, and aluminum oxide. The method for preparing a long afterglow material according to claim 2, wherein a calcium-containing compound, a europium-containing compound, a neodymium-containing compound, an aluminum-containing compound, a tin-containing compound and a solvent are taken in a grinding device In the step, the tin-containing compound is selected from one or a combination of tin sulfate, tin nitrate, tin fluoride, tin chloride, tin sulfide, and tin oxide. The method for preparing a long afterglow material according to claim 2, wherein in the step of subjecting the mixed slurry to a drying treatment, the temperature of the drying treatment is between 50°C and 100°C. The method for preparing a long afterglow material according to claim 2, wherein in the step of performing a calcination treatment on the precursor powder at 800°C to 1500°C, the calcination treatment is performed under a mixed gas, wherein The mixed gas system is one helium and one hydrogen.

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