阅读说明：本技术 一种轻质发光块体的制备方法 (Preparation method of light luminescent block ) 是由 周金水 张瑞君 侯成义 李明财 张志军 陈宝玖 宋长波 郑岩 于 2021-01-22 设计创作，主要内容包括：一种轻质发光块体的制备方法,它包括发光材料颗粒、轻质助剂、硬质助剂,其特征在于：发光材料颗粒、轻质助剂、硬质助剂充分混合,轻质助剂是由孔连剂、稳定剂、助溶剂按比例混合构成；发光材料颗粒、轻质助剂、硬质助剂混合后制备成各种形状的块体或颗粒,在高温500-1300度中烧结3-10小时,再使用表面处理剂处理,形成孔径1-10微米的多孔的轻质发光块体。轻质发光块体内部不规则分布有1-100微米的封闭孔洞,大量的气孔可以使得轻质发光块体表面积增加1.5倍,提高了发光强度,并可漂浮于液体中,表面状态稳定、透光性与发光效率高,轻质发光块体或发光颗粒能加工可形成透明或半透明任意形体。(A preparation method of a light luminescent block comprises luminescent material particles, a light additive and a hard additive, and is characterized in that: the luminescent material particles, the light-weight auxiliary agent and the hard auxiliary agent are fully mixed, and the light-weight auxiliary agent is formed by mixing a pore connecting agent, a stabilizing agent and a cosolvent according to a proportion; the luminescent material particles, the light-weight additive and the hard additive are mixed to prepare blocks or particles with various shapes, and the blocks or particles are sintered for 3 to 10 hours at the high temperature of 500-1300 ℃ and then treated by using a surface treating agent to form the porous light-weight luminescent block with the aperture of 1 to 10 microns. The light-emitting block is internally distributed with closed holes of 1-100 microns irregularly, a large number of air holes can increase the surface area of the light-emitting block by 1.5 times, the light-emitting intensity is improved, the light-emitting block can float in liquid, the surface state is stable, the light transmittance and the light-emitting efficiency are high, and the light-emitting block or the light-emitting particles can be processed into any transparent or semitransparent body.)

1. A preparation method of a light luminescent block comprises luminescent material particles, a light additive and a hard additive, and is characterized in that: the luminescent material particles, the light-weight auxiliary agent and the hard auxiliary agent are fully mixed, and the light-weight auxiliary agent is formed by mixing a pore connecting agent, a stabilizing agent and a cosolvent according to a proportion; the luminescent material particles, the light-weight additive and the hard additive are mixed to prepare blocks or particles with various shapes, and the blocks or particles are sintered for 3 to 10 hours at the high temperature of 500-1300 ℃ and then treated by using a surface treating agent to form the porous light-weight luminescent block with the aperture of 1 to 10 microns.

2. The method according to claim 1, wherein the light-emitting block comprises 80 wt% of the luminescent material particles, 10 wt% of the light-emitting assistant, and 10 wt% of the hard assistant.

3. The method for preparing a light weight luminescent block as claimed in claim 1, wherein the hard aid is one of KAlSi3O8, NaAlSi3O8 or CaAl2Si2O8, and the hard aid is pulverized into powder with a particle size of 1-100 μm.

4. The method according to claim 1, wherein the pore-linking agent is one of sodium fluoride, calcium fluoride and boric acid, the particle size of the pore-linking agent is less than 10 μm, and the amount of the pore-linking agent added is 40% of the weight of the light-weight assistant.

5. The method according to claim 1, wherein the stabilizer in the light-weight assistant is at least one of alumina, silica and titania, the particle size of the stabilizer is less than 50 μm, and the amount of the stabilizer added is 40% of the weight of the light-weight assistant.

6. The method for preparing a light weight luminescent block according to claim 1, wherein the cosolvent in the light weight auxiliary agent is one of calcium carbonate and sodium carbonate, and the particle size of the crushed cosolvent is 10-50 microns; the addition amount of the cosolvent is 20 percent of the weight of the light-weight assistant.

7. The method according to claim 1, wherein the luminescent material particles are inorganic high-temperature-prepared luminescent material powder with a particle size of 1-50 μm, and the luminescent material powder is one of photoluminescent material, cathodoluminescent material, long-afterglow luminescent material, electroluminescent material, X-ray luminescent material, up-conversion luminescent material, and infrared luminescent material.

8. The method according to claim 1, wherein the surface treatment agent is one of potassium silicate and sodium silicate, and an aqueous solution of the surface treatment agent is applied to the surface of the light emitting material, and dried to seal the exposed micropores on the surface.

Technical Field

The invention belongs to the field of luminescent material preparation and display illumination application.

Technical Field

The preparation of inorganic luminescent materials at present is based on the synthesis of inorganic microcrystalline powder, and the inorganic luminescent materials comprise micro-particles and nano-particles, and the common characteristics of the micro-particles and the nano-particles are that the inorganic luminescent materials have independent crystal structures, the luminous efficiency depends on the complete crystal structures and the independent surface states, and the inorganic luminescent materials need to have good scattering characteristics when in use, and the inorganic luminescent materials are often sprayed into films or mixed with plastic pressing plates. Generally, the density and the specific gravity of the luminescent material correspond to the mass and the specific gravity of the main component of the inorganic microcrystal structure, and the specific gravity is concentrated at 3-6g/cm for the inorganic luminescent material, and the inorganic luminescent material needs to be continuously stirred in the application process due to the large mass and the specific gravity; when mixed with plastic or glass to form a formed body, the formed body is excited to emit light only on the surface.

The invention relates to a preparation method of a light luminescent block, which comprises luminescent material particles, a light additive and a hard additive, and is characterized in that: the luminescent material particles, the light-weight auxiliary agent and the hard auxiliary agent are fully mixed, and the light-weight auxiliary agent is formed by mixing a pore connecting agent, a stabilizing agent and a cosolvent according to a proportion; the luminescent material particles, the light auxiliary agent and the hard auxiliary agent are mixed to prepare blocks or particles with various shapes, and the blocks or particles are sintered for 30 minutes at the high temperature of 500-1300 ℃ and then treated by using a surface treating agent to form the porous light luminescent block with the aperture of 1-10 microns.

The invention has the advantages that: the light-emitting block is internally distributed with closed holes of 1-100 microns irregularly, a large number of air holes can increase the surface area of the light-emitting block by 1.5 times, the light-emitting intensity is improved, the light-emitting block can float in liquid, the light-emitting block is good in stability, free of agglomeration and precipitation, stable in surface state and high in light transmittance and light-emitting efficiency, and the light-emitting block or light-emitting particles can be processed into any transparent or semitransparent body. Can be widely applied to the fields of illumination, display and luminescence.

Disclosure of Invention

A preparation method of a light luminescent block comprises luminescent material particles, a light additive and a hard additive, and is characterized in that: the luminescent material particles, the light-weight auxiliary agent and the hard auxiliary agent are fully mixed, and the light-weight auxiliary agent is formed by mixing a pore connecting agent, a stabilizing agent and a cosolvent according to a proportion; the luminescent material particles, the light-weight additive and the hard additive are mixed to prepare blocks or particles with various shapes, and the blocks or particles are sintered for 3 to 10 hours at the high temperature of 500-1300 ℃ and then treated by using a surface treating agent to form the porous light-weight luminescent block with the aperture of 1 to 10 microns. Compared with the material obtained by the prior preparation technology, the light luminescent block prepared by the invention has the advantages that the weight of the material is obviously 0.3-2 times lighter when the volume is the same; or the volume of the luminescent block or particle is obviously larger than that of the traditional luminescent product under the same weight comparison, and the transmission and refraction efficiency of the luminescent intensity to the exciting light due to the transparent or semitransparent inside the block or particle is higher than that of the original material by more than 20%.

The light-weight luminescent block comprises 80% of luminescent material particles, 10% of light-weight auxiliary agent and 10% of hard auxiliary agent by weight. The volume of the luminescent block particles can be increased by adding more light-weight additives, the luminescent intensity can be improved by increasing the adding amount of the luminescent material particles, and the smaller the particle size of the luminescent material and the particle size of the light-weight additives are, the smaller the light-weight luminescent particles are formed. The luminescent material particles and the light-weight auxiliary agent are uniformly and fully mixed, and the mixing mode can be liquid mixing or powder physical mixing, such as stirring, ball milling and the like. Can be pressed into blocks with various shapes by a grinding tool, and can also be prepared into particles with the diameter of micrometer or centimeter grade, and the particle size can be controlled according to the requirement. Then sintering at high temperature, wherein a plurality of closed air holes are formed in the particles by the light auxiliary agent, the light up-conversion luminescent particles are formed by sintering at the better temperature of 500-1300 ℃ for 3-10 hours, the sintering times can be formed for a plurality of times, and the slow temperature rise sintering is favorable for the formation of the air holes. The sintering may be performed in a protective atmosphere, vacuum, or air atmosphere depending on the composition of the material.

The hard assistant in the invention is one of KAlSi3O8, NaAlSi3O8 or CaAl2Si2O8, the hard assistant is crushed into powder with the granularity of 1-100 microns, and the hard assistant taking silica alumina as the main component can improve the hardness and weather resistance of the light luminescent block or particle and is suitable for outdoor use.

The pore connecting agent in the light auxiliary agent is one of sodium fluoride, calcium fluoride and boric acid, pores can form closed connection among the granularity of the luminescent material by the pore connecting agent, the smaller the granularity of the pore connecting agent is, the smaller the formed particles are, the better the effect is, the particle nano-scale is better, and the adding amount of the pore connecting agent accounts for 40% of the total weight of the light auxiliary agent.

The stabilizer in the light auxiliary agent is at least one of aluminum oxide, silicon oxide and titanium oxide, the stabilizer can isolate the luminescent material particles to form uniform pores, the particle size of the stabilizer is important, the particle size is usually less than 50 micrometers, and the particle nano-scale is better. The addition amount of the stabilizer is 40 percent of the total weight of the light-weight auxiliary agent. The particles obtained by using the melt-gelling method for alumina, silica and titania are small.

The cosolvent in the light auxiliary agent is one of calcium carbonate and sodium carbonate, the cosolvent is decomposed at high temperature to form pores, the temperature of the pore connecting agent can be reduced, the pores are small and uniform as the particle size of the cosolvent is smaller, and the particle size of the cosolvent after being crushed by a physical method is 10-50 nanometers; the addition amount of the cosolvent accounts for 20 percent of the total weight of the light-weight auxiliary agent.

The luminescent material particles in the invention are luminescent material powder prepared at inorganic high temperature, the particle size of the powder is 1-50 microns, and the luminescent material powder is one of photoluminescence material, cathode ray luminescent material, long afterglow luminescent material, electroluminescence material, X-ray luminescent material, up-conversion luminescent material and infrared luminescent material. The preparation of the inorganic luminescent material is that high-temperature sintering is carried out to form powder. They can be made into luminous plate, LED white light, X-ray imaging plate porous fluorescence conversion sheet, etc., and can float on water surface.

The surface treating agent in the invention is one of potassium silicate or sodium silicate, the water solution of the surface treating agent is coated on the surface of the light luminescent material, the exposed micropores on the surface are sealed and dried, so that the surface is smooth, and other liquid cannot diffuse into the pores.

Detailed description of the invention

A preparation method of a light luminescent block comprises luminescent material particles, a light additive and a hard additive, and is characterized in that: the luminescent material particles, the light-weight auxiliary agent and the hard auxiliary agent are fully mixed, and the light-weight auxiliary agent is formed by mixing a pore connecting agent, a stabilizing agent and a cosolvent according to a proportion; the luminescent material particles, the light-weight additive and the hard additive are mixed to prepare blocks or particles with various shapes, the blocks or particles are sintered for 30 minutes at the high temperature of 500-1300 ℃, and then the blocks or particles are treated by using a surface treating agent to form porous light-weight luminescent blocks with the aperture of 1-10 microns, wherein the larger the luminescent material particles are, the better the porosity is.

The light-weight luminescent block contains 80% of luminescent material particles, 10% of light-weight auxiliary agent and 10% of hard auxiliary agent by weight, and has good luminescent efficiency and volume. The volume of the porous multi-luminescent particles can be increased by adding a large amount of the light-weight auxiliary agent, and the luminescent intensity can be improved by increasing the addition amount of the luminescent material particles, so that luminescence is facilitated. The smaller the particle size of the luminescent material and the particle size of the light-weight auxiliary agent, the smaller the light-weight luminescent particles are formed. The luminescent material particles, the light-weight auxiliary agent and the hard auxiliary agent are fully mixed, the mixing mode can be liquid mixing or powder physical mixing, such as stirring, ball milling and the like, and the uniform mixing has direct correlation on the distribution and the size of air holes. Typically, the pores are in the range of 1-100 microns, and if the pore diameter is not uniform, the pore diameter can reach millimeter level, which affects the light upconversion luminescence particle size. Sintering at high temperature, wherein a plurality of closed pores are formed in the particles by the light auxiliary agent, the light luminescent block and the particles are formed by sintering at the better temperature of 500-1300 ℃ for 3-10 hours, the pores are formed by slowly and stepwisely heating during sintering, and the sintering can be carried out under the environment of protective atmosphere, vacuum and air according to the components of the material.

The pore connecting agent in the light auxiliary agent is one of sodium fluoride, calcium fluoride and boric acid, the superior grade of the light auxiliary agent has less impurities, and the fluoride is more favorable for luminescence, particularly the sodium fluoride. Boric acid may improve stability. They can be ground or dissolved to form part of the light-weight auxiliary, and commercially available reagent products can be used. The smaller the granularity of the pore-linking agent is, the smaller the particle size is, the better effect is that the particle size is smaller than 10 microns, and the adding amount of the pore-linking agent accounts for 40 percent of the total weight of the light-weight auxiliary agent.

The stabilizer in the light auxiliary agent is at least one of alumina, silicon oxide and titanium oxide, and the adding amount accounts for 40% of the total weight of the light auxiliary agent. The nano silicon oxide is more beneficial to transparency, and the nano aluminum oxide is more beneficial to uniformity of air holes. The stabilizer can isolate nano up-conversion luminescent material particles to form uniform pores, the size of the stabilizer particles is important, and the granularity is preferably 20-30 microns.

The cosolvent in the light auxiliary agent is one of calcium carbonate and sodium carbonate, the cosolvent is decomposed at high temperature to form pores, the temperature of the pore connecting agent can be reduced, the pores are small and uniform as the particle size of the cosolvent is smaller, the cosolvent is kept in a sealed state as much as possible during physical crushing, the porosity of the pores can be kept by the components, and the granularity is preferably 10-30 micrometers; the addition amount of the cosolvent accounts for 20 percent of the total weight of the light-weight auxiliary agent.

The luminescent material particles in the invention are luminescent material powder prepared at inorganic high temperature, the particle size of the powder is 1-50 microns, and the luminescent material powder is photoluminescent material, such as ultraviolet luminescent material; the luminescent material powder is a cathode ray luminescent material; the luminescent material powder is long afterglow luminescent material, such as floating luminous plate; the luminescent material powder is an electroluminescent material, and the luminescent material powder is an X-ray luminescent material, such as a radiographic panel; the luminescent material powder is an up-conversion luminescent material; the luminescent material powder is one of infrared luminescent materials. The preparation of the inorganic luminescent material is that high-temperature sintering is carried out to form powder. They can be made into luminous plate, LED white light, X-ray imaging plate porous fluorescence conversion sheet, etc., and can float on water surface.

The surface treating agent is one of potassium silicate or sodium silicate, is dried at normal temperature or 120 ℃, and the aqueous solution of the surface treating agent is coated on the surface of the light luminescent material to seal the exposed micropores on the surface, prolong the service life, smoothen the surface and prevent water from permeating.

Advantages of the invention

1. The light luminous block can float in liquid, has good stability, no agglomeration and no precipitation, has stable surface state, can control the granularity according to requirements, is prepared into the waterborne floating noctilucent float, has longer service life than plastic, and can be used for more than 20 years.

2. The light up-conversion luminescent particles have high light transmittance and high luminous efficiency, can form any transparent or semitransparent body after being processed, can float on the water surface when being manufactured into a flat ray image, has high hardness which is 2-3 times that of a plastic product, and can be used for road warning and building surfaces. The increased surface area can accept more excitation light.

3. The fluorescent material can be widely applied to the fields of illumination, display, luminescence, biological immunoassay, disease diagnosis, drug screening, microscopic imaging, anti-counterfeiting ink, infrared laser detection and the like. It can be prepared into ceramic with 2-3 times higher hardness than pure rare earth crystal.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

Taking 80 g of green aluminate long afterglow luminescent material particles with the granularity of 30 microns, adding 4 g of boric acid, 4 g of silicon oxide and 2 g of calcium carbonate, adding KAlSi3O8 as a hard auxiliary agent, fully mixing, pressing into a 20 mm thick plate, sintering for 4 hours at the high temperature of 1000 ℃ under the protection of nitrogen, taking out, cooling, spraying potassium silicate on the surface, and drying for 24 hours.

While the foregoing is directed to the preferred embodiment of the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made herein without departing from the spirit and scope of the invention.