阅读说明：本技术 一种荧光透明复合材料的制备方法 (Preparation method of fluorescent transparent composite material ) 是由 缪建文 李敏敏 宋国华 刘欢 于 2020-07-28 设计创作，主要内容包括：本发明公开了一种荧光透明复合材料的制备方法,本发明的荧光透明复合材料由荧光粉末、几丁质纤维骨架和透明聚合物基质构成,透光率可达87.32％；制备方法步骤如下：将天然蟹壳进行预处理,依次去除蟹壳中的碳酸钙、蛋白质、脂质和色素等基质；将荧光粉通过热机械搅拌均匀分散于聚合物单体中,进行预聚；通过真空浸渍法将蟹壳浸渍于预聚合的聚合物基质中,使聚合物基质均匀填充在蟹壳几丁质纤维骨架缝隙内部；取出蟹壳并用锡纸包裹后放入烘箱进行恒温固化,直至聚合物固化完全。本发明制备的荧光透明复合材料不仅透光率高,还具有完整的蟹壳形态,荧光粉末的添加使透明蟹壳在光照下呈现不同的颜色且对透光率影响很小。(The invention discloses a preparation method of a fluorescent transparent composite material, the fluorescent transparent composite material is composed of fluorescent powder, a chitin fiber framework and a transparent polymer matrix, and the light transmittance can reach 87.32%; the preparation method comprises the following steps: pretreating natural crab shells, and sequentially removing substrates such as calcium carbonate, protein, lipid, pigment and the like in the crab shells; uniformly dispersing fluorescent powder in a polymer monomer through thermal mechanical stirring, and carrying out prepolymerization; dipping the crab shells into the prepolymerized polymer matrix by a vacuum dipping method, so that the polymer matrix is uniformly filled in gaps of the chitin fiber skeleton of the crab shells; and taking out the crab shell, wrapping the crab shell with tinfoil, and then putting the crab shell into an oven for constant-temperature curing until the polymer is completely cured. The fluorescent transparent composite material prepared by the invention has high light transmittance and complete crab shell shape, and the transparent crab shell presents different colors under illumination and has little influence on the light transmittance due to the addition of the fluorescent powder.)

1. A preparation method of a fluorescent transparent composite material is characterized by comprising the following steps: the method comprises the following steps:

(1) selecting crab shells or crab shell slices with good shapes, cleaning, and storing in deionized water for later use;

(2) sequentially using low-concentration acid-base and ethanol solutions to dip complete crab shells or crab shell slices until the substrates such as calcium carbonate, protein, lipid, pigment and the like are completely removed, and storing the treated crab shells or crab shell slices in absolute ethanol for later use;

(3) uniformly dispersing the fluorescent material in a polymer monomer through thermal mechanical stirring, and then polymerizing or adding a curing agent for curing;

(4) and taking out the processed crab shells or crab shell slices, immersing the crab shells or crab shell slices in the partially polymerized polymer, vacuumizing and maintaining the pressure in a vacuum drying oven for 15 minutes, repeating the steps for three times, taking out the crab shells or crab shell slices, wrapping the crab shells or crab shell slices with tinfoil, and then carrying out constant-temperature curing.

2. The method for preparing a fluorescent transparent composite material according to claim 1, characterized in that: the crab shell or crab shell slice is a natural crab shell or crab shell slice of hairy crab or portunid with chitin fiber structure; the fluorescent material comprises YAG: ce³⁺The fluorescent powder of (1); the polymer monomer is an optically transparent polymer matrix of epoxy resin and methyl methacrylate.

3. The method for preparing a fluorescent transparent composite material according to claim 1, characterized in that: the acid is low-concentration acidic solution comprising HCl and H₂SO₄、HNO₃And CH₃A dilute solution of COOH with the concentration of 1-2 mol/L; the alkali is low-concentration alkaline solution comprising NaOH, KOH and NaHCO₃The concentration of the dilute solution is 1-2 mol/L.

4. The method for preparing a fluorescent transparent composite material according to claims 1-3, characterized in that: the fluorescent material is powdery, has the particle size of 200-600 meshes, is added in an amount of 0-1 wt% of the polymer matrix, and is uniformly dispersed in the monomer of the polymer matrix through thermomechanical stirring.

5. The method for preparing the fluorescent transparent composite material according to claim 4, wherein: the polymer matrix monomer is epoxy resin, the curing agent is a mixture of polyether ammonia and benzyl alcohol, and the mass ratio of the epoxy resin to the curing agent is 3: 1; the polymer matrix monomer is methyl methacrylate, the initiator is benzoyl peroxide, the mass ratio of the methyl methacrylate to the initiator is 1: 0.005-1: 0.02, the prepolymerization temperature is 70-90 ℃, and the thermal polymerization temperature is 50 ℃.

6. A method of preparing the fluorescent transparent composite material according to claim 5, wherein: soaking the crab shell or crab shell slices with the matrix removed in a prepolymerized polymer matrix by a vacuum impregnation method, keeping the vacuum degree of 0.02-0.06MPa for 15min, and repeating the steps for three times.

Technical Field

The invention relates to a preparation method of a fluorescent transparent composite material, in particular to a fluorescent transparent crab shell slice and a preparation method of a transparent crab shell with a complete structural form.

Background

With the vigorous development of the photoelectric industry and the urgent need in the energy-saving field, the application of the transparent material in the aspects of electronics and energy sources is more and more extensive, the demand is increased, and the sources are more and more diversified. In recent years, a large number of scholars at home and abroad use the natural cellulose skeleton of wood to prepare flexible and transparent cellulose films based on the good mechanical properties of the wood, and the flexible and transparent cellulose films have great potential in the application aspect of the electronic field. For example, chinese patent CN110328727A adopts ethanol to dissolve lignin at low temperature, maintains the original structure of the intact wood, and fills the pores of the wood with polymer matrix, so as to obtain transparent wood with 75% light transmittance; chinese patent CN110603124A prepared a clear wood having an optical transmittance of at least 60% using crabapple with a lignin content of more than 15%; chinese patent CN110181629A adds nano silver bromide and assistant nano copper oxide in high light transmittance resin to obtain reversible photochromic transparent wood with 65-85% optical transmittance; in order to solve the problems of non-transparency, non-magnetism and non-fluorescence of the wood, the Chinese granted patent CN106313221B adds fluorescent magnetic nano particles into transparent resin to prepare fluorescent transparent magnetic wood with 80 percent of light transmittance; chinese patent CN109049215A prepared transparent and conductive flexible wood by depositing a layer of silver nanowire ink on the surface of transparent wood.

The research on preparing transparent materials from wood cellulose skeletons is extensive and intensive, and meanwhile, crab shells have natural chitin fiber skeletons similar to the chemical structure of plant cellulose, but few people research on preparing transparent materials from the crab shell type animal chitin skeletons. And moreover, the crab shell resources in coastal areas of China are rich, and by using the crab shell chitin skeleton as a raw material, a transparent fluorescent material with complete crab shell shape and high light transmittance can be obtained, and the transparent fluorescent material is applied to the fields of photoelectricity and artworks such as lamps and the like, and can reasonably utilize natural resources and reduce environmental pollution.

Disclosure of Invention

The purpose of the invention is as follows: the invention aims to reasonably utilize rich crab shell resources in China and solve the problems of non-transparency, non-fluorescence, frangibility and the like of natural crab shells, and prepares a transparent composite material with a complete crab shell form and a fluorescent transparent composite material.

The technical scheme is as follows: the invention is realized by the following technical scheme: a preparation method of a fluorescent transparent composite material comprises the following specific steps:

(1) selecting crab shells or crab shell slices with good shapes, cleaning, and storing in deionized water for later use.

(2) And (3) sequentially using low-concentration acid-base solution and ethanol solution to dip the complete crab shells or crab shell slices until the substrates such as calcium carbonate, protein, lipid, pigment and the like are completely removed, and storing the treated crab shells or crab shell slices in absolute ethanol for later use.

(3) And uniformly dispersing the fluorescent powder in a polymer monomer through thermomechanical stirring, and then polymerizing or adding a curing agent for curing.

(4) And taking out the processed crab shells or crab shell slices, immersing the crab shells or crab shell slices in the partially polymerized polymer, vacuumizing and maintaining the pressure in a vacuum drying oven for 15 minutes, repeating the steps for three times until the polymer completely fills gaps of the chitin skeleton, and wrapping the crab shells or the crab shell slices with tinfoil and then carrying out constant-temperature curing.

Furthermore, the crab shell or crab shell slice in the fluorescent transparent composite material is natural crab shell or crab shell slice with chitin skeleton structure, such as hairy crab or swimming crab; the fluorescent material includes, but is not limited to, YAG: Ce³⁺A fluorescent powder; the polymer monomer may be an optically clear polymer matrix such as epoxy resin and methyl methacrylate.

Further, the acid is a low-concentration acidic solution comprising HCl and H₂SO₄、HNO₃And CH₃A COOH dilute solution with the concentration of 1-2 mol/L; the alkali is low-concentration alkaline solution comprising NaOH, KOH and NaHCO₃Dilute solution with concentration of 1-2 mol/L.

Furthermore, the fluorescent material is in powder shape, the particle size is 200-600 meshes, the addition amount is 0-1 wt% of the polymer matrix, and the fluorescent material is uniformly dispersed in the monomer of the polymer matrix through thermomechanical stirring.

Further, the polymer matrix monomer can be epoxy resin, the curing agent is a mixture of polyether ammonia and benzyl alcohol, and the mass ratio of the epoxy resin to the curing agent is 3: 1; the polymer matrix monomer can be methyl methacrylate, the initiator is benzoyl peroxide, the mass ratio of the methyl methacrylate to the initiator is 1: 0.005-1: 0.02, the prepolymerization temperature is 70-90 ℃, and the thermal polymerization temperature is 50 ℃.

Further, the crab shell with the substrate removed is immersed in the prepolymerized polymer substrate by a vacuum immersion method, the vacuum degree is 0.02-0.06MPa, the pressure is maintained for 15min, and the steps are repeated for three times.

Has the advantages that: the light transmittance of the transparent composite material and the fluorescent transparent composite material prepared by the invention can reach 87.32%, and the doped fluorescent material has almost no influence on the light transmittance of the transparent crab shell. The addition of the fluorescent powder enlarges the application range of the transparent material, and not only can be applied to the fields of photoelectricity, construction and energy conservation, but also can be applied to the fields of artwork processing and the like by utilizing the natural and complete crab shell form.

The invention combines the optically transparent polymer matrix with the chitin fiber skeleton structure of the crab shell, and the original opaque crab shell can show higher light transmittance due to the light scattering effect, thereby realizing optical transparency.

Drawings

FIG. 1 is a comparison of the appearance of natural crab shell and the crab shell after removal of the substrate;

FIG. 2 is a comparison of the appearance of crab shell pieces filled with different polymer matrices;

FIG. 3 is a comparison of crab shells in different states against background fonts;

FIG. 4 is a comparison diagram of the appearance of the complete crab shell in three states;

FIG. 5 is a scanning electron microscope image of crab shells in different states;

FIG. 6 is an infrared absorption spectrum of crab shell pieces before and after filling EP;

FIG. 7 is an infrared absorption spectrum of crab shell pieces before and after PMMA filling;

FIG. 8 is λ_ex450nm, dopingYAG：Ce³⁺Emission spectrum of EP of phosphor;

FIG. 9 is λ_ex537nm, doped YAG: ce³⁺Excitation spectrum of EP of the phosphor.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.