CN111777779A - Preparation method of fluorescent transparent composite material - Google Patents
Preparation method of fluorescent transparent composite material Download PDFInfo
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- CN111777779A CN111777779A CN202010738548.1A CN202010738548A CN111777779A CN 111777779 A CN111777779 A CN 111777779A CN 202010738548 A CN202010738548 A CN 202010738548A CN 111777779 A CN111777779 A CN 111777779A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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Abstract
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.
Description
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 λex450nm, dopingYAG：Ce3+Emission spectrum of EP of phosphor;
FIG. 9 is λex537nm, 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.
Examples
The preparation steps of the fluorescent transparent composite material are as follows:
(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 solution to soak complete crab shells or crab shell slices until the substrates such as calcium carbonate, protein, lipid and pigment are completely removed, and storing the treated crab shells 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 well-treated crab shells, immersing the crab shells 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, wrapping the crab shells with tinfoil, and then carrying out constant-temperature curing.
The selected crab shells are natural crab shells and crab shell slices with chitin fiber structures, such as hairy crabs or portunids; the fluorescent materials used include, but are not limited to YAG: ce3+A fluorescent powder; the polymer monomer can be an optically transparent polymer matrix such as epoxy resin, methyl methacrylate and the like.
For use in the inventionThe acid is a low-concentration acidic solution, including but not limited to HCl and H2SO4、HNO3And CH3COOH and other dilute solutions with the concentration of 1-2 mol/L; the base is a low concentration alkaline solution, including but not limited to NaOH, KOH and NaHCO3And (3) waiting for diluted solution with the concentration of 1-2 mol/L. (ii) a The fluorescent material is powder, 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.
In the fluorescent transparent composite material, 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 ℃.
The preparation method of the fluorescent transparent composite material mainly adopts a vacuum impregnation method, the crab shells with the matrixes removed are impregnated in a prepolymerized polymer matrix, the vacuum degree is 0.02-0.06MPa, the pressure is maintained for 15min, and the steps are repeated for three times.
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.
Detailed description of the preferred embodiment 1
Preparation of transparent crab shell slices and crab shells with resin (EP) as polymer matrix
(1) Selecting crab shells or crab shell slices with good shapes, cleaning, and storing in deionized water for later use.
(2) Placing crab shell or crab shell slice in beaker, sequentially soaking with HCl dilute solution for 12 hr, repeating for more than 2 times until CaCO is completely removed3(ii) a At 55 deg.C, CaCO will be removed3Soaking the crab shell or the crab shell slices in the prepared NaOH dilute solution for 2h, and repeating for more than 4 times to completely remove protein and lipid in the crab shell; soaking the processed crab shell in anhydrous ethanol at room temperature for more than 12h until the crab is removedPigment in shell and storing in anhydrous alcohol for use.
(3) Adding epoxy resin and a curing agent in a mass ratio of 3:1 into a mold, uniformly mixing, and completely immersing the processed crab shells and crab shell slices into the prepared epoxy resin. And (3) placing the die into a vacuum drying oven, setting the vacuum degree to be 0.03MPa, maintaining the pressure for 15 minutes, repeating the steps for more than 3 times until the epoxy resin completely permeates into the crab shells, taking out the crab shell slices filled with the polymer matrix, and placing the crab shells and the crab shell slices on a watch glass at normal temperature for 24 hours to obtain firm and transparent crab shells and crab shell slices.
Specific example 2
Preparation of transparent crab shell slices with methyl methacrylate as polymer matrix
The method for treating the crab shell-removing inner matrix is the same as the steps (1) and (2) in the example 1.
Weighing 0.02g of benzoyl peroxide and 20g of methyl methacrylate, putting the benzoyl peroxide and the methyl methacrylate into a closed conical flask, heating the mixture in water bath at 85 ℃ until the solution has obvious viscosity change, quickly taking out the conical flask, putting the conical flask into ice water, and continuously shaking to accelerate cooling to obtain the prepolymerized methyl methacrylate. And (3) putting the treated crab shell slices into a small beaker, immersing the crab shell slices by using pre-polymerized methyl methacrylate, then putting the small beaker into a vacuum drying oven, keeping the pressure for 15 minutes when the vacuum degree is 0.03MPa, repeating the step for 3 times, and finally keeping the pressure for 24 hours at the vacuum degree of 0.05 MPa. Taking out the crab shell pieces which are completely penetrated by tweezers, wrapping the crab shell pieces by tinfoil, putting the crab shell pieces into an oven at 50 ℃ for 12 hours, and obtaining the transparent crab shell pieces after the polymers are completely polymerized.
Specific example 3
Preparation of fluorescent transparent crab shell slices
The method for treating the crab shell-removing inner matrix is the same as the steps (1) and (2) in the example 1.
Screening out transparent materials with better performance, and adding 1 wt% of YAG: ce3+Phosphor, and is dispersed uniformly by thermo-mechanical agitation, and then the procedure of infiltrating the polymer matrix in example 1 is repeated to obtain fluorescent transparent crab shell pieces.
The appearance comparison chart of the crab shell slices before and after matrix removal is as follows: FIG. 1 is a comparison of appearance of crab shells before and after acid-base treatment. FIG. 1a shows natural crab shell pieces which are orange red and completely opaque; FIG. 1b shows the crab shell slices prepared by removing the substrates such as calcium carbonate, protein and pigment and soaking in ethanol, and obviously shows that the crab shell slices become thin, and the color is faded, whitened and slightly transparent; fig. 1c shows that the treated crab shell pieces are dried by an oven to remove ethanol, and it can be seen that the crab shell pieces are completely opaque and wrinkled because the crab shell pieces contain a large number of voids after the matrix is removed, and the ethanol is volatilized after drying, and the crab shells shrink in volume to become wrinkled.
Fig. 2 is a comparison of the appearance of crab shell pieces filled with different polymer matrices. 2a is the crab shell filled with PMMA, the crab shell can be obviously seen to be transparent, but the transparency degree is general; fig. 2b shows epoxy resin (EP) filled crab shells that are completely transparent and have a high light transmittance, and the transparency of the filled EP is higher than that of PMMA as can be seen visually, so that epoxy resin is selected and 1 wt% YAG: ce3+Preparing a fluorescent transparent composite material by using fluorescent powder; FIG. 2c is a filled epoxy + YAG: ce3 +Picture of phosphor, it can be seen that addition of YAG: ce3+The transparency of the crab shell slices after the fluorescent powder is not obviously reduced.
Fig. 3 is a comparison of crab shells in different states in background font. FIG. 3d is a photograph of the original crab shell placed over a background font, which is completely invisible, indicating that the original crab shell is opaque; FIG. 3e is a drawing showing the crab shell pieces soaked in alcohol after removing the calcium carbonate and other substrates on the background font, and the font can be seen implicitly, which shows that the transparency of the crab shell pieces is improved; FIG. 3f is a photograph of the dried crab shell pieces of FIG. 3e placed over a background font, with no visible text, illustrating the reduced transparency of the crab shell after drying; FIG. 3g shows the crab shell pieces filled with PMMA, the background characters can be seen, and the definition is high; FIG. 3h shows the crab shell slices filled with EP, the background characters are very clear, and the transparent effect is better than PMMA; FIG. 3i is a filling epoxy and YAG: ce3+The definition ratio of the background characters of the crab shell pieces after the fluorescent powder is only filledThe crab shell slices after epoxy resin slightly decline, but the definition is better than that after PMMA is filled.
Fig. 4 is a comparison of the appearance of the three states of the intact crab shell. FIG. 4a is a view of natural crab shells; fig. 4b shows the crab shell after the substrate is removed, and the volume of the whole crab shell is more obviously shrunk; fig. 4c shows the complete crab shell filled with epoxy resin, and it can be seen that the whole crab shell becomes transparent under the condition of keeping the form of the crab shell, which lays a certain foundation for the application of the transparent crab shell in the fields of photoelectricity and art.
The crab shell slice quality records under several conditions of the invention are shown in tables 1 and 2: tables 1 and 2 show the qualities of the crab shell fragments before and after matrix removal and after infiltration into the polymer matrix, respectively. It can be seen that the treated crab shell slices have much lighter weight than the original crab shells, because calcium carbonate accounts for the largest proportion of the internal weight of the crab shells, and when the calcium carbonate and other matrixes are removed, only chitin nanofiber skeletons are left, so that the quality of the crab shell slices is obviously reduced. When the polymer matrix is refilled with crab shell slices, the overall quality is obviously increased.
TABLE 1 quality of crab shell pieces before and after filling with resin
The light transmittance of the transparent crab shell slices and the fluorescent transparent crab shell slices prepared by the invention is shown in the following table: tables 3 and 4 are a comparison of light transmittance of natural crab shell pieces, crab shell pieces after removal of matrix, and crab shell pieces after filling with PMMA and resin, respectively. The data show that the light transmittance of the natural crab shell slices is about 30%, and the light transmittance of the crab shells after the substrate is removed is obviously increased to about 65% because light absorption factors such as calcium carbonate, pigment and the like do not exist. The light transmittance of the crab shell slices filled with PMMA is above 70%, and meanwhile, the light transmittance of the crab shell slices filled with resin can reach above 85%, and the effect is best. Therefore, resin is selected to be used for manufacturing the fluorescent transparent composite material. Table 5 is the filler resin alone and the filler resin and YAG: ce3+The light transmittance of the crab shell slice after the fluorescent powder can be seen, and the number of times of adding the fluorescent powder can be seenThe light transmittance of the transparent crab shell slices is not influenced.
TABLE 3 light transmittance of samples before and after PMMA filling
TABLE 4 light transmittance of crab shell pieces before and after filling with resin
TABLE 5 light transmittance of phosphor-doped transparent crab shell pieces
The Scanning Electron Microscope (SEM) of the present invention is shown in FIG. 5. FIGS. 5a, 5b, 5c are scanning electron micrographs of natural crab shells at 1000, 5000 and 10000 times, respectively; FIGS. 5d, 5e, 5f are scanning electron micrographs of 1000, 5000, and 10000 times, respectively, of the chitin skeleton of the crab shell after removal of the matrix; 5g, 5h and 5i are respectively the scanning electron micrographs of 1000, 5000 and 10000 times of the transparent crab shell slices filled with PMMA; FIGS. 5j, 5k, 5l are scanning electron micrographs of 1000, 5000, and 10000 times, respectively, of clear crab shell pieces after EP filling.
The infrared absorption spectrum of the present invention is measured as follows: fig. 6 and 7 show the infrared analysis spectra of the natural crab shell, the crab shell after removing the matrix and the crab shell after filling EP, respectively. As can be seen in the figure, the crab shell after removal of the matrix is 875cm, compared to the natural crab shell-1、1220-1330cm-1、1600-1700cm-1、1700cm-1The absorption peak intensity is obviously reduced, 875cm-1Is a C-O single bond in calcium carbonate, 1700cm-1Is C ═ O double bond in calcium carbonate, 1220--1Is the amide I band in the protein, 1600-1700cm-1Is amide III band in protein, which shows that calcium carbonate and protein are processed relatively cleanly in the processing process. In FIG. 6, the thickness of the resin layer is 829cm after filling the resin-1、1249cm-1Appearance of a new absorption peak, 829cm-1Is benzene ring of bisphenol A in epoxy resin, 1249cm-1Is the C-O bond in the epoxy resin, which indicates that the epoxy resin is filled into the crab shell. In FIG. 7, the infrared spectrum after PMMA filling is 1160cm-1、1700cm-1A new absorption peak appears at 1160cm-1Is a C-O bond in methyl methacrylate, 1700cm-1Is the bond C ═ O in methyl methacrylate, indicating that PMMA fills the chitin backbone gap of crab shells.
The fluorescence spectrum analysis of the present invention is shown in FIGS. 8 and 9. Fig. 8 is YAG in transparent fluorescent crab shell material measured at λ 458 nm: ce3+Emission spectrum of the phosphor. As can be seen from the figure: the peak of the emission spectrum is 527nm, which is caused by Ce in YAG phosphor3+A characteristic transition at 5d → 4 f; fig. 9 is YAG in a transparent fluorescent crab shell measured with light at a λ 527 nm: ce3+Excitation spectrum of the phosphor. It can be seen that there are two peaks of the excitation spectrum at 340nm and 458nm, with the peak at 458nm being the largest because of the YAG: ce3+Fluorescent powder 4f energy level ground state orbit2F is cleaved to2F5/2And2F7/2two spectral sub-orbits, with excitation peaks at 340nm corresponding to each other2F5/2Transition of → 5D, excitation peak at 450nm corresponds to2F7/2Transition of → 5D. In fig. 8 and 9, no peak was measured in the crab shells filled with EP only, which confirmed that the filling with epoxy resin +1 wt% YAG: ce3+The crab shell can be used for preparing a transparent composite material with fluorescent property.
Claims (6)
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.
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| CN108818834A (en) * | 2018-07-12 | 2018-11-16 | 东北林业大学 | A kind of preparation method of the laminated transparent timber of long-afterglow fluorescent |
| CN111300583A (en) * | 2020-02-28 | 2020-06-19 | 南通大学 | Method for manufacturing wooden light-emitting lampshade |
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2020
- 2020-07-28 CN CN202010738548.1A patent/CN111777779B/en active Active
- 2020-08-03 WO PCT/CN2020/106516 patent/WO2021223336A1/en active Application Filing
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2021
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| CN104558241A (en) * | 2013-10-17 | 2015-04-29 | 李文金 | Processing technology for producing chitin from crab shells |
| CN104829749A (en) * | 2015-05-08 | 2015-08-12 | 中国科学院理化技术研究所 | Method for one-step preparation of chitosan oligosaccharide by employing shrimp and crab shells as raw materials and adopting enzymolysis method and application |
| US20180194864A1 (en) * | 2017-01-06 | 2018-07-12 | The Board Of Trustees Of The University Of Alabama | Coagulation of chitin from ionic liquid solutions using kosmotropic salts |
| CN109135728A (en) * | 2017-06-28 | 2019-01-04 | 中国科学院化学研究所 | A kind of fluorescent material and its preparation method and application |
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| CN111777779B (en) | 2022-04-05 |
| ZA202109118B (en) | 2022-02-23 |
| WO2021223336A1 (en) | 2021-11-11 |
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