CN109097024B

CN109097024B - Preparation method of vermiculite fluorescent film composite material

Info

Publication number: CN109097024B
Application number: CN201810836354.8A
Authority: CN
Inventors: 田维亮; 葛振红; 马明; 叶林
Original assignee: Tarim University
Current assignee: Tarim University
Priority date: 2018-07-26
Filing date: 2018-07-26
Publication date: 2022-06-03
Anticipated expiration: 2038-07-26
Also published as: CN109097024A

Abstract

The invention provides a method for preparing a transparent fluorescent ultrathin film composite material by adopting a laminated vermiculite material and an organic fluorescent molecular material, which is prepared by a supermolecule assembly method, so that the prepared organic-inorganic fluorescent ultrathin film composite material overcomes the defects of a pure organic material and a pure inorganic material, has the advantages of the organic-inorganic fluorescent ultrathin film composite material and the pure inorganic material, simultaneously realizes the assembly of anions and anions, has longer fluorescent service life, has the characteristics of transparency and solid state, and has very high popularization and application values.

Description

Preparation method of vermiculite fluorescent film composite material

Technical Field

The invention relates to a preparation method of a fluorescent material, in particular to a preparation method of a vermiculite fluorescent film composite material, and belongs to the technical field of inorganic non-metallic mineral material processing.

Background

The definition of supermolecule assembly is a multimolecular group composed of non-covalent bonds, which can be as simple as two molecules, and they can be spherical, rod-shaped or sheet-shaped samples, and the research on supermolecule assembly is to obtain a series of new materials, and the building elements studied by supermolecule assembly are mostly concentrated on the assembly between molecules and nano-scale or between micro-scale and above-micro-scale objects, etc., so that it can effectively control the performance of new materials and implement the leap of product quality.

Vermiculite is one of nonmetal minerals with better resource prospect and potential advantages in China, is an important nonmetal mineral, is also a magnesium-containing aluminosilicate secondary metamorphic mineral with a layered structure, belongs to layered silicate, and is cheap and easy to obtain; the cable can resist high temperature, is a poor thermal conductor and has good electrical insulation; expanded vermiculite is prone to water and moisture absorption; the composite material can be expanded at high temperature and is easy to strip, and has the characteristics of better interlaminar cation exchange capacity, expansion capacity, adsorption capacity, sound insulation, heat insulation, fire resistance, freezing resistance and the like, and has stable chemical properties, water insolubility, no toxicity, no odor and no side effect. In fact, how to construct a new composite material by preparing micron or nanometer powder and assembling is one of the mark achievements for improving the research level of vermiculite. However, vermiculite is a typical anionic clay, is negatively charged, and is difficult to self-assemble to form an ordered body, so how to construct a new material through assembly is a key problem for expanding the research and application of vermiculite foundation. Organic cationic phosphors are widely used in LED products, but have a problem of short life span due to their being organic bodies, thereby greatly affecting the performance of LED products.

Therefore, the technical personnel in the field need to solve the problem how to assemble the vermiculite material and the organic cationic phosphor by utilizing the supermolecular body assembly technology to form the vermiculite fluorescent composite material so as to overcome the defect of short service life of the organic cationic phosphor and construct the vermiculite optical material.

Disclosure of Invention

Aiming at the problems of insufficient development and utilization of vermiculite and short service life of an organic cationic phosphor, the invention aims to provide a preparation method of a vermiculite fluorescent film composite material, wherein macroscopic vermiculite and the organic cationic phosphor are combined to form the composite material.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a vermiculite fluorescent film composite material comprises the following steps:

(1) adding water into vermiculite, ultrasonically heating, peeling, crushing, centrifugally washing and separating, and ultrasonically dispersing the centrifuged precipitate into deionized water to obtain a nanosheet vermiculite solution;

(2) carrying out ultrasonic dispersion and dissolution on fluorescent molecules to obtain a fluorescent molecule solution;

(3) treating transparent quartz glass or a PET film to obtain hydrophilic quartz glass or a PET film;

(4) soaking the quartz glass or PET film treated in the step (3) in a fluorescent molecular solution, washing the film with clear water, soaking the film in a vermiculite colloidal solution, washing the film with clear water, soaking the film in the fluorescent molecular solution, and repeating the soaking process to obtain the transparent composite ultrathin film assembled by vermiculite and organic fluorescent molecules.

The beneficial effect of above-mentioned scheme is: assembling molecular vermiculite and organic fluorescent molecules through supermolecules, and attaching the assembled molecular vermiculite and organic fluorescent molecules to quartz glass or a PET film to form the vermiculite fluorescent ultrathin film composite material.

Preferably, the particle size of the nano-sheet vermiculite obtained in the step (1) is 1-1000 nm, and the concentration of the nano-sheet vermiculite solution is 0.001-1 g/ml.

Preferably, the ultrasonic frequency of the step (1) is 20Hz-1000MHz, the heating temperature is 40-350 ℃, and the centrifugal speed is 8000-.

The beneficial effects of the preferred technical scheme are as follows: through controlling the centrifugal rotating speed, the molecular level of vermiculite in the vermiculite colloidal solution is ensured, and the supermolecule assembly process in the subsequent reaction is facilitated.

Further, the fluorescent molecule in the step (2) is one of pyrrhodine, rhodamine B6G, cadmium sulfide quantum dots, cadmium selenide quantum dots or cadmium telluride quantum dots.

Preferably, the cadmium sulfide quantum dots, the cadmium selenide quantum dots and the cadmium telluride quantum dots are modified by cationic surfactants to prepare the quantum dots with positive charges.

Preferably, the cationic surfactant is cetyl ammonium bromide or cetyl trimethyl pyridine bromide or cetyl pyridine bromide or dodecyl pyridine bromide.

The beneficial effects of the preferred technical scheme are as follows: rhodamine B6G and pyrazoxine are cationic fluorophors, cadmium sulfide quantum dots, cadmium selenide quantum dots and cadmium telluride quantum dots can carry anions, layer-by-layer assembly of the anions and the anions can be realized through modification treatment, and the defect that the assembly cannot be carried out with the same charge is overcome.

Preferably, the treatment of the PET film or the quartz glass in the step (3) is carried out by using plasma with radio frequency power of 0-5000W, radio frequency of 5-1000MHz and ultraviolet ray with ultraviolet ray intensity of 0-3000uW/cm, and the treatment time is 1-30 minutes.

The beneficial effects of the preferred technical scheme are as follows: the plasma and the ultraviolet are simultaneously treated to destroy the surface structure of the quartz glass or the PET, so that the surface of the quartz glass or the PET is hydroxylated and changed from a hydrophobic surface to a hydrophilic surface.

Preferably, the soaking time of the fluorescent molecules and the vermiculite in the step (4) is 0.1-60 min; the washing time is 0.1-30 min.

Preferably, the number of repetitions in step (4) is 2 to 100000 times.

The beneficial effects of the preferred technical scheme are as follows: through repeated soaking and washing, the vermiculite molecules and the organic fluorescent molecules are ensured to form the supermolecule assembled composite material.

In conclusion, the beneficial effects of the invention are as follows: the vermiculite and the organic fluorescent molecular material are covered on a modified quartz glass or PET film through a supermolecule assembly effect to form the fluorescent film composite material, the vermiculite is a typical inorganic matter, the fluorescent molecules are organic matters, the luminescent polymer with negative charges and the layered material are alternately assembled layer by layer to form an inorganic/organic composite ultrathin film, and the luminescent polymer molecules generate a positioning effect between layers, so that the microscopic controllability of the distance between the molecules of the optical functional polymer is realized, the optical functional polymer is uniformly dispersed between the layers, the luminescent quenching phenomenon generated by the accumulation of the optical active molecules is effectively inhibited, and the non-redshift and non-broadening luminescent characteristics are obtained; meanwhile, the method is favorable for improving the physical and chemical stability of the luminescent polymer, solves the problems of poor stability and short service life in the organic luminescent polymer device, has high application value in the field of luminescent materials, and importantly, realizes the assembly of the negatively charged vermiculite and the negatively charged fluorescent quantum dots by the modification control of the micelle structure.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.

FIG. 1 is a graph showing natural light (a) and fluorescence (b) of a fluorescent thin film group based on electrostatic alternate adsorption of a material prepared in example 2 of the present invention;

FIG. 2 is a graph showing a UV spectrum of a fluorescent thin film group based on electrostatic alternative adsorption of the material prepared in example 2 of the present invention;

FIG. 3 is a graph showing linear fitting of the material prepared in example 2 of the present invention based on the electrostatic alternate adsorption fluorescent thin film set at different wavelengths;

FIG. 4 is a graph showing a fluorescence emission spectrum of a fluorescent thin film group based on electrostatic alternative adsorption of the material prepared in example 2 of the present invention;

FIG. 5 is a graph showing linear fitting of fluorescence intensity of a fluorescent thin film set based on electrostatic alternative adsorption of the material prepared in example 2 of the present invention.

Detailed Description

The following further describes the embodiments of the present invention.

The starting materials used in the present invention are commercially available or commonly used in the art, unless otherwise specified.

A preparation method of a vermiculite fluorescent film composite material combines vermiculite and organic cation fluorophor to form a composite material, and specifically adopts the following technical scheme, which comprises the following steps:

(1) adding water into vermiculite, performing ultrasonic treatment at 20Hz-1000MHz, heating to 40-350 ℃, peeling and crushing, then performing centrifugal washing and separation at a rotating speed of 8000-230000rpm, and performing ultrasonic dispersion on the centrifuged precipitate in deionized water to obtain a 1-1000 nanometer nanosheet vermiculite solution, wherein the concentration of the nanosheet vermiculite solution is 0.001-1 g/ml;

(2) carrying out ultrasonic dispersion and dissolution on pyrazoxine or rhodamine B6G or cadmium sulfide quantum dots or cadmium selenide quantum dots or cadmium telluride quantum dots to obtain a fluorescent molecular solution;

(3) treating transparent quartz glass or PET film with plasma with radio frequency power of 0-5000W and radio frequency of 5-1000MHz and ultraviolet ray with ultraviolet intensity of 0-3000uW/cm for 1-30min to obtain hydrophilic quartz glass or PET film;

(4) soaking the quartz glass or PET film treated in the step (3) in a fluorescent molecule solution for 0.1-60min, washing with clear water for 0.1-30min, then soaking in a vermiculite colloid solution for 0.1-60min, washing with clear water for 0.1-30min, then soaking in the fluorescent molecule solution for 0.1-60min, and repeating the soaking and washing processes for 2-100000 times to obtain the transparent composite ultrathin film assembled by vermiculite and organic fluorescent molecules.

In order to further optimize the scheme, the cadmium sulfide quantum dots, the cadmium selenide quantum dots and the cadmium telluride quantum dots are modified by a cationic surfactant to prepare the quantum dots with positive charges, and the cationic surfactant is cetyl ammonium bromide or cetyl trimethyl pyridine bromide or cetyl pyridine bromide or dodecyl pyridine bromide.

The specific embodiments are shown in the following examples.

Example 1

(1) adding water into vermiculite, performing ultrasonic treatment at 20Hz, heating to 40 ℃, peeling and crushing, separating the mixture by a centrifugal machine at the rotation speed of 10000rpm, and dispersing the centrifuged precipitate solid into pure water to obtain a nanosheet vermiculite solution;

(2) ultrasonically dissolving rhodamine B6G to obtain rhodamine B6G fluorescent molecular solution;

(3) treating the transparent PET film with plasma with the radio frequency of 5MHz and ultraviolet rays with the intensity of 3000uW/cm to obtain a hydrophilic PET film;

(4) and (4) soaking the PET film treated in the step (3) in a rhodamine B6G fluorescent molecular solution for 10 minutes, washing the PET film with clear water for 3 minutes, then soaking the PET film in a vermiculite colloidal solution for 10 minutes, washing the PET film with clear water for 3 minutes, and then soaking the PET film in a rhodamine B6G fluorescent molecular solution for 5 minutes, repeating the steps for 32 times to obtain the transparent composite material film assembled by vermiculite and fluorescent molecules.

Example 2

(1) adding water into vermiculite, performing ultrasonic treatment at 200Hz, heating to 100 ℃, peeling and crushing, separating the mixture by a centrifugal machine at the rotating speed of 15000rpm, and re-dispersing the centrifuged precipitate solid into pure water to obtain a nanosheet vermiculite solution;

(2) ultrasonically dissolving cadmium sulfide quantum dots modified by bromohexadecyl trimethyl pyridine to obtain a cadmium sulfide quantum dot fluorescent molecular solution;

(3) treating the transparent quartz glass by using plasma with the radio frequency power of 100W and the radio frequency of 200MHz to obtain hydrophilic quartz glass;

(4) and (4) soaking the quartz glass treated in the step (3) in a cadmium sulfide quantum dot fluorescent molecular solution for 10 minutes, washing the quartz glass with clear water for 5 minutes, soaking the quartz glass in a vermiculite colloidal solution for 10 minutes, washing the quartz glass with clear water for 5 minutes, soaking the quartz glass in the cadmium sulfide quantum dot fluorescent molecular solution again, and repeating the steps for 36 times to obtain the transparent composite material film assembled by the vermiculite and the fluorescent molecules.

Example 3

(1) adding water into vermiculite, performing ultrasonic treatment at 400Hz, heating to 150 ℃, peeling and crushing, separating the mixture by a centrifugal machine at the rotating speed of 20000rpm, and re-dispersing the centrifuged precipitate solid into pure water to obtain a nanosheet vermiculite solution;

(2) ultrasonically dissolving the cadmium telluride quantum dots modified by the hexadecyl ammonium bromide to obtain a cadmium telluride quantum dot fluorescent molecular solution;

(3) treating the transparent PET film with plasma with the radio frequency power of 300W and the radio frequency of 400MHz and ultraviolet rays with the intensity of 2000uW/cm to obtain a hydrophilic PET film;

(4) and (3) soaking the PET film treated in the step (3) in the cadmium telluride quantum dot fluorescent molecular solution for 10 minutes, washing with clear water for 10 minutes, soaking in a vermiculite colloidal solution for 10 minutes, washing with clear water for 10 minutes, soaking in the cadmium telluride quantum dot fluorescent molecular solution, and repeating the steps for 40 times to obtain the transparent composite material film assembled by the vermiculite and the fluorescent molecules.

Example 4

(1) adding 1000Hz ultrasonic water into vermiculite, heating to 350 ℃, peeling and crushing, separating the mixture by a centrifugal machine at the rotating speed of 23000rpm, and re-dispersing the centrifuged precipitate solid into pure water to obtain a nanosheet vermiculite solution;

(2) dissolving the pyrazorubin by ultrasonic to obtain a pyrazorubin fluorescent molecular solution;

(3) treating the transparent PET film with plasma with the radio frequency power of 500W and the radio frequency of 1000MHz and ultraviolet rays with the intensity of 3000uW/cm to obtain a hydrophilic PET film;

(4) and (3) soaking the PET film treated in the step (3) in a pyroxene fluorescent molecular solution for 12 minutes, washing the PET film with clear water for 5 minutes, soaking the PET film in a vermiculite colloidal solution for 12 minutes, washing the PET film with clear water for 5 minutes, soaking the PET film in the pyroxene fluorescent molecular solution, and repeating the steps for 50 times to obtain the transparent composite material film assembled by vermiculite and fluorescent molecules.

Example 5

A preparation method of a graphene fluorescent film composite material comprises the following steps:

(1) adding water into graphene, and dispersing under the conditions that the ultrasonic frequency is 20Hz-1000MHz and the heating temperature is 40-350 ℃ to obtain a graphene colloidal solution;

(2) carrying out ultrasonic dissolution on a cadmium telluride quantum dot, a cadmium selenide quantum dot or a cadmium sulfide quantum dot modified by pyrazosine, rhodamine B6G, hexadecylammonium bromide or bromohexadecyl trimethyl pyridine or pyridine bromide to obtain a fluorescent molecular solution;

(3) treating the transparent quartz glass or PET film by adopting plasma with the radio frequency power of 0-5000W and the radio frequency of 5-1000MHz and ultraviolet rays with the ultraviolet intensity of 0-3000uW/cm for 30 minutes to obtain hydrophilic quartz glass or PET film;

(4) and (3) soaking the quartz glass or PET film treated in the step (3) in an organic fluorescent molecular solution for 11 minutes, washing the film with clear water for 6 minutes, then soaking the film in a graphene colloidal solution for 11 minutes, washing the film with clear water for 6 minutes, soaking the film in the organic fluorescent molecular solution, and repeating the steps for 32 times to obtain the transparent composite material film assembled by graphene and fluorescent molecules.

Example 6

A preparation method of a molybdenum sulfide fluorescent film composite material comprises the following steps:

(1) adding water into molybdenum sulfide, and dispersing under the conditions that the ultrasonic frequency is 20Hz-1000MHz and the heating temperature is 40-350 ℃ to obtain a molybdenum sulfide colloidal solution;

(2) carrying out ultrasonic dissolution on a cadmium telluride quantum dot or a cadmium sulfide quantum dot modified by pyrazoxine or rhodamine B6G or hexadecylammonium bromide or bromohexadecyl trimethyl pyridine or pyridine bromide to obtain an organic fluorescent molecular solution;

(4) and (3) soaking the quartz glass or PET film treated in the step (3) in an organic fluorescent molecular solution for 10 minutes, washing with clear water for 4 minutes, soaking in a molybdenum sulfide colloidal solution for 10 minutes, washing with clear water for 4 minutes, soaking in the organic fluorescent molecular solution, and repeating the steps for 32 times to obtain the transparent composite material film assembled by molybdenum sulfide and fluorescent molecules.

Comparative example 1

The scheme is a pure fluorescent molecular material without supermolecular combination.

Performance testing

The fluorescent film composite material prepared in example 2 was subjected to ultraviolet and fluorescence detection, and the number of layers was analyzed, and the degree of matching of the ultraviolet linear relationship and the fluorescence linear relationship of the film was 0.99 or more, respectively. The fluorescence lifetime is improved by about 13 times. The results are shown in FIGS. 1-5: as can be seen from fig. 1(a), the assembled quartz glass is colorless and transparent under sunlight, and as can be seen from fig. 1(b), the assembled quartz glass is red-fluorescent under ultraviolet light. FIG. 1 shows that the preparation of transparent vermiculite and fluorescent molecular material is realized. FIGS. 2 and 3 show ultraviolet spectra of vermiculite and fluorescent molecules at different layer numbers, FIG. 2 shows that absorbance gradually increases with the increase of the layer number, FIG. 3 shows that fitting curves at wavelengths of 360nm,500nm and 700nm have fitting degrees of above 0.99, and the layer number of the vermiculite is effectively controlled. FIGS. 4 and 5 show fluorescence spectra of vermiculite and fluorescent molecule with different number of layers, FIG. 4 shows that the fluorescence absorbance of the spectrum gradually increases with the increase of the number of layers, FIG. 5 shows a fitting curve with a wavelength of 617.5nm, the fitting degree is also above 0.99, and the number of layers of the fluorescent molecule is effectively controlled. The experiments show that the prepared vermiculite colloidal solution is assembled with fluorescent molecules, the fluorescent life of the vermiculite colloidal solution is greatly prolonged, and the preparation of the transparent fluorescent vermiculite film is realized.

Testing the service life of the fluorescent material:

the fluorescent thin film composites obtained in examples 1 to 6 and the fluorescent molecular material of comparative example 1 were subjected to a luminescence lifetime test, and the results are shown in the following table:

from the test results, the fluorescent film composite material prepared by adopting the technical scheme provided by the invention has longer fluorescence life and has very high popularization and application values in the field of fluorescent materials.

The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.

Claims

1. The preparation method of the vermiculite fluorescent film composite material is characterized by comprising the following steps of:

(4) soaking the quartz glass or PET film treated in the step (3) in a fluorescent molecular solution, washing the film with clear water, soaking the film in a vermiculite colloidal solution, washing the film with clear water, soaking the film in the fluorescent molecular solution, and repeating the soaking process to obtain a transparent composite ultrathin film assembled by vermiculite and organic fluorescent molecules;

the ultrasonic frequency in the step (1) is 20Hz-1000MHz, the heating temperature is 40-350 ℃, and the centrifugal rotating speed is 8000-;

the fluorescent molecule in the step (2) is one of pyrazosine, rhodamine B6G, cadmium sulfide quantum dots, cadmium selenide quantum dots or cadmium telluride quantum dots;

the cadmium sulfide quantum dots, the cadmium selenide quantum dots and the cadmium telluride quantum dots are modified by a cationic surfactant to prepare positively charged quantum dots;

the cationic surfactant is cetyl ammonium bromide or cetyl trimethyl pyridine bromide or cetyl pyridine bromide or dodecyl pyridine bromide;

the PET film or quartz glass treatment in the step (3) is carried out by adopting plasma with radio frequency power of 0-5000W and radio frequency of 5-1000MHz and ultraviolet with ultraviolet intensity of 0-3000uW/cm, and the treatment time is 1-30 minutes.

2. The method for preparing the vermiculite fluorescent thin film composite material according to claim 1, wherein the particle size of the nano-sheet vermiculite obtained in the step (1) is 1-1000 nm, and the concentration of the nano-sheet vermiculite solution is 0.001-1 g/ml.

3. The method for preparing the vermiculite fluorescent film composite material according to claim 1, wherein in the step (4), the soaking time of the fluorescent molecules and the vermiculite is 0.1-60 min; the washing time is 0.1-30 min.

4. The method for preparing a vermiculite fluorescent film composite material according to claim 1, wherein the number of repetition in the step (4) is 2 to 100000 times.

5. A vermiculite fluorescent film composite, characterized in that it is obtained by the process according to any one of claims 1 to 4.