CN108129811B - Quantum dot luminescent composite for 3D printing - Google Patents
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Abstract
The invention discloses a quantum dot luminescent compound for 3D printing, which is prepared from 85-120 parts by mass of high-molecular colloid, 10-80 parts by mass of inorganic matter, 1-3 parts by mass of cross-linking agent and 20-80 parts by mass of oil-soluble quantum dot. Compared with the prior art, the oil-soluble quantum dot, the polymer colloid, the cross-linking agent and the inorganic substance (nano titanium dioxide or nano silicon dioxide) are mixed, the size of the oil-soluble quantum dot in three dimensions is usually less than 10nm, the scattering of the oil-soluble quantum dot is very small compared with fluorescent powder, and after the quantum dot luminescent compound is printed, the quantum dot in the printed luminous body is not agglomerated, so the oil-soluble quantum dot is not precipitated in the polymer colloid.
Description
The invention relates to a divisional application of a parent application 'quantum dot luminescent compound for 3D printing and a preparation method thereof', wherein the parent application has an application number of 2015110336649, and the application date is 2015, 12 and 30.
Technical Field
The invention belongs to the technical field of nano luminescent materials, and particularly relates to a quantum dot luminescent compound for 3D printing.
Background
The 3D printing technology is a widely applied rapid forming technology without excess materials, is already applied to the preparation of complex parts made of materials such as metal, resin, ceramics and the like, and can rapidly and precisely manufacture new product samples in any complex shapes without traditional tools, machine tools and clamps. White light LED is a new kind of semiconductor all solid state lighting source, the commercial white light LED mainstream technology is with blue light chip + yellow phosphor powder and make, at present, there are some patent publications that mix phosphor powder and polymer colloid according to certain proportion, make the polymer colloid that mixes with phosphor powder, print with the polymer colloid that mixes with phosphor powder through the shower nozzle. However, the polymer colloid doped with the phosphor has the following problems: 1) the fluorescent powder has larger particles, and the fluorescent powder is easy to precipitate and cause agglomeration when being mixed with the polymer colloid, so that the fluorescent powder is unevenly distributed in the polymer colloid; 2) because the difference between the refractive indexes of the fluorescent powder and the polymer colloid is large, a strong light scattering effect can be formed on the contact surface of the fluorescent powder and the polymer colloid. 3) Organic matters in the polymer colloid doped with the fluorescent powder and the inorganic fluorescent powder are subjected to chemical reaction, so that the emission spectrum of the fluorescent powder is changed. Therefore, the development of phosphor paste in the field of 3D printing is limited.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a quantum dot luminescent compound for 3D printing, and the compound can be made into luminophors with various shapes through a 3D printer.
The purpose of the invention is realized by the following technical scheme:
a quantum dot luminescent composite for 3D printing comprises 85-120 parts by mass of polymer colloid, 10-80 parts by mass of inorganic matter, 1-3 parts by mass of cross-linking agent and 20-80 parts by mass of oil-soluble quantum dots, wherein the inorganic matter is nano titanium dioxide or nano silicon dioxide, the polymer colloid is ABS resin, PLA resin or a mixture of ABS resin and PLA resin, and the ratio of the ABS resin to the PLA resin in the mixture of the ABS resin and the PLA resin is (0.2-5): 1; the cross-linking agent is benzoyl peroxide, dicumyl peroxide, peroxydicarbonate, di- (tert-butylperoxyisopropyl) benzene or 2, 5-dimethyl-2, 5-di-tert-butylperoxy hexane.
In the technical scheme, the oil-soluble quantum dots are CdZnS/ZnS, CdSeS, CdSe/ZnS, CdS or CdTe.
In the technical scheme, the polymer colloid accounts for 95-110 parts by mass, the inorganic matter accounts for 40-70 parts by mass, the cross-linking agent accounts for 1.5-2.5 parts by mass, the oil-soluble quantum dots account for 40-50 parts by mass, the particle size of the nano silicon dioxide is 30-100 nanometers, and the particle size of the nano titanium dioxide is 50-120 nanometers.
In the above technical solution, in the mixture of ABS resin and PLA resin, the ratio of ABS resin to PLA resin is (1-3): 1.
a preparation method of a quantum dot luminescent compound is carried out according to the following steps:
1) uniformly mixing inorganic matter, ethanol and oil-soluble quantum dots, and drying at 50-100 ℃ for 1-12 hours after mixing until the ethanol is completely volatilized, wherein the oil-soluble quantum dots account for 20-80 parts by mass, the inorganic matter accounts for 10-80 parts by mass, and the ethanol is excessive so that the inorganic matter and the oil-soluble quantum dots are uniformly mixed, wherein the inorganic matter is nano titanium dioxide or nano silicon dioxide;
2) sequentially putting a polymer colloid, the mixture obtained in the step 1) and a cross-linking agent into a double-screw extruder for melting, uniformly mixing, extruding, naturally cooling and granulating to obtain the quantum dot luminescent compound for 3D printing, wherein the extrusion temperature is 182-: 1; the cross-linking agent is benzoyl peroxide, dicumyl peroxide, peroxydicarbonate, di- (tert-butylperoxyisopropyl) benzene or 2, 5-dimethyl-2, 5-di-tert-butylperoxy hexane.
In the technical scheme, the oil-soluble quantum dots are CdZnS/ZnS, CdSeS, CdSe/ZnS, CdS or CdTe.
In the technical scheme, the polymer colloid accounts for 95-110 parts by mass, the inorganic matter accounts for 40-70 parts by mass, the cross-linking agent accounts for 1.5-2.5 parts by mass, the oil-soluble quantum dots account for 40-50 parts by mass, the particle size of the nano silicon dioxide is 30-100 nanometers, and the particle size of the nano titanium dioxide is 50-120 nanometers.
In the technical scheme, the extrusion temperature is 185-195 ℃, the screw rotating speed is 300-360 r/min,
in the above technical solution, in the mixture of ABS resin and PLA resin, the ratio of ABS resin to PLA resin is (1-3): 1.
the application of the quantum dots in 3D printing comprises the steps of putting the quantum dot luminescent compound into a wire feeding mechanism of a 3D printer, melting the quantum dot luminescent compound by the wire feeding mechanism, extruding the quantum dot luminescent compound from a nozzle, naturally cooling to 20-25 ℃ after extrusion, and matching with an excitation light source to obtain luminophors with different shapes and structures.
Compared with the prior art, the oil-soluble quantum dots, the polymer colloid, the cross-linking agent and the inorganic substance (nano titanium dioxide or nano silicon dioxide) are mixed, the size of the oil-soluble quantum dots in three dimensions is usually less than 10nm, the scattering of the oil-soluble quantum dots is very small compared with fluorescent powder, and after the oil-soluble quantum dot luminescent composite is printed, the oil-soluble quantum dots in the printed luminous body are not agglomerated, so the oil-soluble quantum dots are not precipitated in the polymer colloid; the emission wavelength of the mixed oil-soluble quantum dots in the polymer colloid is not changed. The invention enhances the luminous intensity of the oil-soluble quantum dot luminous composite by introducing inorganic substances (nano titanium dioxide or nano silicon dioxide). The oil-soluble quantum dot luminescent compound is placed in a wire feeding mechanism of a 3D printer, the wire feeding mechanism melts the oil-soluble quantum dot luminescent compound and extrudes the oil-soluble quantum dot luminescent compound from a spray head, the oil-soluble quantum dot luminescent compound can be printed into luminophors with different shapes, and the luminophors with different shapes and functions can be manufactured by matching with an excitation light source.
Drawings
FIG. 1 is an emission spectrum of a 3D printed quantum dot luminescent composite prepared with CdZnS/ZnS quantum dots;
FIG. 2 is a transmission electron microscope photograph of a 3D printed quantum dot luminescent composite prepared with CdZnS/ZnS quantum dots;
fig. 3 is an emission spectrum of a 3D printed quantum dot luminescent composite prepared with CdSeS quantum dot quantum dots;
FIG. 4 is an emission spectrum of a 3D printed quantum dot luminescent composite prepared with CdSe/ZnS quantum dots;
fig. 5 is an emission spectrum of a 3D printed quantum dot luminescent composite prepared with CdTe quantum dots.
Detailed Description
The PLA resin in this example was purchased from NatureWorks, usa, ABS resin was purchased from zhenjiangqi beautifying chemical limited, peroxydicarbonate was purchased from shanghai alading biochemical science and technology limited, benzoyl peroxide was purchased from haijing chemical limited, dongyang, dicumyl peroxide was purchased from catabawin chemical limited, bainwei technology limited, 2, 5-dimethyl-2, 5 di-tert-butyl hexane peroxide was purchased from north huosheng biochemical technology limited, nano-titania and nano-silica were purchased from shanghai alading biochemical science and technology limited, wherein the nano-titania had a particle size of 100 nm and the nano-silica had a particle size of 50 nm. The oil-soluble quantum dots in the following examples are all oil-soluble quantum dot powders and are purchased from Beijing Dada technologies, Inc. The ABS resin is a graft copolymer of three monomers of Acrylonitrile (Acrylonitrile), 1, 3-Butadiene (Butadiene) and Styrene (Styrene), wherein, in terms of mole percentage of repeating units, Acrylonitrile accounts for 15% -35%, Butadiene accounts for 5% -30%, Styrene accounts for 40% -60%, in this embodiment, Acrylonitrile: 1, 3-butadiene: styrene is 20:30:50, the weight average relative molecular mass of the ABS resin is 80,000-150,000g/mol, and the rubber content in the ABS resin is 11-60%. The weight average relative molecular mass of the PLA resin was 80,000-300,000 g/mol.
The test method comprises the following steps: the quantum dot luminescent compound is placed in a wire feeding mechanism of a 3D printer, the wire feeding mechanism melts the quantum dot luminescent compound and extrudes the quantum dot luminescent compound from a spray head, the quantum dot luminescent compound is printed into a wafer with the diameter of 1.5 cm and the thickness of 0.1 cm, and the wafer is placed in an EX-1000 fluorescent powder excitation spectrum and thermal quenching analysis system (Hangzhou remote photoelectric information corporation) for excitation test. The transmission electron microscope is model JEM-2010 UHR.
In the examples of the present invention, 1 part by mass was 1 g.
The quantum dot luminescent composite for 3D printing and the preparation method and application thereof according to the present invention will be described in detail with reference to the following embodiments and the accompanying drawings.
Example 1
1) Uniformly mixing nano titanium dioxide, ethanol and CdZnS/ZnS quantum dots, and drying at 60 ℃ for 6 hours after mixing until the ethanol is completely volatilized, wherein the mass ratio of the CdZnS/ZnS quantum dots is 20 parts, the mass ratio of the nano titanium dioxide is 10 parts, and the ethanol is excessive so that the nano titanium dioxide and the CdZnS/ZnS quantum dots are uniformly mixed;
2) and (2) sequentially putting the mixture obtained by the ABS resin, the PLA resin and 1) and benzoyl peroxide into a double-screw extruder for melting, uniformly mixing, extruding, naturally cooling and granulating to obtain the quantum dot luminescent composite for 3D printing, wherein the mass ratio of the ABS resin to the PLA resin is 40 parts, the mass ratio of the PLA resin to the benzoyl peroxide is 1.3 parts, the extrusion temperature is 190 ℃, and the rotation speed of a screw is 220 r/min.
The emission spectrum of the quantum dot luminescent composite obtained in example 1 was tested according to the test method described above: under 390nm blue light excitation, the emission spectrum is shown as curve 1 in fig. 1, and as can be seen from curve 1, the emission wavelength of the blue light is 458nm, which is consistent with the emission wavelength of exciting CdZnS/ZnS quantum dots with 390 nm. Therefore, the organic matter in the quantum dot luminescent composite does not change the emission wavelength of the oil-soluble quantum dot. Fig. 2 is a transmission electron microscope photograph of a 3D printed quantum dot luminescent composite prepared from CdZnS/ZnS quantum dots, and as shown in fig. 2, the CdZnS/ZnS quantum dots are uniformly distributed in the polymer colloid, and no agglomeration phenomenon occurs, and the CdZnS/ZnS quantum dots are not precipitated in the polymer colloid (the transmission electron microscope photograph does not show nano-titania because the nano-titania content in the quantum dot luminescent composite of example 1 is small).
Example 2
Example 2 compared to the examples without addition of inorganic nano-titania, i.e.:
1) uniformly mixing ethanol and CdZnS/ZnS quantum dots, and drying at 60 ℃ for 6 hours after mixing until the ethanol is completely volatilized, wherein the CdZnS/ZnS quantum dots account for 20 parts by mass, and the ethanol is excessive so as to cause the CdZnS/ZnS quantum dots to be mixed and distributed;
2) and (2) sequentially putting the mixture obtained by the ABS resin, the PLA resin and 1) and benzoyl peroxide into a double-screw extruder for melting, uniformly mixing, extruding, naturally cooling and granulating to obtain the quantum dot luminescent composite for 3D printing, wherein the mass ratio of the ABS resin to the PLA resin is 40 parts, the mass ratio of the PLA resin to the benzoyl peroxide is 1.3 parts, the extrusion temperature is 190 ℃, and the rotation speed of a screw is 220 r/min.
The emission spectrum of the oil-soluble quantum dot luminescent composite obtained in example 2 was tested according to the test method described above: under the excitation of 390nm of blue light, the emission spectrum is shown as curve 2 in fig. 1, and as can be seen from curve 2, the emission wavelength of the blue light is 458nm, which is consistent with the emission wavelength of example 1, but the intensity is reduced by 25%, therefore, the inorganic nano titanium dioxide plays a role of enhancing the intensity of the emission spectrum in the quantum dot luminescent composite of the present invention.
Example 3
1) Uniformly mixing nano titanium dioxide, ethanol and CdSeS quantum dots, and drying at 70 ℃ for 6 hours after mixing until the ethanol is completely volatilized, wherein 35 parts by mass of the CdSeS quantum dots, 25 parts by mass of the nano titanium dioxide and excessive ethanol are used to uniformly mix inorganic substances and the CdSeS quantum dots;
2) and (2) sequentially putting the mixture obtained by the ABS resin, the PLA resin and 1) and dicumyl peroxide into a double-screw extruder for melting, uniformly mixing, extruding, naturally cooling and granulating to obtain the quantum dot luminescent composite for 3D printing, wherein the mass ratio of the ABS resin is 45 parts, the mass ratio of the PLA resin is 47 parts, the mass ratio of the dicumyl peroxide is 1.9 parts, the extrusion temperature is 180 ℃, and the screw rotation speed is 220 r/min, so that the quantum dot luminescent composite for 3D printing is obtained.
The emission spectrum of the quantum dot luminescent composite obtained in example 3 was tested according to the test method described above: under the excitation of the blue light of 450nm, the emission spectrum is shown in fig. 3, and as can be seen from the figure, the emission wavelength of the red light is 600nm, and the wavelength of the red light is consistent with the emission wavelength of the CdSeS quantum dots excited by 450 nm. Therefore, the organic matter in the quantum dot luminescent compound prepared by the preparation method does not change the emission wavelength of the oil-soluble quantum dot.
Through observation of a transmission electron microscope, in the quantum dot luminescent composite obtained in example 3, the CdSeS quantum dots are uniformly distributed in the polymer colloid and do not undergo an agglomeration phenomenon, so that the CdSeS quantum dots are not precipitated in the polymer colloid.
Example 4
1) Uniformly mixing nano titanium dioxide, ethanol and CdSe/ZnS quantum dots, and drying at 80 ℃ for 6 hours after mixing until the ethanol is completely volatilized, wherein the CdSe/ZnS quantum dots account for 50 parts by mass, the nano titanium dioxide accounts for 45 parts by mass, and the ethanol is excessive so that the nano titanium dioxide and the CdSe/ZnS quantum dots are uniformly mixed;
2) and (2) sequentially putting the ABS resin, the mixture obtained in the step (1) and di- (tert-butyl peroxy isopropyl) benzene into a double-screw extruder for melting, uniformly mixing, extruding, naturally cooling and granulating to obtain the quantum dot luminescent compound for 3D printing, wherein the mass ratio of the ABS resin is 102 parts, the mass ratio of the di- (tert-butyl peroxy isopropyl) benzene is 2.2 parts, the extrusion temperature is 198 ℃, and the screw rotation speed is 300 revolutions per minute, so that the quantum dot luminescent compound for 3D printing is obtained.
The emission spectrum of the quantum dot luminescent composite obtained in example 4 was tested according to the test method described above: under the excitation of the blue light of 450nm, the emission spectrum is shown in FIG. 4, and the emission wavelength of the red light is 620nm, which is consistent with the emission wavelength of exciting CdSe/ZnS quantum dots by 450 nm. Therefore, the organic matter in the quantum dot luminescent compound prepared by the preparation method does not change the emission wavelength of the oil-soluble quantum dot.
Through observation of a transmission electron microscope, in the quantum dot luminescent composite obtained in example 4, the CdSe/ZnS quantum dots are uniformly distributed in the polymer colloid, and no agglomeration phenomenon occurs, so that it can be concluded that the CdSe/ZnS quantum dots are not precipitated in the polymer colloid.
Example 5
1) Uniformly mixing nano silicon dioxide, ethanol and CdS quantum dots, drying at 90 ℃ for 5 hours after mixing until the ethanol is completely volatilized, wherein 65 parts by mass of the CdS quantum dots, 65 parts by mass of the nano silicon dioxide and excessive ethanol are used so that the nano silicon dioxide and the CdS quantum dots are uniformly mixed;
2) and sequentially putting the PLA resin, the mixture obtained in the step 1) and peroxydicarbonate into a double-screw extruder for melting, uniformly mixing, extruding, naturally cooling and granulating to obtain the quantum dot luminescent composite for 3D printing, wherein the PLA resin is 112 parts by mass, the peroxydicarbonate is 2.5 parts by mass, the extrusion temperature is 184 ℃, and the screw rotation speed is 270 revolutions per minute, so that the quantum dot luminescent composite for 3D printing is obtained.
The emission spectrum of the quantum dot luminescent composite obtained in example 5 was tested according to the test method described above: under the excitation of blue light of 450nm, the emission wavelength of the CdS quantum dot is 640nm, and the emission wavelength of the red light is consistent with that of CdS quantum dot excited by 450 nm. Therefore, the organic matter in the quantum dot luminescent compound prepared by the preparation method does not change the emission wavelength of the oil-soluble quantum dot.
Through observation of a transmission electron microscope, in the quantum dot luminescent compound obtained in example 5, the CdS quantum dots are uniformly distributed in the polymer colloid, and no agglomeration phenomenon occurs, which can be concluded that the CdS quantum dots are not precipitated in the polymer colloid.
Example 6
1) Uniformly mixing nano silicon dioxide, ethanol and CdTe quantum dots, and drying at 100 ℃ for 4 hours after mixing until the ethanol is completely volatilized, wherein the CdTe quantum dots account for 80 parts by mass, the nano silicon dioxide accounts for 80 parts by mass, and the ethanol is excessive so that the nano silicon dioxide and the CdTe quantum dots are uniformly mixed;
2) and (2) sequentially putting the mixture obtained by the step (1) and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide into a double-screw extruder for melting, uniformly mixing, extruding, naturally cooling and granulating to obtain the quantum dot luminescent composite for 3D printing, wherein the mass ratio of the ABS resin to the PLA resin is 30 parts, the mass ratio of the 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide to the PLA resin is 2.7 parts, the extrusion temperature is 190 ℃, and the screw rotation speed is 350 revolutions per minute, so that the quantum dot luminescent composite for 3D printing is obtained.
The emission spectrum of the quantum dot luminescent composite obtained in example 6 was tested according to the test method described above: under the excitation of the blue light of 450nm, the emission spectrum is shown in FIG. 5, and the emission spectrum can emit the red light with the wavelength of 660nm, which is consistent with the emission wavelength for exciting the CdTe quantum dots with 450 nm. Therefore, the organic matter in the quantum dot luminescent compound prepared by the preparation method does not change the emission wavelength of the oil-soluble quantum dot.
Through observation by a transmission electron microscope, in the quantum dot luminescent composite obtained in example 6, the CdTe quantum dots are uniformly distributed in the polymer colloid, and no aggregation phenomenon occurs, which indicates that the CdTe quantum dots are not precipitated in the polymer colloid.
In the invention, the size of the quantum dots in three dimensions is less than 10nm, so that the quantum dots can not generate precipitation in ABS resin, PLA resin or a mixture of the ABS resin and the PLA resin, namely, after the quantum dots are subjected to 3D printing by using the quantum dot luminescent compound, the quantum dots can not generate an agglomeration phenomenon in a luminescent body.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (3)
1. The quantum dot luminescent composite for 3D printing is characterized by consisting of 85-120 parts by mass of high-molecular colloid, 10-80 parts by mass of inorganic matter, 1-3 parts by mass of cross-linking agent and 20-80 parts by mass of oil-soluble quantum dots, wherein the inorganic matter is nano titanium dioxide or nano silicon dioxide, the high-molecular colloid is a mixture of ABS resin and PLA resin, and the ratio of the ABS resin to the PLA resin in the mixture of the ABS resin and the PLA resin is (0.2-5): 1; the cross-linking agent is benzoyl peroxide, dicumyl peroxide, peroxydicarbonate, di- (tert-butylperoxyisopropyl) benzene or 2, 5-dimethyl-2, 5-di-tert-butylperoxy hexane; the oil-soluble quantum dots are CdZnS/ZnS, CdSeS, CdSe/ZnS, CdS or CdTe;
the preparation method of the quantum dot luminescent composite comprises the following steps:
1) uniformly mixing inorganic substances, ethanol and oil-soluble quantum dots, and drying at 50-100 ℃ for 1-12 hours after mixing until the ethanol is completely volatilized, wherein the ethanol is excessive so that the inorganic substances and the oil-soluble quantum dots are uniformly mixed;
2) sequentially putting the polymer colloid, the mixture obtained in the step 1) and the cross-linking agent into a double-screw extruder for melting, uniformly mixing, extruding, naturally cooling and granulating to obtain the quantum dot luminescent compound for 3D printing, wherein the extrusion temperature is 182-198 ℃, and the screw rotating speed is 220-400 revolutions per minute.
2. The quantum dot luminescent composite according to claim 1, wherein the polymer colloid is 95-110 parts by mass, the inorganic substance is 40-70 parts by mass, the cross-linking agent is 1.5-2.5 parts by mass, the oil-soluble quantum dot is 40-50 parts by mass, the nano-silica has a particle size of 30-100 nm, and the nano-titania has a particle size of 50-120 nm.
3. The quantum dot luminescent composite according to claim 1, wherein in the mixture of ABS resin and PLA resin, the ratio of ABS resin and PLA resin is (1-3): 1.
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| CN106848079B (en) * | 2017-02-20 | 2019-08-27 | 纳晶科技股份有限公司 | Shine-charge transmission compound, the ink containing it, preparation method and QLED device |
| US11173664B2 (en) * | 2017-04-24 | 2021-11-16 | The Boeing Company | Nanostructures for process monitoring and feedback control |
| WO2018213256A1 (en) * | 2017-05-15 | 2018-11-22 | Vanderbilt University | Method of three-dimensional printing using quantum dots |
| CN109265946A (en) * | 2018-09-28 | 2019-01-25 | 吕梁学院 | A kind of quantum dot light emitting compound and preparation method thereof for 3D printing |
| CN111196921A (en) * | 2018-11-20 | 2020-05-26 | 苏州星烁纳米科技有限公司 | Fluorescent nanomaterial-polymer complex, method for preparing wavelength conversion element, and light-emitting device |
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| CN111057538B (en) * | 2019-12-30 | 2021-06-01 | 广州工程技术职业学院 | Luminescent material containing rare earth europium complex and preparation method thereof |
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| CN105602546A (en) | 2016-05-25 |
| CN105602546B (en) | 2018-06-22 |
| CN108148571B (en) | 2020-09-29 |
| CN108148571A (en) | 2018-06-12 |
| CN108129811A (en) | 2018-06-08 |
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