CN102094253B - Preparation method of fluorescent submicron particle/complex multicolor fluorescent fibers - Google Patents
Preparation method of fluorescent submicron particle/complex multicolor fluorescent fibers Download PDFInfo
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- CN102094253B CN102094253B CN201010601991A CN201010601991A CN102094253B CN 102094253 B CN102094253 B CN 102094253B CN 201010601991 A CN201010601991 A CN 201010601991A CN 201010601991 A CN201010601991 A CN 201010601991A CN 102094253 B CN102094253 B CN 102094253B
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Abstract
The invention relates to a preparation method of multicolor fluorescent fibers, in particular to a preparation method of fluorescent submicron particle/complex multicolor fluorescent fibers. The preparation method comprises the following steps: preparing CdTe quantum dot suspension from ultrapure water, CdCl2.2.5H20, mercaptoacetic acid and a NaHTe aqueous solution; and then adding tetraethoxysilane, ethanol and ammonia water to prepare SiO2-coated CdTe quantum dot microspheres, mixing the microspheres with polyvinyl alcohol to obtain a spinning solution, and then spinning to obtain the fluorescent submicron particle/complex multicolor fluorescent fibers. The preparation method provided by the invention is simple and economic, and the obtained fluorescent submicron particle/complex multicolor fluorescent fibers have the characteristics of uniformly distributed CdTe quantum dots and no conglobation phenomenon; and the fluorescent fibers are uniform in emitted light colors and narrow in fluorescent color distribution under ultraviolet irradiation, and can emit blue, green, yellow, orange or red fluorescent light under the ultraviolet irradiation.
Description
Technical field
The present invention relates to a kind of preparation method of colorful fluorescent fiber.
Background technology
Along with progress of science and technology, new fluorescent fiber continues to bring out, and it has a wide range of applications in a plurality of fields such as photosensitive colour-changing material, fluorescence ornament materials, optical recording material, storage fiber optics, fiber optics, anti-false fiber, optical fiber.Quantum dot is owing to quantum-mechanical marvellous rule has significant dimensional effect; Basically the light that is higher than specific thresholding all can absorb; And an organic dye molecule only could be raised to higher excitation state from ground state behind the photon that absorbs appropriate energy, and used light must be accurate wavelength or color, and these are obviously different with the semiconductor bulk phase material; And quantum dot will absorb the photon that all are higher than its band-gap energy, but the optical wavelength of being launched (being color) has size-dependent again very much.So the nano semiconductor material of single kind just can produce an emission wavelength label family different, that color is clearly demarcated by change in size, this is that dye molecule can't be realized at all.Compare with traditional dye molecule, quantum dot has multiple advantage really.Inorganic crystallites can be born exciting and light emission repeatedly, and organic molecule can decompose. and lasting stability can let the researcher observe cell and tissue for more time, and has no to carry out the modifying interface connection difficultly.Measuring in the benefit of a maximum is that abundant color is arranged.The complexity of living things system often need be observed several kinds of components simultaneously; If dye with dye molecule; Then need the light of different wave length to excite, measure in point and then do not have this problem, use the nanocrystal of different sizes (and then different colors) to come the different biomolecule of mark.Use single light source just can make the different particles can be by immediately monitoring.The special optical property of quantum dot makes it in researchs such as biochemistry, molecular biology, cell biology, proteomics, drug screening, interaction of biomacromolecules, great application prospect arranged.
Based on above reason, make quantum dot in the preparation of fluorescent fiber, receive attention.But form spinning solution in the polymer solution owing to reasons such as skin effect make quantum dot be difficult to be dispersed in uniformly, be difficult for adopting electrostatic spinning technique to prepare fluorescent fiber.The CdS quantum dot is coated on water soluble (CO) polymers with generated in-situ way and processes fluorescent fiber at present.And owing to reasons such as quantum dot reunion have caused under UV-irradiation, fluorescence color wider distribution, and cancellation easily, the fluorescent fiber irregular colour that spinning obtains is even.
Summary of the invention
The objective of the invention is for the preparation method of the colorful fluorescent fiber of a kind of fluorescence submicron particle/compound is provided; Preparation method of the present invention is simple, economical; The CdTe quantum dot is evenly distributed the color homogeneous in the colorful fluorescent fiber of fluorescence submicron particle/compound that obtains.
The preparation method of the colorful fluorescent fiber of fluorescence submicron particle/compound of the present invention, it is realized through following steps: one, with 100mL ultra-pure water, 91.3mgCdCl
22.5H
2O and 0.0617mL TGA add in the three-necked bottle; Under stirring, in three-necked bottle, drip NaOH solution then, to the pH value be 11, add the 6mL mass concentration again and be 2% the NaHTe aqueous solution; Obtain reactant liquor; Under nitrogen, be heated to 100 ℃ then, backflow 10min, 1h, 2h, 3h or 4h get CdTe quantum dot suspension;
Two, in the CdTe quantum dot suspension that step 1 obtains, add 0.25mL ethyl orthosilicate, 20.55mL ethanol, 9mLH
2The concentration of O and 0.2mL is 28% (quality) ammoniacal liquor, and stirring reaction 3～5h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats;
Three, the SiO that step 2 is prepared
2The CdTe quantum dot microsphere that coats is dissolved in polyvinyl alcohol (PVA) aqueous solution, ultrasonic disperse spinning solution, SiO wherein
2The CdTe quantum dot microsphere that coats and the volume ratio 0.2～2: 1 of polyvinyl alcohol, the mass ratio of polyvinyl alcohol and water is 2: 5 in the polyvinyl alcohol water solution;
Four, the spinning solution that step 3 is prepared into obtains the colorful fluorescent fiber of fluorescence submicron particle/compound through spinning technique, promptly accomplishes the preparation method of the colorful fluorescent fiber of fluorescence submicron particle/compound.
The SiO that step 2 of the present invention prepares
2The particle size range of the CdTe quantum dot microsphere that coats is 50～150nm.
Can also obtain SiO through following steps in the step 2 of the present invention
2The CdTe quantum dot microsphere that coats: in the CdTe quantum dot suspension that step 1 obtains, add 3mL ethyl orthosilicate, 25mL ethanol, 0.5mL H
2The concentration of O and 1.5mL is 28% (quality) ammoniacal liquor, and stirring reaction 3～5h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats.The SiO that obtains
2The particle size range of the CdTe quantum dot microsphere that coats is 160～360nm.
Can also obtain SiO through following steps in the step 2 of the present invention
2The CdTe quantum dot microsphere that coats: in the CdTe quantum dot suspension that step 1 obtains, add 1.3mL ethyl orthosilicate, 22.7mL ethanol, 3mL H
2The concentration of O and 3mL is 28% (quality) ammoniacal liquor, and stirring reaction 3～5h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats.The SiO that obtains
2The particle size range of the CdTe quantum dot microsphere that coats is 1～2 μ m.
Adopt electrostatic spinning technique that the spinning solution spinning is obtained the colorful fluorescent fiber of fluorescence submicron particle/compound in the step 4 of the present invention; Wherein in the electrostatic spinning technique copper wire as anode; Aluminium foil is as negative electrode; Fixed negative pole and anode distance are 15～20cm, under 12～20kV voltage, carry out electrostatic spinning.
The present invention adopts SiO
2Cladding process is with SiO
2Be coated on CdTe quantum dot outside, be used for modifying CdTe quantum dot surface and have the dipolar interaction that can shield between fluorescence nano or the magnetic nano-particle, stop the CdTe quantum dot to reunite SiO
2The CdTe quantum dot microsphere that coats has good biocompatibility, advantages such as hydrophily and extraordinary stability and controllable size.The present invention is coated on SiO with the CdTe quantum dot
2In make nanocrystallinely, nanocrystalline after the coating has fine solubility in the water neutralized alcohol, have extraordinary chemical stability and stronger fluorescent characteristic.With its be dissolved among the PVA spinning solution, be spun into fiber through spining technology again, then obtain appearing the colorful fiber of corresponding quantum dot fluorescent characteristic.
Preparation method of the present invention is simple, economical, and the CdTe quantum dot is evenly distributed no agglomeration in the colorful fluorescent fiber of fluorescence submicron particle/compound that obtains; Fluorescent fiber glow color homogeneous, under UV-irradiation, the fluorescence color narrowly distributing; Under UV-irradiation, can send green grass or young crops, green, yellow, orange or red fluorescence.
Description of drawings
Fig. 1 be the CdTe quantum dot suspension that obtains in the step 1 of the specific embodiment one fluorescence spectrum figure, among the figure from left to right the corresponding respectively return time in peak be 10min, 1h, 2h, 3h and 4h; Fig. 2 is the SiO that the step 2 of the specific embodiment one obtains
2The CdTe quantum dot microsphere scanning electron microscopy shape appearance figure that coats; Fig. 3 is the SiO that the step 2 of the specific embodiment two obtains
2The CdTe quantum dot microsphere scanning electron microscopy shape appearance figure that coats; Fig. 4 is one of them SiO that the step 2 of the specific embodiment two obtains
2The transmission electron microscope photo of the CdTe quantum dot microsphere that coats; Fig. 5 is the SiO that the step 2 of the specific embodiment three obtains
2The CdTe quantum dot microsphere scanning electron microscopy shape appearance figure that coats; Fig. 6 is the transmission electron microscope photo of the colorful fluorescent fiber of fluorescence submicron particle/compound that obtains of the specific embodiment 12; Fig. 7 is the transmission electron microscope photo of the colorful fluorescent fiber of fluorescence submicron particle/compound that obtains of the specific embodiment 14.
The specific embodiment
Technical scheme of the present invention is not limited to the following cited specific embodiment, also comprises the combination in any between each specific embodiment.
The specific embodiment one: the preparation method of the colorful fluorescent fiber of this embodiment fluorescence submicron particle/compound, it is realized through following steps: one, with 100mL ultra-pure water, 91.3mgCdCl
22.5H
2O and 0.0617mL TGA add in the three-necked bottle; Under stirring, in three-necked bottle, drip NaOH solution then, to the pH value be 11, add the 6mL mass concentration again and be 2% the NaHTe aqueous solution; Obtain reactant liquor; Under nitrogen, be heated to 100 ℃ then, backflow 10min, 1h, 2h, 3h or 4h get CdTe quantum dot suspension;
Two, in the CdTe quantum dot suspension that step 1 obtains, add 0.25mL ethyl orthosilicate, 20.55mL ethanol, 9mLH
2The concentration of O and 0.2mL is 28% (quality) ammoniacal liquor, and stirring reaction 3～5h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats;
Three, the SiO that step 2 is prepared
2The CdTe quantum dot microsphere that coats is dissolved in polyvinyl alcohol (PVA) aqueous solution, ultrasonic disperse spinning solution, SiO wherein
2The CdTe quantum dot microsphere that coats and the volume ratio 0.2～2: 1 of polyvinyl alcohol, the mass ratio of polyvinyl alcohol and water is 2: 5 in the polyvinyl alcohol water solution;
Four, the spinning solution that step 3 is prepared into obtains the colorful fluorescent fiber of fluorescence submicron particle/compound through spinning technique, promptly accomplishes the preparation method of the colorful fluorescent fiber of fluorescence submicron particle/compound.
Reflux respectively in this embodiment step 1 five parts of CdTe quantum dot suspension that 10min, 1h, 2h, 3h and 4h obtain fluorescence spectrum figure as shown in Figure 1.Among the figure from left to right the corresponding respectively return time in peak be 10min, 1h, 2h, 3h and 4h, be followed successively by green grass or young crops, green, yellow, orange and red fluorescence.
The average diameter that this embodiment step 2 prepares is the SiO of 50～150nm
2The CdTe quantum dot microsphere that coats, its scanning electron microscopy shape appearance figure is as shown in Figure 2.
The preparation method of this embodiment is simple, economical, and the CdTe quantum dot is evenly distributed no agglomeration in the colorful fluorescent fiber of fluorescence submicron particle/compound that obtains; Fluorescent fiber glow color homogeneous, under UV-irradiation, the fluorescence color narrowly distributing.
The specific embodiment two: what this embodiment and the specific embodiment one were different is can also obtain SiO through following steps in the step 2
2The CdTe quantum dot microsphere that coats: in the CdTe quantum dot suspension that step 1 obtains, add 3mL ethyl orthosilicate, 25mL ethanol, 0.5mL H
2The concentration of O and 1.5mL is 28% (quality) ammoniacal liquor, and stirring reaction 3～5h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats.Other step and parameter are identical with the specific embodiment one.
The SiO that this embodiment step 2 obtains
2The particle size range of the CdTe quantum dot microsphere that coats is 160～360nm.
The SiO that this embodiment step 2 prepares
2The scanning electron microscopy shape appearance figure of the CdTe quantum dot microsphere that coats is as shown in Figure 3.One of them SiO
2The transmission electron microscope photo of the CdTe quantum dot microsphere that coats is as shown in Figure 4.
The specific embodiment three: what this embodiment and the specific embodiment one were different is can also obtain SiO through following steps in the step 2
2The CdTe quantum dot microsphere that coats: in the CdTe quantum dot suspension that step 1 obtains, add 1.3mL ethyl orthosilicate, 22.7mL ethanol, 3mL H
2The concentration of O and 3mL is 28% (quality) ammoniacal liquor, and stirring reaction 3～5h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats.Other step and parameter are identical with the specific embodiment one.
The SiO that this embodiment step 2 obtains
2The particle size range of the CdTe quantum dot microsphere that coats is 1～2 μ m.
This embodiment step 2 prepare SiO
2The scanning electron microscopy shape appearance figure of the CdTe quantum dot microsphere that coats is as shown in Figure 5.
The specific embodiment four: present embodiment and the specific embodiment one, two or three are different is that mass concentration is that the preparation method of 2% the NaHTe aqueous solution is: 4 ℃ of deionized waters that in round-bottomed flask, add 0.36g sodium borohydride powder, 0.51g tellurium powder and 6mL in the step 1; Stir reaction system; Place ice bath then; Reaction 10h gets final product; Wherein reaction system is passed through a little pin hole and atmosphere in the course of reaction.Other step and parameter are identical with the specific embodiment one, two or three.
In course of reaction, the Te powder of black dissolves gradually in this embodiment, forms the water white NaHTe aqueous solution.
The specific embodiment five: this embodiment is different with one of specific embodiment one to four is that the concrete operations of the centrifugal sedimentation described in the step 2 are: discard supernatant liquor after the centrifugal sedimentation; Clean lower floor's microballoon with ultra-pure water then; Centrifugal sedimentation is again cleaned lower floor's microballoon with ultra-pure water and is got final product.Other step and parameter are identical with one of specific embodiment one to four.
Ultra-pure water is in this embodiment: both the conducting medium in the water was almost completely removed, and again the colloidal substance that does not dissociate in the water, gas and organic matter all were removed to the very water of low degree.Resistivity is greater than 18M Ω * cm, or near 18.3M Ω * cm limiting value.
The specific embodiment six: that this embodiment is different with one of specific embodiment one to five is SiO in the step 3
2The CdTe quantum dot microsphere that coats and the volume ratio 0.5～1.5: 1 of polyvinyl alcohol.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment seven: that this embodiment is different with one of specific embodiment one to five is SiO in the step 3
2The CdTe quantum dot microsphere that coats and the volume ratio of polyvinyl alcohol 1: 1.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment eight: what this embodiment was different with one of specific embodiment one to seven is that spinning technique described in the step 4 is fiber elongation method, rotary spinning or electrostatic spinning.Other step and parameter are identical with one of specific embodiment one to seven.
The specific embodiment nine: what this embodiment was different with one of specific embodiment one to seven is that spinning technique described in the step 4 is an electrostatic spinning technique; Wherein in the electrostatic spinning technique copper wire as anode; Aluminium foil is as negative electrode; Fixed negative pole and anode distance are 15～20cm, under 12～20kV voltage, carry out electrostatic spinning.Other step and parameter are identical with one of specific embodiment one to seven.
The specific embodiment ten: the preparation method of the colorful fluorescent fiber of this embodiment fluorescence submicron particle/compound, it is realized through following steps: one, with 100mL ultra-pure water, 91.3mgCdCl
22.5H
2O and 0.0617mL TGA add in the three-necked bottle; Under stirring, in three-necked bottle, drip NaOH solution then, to the pH value be 11, add the 6mL mass concentration again and be 2% the NaHTe aqueous solution; Obtain reactant liquor; Under nitrogen, be heated to 100 ℃ then, backflow 10min gets CdTe quantum dot suspension;
Two, in the CdTe quantum dot suspension that step 1 obtains, add 0.25mL ethyl orthosilicate, 20.55mL ethanol, 9mLH
2The concentration of O and 0.2mL is 28% (quality) ammoniacal liquor, and stirring reaction 4h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats;
Three, the SiO that step 2 is prepared
2The CdTe quantum dot microsphere that coats is dissolved in polyvinyl alcohol (PVA) aqueous solution, ultrasonic disperse spinning solution, SiO wherein
2The CdTe quantum dot microsphere that coats and the volume ratio of polyvinyl alcohol 0.2: 1, the mass ratio of polyvinyl alcohol and water is 2: 5 in the polyvinyl alcohol water solution;
Four, the spinning solution that step 3 is prepared into obtains the colorful fluorescent fiber of fluorescence submicron particle/compound through electrostatic spinning process; Wherein in the electrostatic spinning technique copper wire as anode; Aluminium foil is as negative electrode; Fixed negative pole and anode distance are 15cm, under 12kV voltage, carry out electrostatic spinning, promptly accomplish the preparation method of the colorful fluorescent fiber of fluorescence submicron particle/compound.
The concrete operations of the centrifugal sedimentation described in this embodiment step 2 are: discard supernatant liquor after the centrifugal sedimentation, clean lower floor's microballoon with ultra-pure water then, centrifugal sedimentation is again cleaned lower floor's microballoon with ultra-pure water and is got final product.The SiO that this embodiment step 2 prepares
2The average grain diameter of the CdTe quantum dot microsphere that coats is 80nm.
The colorful fluorescent fiber of fluorescence submicron particle/compound that this embodiment electrostatic spinning obtains issues the fluorescence of cyan, color homogeneous at the UV-irradiation of 365nm.
The specific embodiment 11: that this embodiment and the specific embodiment ten are different is the 2h that refluxes in the step 1.Other step and parameter are identical with the specific embodiment ten.
The SiO that this embodiment step 2 prepares
2The average grain diameter of the CdTe quantum dot microsphere that coats is 80nm.
The fluorescence of the colorful fluorescent fiber of fluorescence submicron particle/compound yellow under the UV-irradiation of 365nm that this embodiment electrostatic spinning obtains, the color homogeneous.
The specific embodiment 12: the preparation method of the colorful fluorescent fiber of this embodiment fluorescence submicron particle/compound, it is realized through following steps: one, with 100mL ultra-pure water, 91.3mgCdCl
22.5H
2O and 0.0617mL TGA add in the three-necked bottle; Under stirring, in three-necked bottle, drip NaOH solution then, to the pH value be 11, add the 6mL mass concentration again and be 2% the NaHTe aqueous solution; Obtain reactant liquor; Under nitrogen, be heated to 100 ℃ then, backflow 1h gets CdTe quantum dot suspension;
Two, in the CdTe quantum dot suspension that step 1 obtains, add 3mL ethyl orthosilicate, 25mL ethanol, 0.5mL H
2The concentration of O and 1.5mL is 28% (quality) ammoniacal liquor, stirring reaction 3～5h, and stirring reaction 4h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats;
Three, the SiO that step 2 is prepared
2The CdTe quantum dot microsphere that coats is dissolved in polyvinyl alcohol (PVA) aqueous solution, ultrasonic disperse spinning solution, SiO wherein
2The CdTe quantum dot microsphere that coats and the volume ratio of polyvinyl alcohol 0.2: 1, the mass ratio of polyvinyl alcohol and water is 2: 5 in the polyvinyl alcohol water solution;
Four, the spinning solution that step 3 is prepared into obtains the colorful fluorescent fiber of fluorescence submicron particle/compound through electrostatic spinning process; Wherein in the electrostatic spinning technique copper wire as anode; Aluminium foil is as negative electrode; Fixed negative pole and anode distance are 15cm, under 12kV voltage, carry out electrostatic spinning, promptly accomplish the preparation method of the colorful fluorescent fiber of fluorescence submicron particle/compound.
The concrete operations of the centrifugal sedimentation described in this embodiment step 2 are: discard supernatant liquor after the centrifugal sedimentation, clean lower floor's microballoon with ultra-pure water then, centrifugal sedimentation is again cleaned lower floor's microballoon with ultra-pure water and is got final product.
The SiO that this embodiment step 2 prepares
2The average grain diameter of the CdTe quantum dot microsphere that coats is 320nm.
The fluorescence of the colorful fluorescent fiber of fluorescence submicron particle/compound green-emitting under the UV-irradiation of 365nm that this embodiment electrostatic spinning obtains, the color homogeneous.
The transmission electron microscope photo of the colorful fluorescent fiber of fluorescence submicron particle/compound that this embodiment electrostatic spinning obtains is as shown in Figure 6.Can know SiO by Fig. 6
2The CdTe quantum dot microsphere that coats is evenly distributed no agglomeration in colorful fluorescent fiber.
The specific embodiment 13: that this embodiment and the specific embodiment 12 are different is the 3h that refluxes in the step 1.Other step and parameter are identical with the specific embodiment 12.
The SiO that this embodiment step 2 prepares
2The average grain diameter of the CdTe quantum dot microsphere that coats is 320m.
The colorful fluorescent fiber of fluorescence submicron particle/compound that this embodiment electrostatic spinning obtains issues orange fluorescence at the UV-irradiation of 365nm, the color homogeneous.
The specific embodiment 14: that this embodiment and the specific embodiment 12 are different is SiO in the step 3
2The CdTe quantum dot microsphere that coats and the volume ratio of polyvinyl alcohol 2: 1.Other step and parameter are identical with the specific embodiment 12.
The SiO that this embodiment step 2 prepares
2The average grain diameter of the CdTe quantum dot microsphere that coats is 320nm.
The fluorescence of the colorful fluorescent fiber of fluorescence submicron particle/compound green-emitting under the UV-irradiation of 365nm that this embodiment electrostatic spinning obtains, the color homogeneous.
The transmission electron microscope photo of the colorful fluorescent fiber of fluorescence submicron particle/compound that this embodiment electrostatic spinning obtains is as shown in Figure 7.Can know SiO by Fig. 7
2The CdTe quantum dot microsphere that coats is evenly distributed no agglomeration in colorful fluorescent fiber.
The specific embodiment 15: the preparation method of the colorful fluorescent fiber of this embodiment fluorescence submicron particle/compound, it is realized through following steps: one, with 100mL ultra-pure water, 91.3mgCdCl
22.5H
2O and 0.0617mL TGA add in the three-necked bottle; Under stirring, in three-necked bottle, drip NaOH solution then, to the pH value be 11, add the 6mL mass concentration again and be 2% the NaHTe aqueous solution; Obtain reactant liquor; Under nitrogen, be heated to 100 ℃ then, backflow 1h gets CdTe quantum dot suspension;
Two, in the CdTe quantum dot suspension that step 1 obtains, add 1.3mL ethyl orthosilicate, 22.7mL ethanol, 3mLH
2The concentration of O and 3mL is 28% (quality) ammoniacal liquor, stirring reaction 3～5h, and stirring reaction 4h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats;
Three, the SiO that step 2 is prepared
2The CdTe quantum dot microsphere that coats is dissolved in polyvinyl alcohol (PVA) aqueous solution, ultrasonic disperse spinning solution, SiO wherein
2The CdTe quantum dot microsphere that coats and the volume ratio of polyvinyl alcohol 0.2: 1, the mass ratio of polyvinyl alcohol and water is 2: 5 in the polyvinyl alcohol water solution;
Four, the spinning solution that step 3 is prepared into obtains the colorful fluorescent fiber of fluorescence submicron particle/compound through electrostatic spinning process; Wherein in the electrostatic spinning technique copper wire as anode; Aluminium foil is as negative electrode; Fixed negative pole and anode distance are 15cm, under 12kV voltage, carry out electrostatic spinning, promptly accomplish the preparation method of the colorful fluorescent fiber of fluorescence submicron particle/compound.
The concrete operations of the centrifugal sedimentation described in this embodiment step 2 are: discard supernatant liquor after the centrifugal sedimentation, clean lower floor's microballoon with ultra-pure water then, centrifugal sedimentation is again cleaned lower floor's microballoon with ultra-pure water and is got final product.
The SiO that this embodiment step 2 prepares
2The average grain diameter of the CdTe quantum dot microsphere that coats is 1.2 μ m.
The fluorescence of the colorful fluorescent fiber of fluorescence submicron particle/compound green-emitting under the UV-irradiation of 365nm that this embodiment electrostatic spinning obtains, the color homogeneous.
Claims (9)
1. the preparation method of the colorful fluorescent fiber of fluorescence submicron particle/compound is characterized in that the preparation method of the colorful fluorescent fiber of fluorescence submicron particle/compound realizes through following steps: one, with 100mL ultra-pure water, 91.3mgCdCl
22.5H
2O and 0.0617mL TGA add in the three-necked bottle; Under stirring, in three-necked bottle, drip NaOH solution then, to the pH value be 11, add the 6mL mass concentration again and be 2% the NaHTe aqueous solution; Obtain reactant liquor; Under nitrogen, be heated to 100 ℃ then, backflow 10min, 1h, 2h, 3h or 4h get CdTe quantum dot suspension;
Two, in the CdTe quantum dot suspension that step 1 obtains, add 0.25mL ethyl orthosilicate, 20.55mL ethanol, 9mLH
2The mass percent concentration of O and 0.2mL is 28% ammoniacal liquor, and stirring reaction 3～5h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats;
Three, the SiO that step 2 is prepared
2The CdTe quantum dot microsphere that coats is dissolved in the polyvinyl alcohol water solution, ultrasonic disperse spinning solution, SiO wherein
2The CdTe quantum dot microsphere that coats and the volume ratio 0.2～2: 1 of polyvinyl alcohol, the mass ratio of polyvinyl alcohol and water is 2: 5 in the polyvinyl alcohol water solution;
Four, the spinning solution that step 3 is prepared into obtains the colorful fluorescent fiber of fluorescence submicron particle/compound through spinning technique, promptly accomplishes the preparation method of the colorful fluorescent fiber of fluorescence submicron particle/compound.
2. the preparation method of the colorful fluorescent fiber of a kind of fluorescence submicron particle/compound according to claim 1 is characterized in that the SiO of step 2
2The preparation process of the CdTe quantum dot microsphere that coats is replaced with following step: in the CdTe quantum dot suspension that step 1 obtains, add 3mL ethyl orthosilicate, 25mL ethanol, 0.5mL H
2The mass percent concentration of O and 1.5mL is 28% ammoniacal liquor, and stirring reaction 3～5h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats.
3. the preparation method of the colorful fluorescent fiber of a kind of fluorescence submicron particle/compound according to claim 1 is characterized in that the SiO of step 2
2The preparation process of the CdTe quantum dot microsphere that coats is replaced with following step: in the CdTe quantum dot suspension that step 1 obtains, add 1.3mL ethyl orthosilicate, 22.7mL ethanol, 3mL H
2The mass percent concentration of O and 3mL is 28% ammoniacal liquor, and stirring reaction 3～5h obtains SiO
2The CdTe quantum dot microsphere suspension that coats, centrifugal sedimentation gets SiO then
2The CdTe quantum dot microsphere that coats.
4. according to the preparation method of claim 1, the colorful fluorescent fiber of 2 or 3 described a kind of fluorescence submicron particle/compounds; It is characterized in that mass concentration in the step 1 is that the preparation method of 2% the NaHTe aqueous solution is: 4 ℃ of deionized waters that in round-bottomed flask, add 0.36g sodium borohydride powder, 0.51g tellurium powder and 6mL; Stir reaction system; Place ice bath then, reaction 10h gets final product; Wherein reaction system is passed through a little pin hole and atmosphere in the course of reaction.
5. according to the preparation method of claim 1, the colorful fluorescent fiber of 2 or 3 described a kind of fluorescence submicron particle/compounds; The concrete operations that it is characterized in that the centrifugal sedimentation described in the step 2 are: discard supernatant liquor after the centrifugal sedimentation; Clean lower floor's microballoon with ultra-pure water then; Centrifugal sedimentation is again cleaned lower floor's microballoon with ultra-pure water and is got final product.
6. according to the preparation method of claim 1, the colorful fluorescent fiber of 2 or 3 described a kind of fluorescence submicron particle/compounds, it is characterized in that SiO in the step 3
2The CdTe quantum dot microsphere that coats and the volume ratio 0.5～1.5: 1 of polyvinyl alcohol.
7. according to the preparation method of claim 1, the colorful fluorescent fiber of 2 or 3 described a kind of fluorescence submicron particle/compounds, it is characterized in that SiO in the step 3
2The CdTe quantum dot microsphere that coats and the volume ratio of polyvinyl alcohol 1: 1.
8. according to the preparation method of claim 1, the colorful fluorescent fiber of 2 or 3 described a kind of fluorescence submicron particle/compounds, it is characterized in that spinning technique described in the step 4 is rotary spinning or electrostatic spinning.
9. according to the preparation method of claim 1, the colorful fluorescent fiber of 2 or 3 described a kind of fluorescence submicron particle/compounds; It is characterized in that spinning technique described in the step 4 is an electrostatic spinning technique; Wherein in the electrostatic spinning technique copper wire as anode; Aluminium foil is as negative electrode, and fixed negative pole and anode distance are 15～20cm, under 12～20kV voltage, carry out electrostatic spinning.
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