CN112980078B - Up-conversion luminescent polyethylene composite resin and preparation method and application thereof - Google Patents

Up-conversion luminescent polyethylene composite resin and preparation method and application thereof Download PDF

Info

Publication number
CN112980078B
CN112980078B CN202110200287.2A CN202110200287A CN112980078B CN 112980078 B CN112980078 B CN 112980078B CN 202110200287 A CN202110200287 A CN 202110200287A CN 112980078 B CN112980078 B CN 112980078B
Authority
CN
China
Prior art keywords
composite resin
conversion
noble metal
particles
polyethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110200287.2A
Other languages
Chinese (zh)
Other versions
CN112980078A (en
Inventor
熊宇杰
王瑶
龙冉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN202110200287.2A priority Critical patent/CN112980078B/en
Publication of CN112980078A publication Critical patent/CN112980078A/en
Application granted granted Critical
Publication of CN112980078B publication Critical patent/CN112980078B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0831—Gold
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Abstract

An up-conversion luminescence polyethylene composite resin and a preparation method and application thereof, wherein the preparation method of the up-conversion luminescence polyethylene composite resin comprises the steps of adding a ligand connecting agent, a noble metal source and a reducing agent into an up-conversion luminescence particle dispersion liquid, and carrying out in-situ reduction reaction to obtain up-conversion luminescence particles with noble metal loaded on the surfaces; mixing up-conversion luminescent particles with noble metal loaded on the surface with polyethylene powder, and then carrying out hot melting and compression to obtain the up-conversion luminescent polyethylene composite resin. The method has the advantages of simple operation, short period, small processing difficulty, easy regulation and control and the like, has low process requirement and high success rate, and has great advantages in future large-scale and industrialization; the upconversion luminous polyethylene composite resin obtained by the invention has potential value in the aspect of successfully expanding the near-infrared light region solid application material.

Description

Up-conversion luminescent polyethylene composite resin and preparation method and application thereof
Technical Field
The invention relates to the field of composite materials, in particular to an up-conversion luminescent polyethylene composite resin and a preparation method and application thereof.
Background
The upconversion luminescence is anti-stokes luminescence, can convert long-wavelength near infrared light into short-wavelength visible light by absorbing one or more photons, and has great application potential in the fields of biological imaging, therapeutics, photonics, sunlight and the like. The upconversion luminescent material follows a typical energy transfer upconversion luminescent principle and comprises three parts: the light absorbing center is excited; energy transfer to the luminescent center; the luminescence center is excited and transits and emits light in returning to the ground state. Due to the principle of reverse luminescence, the luminescence efficiency of the upconversion luminescent material is difficult to break through, so that an efficient upconversion luminescent material is particularly difficult to obtain. On one hand, the nanocrystal with stable structure can be synthesized by a pyrolysis method so as to reduce energy loss in the luminescence process and increase the efficiency of energy transfer so as to improve the luminescence performance; on the other hand, the thermal magnetic field generated by noble metals (such as gold, silver, etc.) with special plasma resonance properties at corresponding wavelengths can further stimulate the enhancement of the upconversion luminous efficiency. The high-efficiency up-conversion luminescent materials can effectively utilize a near-infrared light source, and further improve the comprehensive utilization rate of light.
Meanwhile, the resinification can increase the stability of the up-conversion material, is easier to process and is more suitable for more application scenes, but no method can form stable, light-transmitting, high-efficiency light-emitting and homogeneously-dispersed up-conversion composite resin at present, so that the practical application process is limited. Considering that polyethylene is one of the most common industrial resin materials, and has the advantages of low cost, easy acquisition, simple addition method, wide application, etc., there is a great need in the art for a new method for realizing a polyethylene composite resin in which highly efficient upconversion luminescent particles are homogeneously dispersed in a simple manner.
Disclosure of Invention
In view of the above, one of the main objects of the present invention is to provide an upconversion luminescent polyethylene composite resin, a preparation method and applications thereof, which are intended to at least partially solve at least one of the above technical problems.
In order to achieve the above object, as one aspect of the present invention, there is provided a method for preparing an upconversion luminescent polyethylene composite resin, comprising:
(1) adding a ligand connecting agent, a noble metal source and a reducing agent into the upconversion luminescent particle dispersion liquid, and carrying out in-situ reduction reaction to obtain upconversion luminescent particles with noble metal loaded on the surfaces;
(2) mixing up-conversion luminescent particles with noble metal loaded on the surface with polyethylene powder, and then carrying out hot melting and compression to obtain the up-conversion luminescent polyethylene composite resin.
As another aspect of the present invention, there is also provided an upconversion luminescent polyethylene composite resin obtained by the preparation method as described above.
As a further aspect of the present invention, there is also provided a use of the upconversion luminescent polyethylene composite resin as described above in the field of solid materials in the near infrared region.
Based on the technical scheme, compared with the prior art, the up-conversion luminescent polyethylene composite resin and the preparation method and application thereof have at least one or part of the following advantages:
1. the method of the invention firstly disperses the high-efficiency up-conversion luminescent particles into the polyethylene resin, the polyethylene is one of the most widely applied industrial resins, is often used for cable pipes, agricultural films, packaging films and the like, but is firstly compounded with the up-conversion luminescent material, and the success of the method of the invention provides possibility for expanding the new application direction of the polyethylene material;
2. the method has the advantages of simple operation, short period, small processing difficulty, easy regulation and control and the like, has low process requirement and high success rate, and has great advantages in future large-scale and industrialization;
3. the upconversion luminous polyethylene composite resin successfully reserves the original characteristics of the polyethylene resin, such as the advantages of stable structure, light transmission, easy processing and the like, and lays a foundation for subsequent reprocessing and application;
4. the up-conversion luminescence polyethylene composite resin obtained by the invention successfully shows strong up-conversion luminescence characteristics, and the result shows that the polyethylene resinification of the up-conversion material does not change the luminescence property of the up-conversion material, and stable up-conversion luminescence can still be obtained after the up-conversion material is successfully prepared by observation, namely invisible near-infrared laser is effectively converted into visible light, so that the up-conversion luminescence polyethylene composite resin has potential value in the aspect of expanding solid application materials in a near-infrared region.
5. The upconversion luminous polyethylene composite resin has the characteristic of multiple color changes, on one hand, the color of the resin changes, the pure polyethylene resin is semitransparent initially, the semitransparent color can be changed into light white or white along with the doping of upconversion luminous particles, and the semitransparent color, the light pink color, the pink color and the red color can be synchronously changed due to the doping of the noble metal particles; on the other hand, the up-conversion luminescence color is changed, the up-conversion luminescence color (such as red, yellow, green, blue and the like) can be changed by changing the doped rare earth ions, and the micro change of the luminescence color can be finely regulated and controlled by doping the noble metal; these multiple color changes can be more selective in practical applications and more compound to consumer needs.
Drawings
FIG. 1 is a graph of luminescence spectra of noble metal-controlled high efficiency upconversion luminescent particles obtained in examples of the present invention;
FIG. 2 is a diagram showing an absorption spectrum of gold nanoparticles obtained in example of the present invention;
FIG. 3 is a diagram of a part of polyethylene composite resin obtained in the example of the present invention.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
Through intensive and extensive research by the inventor of the invention, a novel method for preparing the polyethylene composite resin with the uniformly dispersed high-efficiency up-conversion luminescent particles is unexpectedly found, the method is simple and easy to operate, the prepared composite resin has stable property and strong up-conversion luminescent intensity, is uniformly dispersed, has no obvious granular sensation, shows different colors of luminescence under near-infrared excitation light, has the color change from light white to deep red, and has wide processing and application values.
The invention discloses a preparation method of up-conversion luminescent polyethylene composite resin, which comprises the following steps:
(1) adding a ligand connecting agent, a noble metal source and a reducing agent into the upconversion luminescent particle dispersion liquid, and carrying out in-situ reduction reaction to obtain upconversion luminescent particles with noble metal loaded on the surfaces;
(2) mixing up-conversion luminescent particles with noble metal loaded on the surface with polyethylene powder, and then carrying out hot melting and compression to obtain the up-conversion luminescent polyethylene composite resin.
In some embodiments of the present invention, in step (1), the mass ratio of the upconverting luminescent particles to the noble metal source is (126 to 1269): 1, and may be, for example, 211: 1, 215: 1, 220: 1, 230: 1, 250: 1, 280: 1, 300: 1, 400: 1, 500: 1, 600: 1, 700: 1, 800: 1, 900: 1, 1000: 1, 1100: 1, 1200: 1, 1269: 1;
in some embodiments of the present invention, in step (1), the mass ratio of the upconversion luminescent particles to the ligand binding agent is (0.01 to 0.18) to 1, and may be, for example, 0.01: 1, 0.02: 1, 0.05: 1, 0.08: 1, 0.1: 1, 0.12: 1, 0.15: 1, 0.16: 1, 0.18: 1;
in some embodiments of the present invention, in step (1), the mass ratio of the upconversion luminescent particles to the reducing agent is (1 to 3) to 1, for example, may be 1: 1, 2: 1, or 3: 1.
In some embodiments of the invention, in step (1), the noble metal source comprises any one or combination of gold, silver, and indium sources;
in some embodiments of the invention, the gold source comprises any one or combination of chloroauric acid, gold acetate, gold nitrate.
In some embodiments of the invention, in step (1), the ligand linker comprises any one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, cetyltrimethylammonium bromide, dodecyltrimethylammonium chloride;
in some embodiments of the present invention, in step (1), the reducing agent comprises any one or more of ascorbic acid, citric acid, sodium citrate, glucose, sodium borohydride, potassium borohydride;
in some embodiments of the present invention, in step (1), the reaction time of the in-situ reduction reaction is 20 to 40min, for example, 20min, 25min, 30min, 35min, 40 min.
In some embodiments of the invention, in step (1), the upconversion luminescent particles are NaLnF doped with rare earth ions4Particles; wherein the rare earth ions Ln include Y3+、Gd3+、Nd3+、Yb3+、Er3+、Tm3+、Ho3+Any one or a combination of more than one of;
in some embodiments of the present invention, in step (1), the emission color of the upconversion luminescent particles under 980nm or 808nm laser light is any one or more combination of blue, green and red.
In some embodiments of the present invention, in the step (2), the mass ratio of the polyethylene powder to the upconversion luminescent particles with noble metal supported on the surface is (20 to 50): 1, for example, 20: 1, 25: 1, 30: 1, 35: 1, 40: 1, 45: 1, 50: 1.
In some embodiments of the present invention, in step (2), the hot melt temperature is (120 to 150) ° c, and may be, for example, 120 ℃, 130 ℃, 140 ℃, 150 ℃; the hot melting time is (1 to 3) min, for example, 1min, 2min, 3 min;
in some embodiments of the invention, in step (2), the pressure at the time of the compression is (1 to 7) MPa, and for example, may be 1MPa, 2MPa, 3MPa, 5MPa, 7 MPa; the compression time is (8 to 15) min, and may be, for example, 8min, 9min, 10min, 12min, or 15 min.
In some embodiments of the invention, in step (2), the bubble removal operation is performed after the heat-melting step and before the compression step.
The invention also discloses the up-conversion luminescence polyethylene composite resin which is obtained by adopting the preparation method.
The invention also discloses application of the upconversion luminous polyethylene composite resin in the field of near-infrared light region solid materials.
In one exemplary embodiment, the present invention discloses a method for preparing a polyethylene composite resin in which high efficiency upconversion luminescent particles are homogeneously dispersed, the method comprising: and fully grinding and mixing the high-efficiency upconversion luminescent particles and polyethylene powder, and then obtaining the homogeneous upconversion polyethylene composite resin by a hot-plastic method.
Specifically, the method for efficiently up-converting the polyethylene composite resin with uniformly dispersed luminescent particles comprises the following steps:
first, NaLnF is prepared4Upconversion luminescent particles:
in a reactor, 0.5-1.5 mmoL of rare earth ion trifluoroacetate (Ln (CF) is proportionally added3COO)3) Adding sodium trifluoroacetate into 4-8 mL of oleic acid, heating, stirring and dissolving, adding 1-14 mL of octadecene as an organic solvent, vacuumizing, heating to 280-330 ℃, reacting for 40-90 min, finally washing residual organic matters on the surface of a sample by using a mixed solvent of cyclohexane and ethanol in a volume ratio of (1-1.5) to 1, and centrifugally collecting the final NaLnF4Up-conversion of the luminescent product.
Secondly, preparing the NaLnF regulated by the noble metal4Upconversion luminescent particles:
dispersing 25mg of up-conversion luminescent particles into an aqueous solution, adding 1-4 mL of 2.4mM polyvinylpyrrolidone as a ligand connecting agent, adding 10-100 uL of 10mM chloroauric acid trihydrate as a gold source, stirring at room temperature for 10-20 min to enable the three to be in full contact, finally adding 0.45-1.35 mL of 100mM ascorbic acid with dilute concentration as a reducing agent, slowly reducing the gold particles, and directly loading the gold nanoparticles on the surfaces of the up-conversion luminescent particles after reacting for 20-40 min.
Subsequently, a homogeneously dispersed upconverted polyethylene composite resin was prepared:
fully mixing polyethylene powder and the high-efficiency upconversion luminescent particles according to a certain mass ratio, pouring the mixed powder into a mold, thermally melting for 1-3 min, preferably for 2min, repeatedly vacuumizing and deflating for a plurality of times, finally compressing for 8-15 min, preferably for 10min under high pressure, and cooling to obtain the polyethylene composite resin with the homogeneous dispersion of the high-efficiency upconversion luminescent particles regulated and controlled by the noble metal.
In a preferred embodiment, the efficient upconversion luminescent particles are doped rare earth ions (Ln) Y in hexagonal phase3+、Gd3+、Nd3+、Yb3+、Er3+、Tm3+、Ho3+Etc. of one or more of NaLnF4The particles also comprise NaLnF regulated by the load of noble metal4And (3) granules.
In a preferred embodiment, the up-conversion luminescent particles show one or more of blue, green and red luminescent colors under 980nm or 808nm laser, and the luminescent colors are influenced by the doped rare earth ion species on one hand and are also regulated and controlled by the loading of the noble metal on the other hand. The noble metal particle load can regulate and control the color of up-conversion luminescence, including but not limited to when the light absorption characteristic peak of the gold nanoparticles with the wavelength of 4-20nm is about 540nm (green light), the luminescence proportion of a green light region in the up-conversion luminescence result is finally continuously reduced along with the increase of the mass of the gold nanoparticles due to absorption, and the visual luminescence color can be changed into yellow or even red.
In a preferred embodiment, the noble metal particles loaded on the surface of the upconversion luminescent particles can be one or more of gold, silver, platinum, copper and the like with a plasmon resonance effect, but from the viewpoint of the strength of the plasmon resonance effect, gold nanoparticles with a size of 4-20nm are preferred. The metal load with the plasma resonance effect can regulate and control the luminescence performance of the up-conversion particles, on one hand, the up-conversion luminescence efficiency can be enhanced within an effective distance by a thermal magnetic field generated by the plasma resonance effect, and on the other hand, the color of up-conversion luminescence can be changed by specific light absorption corresponding to the plasma resonance effect.
In a preferred embodiment, the ligand linker may be a polyvinylpyrrolidone concentration, the molecular weight of which includes, but is not limited to, 55000.
In a preferred embodiment, the mass ratio of the upconversion luminescent particles to the gold nanoparticles can be controlled by the feeding amount of chloroauric acid trihydrate, and can be, but is not limited to, 10-100 uL 10mM chloroauric acid trihydrate addition amount per 25mg upconversion luminescent particles.
In a preferred embodiment, after the reduction reaction is complete, the noble metal-mediated high efficiency upconversion luminescence product can be isolated by conventional means, such as, but not limited to, using high speed centrifugation (8000rpm/min) to obtain a product precipitate.
In a preferred embodiment, the size of the gold nanoparticles after the reduction reaction is complete can be determined by conventional means, such as, but not limited to, using transmission electron microscopy.
In a preferred embodiment, the size of the obtained gold nanoparticles may be 4 to 20 nm.
In a preferred embodiment, the change in upconversion luminescence intensity after the reduction reaction is complete can be determined by conventional means, such as, but not limited to, using a steady-state-transient fluorescence spectrometer.
In a preferred embodiment, the mass ratio of the upconversion luminescent particles to the gold particles is not particularly limited, but considering that the plasmon resonance of the gold nanoparticles has a limit value in the ability to promote luminescence, the mass ratio may be (1269-126): 1, and the upconversion luminescence intensity is first increased and then decreased as the mass of the gold nanoparticles increases, and may preferably be 634: 1 according to the luminescence enhancement amplitude, and at this mass ratio, the luminescence intensity is further enhanced to 2.76 times.
In a preferred embodiment, the mass ratio of the polyethylene powder to the high efficiency upconversion luminescent particles regulated by the noble metal is not particularly limited, but the less the polyethylene powder, the less the light transmittance of the formed composite resin, and preferably, the mass ratio may be (20 to 50): 1.
In a preferred embodiment, the intensive mixing of the polyethylene powder with the high efficiency upconversion luminescent particles regulated with noble metals is an important step to ensure homogeneous dispersion, preferably, the objective of homogeneous mixing can be achieved by intensive grinding.
In a preferred embodiment, the processing temperature in the thermoplastic process is slightly higher than the melting point of polyethylene (110 ℃), but too high a temperature not only causes higher processing difficulty, but also affects the stability of the nanoparticles, so that a reasonable processing temperature can be, but is not limited to, 120-150 ℃, preferably 140 ℃.
In a preferred embodiment, in order to increase the uniformity of the dispersion of the highly efficient upconversion luminescent particles in the thermoplastic process, it is necessary to rapidly and repeatedly perform vacuum and degassing processes at the processing temperature to remove bubbles and prevent the particles from agglomerating, and the number thereof is not particularly limited, but the number may be optimally, but not limited to, four times from the viewpoint of removing bubbles as much as possible and simplifying experimental conditions.
In a preferred embodiment, the pressure at the time of hot melt compression may be, but is not limited to, 1 to 7 MPa.
In a preferred embodiment, after hot melt compression is complete, the temperature can be reduced by conventional means, such as, but not limited to, natural cooling and ice-cooling.
In a preferred embodiment, the composite resin has the advantages of stable property, reusability, easy processing and the like of polyethylene resin, and simultaneously has the characteristic of high-efficiency up-conversion luminescence.
In a preferred embodiment, the high efficiency upconversion luminescent particles are homogeneously distributed in the composite resin without significant particulate feel.
In a preferred embodiment, the color of the composite resin varies with the added upconversion luminescent particles, and may be, but is not limited to, translucent, pale white, pink, red, and the like.
In a preferred embodiment, the shape of the composite resin is limited to a mold, and may be, but is not limited to, a film, a sheet and a block, which has a wide industrial prospect.
The present invention is further described with reference to the following embodiments, which are only some preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Unless otherwise specified, all starting materials used in the present invention are not particularly limited in their source and are commercially available; meanwhile, the purity is not particularly limited, and analytical purification is preferably employed in the present invention.
The reaction or detection apparatus or device used in the present invention is not particularly limited as long as the object can be achieved, and any conventional apparatus or device known to those skilled in the art can be used.
Example 1
In a reactor, 1mmoL of rare earth ion trifluoroacetate (0.78mmoL Gd (CF) is proportioned3COO)3，0.2mmoL Yb(CF3COO)3，0.02mmoL Er(CF3COO)3) Adding sodium trifluoroacetate into 6.4mL of oleic acid, heating, stirring and dissolving, adding 12.8mL of octadecene as an organic solvent, vacuumizing for 20min, heating to 300 ℃, reacting for 1h, finally washing off residual organic matters on the surface of a sample by using a mixed solvent of cyclohexane and ethanol in a volume ratio of 1: 1, and collecting the final NaGdF through centrifugation4Yb, Er upconversion luminescent products.
In a 20mL glass vial, 25mg of NaGdF4Yb, Er particles are dispersed in an aqueous solution, 2mL of 2.4mM polyvinylpyrrolidone (molecular weight 55000) is added as a ligand linker, and 10uL 1 is added0mM chloroauric acid trihydrate is used as a gold source, the three are stirred for 15min at room temperature to be in full contact, 900uL 100mM ascorbic acid with dilute concentration is finally added as a reducing agent, and gold nanoparticles are directly loaded on the surface of the upconversion luminescent particles through a slow reduction process for 30min, wherein the size of the gold nanoparticles is 4-20 nm.
And after the reaction is finished, taking the sample powder before and after loading, and testing the luminous intensity by a steady-state-transient luminous spectrometer. The detection conditions of the luminescence spectrum are as follows: JY Fluorolog-3-Tou, 980nm exciting light, power is 192.4mW cm-2The scanning range is 300-750 nm. FIG. 1 is a luminescence spectrum of the sample, under the excitation of 980nm laser, the sample can emit green visible light, and can be obtained by integrating the luminescence spectrum, under the mass ratio of 1269: 1, the luminous capacity is enhanced to 1.39 times under the action of the plasma resonance of the gold nanoparticles.
Fully grinding and mixing 100mg of polyethylene powder and 2mg of the obtained noble metal/up-conversion luminescent particles in a mortar, pouring the mixed powder into a mold, carrying out hot melting at the high temperature of 140 ℃ for 2min, repeatedly vacuumizing and deflating for four times to remove air bubbles as far as possible, finally pressurizing to 7MPa, compressing for 10min, and naturally cooling to obtain the homogeneously dispersed high-efficiency up-conversion-polyethylene composite resin, wherein the finally obtained composite resin is light pink in color, has better light transmittance and stability, also has stronger up-conversion luminescent property, and shows the potential of industrial application.
Example 2
The specific reaction procedure and detection method were the same as in example 1 except that 20uL of 10mM chloroauric acid trihydrate was used as the gold source. Through detection, the mass ratio of the up-conversion luminescent particles to the gold particles is 634: 1, the luminescent capability is enhanced to 2.76 times under the plasma resonance effect of the gold nanoparticles, and the color of the finally obtained composite resin is pink.
Example 3
The specific reaction procedure and detection method were the same as in example 1 except that 60uL of 10mM chloroauric acid trihydrate was used as the gold source. Through detection, the mass ratio of the up-conversion luminescent particles to the gold particles is 211: 1, the luminescent capability is enhanced to 1.21 times under the plasma resonance effect of the gold nanoparticles, and finally the color of the obtained composite resin is red.
Example 4
The specific reaction procedure and detection method were the same as in example 1 except that 80uL of 10mM chloroauric acid trihydrate was used as the gold source. Through detection, the mass ratio of the up-conversion luminescent particles to the gold particles is 158: 1, the luminescent capability is weakened to 0.68 time under the plasma resonance effect of the gold nanoparticles, and finally the color of the obtained composite resin is dark red.
While the gold particle plasma resonance effect enhances the luminescence, the plasma resonance characteristic light absorption is also accompanied (as shown in FIG. 2, the light absorption characteristic peak is just matched with NaGdF4Yb and Er up-converted in the green region, 520-540 nm), the increase of the emission reaches the limit with the increase of the gold particles, but the light absorption effect increases with the increase of the emission, so that the emission (mainly green light) is weakened, and the red region is not influenced by the weakening because the light absorption of the gold particles is not matched, so that the color of the up-converted emission begins to change obviously from green to yellow or even red.
Example 5
The specific reaction procedure and detection method were the same as in example 1 except that 100uL of 10mM chloroauric acid trihydrate was used as the gold source. Through detection, the mass ratio of the up-conversion luminescent particles to the gold particles is 126: 1, the luminescent capability is continuously weakened under the plasma resonance effect of the gold nanoparticles, and finally the color of the obtained composite resin is dark purplish red, and the color of the up-conversion luminescent particles is changed to yellow or even red under the excitation of 980nm laser.
Example 6
The specific reaction process and detection method are the same as example 1, except that 100mg of polyethylene powder and 2mg of NaGdF are directly placed in a mortar without loading gold nanoparticles4Fully grinding and mixing Yb and Er particles, pouring the mixed powder into a mold, thermally melting for 2min at the high temperature of 140 ℃, repeatedly vacuumizing and deflating for four times to remove air bubbles as far as possible, finally pressurizing to 7MPa, compressing for 10min, and naturally cooling to obtain the homogeneously dispersed high-efficiency up-conversion-polyethylene composite resin, wherein the color of the finally obtained composite resin is light white.
Example 7
The specific reaction process and detection method are the same as example 1, except that 100mg of polyethylene powder and 5mg of NaGdF are directly placed in a mortar without loading gold nanoparticles4Fully grinding and mixing Yb and Tm particles, pouring the mixed powder into a mould, thermally melting for 2min at the high temperature of 140 ℃, repeatedly vacuumizing and deflating for four times to remove bubbles as far as possible, finally pressurizing to 7MPa, compressing for 10min, and naturally cooling to obtain the uniformly dispersed high-efficiency up-conversion-polyethylene composite resin, wherein the color of the finally obtained composite resin is white.
Example 8
The specific reaction process and detection method are the same as those of example 1, except that NaGdF is added4Yb, Tm up-conversion particles as a matrix for supporting gold particles, the sample can emit blue visible light under 980nm excitation luminescence, and the size of the finally grown gold particles and the color of the composite resin are the same as those in example 1.
Example 9
The specific reaction process and detection method are the same as those of example 1, except that NaGdF is added4Yb, Ho upconverting particles as a matrix for supporting gold particles, the sample can emit red visible light under 980nm excitation luminescence, and the size of the finally grown gold particles and the color of the composite resin are the same as those of example 1.
Examples 10 to 12
The specific reaction process and detection method are the same as example 1, except that NaYF is used4:Yb，Er、NaYF4:Yb，Tm、NaYF4The Yb upconversion particles and the Ho upconversion particles are respectively used as substrates for loading the gold particles, the samples can respectively emit green, blue and red visible lights under 980nm excitation luminescence, and the size of the finally grown gold particles and the color of the composite resin are the same as those of the example 1.
Examples 13 to 18
The specific reaction process and detection method are the same as those of example 1, except that NaGdF is added4:Nd，Yb，Er、NaGdF4:Nd，Yb，Tm、NaGdF4:Nd，Yb，Ho、NaYF4:Nd，Yb，Er、NaYF4:Nd，Yb，Tm、NaYF4Nd, Yb and Ho as the matrix for supporting the gold particles, the samples can emit green, blue, red, green, blue and red visible lights under the excitation luminescence of 808nm, and the size of the gold particles grown finally and the color of the composite resin are the same as those in example 1. FIG. 3 is a diagram showing the above resin, wherein a is a white resin sheet which emits blue light under 980nm near infrared light; b, a light white resin sheet, which emits green light under 980nm near infrared light irradiation; the colors of the resin sheets of the c-f diagrams are light pink, red and dark red respectively, namely the colors are gradually deepened, and the colors are gradually changed from green to yellow under the irradiation of 980nm near infrared light.
Examples 19 to 20
The specific reaction process and detection method are the same as those in example 1, except that the molecular weights of polyvinylpyrrolidone are 40000 and 44000 respectively, and gold nanoparticles with the sizes of 4-20nm can still be successfully loaded.
Examples 21 to 22
The specific reaction procedure and detection method were the same as in example 1 except that the amounts of the added ligand-linking agent were changed to 1mL and 4mL of 2.4mM polyvinylpyrrolidone, at which the mass ratios of the up-conversion luminescent particles to the ligand-linking agent (polyvinylpyrrolidone) were 0.01 and 0.18: 1.
Examples 23 to 26
The specific reaction process and detection method are the same as those in example 1, except that the ligand linker is replaced by polyvinyl alcohol (PVA), polyethylene glycol (PEG), cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium chloride (BTAC).
Examples 27 to 28
The specific reaction process and detection method were the same as in example 1 except that the gold source was replaced with the same molar amounts of gold acetate and gold nitrate.
Example 29
The specific reaction process and detection method are the same as in example 1 except that the noble metal source is replaced with a silver source (silver nitrate) of the same molar amount.
Example 30
The specific reaction procedure and detection method were the same as in example 1 except that the noble metal source was replaced with the same molar amount of copper source (copper nitrate).
Example 31
The specific reaction procedure and detection method were the same as in example 1 except that the noble metal source was replaced with the same molar amount of indium source (indium acetate).
Examples 32 to 33
The specific reaction process and detection method were the same as in example 1 except that the mass ratio of the up-conversion luminescent particles to the reducing agent (ascorbic acid) was 1 and 3: 1.
Examples 34 to 38
The specific reaction process and detection method are the same as those in example 1, except that the reducing agents are replaced by Citric Acid (CA), sodium citrate, glucose, sodium borohydride and potassium borohydride in the same molar amount, and the reducing agents can reduce the noble metal ions into the elemental metal.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A preparation method of an up-conversion luminescence polyethylene composite resin comprises the following steps:
(1) adding a ligand connecting agent, a noble metal source and a reducing agent into the upconversion luminescent particle dispersion liquid, and carrying out in-situ reduction reaction to obtain upconversion luminescent particles with noble metal loaded on the surfaces;
(2) mixing up-conversion luminescent particles with noble metal loaded on the surface with polyethylene powder, and then carrying out hot melting and compression to obtain the up-conversion luminescent polyethylene composite resin;
in the step (1), the mass ratio of the up-conversion luminescent particles to the noble metal source is (126 to 1269): 1;
wherein, in the step (1), the mass ratio of the up-conversion luminescent particles to the ligand connecting agent is (0.01 to 0.18): 1;
in the step (1), the mass ratio of the up-conversion luminescent particles to the reducing agent is (1-3): 1;
wherein in the step (1), the noble metal source comprises any one or more of a copper source and an indium source;
in the step (2), the mass ratio of the polyethylene powder to the upconversion luminescent particles with the noble metal loaded on the surface is (20-50): 1.
2. the production method according to claim 1,
in the step (1), the ligand linking agent comprises any one or a combination of polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene glycol, hexadecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium chloride;
in the step (1), the reducing agent comprises any one or a combination of more of ascorbic acid, citric acid, sodium citrate, glucose, sodium borohydride and potassium borohydride;
in the step (1), the reaction time of the in-situ reduction reaction is 20 to 40 min.
3. The production method according to claim 1,
in the step (1), the up-conversion luminescent particles are NaLnF doped with rare earth ions4Particles; wherein the rare earth ions Ln include Y3+、Gd3+、Nd3+、Yb3+、Er3+、Tm3+、Ho3+Any one or more combinations of;
in the step (1), the emission color of the up-conversion luminescent particles under the laser of 980nm or 808nm is any one or combination of blue, green and red.
4. The production method according to claim 1,
in the step (2), the hot melting temperature is (120 to 150) DEG C; the hot melting time is (1 to 3) min;
in the step (2), the pressure during compression is (1 to 7) MPa; the compression time was (8 to 15) min.
5. The production method according to claim 1,
in the step (2), the bubble removal operation is performed after the hot-melting step and before the compression step.
6. An upconversion luminescent polyethylene composite resin obtained by the production method according to any one of claims 1 to 5.
7. The upconversion luminescent polyethylene composite resin according to claim 6, applied to the field of solid materials in a near infrared region.
CN202110200287.2A 2021-02-22 2021-02-22 Up-conversion luminescent polyethylene composite resin and preparation method and application thereof Active CN112980078B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110200287.2A CN112980078B (en) 2021-02-22 2021-02-22 Up-conversion luminescent polyethylene composite resin and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110200287.2A CN112980078B (en) 2021-02-22 2021-02-22 Up-conversion luminescent polyethylene composite resin and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112980078A CN112980078A (en) 2021-06-18
CN112980078B true CN112980078B (en) 2022-05-17

Family

ID=76349569

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110200287.2A Active CN112980078B (en) 2021-02-22 2021-02-22 Up-conversion luminescent polyethylene composite resin and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112980078B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102127444A (en) * 2010-12-10 2011-07-20 吉林大学 Nanogold modified enhanced up-conversion luminescence composite material and preparation method thereof
CN108904800A (en) * 2018-07-07 2018-11-30 上海大学 Upper conversion nano hybrid systems, preparation method and application based on Technique of Nano Pd Heteroepitaxy
CN109705867A (en) * 2019-01-11 2019-05-03 山东师范大学 Up-conversion NaYF4: the preparation and application of Yb, Er@M
CN110607176A (en) * 2019-09-20 2019-12-24 大连伽马光电科技有限公司 Composite film with enhanced noble metal/semiconductor induced up-conversion

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102127444A (en) * 2010-12-10 2011-07-20 吉林大学 Nanogold modified enhanced up-conversion luminescence composite material and preparation method thereof
CN108904800A (en) * 2018-07-07 2018-11-30 上海大学 Upper conversion nano hybrid systems, preparation method and application based on Technique of Nano Pd Heteroepitaxy
CN109705867A (en) * 2019-01-11 2019-05-03 山东师范大学 Up-conversion NaYF4: the preparation and application of Yb, Er@M
CN110607176A (en) * 2019-09-20 2019-12-24 大连伽马光电科技有限公司 Composite film with enhanced noble metal/semiconductor induced up-conversion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"红 外变可见上转换材料薄膜";彭桂芳、洪广言、贾庆新、李有漠;《中国激光》;19940131;第21卷(第1期);第36-39页 *

Also Published As

Publication number Publication date
CN112980078A (en) 2021-06-18

Similar Documents

Publication Publication Date Title
CN109264771B (en) All-inorganic halogen perovskite nanocrystal and preparation method thereof
CN102268259B (en) Luminescent centre regionally doped rare earth upconversion luminescent material and preparation method thereof
CN110423615B (en) Single-particle nano crystal with three-primary-color luminescence and preparation method thereof
EP3405552B1 (en) Lanthanide based upconverting microrods and application thereof
CN112080278B (en) Up/down conversion dual-mode luminescent nanocrystal and preparation method and application thereof
CN102974837A (en) Preparation method for flaky nanometer silver powder
CN105679894B (en) A kind of production method of the high colour gamut white light LEDs lamp bead based on red light quantum point
De et al. Bright-green upconversion emission of hexagonal LaF3: Yb3+, Er3+ nanocrystals
Lin et al. Plasmon-enhanced broad-band quantum-cutting of NaBaPO4: Eu2+, Yb3+ phosphor decorated with Ag nano-particles
Liu et al. Two distinct simultaneous NIR looping behaviours of Er3+ singly doped BiOBr: The underlying nature of the Er3+ ion photon avalanche emission induced by a layered structure
Zhu et al. Plasmon multiwavelength-sensitized luminescence enhancement of highly transparent Ag/YVO4: Eu3+/PMMA film
CN102134485A (en) Method for mass production of water-soluble fluorescent carbon nanoparticles
CN112980078B (en) Up-conversion luminescent polyethylene composite resin and preparation method and application thereof
Rai et al. Effect of CdS nanoparticles on photoluminescence spectra of Tb 3+ in sol–gel-derived silica glasses
Zheng et al. Enhancement of three-photon near-infrared quantum cutting in β-NaYF4: Er3+ nanoparticles by Ag nanocubes
CN106010536A (en) Method for synthesizing monodisperse rare earth doped up-converted fluorescence nanocrystalline through microwave assistance, and product thereof and application
Ferhi et al. Hydrothermal synthesis and luminescence properties of nanospherical SiO2@ LaPO4: Eu3+ (5%) composite
CN104232091B (en) Up-conversion nano material NaYbF4: Tm and its preparation method
CN105754585B (en) A kind of nanocrystalline preparation method of the Coated with Oleic Acid rare earth calcirm-fluoride of High Efficiency Luminescence
CN102504821A (en) Preparation method of rare earth-doped sodium gadolinium tetrafluoride nanomaterial
CN101947654A (en) Method for producing water-soluble fluorescent silver nanoclusters
CN112980192B (en) Up-conversion luminescence composite flexible transparent resin and preparation method and application thereof
CN102942932B (en) Preparation method of rare earth doped fluoride nano dispersion liquid
CN110330963A (en) The discoloration rare earth supermolecular gel fluorescent material of redox response and its preparation
CN112574749B (en) Three-dimensional NaYF4Up-conversion luminous micro-flower and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant