阅读说明：本技术 一种具有蓝光屏蔽性能的涂层材料ZnO的制备方法 (Preparation method of coating material ZnO with blue light shielding performance ) 是由 连俊林 王达 于 2021-08-24 设计创作，主要内容包括：本发明属于纳米无机材料技术领域,尤其为一种具有蓝光屏蔽性能的涂层材料ZnO的制备方法,该具有蓝光屏蔽性能的涂层材料ZnO的制备方法利用激光多次快速辐照ZnO颗粒,并且在最大程度上抑制了ZnO颗粒表面无序结构或体相缺陷的产生,维持ZnO颗粒完整的晶体结构,避免了ZnO晶格畸变,这样,使得制备的ZnO颗粒在能够屏蔽紫外光-蓝光的同时,还具有良好的可见光透过性能；并且由于所采用的是激光辐照技术,制备过程清洁、无污染,没有引入其他杂质元素,而且所需反应时间短,制备效率高,制备的ZnO颗粒可用于加工高质量的具有可见光透过性能并同时屏蔽紫外光-蓝光的ZnO涂层材料。(The invention belongs to the technical field of nano inorganic materials, in particular to a preparation method of a coating material ZnO with blue light shielding performance, which utilizes laser to rapidly irradiate ZnO particles for many times, inhibits the generation of a disordered structure or a bulk phase defect on the surface of the ZnO particles to the greatest extent, maintains the complete crystal structure of the ZnO particles, and avoids ZnO lattice distortion, so that the prepared ZnO particles have good visible light transmission performance while shielding ultraviolet light-blue light; and because the adopted laser irradiation technology, the preparation process is clean and pollution-free, other impurity elements are not introduced, the required reaction time is short, the preparation efficiency is high, and the prepared ZnO particles can be used for processing high-quality ZnO coating materials with visible light transmission performance and ultraviolet-blue light shielding performance.)

1. A preparation method of a coating material ZnO with blue light shielding performance is characterized by comprising the following steps:

(1) carrying out preheating treatment on the nano ZnO particles to clean the surfaces of the nano ZnO particles;

(2) tabletting the preheated ZnO particles, and ensuring the flatness of the tabletted ZnO particles;

(3) carrying out irradiation treatment on ZnO by using laser;

(4) remixing the ZnO particles irradiated in the step (3) uniformly;

and (4) repeating the step (2), the step (3) and the step (4) for a plurality of times until the color of the ZnO particles is uniform.

2. The preparation method of the coating material ZnO with the blue-light shielding property according to claim 1, wherein the crystal form of the ZnO particles is wurtzite, sphalerite, NaCl or CsCl.

3. The method for preparing the coating material ZnO with the blue light shielding performance, according to claim 1, wherein the particle size of the ZnO particles is 5nm-5000 nm.

4. The method for preparing the coating material ZnO with the blue light shielding performance according to claim 1, wherein the particle size of the ZnO particles is 100 nm.

5. The preparation method of the coating material ZnO with the blue light shielding performance, according to claim 1, characterized in that the light source wavelength of the laser is 300nm-1700 nm; the light source power of the laser is 1W-100W; the pulse width of the light source of the laser is 1 picosecond-1000 nanoseconds; the pulse frequency of the laser light source is 10 Hz-10000 Hz.

6. The method for preparing coating material ZnO with blue light shielding property according to claim 1,

in the step (1), the preheating treatment of the nano ZnO particles is carried out in a muffle furnace, and the temperature range of the preheating treatment is 200-500 ℃; alternatively, the first and second electrodes may be,

and carrying out preheating treatment on the nano ZnO particles in a tubular furnace under the protection of inert gas.

7. The method for preparing coating material ZnO with blue light shielding property according to claim 1, wherein the irradiation treatment time in the step (3) is 3-8 seconds.

8. The method for preparing the coating material ZnO with the blue light shielding performance according to claim 1, wherein the steps (2), (3) and (4) are repeated for 5-10 times.

9. The method for preparing ZnO as claimed in claim 1, wherein in the step (2), the preheated ZnO particle sample is tableted on a quartz glass substrate, and the upper layer is tableted glass after the ZnO particle sample is spread to be thin; in the step (3), when the color of the pressed glass changes from transparent to dark black after laser irradiation, the pressed glass is replaced.

Technical Field

The invention belongs to the technical field of nano inorganic materials, and particularly relates to a preparation method of a coating material ZnO with blue light shielding performance.

Background

ZnO (zinc oxide) is an important industrial inorganic raw material, and has a wide application field, for example, ZnO is applied to the manufacture of products such as plastics, silicate products, synthetic rubber, lubricating oil, paint coatings, ointments, adhesives, foods, batteries, flame retardants and the like. And ZnO has larger energy band gap and exciton constraint energy, high transparency and excellent normal temperature luminous performance, and is also applied to products such as liquid crystal displays, thin film transistors, light emitting diodes and the like in the field of semiconductors.

In addition, ZnO can well absorb ultraviolet light in the solar spectrum to play a role in shielding the ultraviolet light, and ZnO is an environment-friendly material, has good compatibility with organisms, cannot cause harm to human health, cannot influence the environment of daily life of human beings, and therefore, the ZnO also has application in the field of daily necessities, for example, zinc oxide is widely applied to physical sun-screening agents and can provide broad-spectrum ultraviolet protection.

The applications of the zinc oxide are generally modified or combined with other substances, for example, the currently common method for preparing a ZnO semiconductor material with visible light transmission and ultraviolet-blue light shielding is element doping and semiconductor compounding.

Among them, the element doping method is considered as the most direct and effective method for adjusting the light absorption performance of ZnO, and in the method, the energy band structure of ZnO is directly adjusted by element doping, so that the ZnO can absorb ultraviolet light-blue light of different wave bands. In the prior art, for example, Liu et al (Journal of Alloys and Compounds, 2021,880, 160501) utilizes Ag element to dope ZnO, which enhances the high-efficiency absorption of blue-violet light at 400-450 nm; mohsin et al (Applied Materials Today, 2021,23, 101047) use Fe element doped ZnO to enhance the absorption of blue-violet light at 400-450 nm. However, the distribution of the elements introduced by the element doping method in the ZnO bulk phase or the surface is not controllable, and distortion of the ZnO lattice structure is caused, so that defects of ZnO are increased, scattering of visible light by ZnO is increased, light transmittance is reduced, and light transmission and shielding performance of ZnO is seriously affected.

As for another semiconductor compounding method, in the prior art, for example, Ma et al (Materials 2021,14,3299) utilize TiO2 to carry out semiconductor compounding with ZnO, and the absorption of blue-violet light is increased by inducing oxygen vacancies at the interface, so that the absorption efficiency of the material for the blue-violet light at 400-450nm is increased by 20%; gandotra et al (Journal of Alloys and Compounds, 2021,873, 159769) use CuxO composite ZnO to obtain composite semiconductor material, which enhances the blue-violet absorption efficiency at 400-450 nm; oamar et al (Journal of Environmental Chemical Engineering, 2021,9, 105534) utilize g-C3N4 composite ZnO materials which increase the efficiency of blue-violet absorption at 400-450nm by nearly 3 times; in addition, the reduction treatment of the ZnO surface by some metal high-temperature steam with reduction performance can also enhance the absorption performance of ZnO on blue-violet light; however, the ZnO surface treated by this method has a disordered structure, which is disadvantageous to the transmission and shielding of light in the ZnO material.

Disclosure of Invention

The invention aims to provide a preparation method of a coating material ZnO with blue light shielding performance, and solves the technical problems that the ZnO material has a blue and violet light filtering function and simultaneously the light transmittance is reduced due to the fact that the ZnO material is distorted in lattice structure and disordered structure on the surface of the ZnO material caused by a processing mode of the ZnO material in the prior art.

In order to solve the technical problems, the invention adopts the following technical scheme:

the preparation method of the coating material ZnO with the blue light shielding performance comprises the following steps:

(1) carrying out preheating treatment on the nano ZnO particles to clean the surfaces of the nano ZnO particles;

(2) tabletting the preheated ZnO particles, and ensuring the flatness of the tabletted ZnO particles;

(3) carrying out irradiation treatment on ZnO by using laser;

(4) remixing the ZnO particles irradiated in the step (3) uniformly;

and (4) repeating the step (2), the step (3) and the step (4) for a plurality of times until the color of the ZnO particles is uniform.

Preferably, the crystal form of the ZnO particles is wurtzite, sphalerite, NaCl or CsCl.

Preferably, the particle size of the ZnO particles is 5nm-5000 nm.

Preferably, the ZnO particles have a particle size of 100 nm.

Preferably, the light source wavelength of the laser is 300nm-1700 nm; the light source power of the laser is 1W-100W; the pulse width of the light source of the laser is 1 picosecond-1000 nanoseconds; the pulse frequency of the laser light source is 10 Hz-10000 Hz.

Preferably, in the step (1), the preheating treatment of the nano ZnO particles is performed in a muffle furnace, and the temperature range of the preheating treatment is 200-500 ℃; alternatively, the first and second electrodes may be,

and carrying out preheating treatment on the nano ZnO particles in a tubular furnace under the protection of inert gas.

Preferably, in the step (3), the irradiation treatment is performed for 3 to 8 seconds.

Preferably, the steps (2), (3) and (4) are repeated for 5 to 10 times.

Preferably, in the step (2), the ZnO particle sample after the preheating treatment is tableted on a quartz glass substrate, and the upper layer of the ZnO particle sample after being spread is tableted glass; in the step (3), when the color of the pressed glass changes from transparent to dark black after laser irradiation, the pressed glass is replaced.

Compared with the prior art, the invention has the beneficial effects that:

1. according to the preparation method of the coating material ZnO with the blue light shielding performance, the ZnO particles are rapidly irradiated by laser for multiple times, the generation of disordered structures or bulk phase defects on the surfaces of the ZnO particles is inhibited to the greatest extent, the complete crystal structure of the ZnO particles is maintained, and the lattice distortion of ZnO is avoided, so that the prepared ZnO particles have good visible light transmission performance while being capable of shielding ultraviolet light-blue light, and the irradiated ZnO particles can be applied to the coating material with the blue light shielding performance.

2. Because the laser irradiation technology is adopted, the preparation process is clean and pollution-free, other impurity elements are not introduced, the required reaction time is short, the preparation efficiency is high, and the prepared ZnO particles can be used for processing high-quality ZnO coating materials with visible light transmission performance and ultraviolet-blue light shielding performance.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

fig. 1 is a schematic diagram of laser irradiation in an embodiment of a preparation method of a coating material ZnO with blue light shielding performance according to the present invention.

Fig. 2 is a schematic diagram of comparison between an optical photograph of a ZnO particle sample obtained after laser irradiation and a raw material in an embodiment of a method for preparing a coating material ZnO with a blue light shielding property according to the present invention.

Fig. 3 is a comparison graph of crystal form test results of ZnO particle samples subjected to laser irradiation and raw materials in an embodiment of the preparation method of the coating material ZnO with blue light shielding performance of the present invention.

Fig. 4 is a graph comparing the results of the ultraviolet-blue light absorption rate test of the ZnO particle sample subjected to laser irradiation and the raw material in one embodiment of the method for preparing the coating material ZnO with the blue light shielding performance of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

a preparation method of coating material ZnO with blue light shielding performance comprises the following steps:

(1) and (4) carrying out preheating treatment on the nano ZnO particles, and cleaning the surfaces of the nano ZnO particles.

In this step, the crystal form of the ZnO particles is wurtzite, the particle size of the ZnO particles is 5nm, and the nano ZnO particles are preheated in a muffle furnace at 200 ℃ to clean the surfaces thereof, for example, the impurities such as moisture on the surfaces of the ZnO particles gasified by heat can be removed by the preheating treatment.

(2) And tabletting the ZnO particles subjected to preheating treatment, and ensuring the flatness of the ZnO particles subjected to tabletting.

Referring to fig. 1, in this step, a ZnO particle sample after preheating treatment is tableted on a quartz glass substrate, and the upper layer is tableted glass after the ZnO particle sample is spread.

(3) And (4) irradiating the ZnO by using laser.

In the step, the light source wavelength of the laser is 300nm, the light source power is 1W, the light source pulse width is 1 picosecond, and the light source pulse frequency of the laser is 1000 Hz; and the duration of the irradiation treatment was 5 seconds, to obtain gray ZnO nanoparticles.

In the step, the reaction time of laser irradiation is short, so that the generation of ZnO particle surface or bulk phase defects can be inhibited to the greatest extent, the complete crystal structure is maintained, and the lattice distortion of ZnO particles is avoided.

Here, the laser irradiation time is selected according to the difference of the laser wavelength, the difference of the selected laser power, and the difference of the ZnO particle size, and in principle, the shorter the laser wavelength, the larger the laser power, and the smaller the ZnO particle size, the shorter the laser irradiation time.

Referring to fig. 1, in this step, the laser light source reaches the ZnO particle sample after being reflected by two reflectors, and the purpose of the two reflections is to focus the laser light and ensure the brightness and energy of the light spot.

(4) And (4) remixing the ZnO particles irradiated in the step (3) uniformly.

The purpose of remixing in this step is to prepare for repeating step (2), step (3), and step (4).

In this example, the steps (2), (3) and (4) were repeated 6 times in total to obtain ZnO particles having uniform color. Here, the number of times of repetitive irradiation of the ZnO particle sample is influenced by several factors of a difference in laser wavelength, a difference in selected laser power, and a difference in particle size of the ZnO particles, and in principle, the shorter the laser wavelength, the larger the selected laser power, and the smaller the particle size of the ZnO particles, the smaller the number of times of repetitive irradiation of the ZnO particle sample.

Example 2:

a preparation method of coating material ZnO with blue light shielding performance comprises the following steps:

(1) and (4) carrying out preheating treatment on the nano ZnO particles, and cleaning the surfaces of the nano ZnO particles.

In the step, the crystal form of the adopted ZnO particles is sphalerite, the particle size of the adopted ZnO particles is 100nm, and the mode of preheating the nano ZnO particles is to preheat the nano ZnO particles in a muffle furnace at 300 ℃ to clean the surfaces of the nano ZnO particles.

(2) And tabletting the ZnO particles subjected to preheating treatment, and ensuring the flatness of the ZnO particles subjected to tabletting.

(3) And (4) irradiating the ZnO by using laser.

In the step, the light source wavelength of the laser is 1064nm, the light source power is 2W, the light source pulse width is 100 picoseconds, and the light source pulse frequency of the laser is 10 Hz; and the duration of the irradiation treatment was 3 seconds.

(4) And (4) remixing the ZnO particles irradiated in the step (3) uniformly.

In this example, the steps (2), (3) and (4) were repeated 10 times in total to obtain ZnO particles having a uniform color.

Example 3:

a preparation method of coating material ZnO with blue light shielding performance comprises the following steps:

(1) and (4) carrying out preheating treatment on the nano ZnO particles, and cleaning the surfaces of the nano ZnO particles.

In the step, the adopted crystal form of the ZnO particles is NaCl crystal form, the particle size of the adopted ZnO particles is 5000nm, and the nano ZnO particles are preheated in a muffle furnace at 500 ℃ to clean the surfaces of the nano ZnO particles.

(2) And tabletting the ZnO particles subjected to preheating treatment, and ensuring the flatness of the ZnO particles subjected to tabletting.

(3) And (4) irradiating the ZnO by using laser.

In the step, the light source wavelength of the laser is 1700nm, the light source power is 100W, the light source pulse width is 1000 nanoseconds, and the light source pulse frequency of the laser is 10000 Hz; and the duration of the irradiation treatment was 8 seconds.

(4) And (4) remixing the ZnO particles irradiated in the step (3) uniformly.

In this example, the steps (2), (3) and (4) were repeated 5 times in total to obtain ZnO particles having a uniform color.

Example 4:

a preparation method of coating material ZnO with blue light shielding performance comprises the following steps:

(1) and (4) carrying out preheating treatment on the nano ZnO particles, and cleaning the surfaces of the nano ZnO particles.

In the step, the adopted crystal form of the ZnO particles is CsCl crystal form, the particle size of the adopted ZnO particles is 100nm, and the nano ZnO particles are preheated in a muffle furnace at 200 ℃ to clean the surfaces of the nano ZnO particles.

(2) And tabletting the ZnO particles subjected to preheating treatment, and ensuring the flatness of the ZnO particles subjected to tabletting.

(3) And (4) irradiating the ZnO by using laser.

In the step, the light source wavelength of the laser is 355nm, the light source power is 1W, the light source pulse width is 100 picoseconds, and the light source pulse frequency of the laser is 1000 Hz; and the duration of the irradiation treatment was 3 seconds.

(4) And (4) remixing the ZnO particles irradiated in the step (3) uniformly.

In this example, the steps (2), (3) and (4) were repeated 8 times in total to obtain ZnO particles having uniform color.

Example 5:

a preparation method of coating material ZnO with blue light shielding performance comprises the following steps:

(1) and (4) carrying out preheating treatment on the nano ZnO particles, and cleaning the surfaces of the nano ZnO particles.

In the step, the crystal form of the adopted ZnO particles is sphalerite, the particle size of the adopted ZnO particles is 500nm, and the mode of preheating the nano ZnO particles is to preheat the nano ZnO particles in a muffle furnace at 200 ℃ to clean the surfaces of the nano ZnO particles.

(2) And tabletting the ZnO particles subjected to preheating treatment, and ensuring the flatness of the ZnO particles subjected to tabletting.

(3) And (4) irradiating the ZnO by using laser.

In the step, the light source wavelength of the laser is 1064nm, the light source power is 1W, the light source pulse width is 100 picoseconds, and the light source pulse frequency of the laser is 1000 Hz; and the duration of the irradiation treatment was 8 seconds.

(4) And (4) remixing the ZnO particles irradiated in the step (3) uniformly.

In this example, the steps (2), (3) and (4) were repeated 10 times in total to obtain ZnO particles having a uniform color.

The zinc oxide particles prepared by the preparation method of the coating material ZnO with blue light shielding performance in the above embodiment have visible light transmission performance, and can shield ultraviolet light-blue light at the same time, and the performance of the zinc oxide particles prepared in the above embodiment 1 is specifically analyzed with reference to fig. 2 to 4: as shown in fig. 2, the irradiated zinc oxide particles have a darker color than the zinc oxide particles before irradiation, so that the irradiated zinc oxide particles can absorb ultraviolet light and blue light; in fig. 3, θ represents a diffraction angle, and the intensity of the ordinate represents the intensity of a diffraction peak, and by adopting XRD powder diffraction test, the crystal form change of the ZnO particle sample before and after laser irradiation can be obtained, as shown in fig. 3, the positions and peak forms of the diffraction peaks of the crystal form pattern of the ZnO particle sample before irradiation and the crystal form pattern of the ZnO particle sample after irradiation are kept consistent, which indicates that the crystal structure of the ZnO particle sample is the same and complete before and after laser irradiation, and no distortion occurs. As shown in fig. 4, the position of the ordinate of the irradiated ZnO particle sample material at 400-450nm is higher, which indicates that the sample material has a strong absorption property for blue light in this wavelength band, and the absorption property of the irradiated ZnO particle sample is significantly enhanced compared with that of the ZnO particle sample before laser irradiation.

Here, the reason why the ZnO particle sample can absorb ultraviolet light in the solar spectrum is that zinc oxide is an N-type semiconductor, and the principle of shielding ultraviolet light is absorption and scattering, electrons on the valence band of ZnO can undergo transition by energy in ultraviolet light to achieve the purpose of absorbing ultraviolet light, and the function of scattering ultraviolet light is related to the particle size of the material, and when the size is much smaller than the wavelength of ultraviolet light, the particles can scatter ultraviolet light acting thereon in all directions to reduce the ultraviolet light intensity in the irradiation direction, so that the nano-sized ZnO particles have a significant advantage over the normal size. In the embodiment, the crystal structure of the ZnO particles subjected to laser irradiation is the same as and complete with that before irradiation, and no distortion occurs, so that the treatment method avoids the defects of the ZnO particles, prevents the ZnO particles from scattering visible light, further avoids the reduction of the light transmittance, and enables the ZnO particles subjected to laser irradiation to keep good visible light transmittance while shielding the violet light and the blue light.

It should be noted that, in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.