阅读说明：本技术 一种硒化锌粉体的制备方法 (Preparation method of zinc selenide powder ) 是由 张高峰 张荣实 甘硕文 廉伟艳 刘孟寅 张彤 周珺 杨勇 于 2021-10-14 设计创作，主要内容包括：本申请提供有一种硒化锌粉体的制备方法,包括如下步骤：取一定比例的氯化锌溶液和草酸溶液进行充分反应,过滤后得到草酸锌沉淀物,再经清洗烘干研磨后与硒粉混合,充分研磨后,放入石英真空管式炉进行反应,得到硒化锌粉体。该方法简单高效,易于操作,可制备粒径为2～10μm的高品质硒化锌粉体原料,该粉体原料可直接应用于硒化锌红外光学材料的应用领域。(The application provides a preparation method of zinc selenide powder, which comprises the following steps: taking a certain proportion of zinc chloride solution and oxalic acid solution for full reaction, filtering to obtain zinc oxalate precipitate, cleaning, drying, grinding, mixing with selenium powder, fully grinding, and reacting in a quartz vacuum tube furnace to obtain zinc selenide powder. The method is simple and efficient, is easy to operate, can be used for preparing the high-quality zinc selenide powder raw material with the particle size of 2-10 mu m, and can be directly applied to the application field of zinc selenide infrared optical materials.)

1. A preparation method of zinc selenide powder is characterized by comprising the following steps:

the method comprises the following steps:

mixing the zinc chloride solution and the oxalic acid solution for reaction and filtering to obtain zinc oxalate precipitate;

cleaning, drying and grinding the zinc oxalate precipitate to obtain zinc oxalate powder;

and mixing and reacting the zinc oxalate powder and the selenium powder to obtain the zinc selenide powder.

2. The method for preparing zinc selenide powder according to claim 1, wherein the method comprises the following steps: the concentration of the zinc chloride solution is 0.1-0.2 mol/L, and the concentration of the oxalic acid solution is 0.1-0.2 mol/L.

3. The method for preparing zinc selenide powder according to claim 2, wherein the method comprises the following steps: the molar ratio of the zinc chloride solution to the oxalic acid solution is 1: 1.

4. The method for preparing zinc selenide powder according to claim 1, wherein the method comprises the following steps:

the method for cleaning the zinc oxalate precipitate comprises the following steps:

washing with deionized water for at least 1 time;

washing with alcohol at least 1 time.

5. The method for preparing zinc selenide powder according to claim 1, wherein the method comprises the following steps: the temperature for drying the zinc oxalate precipitate is 80-110 ℃.

6. The method for preparing zinc selenide powder according to claim 1, wherein the method comprises the following steps: the molar ratio of the zinc oxalate powder to the selenium powder is 1: 1.

7. The method for preparing zinc selenide powder according to claim 1, wherein the method comprises the following steps: and the zinc oxalate powder and the selenium powder are reacted in a quartz vacuum tube furnace.

8. The method for preparing zinc selenide powder according to claim 7, wherein the method comprises the following steps:

the reaction of the zinc oxalate powder and the selenium powder in a quartz vacuum tube furnace comprises the following steps:

heating to 300-350 ℃;

and preserving the heat for 600-720 min.

Technical Field

The invention relates to the technical field of zinc selenide lens materials and infrared optical materials, in particular to a method for preparing a zinc selenide powder raw material.

Background

Zinc selenide (ZnSe) is an infrared optical material with excellent performance, has good transmission performance in a wide waveband of 0.5-20 mu m, has high transmittance ratio and low absorption coefficient, has small variation of thermo-optic coefficient along with temperature, and is widely applied to the aspects of infrared lenses, infrared thermo-phase instruments and high-power CO2 lasers. As a raw material for preparing the PVD ZnSe optical material, the quality of the ZnSe powder raw material has a crucial influence on the performance of the ZnSe optical material. Therefore, the selection of a proper method for preparing the high-quality ZnSe powder raw material is a key technology for obtaining the high-performance ZnSe optical material.

In the prior art, most of ZnSe powder raw materials adopt elemental selenium powder (Se) and elemental zinc powder (Zn) as manufacturing raw materials, but the method usually needs high-temperature reaction conditions of over 700 ℃ or reaction auxiliary agents are added for reaction under high-pressure conditions, and the manufacturing process conditions are complex and have high requirements. Therefore, a simple and efficient preparation method of ZnSe powder raw material is needed.

Disclosure of Invention

In view of the above-mentioned defects or shortcomings in the prior art, the present application aims to provide a method for preparing zinc selenide powder, which has a simple preparation process, a short time and a greatly reduced reaction temperature compared with the prior art.

The application provides a preparation method of zinc selenide powder, which comprises the following steps:

mixing the zinc chloride solution and the oxalic acid solution for reaction and filtering to obtain zinc oxalate precipitate;

cleaning, drying and grinding the zinc oxalate precipitate to obtain zinc oxalate powder;

and mixing and reacting the zinc oxalate powder and the selenium powder to obtain the zinc selenide powder.

Preferably, the concentration of the zinc chloride solution is 0.1-0.2 mol/L, and the concentration of the oxalic acid solution is 0.1-0.2 mol/L.

Preferably, the molar ratio of the zinc chloride solution to the oxalic acid solution is 1: 1.

Preferably, the step of washing the zinc oxalate precipitate comprises the steps of:

washing with deionized water for at least 1 time;

washing with alcohol at least 1 time.

Preferably, the temperature for drying the zinc oxalate precipitate is 80-110 ℃.

Preferably, the molar ratio of the zinc oxalate powder to the selenium powder is 1: 1.

Preferably, the zinc oxalate powder and the selenium powder are reacted in a quartz vacuum tube furnace.

Preferably, the reaction of the zinc oxalate powder and the selenium powder in a quartz vacuum tube furnace comprises the following steps:

heating to 300-350 ℃;

and preserving the heat for 600-720 min.

The starting materials used in the present invention may be purchased from commercially available sources, unless otherwise specified. Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.

In summary, the application discloses a preparation method of zinc selenide powder, and the preparation method has the beneficial effects that three common raw materials of zinc chloride, oxalic acid and selenium powder in the market are adopted, the principle of chemical displacement reaction is utilized, the reactant zinc oxalate of the zinc chloride and the oxalic acid is filtered, cleaned, dried and ground, and then the reactant zinc oxalate is fully mixed with the selenium powder to react to obtain the zinc selenide powder raw material with high purity and particle size within the range of 2-10 microns. Compared with the prior art, the preparation method has the advantages of simple process, low process condition requirement (reaction temperature is 300-350 ℃), easily obtained reaction raw materials, and the final product zinc selenide powder can be directly used as a raw material for preparing the zinc selenide optical material.

In addition to the technical problems addressed by the present invention, the technical features constituting the technical solutions, and the advantages brought by the technical features of the technical solutions described above, other technical problems solved by the present invention, other technical features included in the technical solutions, and advantages brought by the technical features will be described in further detail below.

Drawings

Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:

fig. 1 is an XRD spectrum of the zinc selenide powder prepared in example 1.

Fig. 2 is an SEM image of the zinc selenide powder prepared in example 1.

Detailed Description

The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention. It should be noted that, for convenience of description, only the portions related to the present invention are shown in the drawings.

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.

Example 1

The embodiment provides a preparation method of zinc selenide powder, which comprises the following steps:

s1, mixing the zinc chloride solution and the oxalic acid solution for reaction and filtering to obtain zinc oxalate precipitate;

specifically, 200ml of each of a zinc chloride solution and an oxalic acid solution with the solution concentration of 0.1mol/L are taken according to the molar ratio of 1:1, then the zinc chloride solution is slowly poured into the oxalic acid solution and stirred in the process to prevent the zinc oxalate precipitate from agglomerating and condensing, improve the uniformity of the size of the zinc oxalate precipitate, stirring is continued for 60min after the mixing is finished to promote the reaction to be complete, and finally, the zinc oxalate precipitate is filtered from the reaction solution by a suction filter to obtain the zinc oxalate precipitate.

S2, cleaning, drying and grinding the zinc oxalate precipitate to obtain zinc oxalate powder;

specifically, the zinc oxalate precipitate is repeatedly washed for 3 times by deionized water, then repeatedly washed for 3 times by alcohol, then placed in a vacuum drying oven, heated to 90 ℃ for drying, cooled to room temperature after drying, taken out for full grinding to obtain zinc oxalate powder, so that the zinc oxalate powder is fully mixed with selenium powder.

S3, mixing and reacting the zinc oxalate powder with the selenium powder to obtain the zinc selenide powder.

Specifically, firstly, mixing zinc oxalate powder and selenium powder according to a molar ratio of 1:1 to obtain a mixture of the zinc oxalate powder and the selenium powder, and fully grinding the mixture to ensure that the zinc oxalate powder and the selenium powder can fully react. And then putting the mixture of the zinc oxalate powder and the selenium powder into a quartz vacuum tube furnace, vacuumizing until a mechanical pressure gauge shows-0.1 Mpa, heating to 330 ℃, preserving heat for 720min for full reaction, cooling the furnace to room temperature after heat preservation, and taking out to obtain the zinc selenide powder raw material.

The XRD pattern and SEM pattern of the zinc selenide powder prepared by the preparation method are shown in figure 1 and figure 2 respectively.

Example 2

The embodiment provides a preparation method of zinc selenide powder, which comprises the following steps:

s1, mixing the zinc chloride solution and the oxalic acid solution for reaction and filtering to obtain zinc oxalate precipitate;

specifically, taking 150ml of zinc chloride solution and 150ml of oxalic acid solution with the solution concentration of 0.2mol/L respectively according to the molar ratio of 1:1, slowly pouring the zinc chloride solution into the oxalic acid solution, stirring in the process to prevent the zinc oxalate precipitate from agglomerating and condensing, improving the uniformity of the size of the zinc oxalate precipitate, continuously stirring for 70min after mixing is completed to promote the reaction to be complete, and finally, performing suction filtration on the zinc oxalate precipitate from the reaction solution by using a suction filtration machine to obtain the zinc oxalate precipitate.

S2, cleaning, drying and grinding the zinc oxalate precipitate to obtain zinc oxalate powder;

specifically, the zinc oxalate precipitate is repeatedly washed for 5 times by deionized water, then repeatedly washed for 5 times by alcohol, then placed in a vacuum drying oven, heated to 110 ℃ for drying, cooled to room temperature after drying, taken out for full grinding to obtain zinc oxalate powder, so that the zinc oxalate powder is fully mixed with selenium powder.

S3, mixing and reacting the zinc oxalate powder with the selenium powder to obtain the zinc selenide powder.

Specifically, firstly, mixing zinc oxalate powder and selenium powder according to a molar ratio of 1:1 to obtain a mixture of the zinc oxalate powder and the selenium powder, and fully grinding the mixture to ensure that the zinc oxalate powder and the selenium powder can fully react. And then putting the mixture of the zinc oxalate powder and the selenium powder into a quartz vacuum tube furnace, vacuumizing until a mechanical pressure gauge shows-0.1 Mpa, heating to 350 ℃, preserving heat for 700min for full reaction, cooling the furnace to room temperature after heat preservation, and taking out to obtain the zinc selenide powder raw material.

Example 3

The embodiment provides a preparation method of zinc selenide powder, which comprises the following steps:

s1, mixing the zinc chloride solution and the oxalic acid solution for reaction and filtering to obtain zinc oxalate precipitate;

specifically, 200ml of each of a zinc chloride solution and an oxalic acid solution with the solution concentration of 0.15mol/L are taken according to the molar ratio of 1:1, then the zinc chloride solution is slowly poured into the oxalic acid solution and stirred in the process to prevent the zinc oxalate precipitate from agglomerating and condensing, improve the uniformity of the size of the zinc oxalate precipitate, the mixture is continuously stirred for 65min after being mixed to promote the reaction to be complete, and finally, the zinc oxalate precipitate is filtered from the reaction solution by a suction filter to obtain the zinc oxalate precipitate.

S2, cleaning, drying and grinding the zinc oxalate precipitate to obtain zinc oxalate powder;

specifically, the zinc oxalate precipitate is repeatedly washed by deionized water for 4 times, then repeatedly washed by alcohol for 5 times, then placed in a vacuum drying oven, heated to 100 ℃ for drying, cooled to room temperature after drying, taken out for full grinding to obtain zinc oxalate powder, so that the zinc oxalate powder is fully mixed with selenium powder.

S3, mixing and reacting the zinc oxalate powder with the selenium powder to obtain the zinc selenide powder.

Specifically, firstly, mixing zinc oxalate powder and selenium powder according to a molar ratio of 1:1 to obtain a mixture of the zinc oxalate powder and the selenium powder, and fully grinding the mixture to ensure that the zinc oxalate powder and the selenium powder can fully react. And then putting the mixture of the zinc oxalate powder and the selenium powder into a quartz vacuum tube furnace, vacuumizing until a mechanical pressure gauge shows-0.1 Mpa, heating to 300 ℃, preserving heat for 720min for full reaction, cooling the furnace to room temperature after heat preservation, and taking out to obtain the zinc selenide powder raw material.

Example 4

The embodiment provides a preparation method of zinc selenide powder, which comprises the following steps:

s1, mixing the zinc chloride solution and the oxalic acid solution for reaction and filtering to obtain zinc oxalate precipitate;

specifically, 100ml of each of a zinc chloride solution and an oxalic acid solution with the solution concentration of 0.1mol/L is taken according to the molar ratio of 1:1, then the zinc chloride solution is slowly poured into the oxalic acid solution and stirred in the process to prevent the zinc oxalate precipitate from agglomerating and condensing, improve the uniformity of the size of the zinc oxalate precipitate, the mixture is continuously stirred for 30min after being mixed to promote the reaction to be complete, and finally, the zinc oxalate precipitate is filtered from the reaction solution by a suction filter to obtain the zinc oxalate precipitate.

S2, cleaning, drying and grinding the zinc oxalate precipitate to obtain zinc oxalate powder;

specifically, the zinc oxalate precipitate is repeatedly washed for 3 times by deionized water, then repeatedly washed for 3 times by alcohol, then placed in a vacuum drying oven, heated to 80 ℃ for drying, cooled to room temperature after drying, taken out for full grinding to obtain zinc oxalate powder, so as to be fully mixed with selenium powder.

S3, mixing and reacting the zinc oxalate powder with the selenium powder to obtain the zinc selenide powder.

Specifically, firstly, mixing zinc oxalate powder and selenium powder according to a molar ratio of 1:1 to obtain a mixture of the zinc oxalate powder and the selenium powder, and fully grinding the mixture to ensure that the zinc oxalate powder and the selenium powder can fully react. And then putting the mixture of the zinc oxalate powder and the selenium powder into a quartz vacuum tube furnace, vacuumizing until a mechanical pressure gauge shows-0.1 Mpa, heating to 340 ℃, preserving heat for 600min for full reaction, cooling the furnace to room temperature after heat preservation, and taking out to obtain the zinc selenide powder raw material.

Example 5

The embodiment provides a preparation method of zinc selenide powder, which comprises the following steps:

s1, mixing the zinc chloride solution and the oxalic acid solution for reaction and filtering to obtain zinc oxalate precipitate;

specifically, 200ml of zinc chloride solution with the solution concentration of 0.1mol/L and 100ml of oxalic acid solution with the solution concentration of 0.2mol/L are taken according to the molar ratio of 1:1, then the zinc chloride solution is slowly poured into the oxalic acid solution and stirred in the process to prevent the zinc oxalate precipitate from agglomerating and coagulating, improve the uniformity of the size of the zinc oxalate precipitate, continuously stirred for 55min after the mixture is finished to promote the reaction to be complete, and finally the zinc oxalate precipitate is filtered from the reaction solution by a suction filter to obtain the zinc oxalate precipitate.

S2, cleaning, drying and grinding the zinc oxalate precipitate to obtain zinc oxalate powder;

specifically, the zinc oxalate precipitate is repeatedly washed by deionized water for 4 times, then repeatedly washed by alcohol for 3 times, then placed in a vacuum drying oven, heated to 100 ℃ for drying, cooled to room temperature after drying, taken out for full grinding to obtain zinc oxalate powder, so that the zinc oxalate powder is fully mixed with selenium powder.

S3, mixing and reacting the zinc oxalate powder with the selenium powder to obtain the zinc selenide powder.

Specifically, firstly, mixing zinc oxalate powder and selenium powder according to a molar ratio of 1:1 to obtain a mixture of the zinc oxalate powder and the selenium powder, and fully grinding the mixture to ensure that the zinc oxalate powder and the selenium powder can fully react. And then putting the mixture of the zinc oxalate powder and the selenium powder into a quartz vacuum tube furnace, vacuumizing until a mechanical pressure gauge shows-0.1 Mpa, heating to 340 ℃, preserving heat for 680min for full reaction, cooling the furnace to room temperature after heat preservation, and taking out to obtain the zinc selenide powder raw material.

The zinc selenide powder obtained in the above embodiment is a substance with the same chemical structure and the same chemical characteristics, so that an XRD (X-ray diffraction) pattern and an SEM (scanning Electron microscope) pattern are not repeatedly displayed.

It can be seen from the above examples that the zinc selenide powder raw material with high purity and particle size of 2-10 μm is obtained by adopting three common raw materials of zinc chloride, oxalic acid and selenium powder in the market, filtering, cleaning, drying and grinding the zinc oxalate which is the reactant of zinc chloride and oxalic acid by utilizing the principle of chemical displacement reaction, mixing with the selenium powder, and reacting in a quartz vacuum tube furnace. Compared with the prior art, the preparation method has the advantages of simple process, low process condition requirement (reaction temperature is 300-350 ℃), easily obtained reaction raw materials, and the final product zinc selenide powder can be directly used as a raw material for preparing the zinc selenide optical material.

It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be made within the scope of the present invention.

The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.