阅读说明：本技术 一种碳化钛和钴镍合金复合吸波材料及其制备方法 (Titanium carbide and cobalt-nickel alloy composite wave-absorbing material and preparation method thereof ) 是由 陈甜甜 姚建涛 张贵泉 陈君 刘薇 于 2021-09-29 设计创作，主要内容包括：本发明公开了一种碳化钛和钴镍合金复合吸波材料及其制备方法,该复合吸波材料包括两部分：Ti-(3)C-(2)T-(X)和钴镍合金,其中,Ti-(3)C-(2)T-(X)呈层状结构,钴镍合金呈颗粒状,形成二维复合材料。其制备方法包括：通过HF刻蚀得到层状Ti-(3)C-(2)T-(X),将Ti-(3)C-(2)T-(X)与乙酸钴、乙酸镍和氢氧化钠混合,采用溶剂热法制备得到碳化钛和钴镍合金复合吸波材料。本发明制备的碳化钛和钴镍合金复合吸波材料具有良好的电磁吸收性能,制备过程简单,适合工业化大规模生产。(The invention discloses a titanium carbide and cobalt-nickel alloy composite wave-absorbing material and a preparation method thereof, wherein the composite wave-absorbing material comprises two parts: ti 3 C 2 T X And cobalt-nickel alloys of which Ti is 3 C 2 T X The cobalt-nickel alloy is in a layered structure and granular, and forms a two-dimensional composite material. The preparation method comprises the following steps: obtaining layered Ti by HF etching 3 C 2 T X Is prepared from Ti 3 C 2 T X Mixing with cobalt acetate, nickel acetate and sodium hydroxide, and preparing the titanium carbide and cobalt-nickel alloy composite wave-absorbing material by adopting a solvothermal method. The titanium carbide and cobalt-nickel alloy composite wave-absorbing material prepared by the invention has good electromagnetic absorption performance, is simple in preparation process and is suitable for industrial large-scale production.)

1. A preparation method of a titanium carbide and cobalt-nickel alloy composite wave-absorbing material is characterized by comprising the following steps:

mixing Ti₃AlC₂Adding the powder into HF solution, and uniformly stirring for reaction;

centrifuging and drying after the reaction is finished to obtain multilayer Ti₃C₂T_XPowder;

mixing Ti₃C₂T_XDispersing in ethylene glycol, adding cobalt acetate, nickel acetate and sodium hydroxide, and uniformly stirring to obtain a mixed solution;

transferring the mixed solution to a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, heating to 180-220 ℃, and carrying out heat preservation reaction;

and washing and drying the solution after the reaction is finished to obtain the final composite wave-absorbing material.

2. The method of claim 1, wherein Ti is₃AlC₂The proportion of the powder to the HF solution is 1g (0.1-0.15) L.

3. The method of claim 1, wherein Ti is₃C₂T_XThe ratio of the cobalt acetate to the ethylene glycol is (1:1) - (1:2), the mass ratio of the cobalt acetate to the nickel acetate is (1:1) - (1:2), the mass ratio of the cobalt acetate to the sodium hydroxide is (1:3) - (1:4), and the ratio of the cobalt acetate to the ethylene glycol is (4-8) g: 1L.

4. The method according to claim 1, wherein the reaction mixture,

and after the reaction is finished, centrifuging by using deionized water, and repeating for several times until the pH value is approximately equal to 6.

5. The method according to claim 1, wherein the reaction mixture,

and washing the solution after the reaction is finished by adopting ethanol.

6. The method according to claim 1, wherein the reaction mixture,

the two drying conditions are vacuum drying for 8-12 h at 60-100 ℃.

7. The titanium carbide and cobalt-nickel alloy composite wave-absorbing material is characterized by comprising Ti₃C₂T_XAnd cobalt-nickel alloy, wherein the reflectivity peak value of the material is-32.4 dB at 4.4 GHz.

8. The titanium carbide and cobalt-nickel alloy composite wave-absorbing material as claimed in claim 1, wherein the Ti is Ti₃C₂T_XThe mass percentage of the cobalt-nickel alloy is 20-40% of the wave-absorbing material, and the mass percentage of the cobalt-nickel alloy is 60-80% of the wave-absorbing material.

Technical Field

The invention belongs to the field of wave-absorbing materials, and particularly relates to a titanium carbide and cobalt-nickel alloy composite wave-absorbing material and a preparation method thereof.

Background

In recent years, the explosion of the communication industry and the popularization of various electronic devices have brought about an increasingly prominent problem of electromagnetic pollution while providing great convenience to people's lives. Designing and preparing the high-efficiency wave-absorbing material become keys for protecting human health and ensuring normal operation of electronic equipment.

The soft magnetic materials of iron, cobalt, nickel and other metals and alloys thereof have high saturation magnetization and high Snoek limit in the GHz range, and thus have more ideal electromagnetic wave absorption capability than other materials. The cobalt-nickel alloy has strong magnetic loss, low price and simple preparation process, and is widely concerned in the field of wave absorption. However, the single-component cobalt-nickel alloy has the disadvantages of high density, single electromagnetic wave attenuation mechanism and the like.

Ti₃C₂T_XTi obtained by etching and having a two-dimensional structure and properties similar to those of graphene₃C₂T_XThere are a large number of functional groups and defects that can optimize impedance matching to some extent. Further, Ti₃C₂T_XHas the characteristic of nonlinear response to frequency radiation, has certain electrical loss capacity, and simultaneously Ti₃C₂T_XHas larger surface area and special layered structure, is easy to meet the requirements of thin, light, wide and strong wave-absorbing material materials, and is a novel wave-absorbing agent with great development prospect.

Disclosure of Invention

In order to improve the electromagnetic absorption performance of the composite material, the invention mainly aims to provide the titanium carbide and cobalt-nickel alloy composite wave-absorbing material and the preparation method thereof, so as to achieve the purposes of optimizing impedance matching and realizing multiple losses, thereby improving the electromagnetic absorption performance of the material.

In order to achieve the purpose, the invention adopts the technical scheme that:

a preparation method of a titanium carbide and cobalt-nickel alloy composite wave-absorbing material comprises the following steps:

mixing Ti₃AlC₂Adding the powder into HF solution, and uniformly stirring for reaction;

centrifuging and drying after the reaction is finished to obtain multilayer Ti₃C₂T_XPowder;

mixing Ti₃C₂T_XDispersing in ethylene glycol, adding cobalt acetate, nickel acetate and sodium hydroxide, and uniformly stirring to obtain a mixed solution;

transferring the mixed solution to a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, heating to 180-220 ℃, and carrying out heat preservation reaction;

and washing and drying the solution after the reaction is finished to obtain the final composite wave-absorbing material.

As a further improvement of the present invention, Ti₃AlC₂The proportion of the powder to the HF solution is 1g (0.1-0.15) L.

As a further improvement of the present invention, Ti₃C₂T_XThe ratio of the cobalt acetate to the ethylene glycol is (1:1) - (1:2), the mass ratio of the cobalt acetate to the nickel acetate is (1:1) - (1:2), the mass ratio of the cobalt acetate to the sodium hydroxide is (1:3) - (1:4), and the ratio of the cobalt acetate to the ethylene glycol is (4-8) g: 1L.

As a further improvement of the invention, after the reaction is finished, the centrifugation is carried out by using deionized water, and the centrifugation is repeated for a plurality of times until the pH is approximately equal to 6.

As a further improvement of the invention, in the washing of the solution after the reaction is finished, ethanol is used for washing.

As a further improvement of the invention, the two drying conditions are vacuum drying for 8-12 h at 60-100 ℃.

A titanium carbide and cobalt-nickel alloy composite wave-absorbing material comprises Ti₃C₂T_XAnd cobalt-nickel alloy, wherein the reflectivity peak value of the material is-32.4 dB at 4.4 GHz.

The Ti₃C₂T_XThe mass percentage of the cobalt-nickel alloy is 20-40% of the wave-absorbing material, and the mass percentage of the cobalt-nickel alloy is 60-80% of the wave-absorbing material.

The technical scheme provided by the invention has the following beneficial effects:

according to the invention, titanium carbide and cobalt-nickel alloy are compounded to prepare the multi-element composite material, so that impedance matching is optimized, and the electromagnetic absorption performance of the material is improved; the invention adopts a solvothermal method, and obtains better electromagnetic absorption performance by changing the content of the cobalt-nickel alloy; the preparation method is simple, low in production cost, simple and convenient in subsequent treatment and free of complex synthesis equipment.

The titanium carbide and cobalt-nickel alloy composite wave-absorbing material prepared by the invention has good electromagnetic absorption performance, and can realize multiple electromagnetic losses of the composite material and improve the electromagnetic absorption performance of the composite material by compounding the titanium carbide and the cobalt-nickel alloy. The preparation process is simple and is suitable for industrial large-scale production.

Drawings

FIG. 1 is an SEM image of a titanium carbide and cobalt-nickel alloy composite wave-absorbing material prepared in example 1;

FIG. 2 is a reflectivity curve of the composite wave-absorbing material of titanium carbide and cobalt-nickel alloy prepared in example 1.

Detailed Description

To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.

All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.

Unless otherwise specified herein, "comprising," including, "" containing, "" having, "or the like, means" consisting of … … "and" consisting essentially of … …, "e.g.," a comprises a "means" a comprises a and the other, "and" a comprises a only.

In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.

The invention provides a preparation method of a titanium carbide and cobalt-nickel alloy composite wave-absorbing material, which comprises the following steps:

1) mixing Ti₃AlC₂Adding the powder into an HF solution, and stirring at room temperature for 24-48 h; ti₃AlC₂The proportion of the powder to the HF solution is 1g (0.1-0.15) L.

2) After the reaction is finished, centrifuging by deionized water, and repeating for several times until the pH value is approximately equal to 6;

3) vacuum drying at 60-100 ℃ for 8-12 h to obtain multilayer Ti₃C₂T_XPowder;

4) mixing Ti₃C₂T_XDispersing in ethylene glycol, adding cobalt acetate, nickel acetate and sodium hydroxide, and uniformly stirring to obtain a mixed solution; ti₃C₂T_XThe ratio of the cobalt acetate to the ethylene glycol is 1: 1-1: 2, the mass ratio of the cobalt acetate to the nickel acetate is 1: 1-1: 2, the mass ratio of the cobalt acetate to the sodium hydroxide is 1: 3-1: 4, and the ratio of the cobalt acetate to the ethylene glycol is (4-8) g: 1L.

5) Transferring the mixed solution to a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, heating to 180-220 ℃, and keeping the temperature for 8-16 hours;

6) and washing the solution after the reaction is finished with ethanol for several times, and drying the solution in a vacuum drying oven at the temperature of 60-100 ℃ for 8-12 hours to obtain the final composite wave-absorbing material.

The invention also provides a titanium carbide and cobalt-nickel alloy composite wave-absorbing material based on the methodIs prepared from Ti₃C₂T_XAnd cobalt-nickel alloy, wherein the reflectivity peak value of the material is-32.4 dB at 4.4 GHz.

The Ti₃C₂T_XThe mass of the cobalt-nickel alloy is 20-40% of the wave-absorbing material, and the mass of the cobalt-nickel alloy is 60-80% of the wave-absorbing material.

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.

Example 1

The method comprises the following steps: 0.2g of Ti₃AlC₂The powder was dissolved in 30mL HF solution, stirred at room temperature for 24h, and after the reaction was complete, centrifuged through deionized water, repeated several times until pH ≈ 6.

Step two: vacuum drying the solution obtained in the step one in a drying oven at 60 ℃ for 12 hours to obtain multilayer Ti₃C₂T_XAnd (3) powder.

Step three: mixing Ti₃C₂T_XThe powder was dispersed in 50mL of ethylene glycol, and 0.2g of cobalt acetate, 0.2g of nickel acetate and 0.6g of sodium hydroxide were added and stirred uniformly to obtain a mixed solution.

Step four: transferring the mixed solution obtained in the third step to a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, gradually increasing the temperature to 180 ℃, and preserving the temperature for 16 hours to obtain the productTi₃C₂T_XAnd cobalt nickel alloy solutions.

Step five: ti obtained in the fourth step₃C₂T_XAnd washing the cobalt-nickel alloy solution with ethanol for several times, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the final composite wave-absorbing material.

Example 2

The method comprises the following steps: 0.2g of Ti₃AlC₂The powder was dissolved in 20mL HF solution, stirred at room temperature for 48h, and after the reaction was complete, centrifuged through deionized water, repeated several times until pH ≈ 6.

Step two: vacuum drying the solution obtained in the step one in a drying oven at 100 ℃ for 8 hours to obtain multilayer Ti₃C₂T_XAnd (3) powder.

Step three: mixing Ti₃C₂T_XThe powder was dispersed in 50mL of ethylene glycol, and 0.4g of cobalt acetate, 0.4g of nickel acetate and 1.2g of sodium hydroxide were added and stirred uniformly to obtain a mixed solution.

Step four: transferring the mixed solution obtained in the third step to a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, gradually increasing the temperature to 220 ℃, and preserving the temperature for 8 hours to obtain Ti₃C₂T_XAnd cobalt nickel alloy solutions.

Step five: ti obtained in the fourth step₃C₂T_XAnd washing the cobalt-nickel alloy solution with ethanol for several times, and drying in a vacuum drying oven at 100 ℃ for 8 hours to obtain the final composite wave-absorbing material.

Example 3

The method comprises the following steps: 0.2g of Ti₃AlC₂The powder was dissolved in 25mL HF solution, stirred at room temperature for 30h, and after the reaction was complete, centrifuged through deionized water, repeated several times until pH ≈ 6.

Step two: vacuum drying the solution obtained in the step one in a drying oven at 80 ℃ for 10 hours to obtain multilayer Ti₃C₂T_XAnd (3) powder.

Step three: mixing Ti₃C₂T_XThe powder was dispersed in 50mL of ethylene glycol, 0.2g of cobalt acetate, 0.3g of nickel acetate and 0.7g of sodium hydroxide were added,and stirring uniformly to obtain a mixed solution.

Step four: transferring the mixed solution obtained in the third step to a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, gradually increasing the temperature to 200 ℃, and preserving the temperature for 12 hours to obtain Ti₃C₂T_XAnd cobalt nickel alloy solutions.

Step five: ti obtained in the fourth step₃C₂T_XAnd washing the cobalt-nickel alloy solution with ethanol for several times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the final composite wave-absorbing material.

Example 4

The method comprises the following steps: 0.2g of Ti₃AlC₂The powder was dissolved in 25mL HF solution, stirred at room temperature for 30h, and after the reaction was complete, centrifuged through deionized water, repeated several times until pH ≈ 6.

Step two: vacuum drying the solution obtained in the step one in a drying oven at 80 ℃ for 10 hours to obtain multilayer Ti₃C₂T_XAnd (3) powder.

Step three: mixing Ti₃C₂T_XThe powder was dispersed in 50mL of ethylene glycol, and 0.2g of cobalt acetate, 0.4g of nickel acetate and 0.8g of sodium hydroxide were added and stirred uniformly to obtain a mixed solution.

Step four: transferring the mixed solution obtained in the third step to a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, gradually increasing the temperature to 200 ℃, and preserving the temperature for 12 hours to obtain Ti₃C₂T_XAnd cobalt nickel alloy solutions.

Step five: ti obtained in the fourth step₃C₂T_XAnd washing the cobalt-nickel alloy solution with ethanol for several times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the final composite wave-absorbing material.

Example 5

The method comprises the following steps: 0.2g of Ti₃AlC₂The powder was dissolved in 25mL HF solution, stirred at room temperature for 24h, and after the reaction was complete, centrifuged through deionized water, repeated several times until pH ≈ 6.

Step two: vacuum drying the solution obtained in the step one in a drying oven at 80 ℃ for 10 hours to obtain multilayer Ti₃C₂T_XAnd (3) powder.

Step three: mixing Ti₃C₂T_XThe powder was dispersed in 50mL of ethylene glycol, and 0.3g of cobalt acetate, 0.5g of nickel acetate and 1g of sodium hydroxide were added and stirred uniformly to obtain a mixed solution.

Step four: transferring the mixed solution obtained in the third step to a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, gradually increasing the temperature to 180 ℃, and preserving the temperature for 12 hours to obtain Ti₃C₂T_XAnd cobalt nickel alloy solutions.

Step five: ti obtained in the fourth step₃C₂T_XAnd washing the cobalt-nickel alloy solution with ethanol for several times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the final composite wave-absorbing material.

The invention is described in further detail below with reference to the accompanying drawings:

referring to fig. 1, which is an SEM image of the titanium carbide and cobalt-nickel alloy composite wave-absorbing material prepared in example 1 of the present invention, it can be seen that Ti₃C₂T_XThe cobalt-nickel alloy is in a layered structure and granular.

Referring to fig. 2, it can be seen from analysis that the reflectivity peak of the reflectivity curve of the titanium carbide and cobalt-nickel alloy composite wave-absorbing material prepared in embodiment 1 of the present invention is-32.4 dB at 4.4 GHz.

Therefore, the titanium carbide and cobalt-nickel alloy composite wave-absorbing material prepared by the invention has the reflectivity peak value of-32.4 dB at 4.4GHz, and obtains better electromagnetic absorption performance.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.