阅读说明：本技术 一种电磁屏蔽功能层材料的制备方法及应用 (Preparation method and application of electromagnetic shielding function layer material ) 是由 杨景 陈建 崔江舟 胡月 刘彦妮 武慧恩 雷晓军 郭佳敏 金世婧 常慧芳 宋秀峰 于 2021-09-10 设计创作，主要内容包括：本发明涉及复合材料领域,将过渡金属基材料的前驱体与离子交换树脂充分混合,并在表面活性剂作用下均匀吸附在树脂表面,形成杂化前驱体；然后进行惰性气氛高温煅烧,金属前驱体热分解形成金属氧化物,树脂碳化形成三维石墨烯框架,最终得到过渡金属氧化物/三维石墨烯框架复合材料；配制含有磁性金属或金属氧化物纳米颗粒和碳纳米管导电剂的浆料,与过渡金属氧化物/石墨烯框架复合材料充分混合并鼓风干燥,制备负载有磁性金属氧化物纳米颗粒的石墨烯/碳纳米管复合材料,即电磁屏蔽功能层材料；并且将电磁屏蔽功能层材料应用于篷布不仅增加电磁波的屏蔽范围,并且优化其屏蔽效能。(The invention relates to the field of composite materials, wherein a precursor of a transition metal-based material is fully mixed with ion exchange resin and is uniformly adsorbed on the surface of the resin under the action of a surfactant to form a hybrid precursor; then carrying out high-temperature calcination in an inert atmosphere, carrying out thermal decomposition on the metal precursor to form a metal oxide, carbonizing resin to form a three-dimensional graphene frame, and finally obtaining a transition metal oxide/three-dimensional graphene frame composite material; preparing slurry containing magnetic metal or metal oxide nano particles and a carbon nano tube conductive agent, fully mixing the slurry with a transition metal oxide/graphene framework composite material, and performing forced air drying to prepare the graphene/carbon nano tube composite material loaded with the magnetic metal oxide nano particles, namely an electromagnetic shielding function layer material; and the electromagnetic shielding functional layer material is applied to the tarpaulin, so that the shielding range of electromagnetic waves is enlarged, and the shielding effectiveness of the tarpaulin is optimized.)

1. A preparation method of an electromagnetic shielding function layer material is characterized in that a precursor of a transition metal-based material is fully mixed with ion exchange resin and is uniformly adsorbed on the surface of the resin under the action of a surfactant to form a hybrid precursor; then carrying out high-temperature calcination in an inert atmosphere, carrying out thermal decomposition on the metal precursor to form a metal oxide, carbonizing resin to form a three-dimensional graphene frame, and finally obtaining a transition metal oxide/three-dimensional graphene frame composite material; preparing slurry containing magnetic metal or metal oxide nano particles and a carbon nano tube conductive agent, fully mixing with the transition metal oxide/graphene framework composite material, and drying by blowing to prepare the graphene/carbon nano tube composite material loaded with the magnetic metal oxide nano particles, namely the electromagnetic shielding function layer material.

2. The method for preparing the material of the electromagnetic shielding functional layer according to claim 1, which comprises the following steps:

(1) mixing material

Adding ion exchange resin and surfactant into the transition metal salt aqueous solution, and stirring at open room temperature to fully mix the transition metal salt aqueous solution and the transition metal salt aqueous solution at the rotating speed of 800r/min so as to fully adsorb metal ions on the surface of the ion exchange resin;

(2) roasting

Roasting the dried mixture obtained in the step (1) for 8 hours at 800 ℃ in a nitrogen atmosphere to prepare a transition metal oxide/three-dimensional graphene framework composite material uniformly loaded with metal oxide nanoparticles;

(3) shielding agent mixing

Preparing slurry containing magnetic nano metal or metal oxide and a carbon nanotube conductive agent, and fully mixing the slurry with the transition metal oxide/three-dimensional graphene frame composite material obtained in the step (2) to obtain shielding agent slurry, namely the electromagnetic shielding function layer material.

3. The method of claim 2, wherein the transition metal salt in step (1) is one of nickel sulfate, nickel acetate, ferric sulfate and copper sulfate.

4. The method for preparing an electromagnetic shielding layer material according to claim 2, wherein the surfactant in step (1) is sodium hexadecylbenzene sulfonate.

5. The method for preparing a material of an electromagnetic shielding functional layer according to claim 2, wherein the magnetic metal in step (3) is copper or silver, and the magnetic metal oxide is nickel oxide or ferroferric oxide.

6. The method for preparing an electromagnetic shielding functional layer material according to claim 2, wherein the mass ratio of the transition metal salt, the ion exchange resin, the surfactant, the magnetic nano metal or metal oxide of step (3), and the carbon nanotubes in step (1) is 10 to 15: 70-80: 1-2: 5-8: 10-15.

7. Use of the material for electromagnetic shielding function layer prepared by the preparation method according to any one of claims 1 to 6 in the manufacture of tarpaulin, protective clothing and device liner.

8. The use of the material for electromagnetic shielding function layer prepared by the preparation method according to any one of claims 1 to 6 in the preparation of broadband high-efficiency electromagnetic shielding tarpaulin.

Technical Field

The invention relates to the field of composite materials, in particular to a preparation method and application of an electromagnetic shielding functional layer material.

Background

The electromagnetic shielding tarpaulin is a main functional material used for field battlefield communication command, precise electronic instrument and equipment storage and important personnel office tents, and has important significance in the field of civil and military communication protection. The electromagnetic shielding coating is mostly processed by uniformly dispersing high-conductivity filler or high-permeability filler in a polymer matrix. However, the prepared electromagnetic shielding material has the problems of narrow electromagnetic shielding frequency band, unsatisfactory low-frequency band shielding efficiency and the like due to single shielding mechanism. However, the currently widely adopted multi-functional material compounding method can complicate the preparation process, thereby hindering the large-scale production and application thereof.

Disclosure of Invention

The invention provides a preparation method of an electromagnetic shielding function layer material, and the electromagnetic shielding function layer material is applied to tarpaulin, so that the shielding range of electromagnetic waves is enlarged, and the shielding efficiency of the tarpaulin is optimized.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a preparation method of an electromagnetic shielding function layer material comprises the steps of fully mixing a precursor of a transition metal-based material with ion exchange resin, and uniformly adsorbing the precursor on the surface of the resin under the action of a surfactant to form a hybrid precursor; then carrying out high-temperature calcination in an inert atmosphere, carrying out thermal decomposition on the metal precursor to form a metal oxide, carbonizing resin to form a three-dimensional graphene frame, and finally obtaining a transition metal oxide/three-dimensional graphene frame composite material; preparing slurry containing magnetic metal or metal oxide nano particles and a carbon nano tube conductive agent, fully mixing with the transition metal oxide/graphene framework composite material, and drying by blowing to prepare the graphene/carbon nano tube composite material loaded with the magnetic metal oxide nano particles, namely the electromagnetic shielding function layer material.

Further, the preparation method specifically comprises the following steps:

(1) mixing material

Adding ion exchange resin and surfactant into the transition metal salt aqueous solution, and stirring at open room temperature to fully mix the transition metal salt aqueous solution and the transition metal salt aqueous solution at the rotating speed of 800r/min so as to fully adsorb metal ions on the surface of the ion exchange resin;

(2) roasting

Roasting the dried mixture obtained in the step (1) for 8 hours at 800 ℃ in a nitrogen atmosphere to prepare a transition metal oxide/three-dimensional graphene framework composite material uniformly loaded with metal oxide nanoparticles;

(3) shielding agent mixing

Preparing slurry containing magnetic nano metal or metal oxide and a carbon nanotube conductive agent, and fully mixing the slurry with the transition metal oxide/three-dimensional graphene frame composite material obtained in the step (2) to obtain shielding agent slurry, namely the electromagnetic shielding function layer material.

Further, the transition metal salt in the step (1) is one of nickel sulfate, nickel acetate, ferric sulfate and copper sulfate.

Further, the surfactant in the step (1) is sodium hexadecylbenzene sulfonate.

Further, the magnetic metal in the step (3) is copper or silver, and the magnetic metal oxide is nickel oxide or ferroferric oxide.

Preferably, the mass ratio of the transition metal salt, the ion exchange resin, the surfactant, the magnetic nano metal or metal oxide of the step (3) and the carbon nanotubes in the step (1) is 10-15: 70-80: 1-2: 5-8: 10-15.

In addition, the invention also provides application of the electromagnetic shielding functional layer material prepared by the preparation method in manufacturing tarpaulin, protective clothing and device liners, and the electromagnetic shielding functional layer material has the function of preventing internal electromagnetic information leakage or external electromagnetic pulse interference.

And uniformly coating the electromagnetic shielding function layer material on the surface of the conductive base cloth to form an electromagnetic shielding function layer, wherein the thickness of the electromagnetic shielding function layer is 0.3mm, and thus the broadband efficient electromagnetic shielding tarpaulin is formed.

Further, a flexible protective film is coated on the surface of the electromagnetic shielding function layer, the coatings are adhered by an adhesive to form a firm composite layer, and the composite layer is dried at 80 ℃ and then cut to form the broadband efficient electromagnetic shielding tarpaulin.

Preferably, the flexible protective film is a flexible polyurethane film

Furthermore, the mass ratio of the carbon nanotubes used by the electromagnetic shielding functional layer material to the conductive base cloth and the flexible protective film is 10-15: 13-20: 5-15.

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

the invention breaks through the traditional single electromagnetic shielding means, fully utilizes the structure and property advantages of the graphene framework material, uniformly arranges magnetic nano particles with high specific surface area in the three-dimensional direction, and forms an interpenetrating network by compounding the nano particles with the carbon nano tube with high length-diameter ratio, so that the three-dimensional graphene framework structure is utilized to construct a closed conducting layer with high magnetic permeability, and the dual functions of conducting and conducting are realized.

The high-frequency protective conductive base cloth is compounded by the adhesive, so that the comprehensive high-efficiency protective effect of high frequency and low frequency is realized. In addition, a protective film is added outside the electromagnetic shielding coating, so that the flexibility and the weather resistance of the tarpaulin are greatly improved.

Drawings

Fig. 1 is a three-dimensional graphene frame structure diagram.

Fig. 2 is a structure diagram of a nickel nanoparticle-carbon nanotube composite.

Detailed Description

The present invention is further illustrated by the following specific examples.

The method for preparing the broadband high-efficiency electromagnetic shielding tarpaulin by using the electromagnetic shielding functional layer material comprises the following steps of:

(1) mixing material

Adding ion exchange resin and surfactant into the transition metal salt water solution, and stirring at open room temperature to fully mix the transition metal salt water solution and the transition metal salt water solution at the rotating speed of 800r/min so as to fully adsorb metal ions on the surface of the ion exchange resin.

(2) Roasting

And roasting the dried mixture for 8 hours at 800 ℃ in a nitrogen atmosphere to prepare the three-dimensional graphene frame composite material uniformly loaded with the metal oxide nanoparticles.

(3) Shielding agent mixing

Preparing slurry containing magnetic nano metal or metal oxide, carbon nano tubes and other conductive agents, and fully mixing the slurry with the transition metal oxide/graphene framework composite material.

(4) Coating of

And (3) coating the slurry, and uniformly coating the slurry on conductive base cloth to prepare the electromagnetic shielding tarpaulin with the thickness of 0.3mm (the thickness of the electromagnetic shielding function layer). And continuously coating the surface of the flexible protective film, and bonding the coatings by adopting an adhesive to form a firm composite layer.

(5) Drying and forming

The materials are dried at 80 ℃ and cut to form, and can be properly painted.

Examples 1 to 5 were carried out according to the preparation method described above, wherein the selection and the formulation of the components were carried out according to table 1:

TABLE 1

The above examples 1-5 were tested for performance and the results are shown in Table 2:

TABLE 2