Multifunctional three-dimensional porous composite material and preparation method thereof

Abstract

The invention belongs to the technical field of magnetic materials, and particularly relates to a multifunctional three-dimensional porous composite material and a preparation method thereof. The composite material comprises the following components in percentage by weight: 75-90% of ferrite and 10-25% of a ferrite / graphene composite material. The invention relates to a preparation method of a multifunctional three-dimensional porous composite material. The preparation method comprises the steps of ferrite precursor preparation, fullerene precursor preparation, ferrite / graphene composite powder preparation and composite material preparation. The invention develops a multifunctional ferrite material compounded with graphene, fullerene and a negative ion material and a preparation method thereof, and the material has high magnetic strength, infrared radiation function and negative ion release function, and can be widely applied to the fields of environmental protection, medical treatment, health care, sanitation and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of magnetic materials, and particularly relates to a multifunctional three-dimensional porous composite material and a preparation method thereof. Background Art

[0002] Ferrites are mainly composed of iron oxide and other metal oxides. It has good magnetic properties and chemical stability, and has been widely used in composite materials, electronics, sensors, biomedicine and other fields. Ferrites have high magnetization intensity and remanence intensity, can generate stable magnetic field output, and have good magnetic coupling effect. The physical properties of ferrite materials are stable, not affected by environmental factors such as temperature and humidity, and can maintain stable electrical properties for a long time. Ferrites have good chemical stability, can withstand the erosion of corrosive media such as acids and alkalis, and will not corrode or deform. The defects of ferrites mainly include low remanence, large magnetic induction temperature coefficient, hard and brittle after sintering, and difficult machining, which limit their application in multifunctional scenarios. In the prior art, carbon material modification of ferrites can improve conductivity, but it is easy to cause magnetic attenuation; the introduction of anion materials is often through physical mixing, which has problems of uneven dispersion and poor functional stability. In addition, how to simultaneously retain magnetism and achieve the synergistic effect of infrared radiation and anion release is still a technical difficulty. Summary of the Invention

[0003] The purpose of the present invention is to provide a preparation method of a multifunctional composite material with high magnetic strength, infrared radiation function, and anion release function.

[0004] In order to solve the problems existing in the prior art, the present invention adopts the following technical solutions: A multifunctional three-dimensional porous composite material, by weight percentage, includes 75-90% ferrites and 10-25% graphene composite powder materials.

[0005] In the above-mentioned multifunctional three-dimensional porous composite material, the graphene composite powder material includes the following raw materials and a mixture made according to the following weight percentages: 40-60% anion material, 10-20% fullerene, 5-15% graphene, and the rest are additives; the anion material includes one or a mixture of two of tourmaline material and opal material.

[0006] A preparation method of a multifunctional three-dimensional porous composite material, which includes the following steps: (1) Preparation of ferrite precursor: Weigh an appropriate amount of ferrite raw materials according to weight percentage, ball-mill the ferrite raw materials for 4-6 hours, the particle size reaches 50-100 nm, and obtain ferrite powder through low-temperature sintering and nitrogen protection for 2 hours; (2) Preparation of fullerene precursor: Weigh fullerene and polymer material according to the ratio of 1:7 by weight percentage. Dissolve the mixture of fullerene and polymer material in deionized water, stir evenly, and then perform ultrasonic treatment for 1 - 2 h. Let it stand for 2 - 3 hours to obtain a stable fullerene precursor colloid. The polymer material is selected from one of polyacrylonitrile, polyvinylpyrrolidone, polystyrene, polyvinyl alcohol, and polypropylene. (3) Preparation of ferrite / graphene composite powder: Disperse graphene in ethylene glycol, and then add ferrite powder. Carry out hydrothermal reaction at 180 - 200 °C for 12 - 18 h, stir at 2000 - 3000 revolutions per minute until the sol is evenly mixed, and perform ultrasonic treatment for 30 - 60 min. Obtain ferrite / graphene composite powder material by spray drying and form a core - shell structure. (4) Preparation of composite material: Ultrasonically mix the ferrite / graphene composite powder material and the negative ion material in ethanol for 3 - 5 h and combine them by electrostatic adsorption. Dropwise add the fullerene precursor colloid, heat to 360 - 400 °C, stir at 3000 - 3500 revolutions per minute for 4 - 6 h to form a π - π bond and hydrogen bond cross - linked network. Then pre - freeze at - 80 - - 50 °C for 24 - 36 h and vacuum freeze - dry to obtain a three - dimensional porous multifunctional composite material.

[0007] For the preparation method of the above - mentioned multifunctional three - dimensional porous composite material, the particle size of the negative ion material is 0.1 - 5 µm, and the negative ion material includes one or a mixture of two of tourmaline material and opal material.

[0008] Compared with the prior art, the present invention has the following beneficial effects: The present invention develops a multifunctional ferrite material composite with graphene, fullerene, and negative ion materials and its preparation method. This material has both high magnetic strength, infrared radiation function, and negative ion release function, and can be widely applied in the fields of environmental protection, medical treatment, health care, hygiene, etc. Specific embodiments

[0009] To make the above - mentioned objects, features, and advantages of the present invention more obvious and understandable, the specific embodiments of the present invention will be described in detail below in conjunction with the embodiments of the specification.

[0010] Many specific details are set forth in the following description in order to fully understand the present invention. However, the present invention can also be implemented in other ways different from those described herein. Those skilled in the art can make similar generalizations without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0011] Second, the so-called "one embodiment" or "embodiment" herein refers to specific features, structures or characteristics that may be included in at least one implementation manner of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it an individual or alternative embodiment that mutually excludes other embodiments.

[0012] Unless otherwise specified, the raw materials used in the embodiments are all commercially purchased.

[0013] Example 1

[0014] This example provides a multifunctional three-dimensional porous composite material, which, by weight percentage, includes 90% ferrite and 10% graphene composite powder material. Among them, the graphene composite powder material includes the following raw materials and a mixture made according to the following weight percentages: 60% tourmaline material, 10% fullerene, 15% graphene, and the rest are additives.

[0015] The above-mentioned multifunctional three-dimensional porous composite material is obtained through the following steps: (1) Preparation of ferrite precursor: Calculated by weight percentage, weigh 150 grams of iron oxide ferrite raw material, ball-mill the ferrite raw material for 6 hours until the particle size reaches 80 nm, and obtain ferrite powder through low-temperature sintering and nitrogen protection for 2 hours; (2) Preparation of fullerene precursor: Calculated by weight percentage, weigh 1.5 grams of fullerene, mix the fullerene with 1 wt% polyvinylpyrrolidone in a ratio of 1:7 and dissolve it in 1000 mL of deionized water. After stirring at room temperature for 1.5 hours, perform ultrasonic treatment for 1 h, and let it stand for 2 hours to obtain a stable colloidal solution; (3) Preparation of ferrite / graphene composite powder material: Calculated by weight percentage, weigh 2.25 grams of graphene, disperse the graphene in ethylene glycol, and add the prepared ferrite powder; perform hydrothermal reaction at 180 °C for 12 h, stir at 2000 revolutions per minute until the sol is mixed evenly, perform ultrasonic treatment for 30 min, and obtain the ferrite / graphene composite powder material through spray drying to form a core-shell structure; (4) Preparation of composite material: Weigh 9 grams of tourmaline material, a negative ion material with a particle size of 0.1 µm, ultrasonically mix the ferrite / graphene composite powder material and the tourmaline material, a negative ion material, in ethanol for 3 h, and combine them through electrostatic adsorption; dropwise add the fullerene precursor colloid, heat to 400 °C and stir at 3000 revolutions per minute for 4 h to form a π-π bond and hydrogen bond cross-linked network, and then pre-freeze at -80 °C for 24 h and then perform vacuum freeze-drying to obtain a three-dimensional porous multifunctional composite material.

[0016] Finally, magnetic field-assisted pressing molding is used to make the ferrite magnetically oriented.

[0017] The measured magnetic field strength is ≥1350 Gs, the negative ion release is ≥3300 ions / cm³, and the far-infrared radiation (emissivity ≥0.88).

[0018] Example 2

[0019] This example provides a multifunctional three-dimensional porous composite material, which, by weight percentage, includes 75% ferrite and 25% graphene composite powder material. Among them, the graphene composite powder material includes the following raw materials and a mixture made according to the following weight percentages: 55% opal material, 20% fullerene, 10% graphene, and the rest are additives.

[0020] The above-mentioned multifunctional three-dimensional porous composite material is obtained through the following steps: (1) Preparation of ferrite precursor: Calculated by weight percentage, 150 grams of iron oxide ferrite raw materials are weighed, the ferrite raw materials are ball-milled for 4 hours until the particle size reaches 50 nm, and ferrite powder is obtained through low-temperature sintering and nitrogen protection for 2 hours; (2) Preparation of fullerene precursor: Calculated by weight percentage, 7.5 grams of fullerene are weighed, the fullerene and 1 wt% polyvinyl alcohol are mixed in a ratio of 1:7 and dissolved in 1000 mL of deionized water, ultrasonic-treated for 2 h, and left standing for 2.5 hours to obtain a stable colloidal solution; (3) Preparation of ferrite / graphene composite powder material: Calculated by weight percentage, 3.75 grams of graphene are weighed, the graphene is dispersed in ethylene glycol, and the prepared ferrite powder is added; hydrothermal reaction is carried out at 200 °C for 18 h, stirred at 2500 revolutions per minute until the sol is mixed evenly, ultrasonic-treated for 60 min, and the ferrite / graphene composite powder material is obtained through spray drying, forming a core-shell structure; (4) Preparation of composite material: Calculated by weight percentage, 20.625 grams of opal material with a particle size of 2 µm are weighed, the ferrite / graphene composite powder and the opal material are ultrasonically mixed in ethanol for 5 h and electrostatically adsorbed and combined; the fullerene precursor colloid is dropped, stirred at 360 °C at 3500 revolutions per minute for 6 h to form a π-π bond and hydrogen bond cross-linking network, and then pre-frozen at -50 °C for 36 h and vacuum freeze-dried to obtain a three-dimensional porous multifunctional composite material.

[0021] The measured magnetic field strength is ≥1300 Gs, the negative ion release is ≥3000 ions / cm³, and the far-infrared radiation (emissivity ≥0.83).

[0022] Example 3

[0023] This embodiment provides a multifunctional three-dimensional porous composite material, which, by weight percentage, comprises 80% ferrite and 20% graphene composite powder material. Among them, the graphene composite powder material includes the following raw materials and a mixture made according to the following weight percentages: a mixture of 40% tourmaline material and opal material, 5% fullerene, 5% graphene, and the rest are additives.

[0024] The above-mentioned multifunctional three-dimensional porous composite material is prepared through the following steps: (1) Preparation of ferrite precursor: Calculated by weight percentage, weigh 150 grams of iron oxide ferrite raw materials, ball-mill the ferrite raw materials for 5 hours until the particle size reaches 100 nm, and obtain ferrite powder through low-temperature sintering and nitrogen protection for 2 hours; (2) Preparation of fullerene precursor: Weigh 1.5 grams of fullerene by weight percentage, mix the fullerene with 1 wt% polyacrylonitrile in a ratio of 1:7 and dissolve it in 1000 mL of deionized water, ultrasonically treat it for 1.5 h, and let it stand for 3 hours to obtain a stable colloidal solution; (3) Preparation of ferrite / graphene composite powder material: Weigh 1.5 grams of graphene by weight percentage, disperse graphene oxide in ethylene glycol, and add the prepared ferrite powder; conduct a hydrothermal reaction at 190 °C for 15 h, stir at 3000 revolutions per minute until the sol is evenly mixed, ultrasonically treat it for 45 min, and obtain the ferrite / graphene composite powder material through spray drying, forming a core-shell structure; (4) Preparation of composite material: Weigh 12 grams of a mixture of tourmaline material and opal material with a particle size of 5 µm by weight percentage, ultrasonically mix the ferrite / graphene composite powder material with the mixture of tourmaline material and opal material in ethanol for 4 h, and electrostatically adsorb and combine them; dropwise add the fullerene precursor colloid, stir at 380 °C at 3300 revolutions per minute for 5 h to form a π-π bond and hydrogen bond cross-linking network, and then pre-freeze at -75 °C for 28 h and then vacuum freeze-dry to obtain a three-dimensional porous multifunctional composite material.

[0025] The measured magnetic field strength ≥ 1300 Gs, negative ion release ≥ 3200 pieces / cm³, far-infrared radiation (emissivity ≥ 0.85).

[0026] Example 4

[0027] The difference between this embodiment and Example 1 lies in the preparation step of the fullerene precursor. Calculated by weight percentage, weigh 1.5 grams of fullerene, mix the fullerene with 1 wt% polystyrene in a ratio of 1:7 and dissolve it in 1000 mL of deionized water, stir at room temperature for 1.5 hours, then ultrasonically treat it for 1 h, and let it stand for 2 hours to obtain a stable colloidal solution.

[0028] Example 5

[0029] The difference between this embodiment and Embodiment 1 lies in the preparation steps of the fullerene precursor. By weight percentage, 1.5 grams of fullerene is weighed, and the fullerene and 1 wt% of polypropylene are mixed in a ratio of 1:7 and dissolved in 1000 mL of deionized water. After stirring at room temperature for 1.5 hours, it is ultrasonically treated for 1 h and left standing for 2 hours to obtain a stable colloidal solution.

[0030] The technical advantages of the present invention are as follows: 1. Through precise optimization of the material ratio, the present invention successfully ensures the integrity of the ferrite crystal structure, while achieving the uniform dispersion of other materials and avoiding the formation of excessive non-magnetic phases. With the help of advanced technologies such as ball milling and ultrasonic dispersion, graphene and ferrite particles are uniformly mixed, thus constructing a three-dimensional magnetic-conductive and conductive double pathway, significantly improving the infrared performance of the material.

[0031] 2. Fullerene, with its high electron affinity, antioxidant property, photocatalytic activity and conductivity, becomes an ideal choice for filling the grain boundary voids of the composite material. It not only protects the magnetic field strength of the ferrite material, but also significantly increases the concentration of negative ions.

[0032] 3. The synergistic effect of negative ions, infrared and magnetic field strength: The negative ion material treated by electrostatic adsorption binding combines with fullerene through covalent bonds to form a π-π bond and hydrogen bond cross-linking network, enhancing the polarization effect. Under the action of a magnetic field (magnetic field strength ≥ 1350 Gs), continuous negative ion release (≥ 3000 pieces / cm³) and 8-14 μm far-infrared radiation (emissivity ≥ 0.83) are excited.

[0033] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not restrictive. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the claims of the present invention.

Claims

1. A multifunctional three-dimensional porous composite material, characterized in that, By weight percentage, it includes 75-90% ferrite and 10-25% graphene composite powder material.

2. The multifunctional three-dimensional porous composite material according to claim 1, characterized in that, The graphene composite powder material includes the following raw materials and a mixture made according to the following weight percentages: 40-60% negative ion material, 5-20% fullerene, 5-15% graphene, and the rest is additives; the negative ion material includes one or a mixture of two of tourmaline material and opal material.

3. The preparation method of a multifunctional three-dimensional porous composite material according to claim 1 or 2, characterized in that, It includes the following steps: (1) Preparation of ferrite precursor: Weigh an appropriate amount of iron oxide ferrite raw materials according to weight percentage, ball-mill the ferrite raw materials for 4-6 hours until the particle size reaches 50-100 nm, and obtain ferrite powder through low-temperature sintering and nitrogen protection for 2 hours. (2) Preparation of fullerene precursor: Weigh fullerene and polymer material in a ratio of 1:7 by weight percentage, dissolve the mixture of fullerene and polymer material in deionized water, stir evenly and then perform ultrasonic treatment for 1-2 h, and let it stand for 2-3 hours to obtain a stable fullerene precursor colloid; the polymer material is selected from one of polyacrylonitrile, polyvinylpyrrolidone, polystyrene, polyvinyl alcohol, and polypropylene. (3) Preparation of ferrite / graphene composite powder material: Disperse graphene in ethylene glycol, and then add ferrite powder; perform hydrothermal reaction at 180-200 °C for 12-18 h, stir at 2000-3000 revolutions per minute until the sol is mixed evenly, perform ultrasonic treatment for 30-60 min, and obtain ferrite / graphene composite powder material through spray drying and form a core-shell structure. (4) Preparation of composite material: Ultrasonically mix the ferrite / graphene composite powder material and the negative ion material in ethanol for 3-5 h and combine them by electrostatic adsorption; dropwise add the fullerene precursor colloid, heat to 360-400 °C and stir at 3000-3500 revolutions per minute for 4-6 h to form a π-π bond and hydrogen bond cross-linked network, and then pre-freeze at -80--50 °C for 24-36 h and then vacuum freeze-dry to obtain a three-dimensional porous multifunctional composite material.

4. The preparation method of a multifunctional three-dimensional porous composite material according to claim 3, characterized in that, The particle size of the negative ion material is 0.1-5 µm, and the negative ion material includes one or a mixture of two of tourmaline material and opal material.