CN111818785B - Low-temperature foaming process for preparing thin-layer carbon-loaded nano ZnO wave-absorbing material in batches - Google Patents

Low-temperature foaming process for preparing thin-layer carbon-loaded nano ZnO wave-absorbing material in batches Download PDF

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CN111818785B
CN111818785B CN202010727557.0A CN202010727557A CN111818785B CN 111818785 B CN111818785 B CN 111818785B CN 202010727557 A CN202010727557 A CN 202010727557A CN 111818785 B CN111818785 B CN 111818785B
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loaded nano
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CN111818785A (en
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丁春艳
吴松松
张文婷
温广武
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Shandong University of Technology
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    • H—ELECTRICITY
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    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/22—Oxides; Hydroxides of metals
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention provides a low-temperature foaming process for preparing thin-layer carbon-loaded nano ZnO wave-absorbing material in batches, which comprises the following steps: glucose and zinc nitrate are used as raw materials, the glucose and metal zinc nitrate are dissolved in deionized water at room temperature to form a uniform and single mixed solution, and the mixed solution is moved to a forced air drying oven. Foaming and expanding at 120 ℃ to form a porous and light precursor, and performing heat treatment at 700 ℃ to obtain the thin-layer carbon-loaded nano ZnO wave-absorbing material. The method belongs to the fields of aerospace and electromagnetic absorption, can realize the regulation and control of the pore structure of the composite material by a low-temperature foaming method, has simple preparation process, and the prepared wave-absorbing material has excellent wave-absorbing performance, thin thickness and light weight, solves the problem of narrow wave-absorbing frequency band of the traditional wave-absorbing material, and can completely cover X and Ku wave bands. The low-temperature foaming method is expected to be popularized as a universal porous thin-layer carbon-loaded nano metal oxide wave-absorbing material and lays an experimental foundation for establishing a variable relation between a porous structure and wave-absorbing performance in the later period.

Description

Low-temperature foaming process for preparing thin-layer carbon-loaded nano ZnO wave-absorbing material in batches
Technical Field
The invention belongs to the field of aerospace and electromagnetic absorption, and particularly relates to a low-temperature foaming process for preparing thin-layer carbon-loaded nano ZnO wave-absorbing materials in batches.
Background
The wave-absorbing material is a material which can effectively absorb incident electromagnetic waves and convert electromagnetic energy into heat energy for consumption, so that the returned electromagnetic waves are obviously weakened. The wave-absorbing material with ideal comprehensive performance has the characteristics of thinness, lightness, width and strength, namely, the material has small thickness, small density, wide absorption bandwidth and strong absorption strength, and simultaneously, the material also has good physical and chemical stability and the like. In recent years, with the widening of the application scenes and the application fields of electromagnetic waves, the wide application of the electromagnetic waves brings serious electromagnetic pollution, and the situation that the health of human beings is threatened is achieved. The wave-absorbing material has the characteristic of low reflectivity, so that the electromagnetic waves entering the wave-absorbing material can be effectively lost, and the wave-absorbing material has wide development prospect in the aspects of electromagnetic shielding and electromagnetic protection. In practical application, the absorption bandwidth is often one of important performance indexes, the previously reported material adopts high-temperature pyrolysis method to decompose the dissimilar bimetallic zeolite imidazolate framework (Co/Zn-ZIFs) to prepare the nitrogen-doped cobalt oxide/cobalt/carbon (CoO/Co/C) nano composite material, RL = -66.7dB at 7.2GHz and the effective bandwidth is 5.1GHz, and although the material has high wave-absorbing strength, the material has the inevitable defects of narrow wave-absorbing frequency band, high cost, complex synthesis steps and the like, thereby often limiting the common application of the material.
The invention uses glucose as a carbon source by a low-temperature foaming method to prepare the ultra-bandwidth thin-layer carbon-loaded nano ZnO wave-absorbing material in batches, and the process is simple, and the required raw materials are cheap and easy to obtain. Porous carbon is a typical dielectric loss material and has good electromagnetic absorption performance, but only dielectric loss weakens electromagnetic impedance matching on the basis of an absorption mechanism. The addition of the metal oxide into the porous carbon can further enhance the microwave absorption, the concentration of zinc ions is regulated and controlled by a low-temperature foaming method, the wall thickness and the structure of the hierarchical pores of the material are further regulated and controlled, the material is converted into a 3D rod-shaped network structure from a 2D sheet-shaped nano structure, the electromagnetic parameters are optimized, the balance of impedance matching and attenuation characteristics of the material is regulated, and the wave-absorbing material has the characteristics of perfect absorption, thin thickness, light weight and wide absorption frequency band.
Disclosure of Invention
The invention aims to provide a low-temperature foaming process for preparing thin-layer carbon-loaded nano ZnO wave-absorbing materials in batches. The concentration of zinc ions can be regulated and controlled according to a low-temperature foaming method, and further the wall thickness and the structure of the multilevel pores of the material are regulated and controlled, so that the material shows the characteristic of broadband absorption.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
a low-temperature foaming process for preparing thin-layer carbon-loaded nano ZnO wave-absorbing material in batches is characterized by comprising the following steps:
(1) Glucose and metallic zinc nitrate were dissolved in deionized water to form a homogeneous single mixed solution.
The above experimental protocol (1) is characterized in that the mass of glucose used for preparing the uniformly mixed solution is 1g, the mass of metallic zinc nitrate is 2g, and the solution is dissolved in 10 mL deionized water.
(2) And (3) transferring the solution prepared in the step (1) to a forced air drying oven, and carrying out foaming polymerization at a low temperature to obtain a porous and light expanded precursor.
The above experimental protocol (2) is characterized in that it is dried at 120 ℃ for 12 hours.
(3) And (3) transferring the precursor prepared in the step (2) into a tubular furnace, heating to a certain temperature in a protective atmosphere, preserving the heat for 2 hours, and annealing to obtain the thin-layer carbon-loaded nano ZnO wave-absorbing material.
The above experimental scheme (3) is characterized in that the temperature is raised to 700 ℃ at 5 ℃/min under the atmosphere of protective atmosphere nitrogen, and the temperature is kept at 700 ℃ for 2 hours.
(4) And (4) loading the thin-layer carbon-loaded nano ZnO wave-absorbing material prepared in the step (3) according to the following steps: paraffin =1:10 until the mixture is uniformly mixed, pressing the mixture into a ring test wave-absorbing material with the outer diameter of 7.0 mm and the inner diameter of 3.0 mm.
Compared with other processes, the method has the characteristics that:
(1) The method has simple process, low cost and easy process production;
(2) The concentration of zinc ions is adjusted by a low-temperature foaming method, so that the wall thickness and the pore structure of the material are regulated and controlled, the electromagnetic parameters are optimized, and the balance of impedance matching and attenuation characteristics of the wave-absorbing material is adjusted. The special hierarchical pore structure of the thin-layer carbon-loaded nano ZnO wave-absorbing material enables electromagnetic waves to be scattered and reflected for multiple times in the material, further enhances the loss of the electromagnetic waves and effectively widens the wave-absorbing frequency band.
(3) The thin-layer carbon-loaded nano ZnO wave-absorbing material carbonized at 700 ℃ has excellent ultra-bandwidth wide-frequency wave-absorbing performance. The absorbing frequency bandwidth of the wave-absorbing material reaches 7.9 GHz, can span a half X wave band and completely cover the whole KU wave band, and has strong electromagnetic wave absorbing capacity.
(4) The experimental project is that the dielectric constant of the thin-layer carbon-loaded nano ZnO wave-absorbing material is further adjusted through the interface combination of porous carbon and zinc oxide particles, and the micro capacitor structure is formed by attaching the zinc oxide particles to the porous carbon so as to enhance the wave-absorbing performance of the thin-layer carbon-loaded nano ZnO wave-absorbing material. And the loading of the material was low, only 11.11 wt.%, and could be made in large quantities. The material has thin, light and wide wave-absorbing performance, can be widely applied to the industrial and military fields, and opens up a new way for developing various new high-performance wave-absorbing materials for application.
Description of the drawings:
FIG. 1 is a diagram of an expanded precursor of foam polymerization in example 1 by a low-temperature foaming method.
FIG. 2 is an XRD pattern of the thin-layer carbon-supported nano ZnO wave-absorbing material in example 1.
FIG. 3 is a three-dimensional wave-absorbing diagram of the thin-layer carbon-loaded nano ZnO wave-absorbing material in example 1.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
Glucose 1g and zinc nitrate 2g were dissolved in 10 mL deionized water to form a uniformly mixed solution. And transferring the prepared solution to a forced air drying oven, drying for 12 hours at 120 ℃, and carrying out foaming polymerization to obtain a porous and light expanded precursor. And transferring the prepared precursor into a tube furnace, heating to 700 ℃ at 5 ℃/min under the atmosphere of protective atmosphere nitrogen, preserving the heat at 700 ℃ for 2 hours, and annealing to obtain the thin-layer carbon-loaded nano ZnO wave-absorbing material. Then loading the nano ZnO wave-absorbing material according to the thin carbon: paraffin =1:10 until the mixture is uniformly mixed, pressing the mixture into a ring with the outer diameter of 7.0 mm and the inner diameter of 3.0 mm, and testing the wave absorbing performance of the ring.
Fig. 1 is a diagram of an expanded precursor obtained by foaming polymerization in the low-temperature foaming method according to example 1, and it can be seen that the expanded precursor has a porous honeycomb shape. Fig. 2 is an XRD pattern of the thin-layer carbon-supported nano ZnO wave-absorbing material of example 1, and it can be seen that a plurality of diffraction peaks respectively correspond to different crystal planes of ZnO, and that the peak intensity is large and the half-peak width is narrow, which indicates that the ZnO crystal grains obtained under such conditions are relatively complete. FIG. 3 is a three-dimensional wave-absorbing diagram of the thin-layer carbon-supported nano ZnO wave-absorbing material in example 1. The graph shows that the RL value of the sample is-24 dB when the thickness is 3mm and the frequency is 13 GHz, the bandwidth reaches 7.9 GHz, and the whole Ku waveband is covered. When the thickness is 4mm and the frequency is 9GHz, the RL value is-19.9 dB, and the bandwidth reaches 5 GHz and covers the whole X wave band.
The above description is only a preferred embodiment of the present invention, and it should be understood by those skilled in the art that the present invention is not limited by the examples, and several modifications and decorations can be made, and these modifications and decorations are also within the scope of the present invention.

Claims (1)

1. A low-temperature foaming process for preparing a thin-layer carbon-loaded nano ZnO wave-absorbing material in batches is characterized by comprising the following steps:
(1) Dissolving 1g glucose and 2g zinc nitrate in 10 mL deionized water to form a uniform single mixed solution;
(2) Transferring the solution prepared in the step 1 to a forced air drying oven, drying for 12 hours at 120 ℃, and carrying out foaming polymerization to obtain a porous and light expanded precursor;
(3) Transferring the precursor prepared in the step 2 into a tube furnace, heating to 700 ℃ at 5 ℃/min under the atmosphere of protective atmosphere nitrogen, preserving heat at 700 ℃ for 2 hours, and annealing to obtain the thin-layer carbon-loaded nano ZnO wave-absorbing material;
(4) And (3) loading the thin-layer carbon loaded nano ZnO wave-absorbing material prepared in the step (3) according to the following steps: paraffin =1:10 until the mixture is uniformly mixed, pressing the mixture into a ring test wave-absorbing material with the outer diameter of 7.0 mm and the inner diameter of 3.0 mm.
CN202010727557.0A 2020-07-27 2020-07-27 Low-temperature foaming process for preparing thin-layer carbon-loaded nano ZnO wave-absorbing material in batches Active CN111818785B (en)

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CN112250057A (en) * 2020-10-30 2021-01-22 山东理工大学 Preparation method of ammonium nitrate-assisted macroporous thin-layer carbon
CN112979332A (en) * 2021-03-23 2021-06-18 陕西科技大学 ZnO-C/Al2SiO5Low-density high-loss complex phase wave-absorbing ceramic and preparation method thereof
CN116004184B (en) * 2023-02-07 2024-04-16 西南石油大学 Nano metal oxide/carbon composite wave-absorbing material and preparation method thereof

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CN109108304A (en) * 2018-08-20 2019-01-01 江苏大学 A kind of preparation method and its usage of silver-ZnO composite nanometer particle
CN109548392A (en) * 2017-09-22 2019-03-29 北京碳极极电科技有限公司 A kind of preparation method of ferroso-ferric oxide-porous carbon composite wave-suction material

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