Core-shell structure absorber with nickel-plated hollow microspheres as core and conductive polymer coating and preparation method thereof
By preparing a conductive polymer core-shell structure absorber with nickel-plated hollow microbeads as the core, the problems of lightweight and corrosion resistance of electromagnetic wave absorption materials in weapons and equipment were solved, and efficient electromagnetic wave absorption and stealth performance were improved.
Patent Information
- Application Number
- CN202211170025.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-09-22
- Publication Date
- 2025-09-09
- Estimated Expiration
- 2042-09-22
AI Technical Summary
Existing technologies make it difficult to achieve the comprehensive performance of efficient broadband electromagnetic wave absorption, lightweight and resistance to special environments in weapons and equipment, especially in equipment such as ships, where it is difficult to improve radar stealth performance.
Nickel-plated hollow microspheres are used as the core and coated with a core-shell structure absorber of conductive polymer. A lightweight and corrosion-resistant electromagnetic wave absorbing material is prepared through multi-step chemical treatment and nickel plating process.
It achieves efficient absorption of electromagnetic waves at low density, improves the radar stealth performance and corrosion resistance of weapons and equipment, and meets the comprehensive performance requirements of modern equipment.
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of electromagnetic absorbing materials, and particularly relates to a core-shell structured absorber with nickel-plated hollow microbeads as cores and coated with a conductive polymer, and a preparation method thereof. Background Art
[0002] The stealth performance of weapons and equipment, such as fighter jets and ships, is a crucial factor in determining their battlefield survivability. The use of electromagnetic (shielding / absorbing) materials can effectively enhance the radar stealth performance of these equipment, thereby increasing their battlefield survivability. Modern equipment places higher demands on comprehensive performance, including high-efficiency broadband electromagnetic shielding / absorbing, lightweight design, resistance to special (marine) environments, and mechanical properties. Hollow microbeads offer advantages such as low density, pressure resistance, and light weight. Conductive polymers such as polypyrrole and polyaniline offer excellent electrical conductivity and chemical stability. Metallic nickel or its compounds offer excellent magnetic conductivity and corrosion resistance. Combining these three materials can produce a lightweight, highly efficient electromagnetic wave absorbing material with a core-shell structure. Summary of the Invention
[0003] The purpose of the present invention is to provide a core-shell structure absorber with nickel-plated hollow microspheres as the core and coated with a conductive polymer and a preparation method, so as to prepare an electromagnetic wave absorbing material with "light weight, low density and good absorption".
[0004] The purpose of the present invention can be achieved by the following technical solutions:
[0005] Step 1: Take any kind of hollow microspheres, disperse them in a hydrofluoric acid solution or a mixed solution of sodium fluoride and hydrochloric acid, stir them, perform surface treatment, filter them, and then wash them with deionized water.
[0006] Step 2: soaking the surface-treated hollow microbeads in a silane coupling agent solution to react, so that the surface of the hollow microbeads is easy to adsorb palladium ions or other ions with catalytic effects, and then filtering and washing with deionized water.
[0007] Step 3: Disperse the hollow microbeads treated in step 2 in a solution of palladium chloride or other catalytic salts, stir under heating conditions, and filter after the reaction.
[0008] Step 4: dispersing the hollow microbeads treated in step 3 in a stannous chloride solution or other sensitizing solution, stirring under heating conditions, and filtering after the reaction.
[0009] Step 5: Disperse the hollow microspheres treated in step 4 in a nickel plating solution, react under heating conditions, and plate nickel on the surface of the hollow microspheres. After the reaction, filter and wash with deionized water.
[0010] Step 6: Disperse the hollow microspheres treated in step 5 in a pyrrole or aniline solution, add ferric chloride or ammonium persulfate solution at 0°C, and perform oxidative polymerization. After the reaction, filter, wash with deionized water, and dry in an oven.
[0011] In step 1, 20 g of hollow microspheres were taken, the concentration of hydrofluoric acid was 2%, the volume was 200 ml, and the reaction time was 30 min.
[0012] In step 2, 2 g of the hollow microbeads prepared in the previous step and 100 ml of a 30 g / L ethanol solution of the silane coupling agent were prepared.
[0013] The reaction temperature in step 2 is 50° C. and the stirring time is 2 h.
[0014] The palladium chloride solution in step 3 is 50 ml of PdCl2 (0.0015 M) + HCl (0.25 M).
[0015] The reaction temperature in step 3 is 60° C. and the reaction time is 1 h.
[0016] The stannous chloride solution in step 4 is 50 ml of SnCl2 (0.1 M) + HCl (0.1 M).
[0017] The reaction temperature in step 4 is 50° C. and the stirring time is 2 h.
[0018] Step 5: The plating solution composition is NiSO4·6H2O (25g / L), NaH2PO2·H2O (25g / L), C6H5Na3O7·2H2O (25g / L), CH3COONa·3H2O (15g / L), lactic acid (10g / L)
[0019] The reaction temperature in step 5 is 75° C. and the reaction time is 1 h.
[0020] In step 6, 0.5 g of hollow microspheres from the previous step, 0.75 g of pyrrole, a solvent of a mixture of 50 ml of water and 10 ml of ethanol, and a ferric chloride solution of 1.82 g of FeCl 3 + 50 ml of H 2 O were used.
[0021] The reaction temperature in step 6 is 0°C and the reaction time is 10 hours.
[0022] The drying temperature in step 6 is 60° C. and the drying time is 12 h.
[0023] The core-shell structured absorber prepared by the present invention, which has nickel-plated hollow microspheres as cores and coated with conductive polymers, has the following characteristics:
[0024] 1) The hollow microspheres prepared by the present invention are core-shell structure absorbers in which the core is nickel-plated and then coated with a conductive polymer, and have light weight and corrosion resistance.
[0025] 2) The hollow microspheres prepared by the present invention are core-shell structure absorbers with a conductive polymer coated after the core is nickel-plated, which has the advantage of having a high electromagnetic wave absorption effect at low density. DETAILED DESCRIPTION
[0026] The present invention is described in detail below through examples. It is necessary to point out that the following examples are not to be construed as limiting the scope of protection of the present invention. If a person skilled in the art makes some non-essential improvements and adjustments to the present invention based on the above-mentioned invention content, they still fall within the scope of the present invention.
[0027] Example 1
[0028] A method for preparing a core-shell structured absorber with nickel-plated hollow microspheres as the core and coated with a conductive polymer, the preparation steps are as follows:
[0029] Step 1: Take any kind of hollow microspheres, disperse them in a hydrofluoric acid solution, stir them, perform surface treatment, filter them, and then wash them with deionized water.
[0030] Step 2: soaking the surface-treated hollow microbeads in a silane coupling agent solution to react so as to aminize the surface of the hollow microbeads, and then filtering and washing with deionized water.
[0031] Step 3: Disperse the hollow microbeads treated in step 2 in a palladium chloride solution, stir under heating conditions, and filter after the reaction.
[0032] Step 4: dispersing the hollow microbeads treated in step 3 in a stannous chloride solution, stirring under heating conditions, and filtering after the reaction.
[0033] Step 5: Disperse the hollow microspheres treated in step 4 in a nickel plating solution, react under heating conditions, and plate nickel on the surface of the hollow microspheres. After the reaction, filter and wash with deionized water.
[0034] Step 6: Take the hollow microbeads treated in step 5, disperse them in pyrrole solution, add ferric chloride solution at 0° C., and carry out oxidative polymerization. After the reaction, filter, wash with deionized water, and dry in an oven.
[0035] In step 1, 20 g of hollow microspheres were taken, the concentration of hydrofluoric acid was 2%, the volume was 200 ml, and the reaction time was 30 min.
[0036] In step 2, 2 g of the hollow microbeads prepared in the previous step and 100 ml of a 30 g / L ethanol solution of the silane coupling agent were prepared.
[0037] The reaction temperature in step 2 is 50° C. and the stirring time is 2 h.
[0038] The palladium chloride solution in step 3 is 50 ml of PdCl2 (0.0015 M) + HCl (0.25 M).
[0039] The reaction temperature in step 3 is 60° C. and the reaction time is 1 h.
[0040] The stannous chloride solution in step 4 is 50 ml of SnCl2 (0.1 M) + HCl (0.1 M).
[0041] The reaction temperature in step 4 is 50° C. and the stirring time is 2 h.
[0042] Step 5: The plating solution composition is NiSO4·6H2O (25g / L), NaH2PO2·H2O (25g / L), C6H5Na3O7·2H2O (25g / L), CH3COONa·3H2O (15g / L), lactic acid (10g / L)
[0043] The reaction temperature in step 5 is 75° C. and the reaction time is 1 h.
[0044] In step 6, 0.5 g of hollow microspheres from the previous step, 2 g of pyrrole, a solvent of a mixture of 50 ml of water and 10 ml of ethanol, and a ferric chloride solution of 4.83 g of FeCl 3 + 50 ml of H 2 O were used.
[0045] The reaction temperature in step 6 is 0°C and the reaction time is 10 hours.
[0046] The drying temperature in step 6 is 60° C. and the drying time is 12 h.
[0047] Example 2
[0048] A method for preparing a core-shell structured wave absorber with nickel-plated hollow microspheres as the core and coated with a conductive polymer, the preparation steps of which are as follows:
[0049] Step 1: Take any kind of hollow microspheres, disperse them in sodium fluoride and hydrochloric acid solution, stir them, perform surface treatment, filter them, and then wash them with deionized water.
[0050] Step 2: soaking the surface-treated hollow microbeads in a silane coupling agent solution to react so as to aminize the surface of the hollow microbeads, and then filtering and washing with deionized water.
[0051] Step 3: Disperse the hollow microbeads treated in step 2 in a palladium chloride solution, stir under heating conditions, and filter after the reaction.
[0052] Step 4: dispersing the hollow microbeads treated in step 3 in a stannous chloride solution, stirring under heating conditions, and filtering after the reaction.
[0053] Step 5: Disperse the hollow microspheres treated in step 4 in a nickel plating solution, react under heating conditions, and plate nickel on the surface of the hollow microspheres. After the reaction, filter and wash with deionized water.
[0054] Step 6: Take the hollow microbeads treated in step 5, disperse them in pyrrole solution, add ammonium persulfate solution at 0° C. to carry out oxidative polymerization. After the reaction, filter, wash with deionized water, and dry in an oven.
[0055] In step 1, 20 g of hollow microspheres were taken, the concentration of hydrofluoric acid was 4%, the volume was 400 ml, and the reaction time was 30 min.
[0056] In step 2, 2 g of the hollow microbeads prepared in the previous step and 100 ml of a 30 g / L ethanol solution of the silane coupling agent were prepared.
[0057] The reaction temperature in step 2 is 50° C. and the stirring time is 2 h.
[0058] The palladium chloride solution in step 3 is 50 ml of PdCl2 (0.002 M) + HCl (0.25 M).
[0059] The reaction temperature in step 3 is 60° C. and the reaction time is 1 h.
[0060] The stannous chloride solution in step 4 is 50 ml of SnCl2 (0.1 M) + HCl (0.1 M).
[0061] The reaction temperature in step 4 is 50° C. and the stirring time is 2 h.
[0062] Step 5: The plating solution composition is NiSO4·6H2O (25g / L), NaH2PO2·H2O (25g / L), C6H5Na3O7·2H2O (25g / L), CH3COONa·3H2O (15g / L), lactic acid (10g / L)
[0063] The reaction temperature in step 5 is 60° C. and the reaction time is 1 h.
[0064] In step 6, 0.5 g of hollow microspheres from the previous step, 2 g of aniline, a solvent of a mixture of 50 ml of water and 10 ml of ethanol, and an ammonium persulfate solution of 6.8 g (NH4)2S2O8 + 50 ml of H2O were used.
[0065] The reaction temperature in step 6 is 0°C and the reaction time is 10 hours.
[0066] The drying temperature in step 6 is 60° C. and the drying time is 12 h.
[0067] The present invention provides a core-shell structure absorber with nickel-plated hollow microspheres as the core and a conductive polymer coated thereon, and belongs to the technical field of electromagnetic wave absorbing materials. The present invention comprises the following steps: (1) taking any hollow microsphere, dispersing it in a hydrofluoric acid solution or a mixed solution of sodium fluoride and hydrochloric acid, stirring it, performing surface treatment, filtering it, and washing it with deionized water. (2) taking the hollow microspheres after surface treatment, soaking them in a silane coupling agent solution for reaction, so that the surface of the hollow microspheres is easy to adsorb palladium ions or other ions with catalytic effects, filtering it, and washing it with deionized water. (3) taking the hollow microspheres treated in step 2, dispersing them in a palladium chloride solution or other salt solution with catalytic effects, stirring it under heating conditions, and filtering it after the reaction. (4) taking the hollow microspheres treated in step 3, dispersing them in a stannous chloride solution or other solution with sensitization effects, stirring it under heating conditions, and filtering it after the reaction. (5) taking the hollow microspheres treated in step 4, dispersing them in a nickel plating solution, reacting it under heating conditions, and plating nickel on the surface of the hollow microspheres. After the reaction, the mixture is filtered and washed with deionized water. (6) The hollow microbeads treated in step 5 are dispersed in a pyrrole or aniline solution, and ferric chloride or ammonium persulfate solution is added at 0°C to carry out oxidative polymerization. After the reaction, the mixture is filtered and washed with deionized water, and then placed in an oven for drying. The nickel-plated hollow microbeads prepared by the present invention are core-shell structure absorbers with a core-coated conductive polymer, which are lightweight and corrosion-resistant; they have the advantage of having a high electromagnetic wave absorption effect at low density.
Claims
1. A method for preparing a core-shell structured absorber comprising nickel-plated hollow microspheres as cores and coated with a conductive polymer, characterized by: The following steps are involved: (1) Take any kind of hollow microspheres, disperse them in a hydrofluoric acid solution, stir them, perform surface treatment, filter them, and then wash them with deionized water; The hollow microspheres are 20 g, the concentration of hydrofluoric acid is 2%, the volume is 200 ml, and the reaction time is 30 min; (2) 2 g of hollow microspheres after surface treatment in step (1) were soaked in a silane coupling agent solution to react so that the surface of the hollow microspheres was easily adsorbed with palladium ions, and then filtered and washed with deionized water; The silane coupling agent is 100 ml of ethanol solution with a content of 30 g / L; the reaction temperature is 50°C and the stirring time is 2 hours; (3) The hollow microspheres treated in step (2) are dispersed in a palladium chloride hydrochloric acid solution, stirred under heating conditions, and filtered after the reaction; the palladium chloride hydrochloric acid solution is 0.0015M PdCl2 + 0.25M HCl 50ml, the reaction temperature is 60°C, and the reaction time is 1h; (4) dispersing the hollow microbeads treated in step (3) in a stannous chloride solution, stirring under heating conditions, and filtering after the reaction; The stannous chloride solution is 0.1M SnCl2+0.1M HCl 50ml; the reaction temperature is 50°C and the stirring time is 2h; (5) dispersing the hollow microspheres treated in step (4) in a nickel plating solution, reacting under heating conditions to plate nickel on the surface of the hollow microspheres, filtering after the reaction, and washing with deionized water; The nickel plating solution comprises 25 g / L NiSO4·6H2O, 25 g / L NaH2PO2·H2O, 25 g / L C6H5Na3O7·2H2O, 15 g / L CH3COONa·3H2O, and 10 g / L lactic acid; the reaction temperature is 75°C and the reaction time is 1 hour; (6) Take 0.5 g of the hollow microspheres treated in step (5) and disperse them in a mixture of 2 g of pyrrole, 50 ml of water and 10 ml of ethanol. Add 4.83 g of FeCl3 + 50 ml of ferric chloride solution of H2O at 0°C to carry out oxidative polymerization. The reaction temperature is 0°C and the reaction time is 10 h. After the reaction, filter and wash with deionized water, and place in an oven to dry at 60°C for 12 h.
2. A core-shell structured absorber with nickel-plated hollow microspheres as the core and a conductive polymer coated thereon, characterized by: Prepared by the method of claim 1.
Citation Information
Patent Citations
Method for preparing conductive hollow glass microspheres
CN101704634A
Nickel plating silvered glass bead and preparation method thereof
CN103130421A