CN109971243B - Ink for wave-absorbing coating, wave-absorbing coating material and preparation method thereof - Google Patents
Ink for wave-absorbing coating, wave-absorbing coating material and preparation method thereof Download PDFInfo
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- CN109971243B CN109971243B CN201711448686.0A CN201711448686A CN109971243B CN 109971243 B CN109971243 B CN 109971243B CN 201711448686 A CN201711448686 A CN 201711448686A CN 109971243 B CN109971243 B CN 109971243B
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Abstract
The invention relates to the field of wave-absorbing materials, and discloses ink for a wave-absorbing coating, a wave-absorbing coating material and a preparation method thereof. The ink for the wave absorbing coating comprises 2-20 wt% of poly (3, 4-ethylenedioxythiophene), 10-39 wt% of magnetic nano material, 35-65 wt% of dispersant, 1-2 wt% of polyvinylpyrrolidone, 1.5-2 wt% of polyvinyl alcohol and 0.5-2 wt% of glycol. The wave-absorbing coating material has the advantages of strong low-frequency-band wave-absorbing capability, wide wave-absorbing frequency band, wide application range and low cost.
Description
Technical Field
The invention relates to the field of wave-absorbing materials, in particular to ink for a wave-absorbing coating, a wave-absorbing coating material and a preparation method thereof.
Background
With the development of modern science and technology, stealth technology has become the most important and most effective penetration tactical technology in three-dimensional modern war integrating six dimensions of land, sea, air, sky, electricity and magnetism as an effective means for improving the survival, penetration and deep striking capability of weapon system, and has been highly valued by countries in the world. Radar is widely applied as a mature military detection means, so stealth technology research is mainly focused on radar characteristic signal control of a target, research work of infrared, sound, video and other characteristic signal control is simultaneously carried out, and finally development towards multifunctional and high-performance stealth direction becomes a key point of domestic and foreign research. The pollution control of electromagnetic waves in both stealth of military facilities and living environments is closely related to wave-absorbing materials, and the search for a material capable of resisting and weakening electromagnetic wave radiation, namely a wave-absorbing material, becomes a major subject of material science. The ideal wave-absorbing material should have the characteristics of strong absorption, wide frequency band, thin thickness and light weight. At present, experts and scholars at home and abroad have made intensive research on wave absorbing materials, for example, CN106479433A discloses a graphene composite wave absorbing material and a preparation method thereof, the thickness is 1.5-4.0 mm, the use frequency is 2-18 GHz, and the highest absorption rate can reach-41.83 dB; CN105255446A discloses a microwave absorbing material compounded by reduced graphene oxide and nano cerium oxide and a preparation method thereof, the thickness is 1.5-4.0 mm, and the absorption rate at the frequency of 4.3-17 GHz is-32-l 0 dB; japan electric Co LtdPrepared ferrite and Fe3O4The composite wave-absorbing material is 1.5-2.5 mm in thickness, 5-10 GHz in service frequency and-30 dB in absorption rate; the polycrystalline iron fiber microwave absorbing material prepared by GAMMA company in America has the use frequency of 2-18 GHz, and the maximum absorption can reach-34 dB. However, people have little research on low-frequency band (500-5500 MHz) composite wave-absorbing materials. Therefore, it has become a hot point to improve the wave absorbing performance of the wave absorbing material under the low frequency condition.
The ferrite material is a low-frequency wave-absorbing material which is researched more and developed more mature, has the advantages of high magnetic conductivity, high resistivity and the like, has the loss characteristics of two materials of magnetism and dielectric due to the characteristics of magnetism and dielectric, and enables electromagnetic waves to enter easily and be attenuated quickly. Therefore, ferrites are widely used in the fields of anti-electromagnetic interference, electromagnetic compatibility, waveguide or coaxial absorption elements, electromagnetic pollution prevention and control, stealth technology, and the like of communication and navigation systems. In the low-frequency microwave band, the ferrite has a small dielectric constant adjustment range, resulting in a small dielectric loss, which affects the improvement of the wave absorption performance and the expansion of the absorption band.
Disclosure of Invention
The invention aims to overcome the problems of weak low-frequency-band wave-absorbing capacity and narrow wave-absorbing frequency band in the prior art, and provides ink for a wave-absorbing coating, a wave-absorbing coating material and a preparation method thereof.
In order to achieve the above object, the first aspect of the present invention provides an ink for a wave-absorbing coating, wherein the ink contains 2-20 wt% of poly (3, 4-ethylenedioxythiophene), 10-39 wt% of magnetic nanomaterial, 35-65 wt% of dispersant, 1-2 wt% of polyvinylpyrrolidone, 1.5-2 wt% of polyvinyl alcohol, and 0.5-2 wt% of ethylene glycol.
Preferably, the magnetic nano material is NiZnFe2O4/SiO2、Fe3O4、NiZnFe2O4、BaZnCoCuFe2O4And NiZnCuFe2O4One or more of
Preferably, the magnetic nano material has a particle size of 30-70 nm.
The invention provides a preparation method of a wave-absorbing coating material in a second aspect, which comprises the following steps:
(A) formation of TiO on a substrate 12 Layer 2, and applying the absorbing coating ink on TiO2Printing the surface of the layer 2 to form a patterned wave-absorbing layer 3 and drying to obtain the film containing the substrate 1 and TiO2The wave absorbing units of the layer 2 and the patterned wave absorbing layer 3;
(B) repeating the step (A) to form x wave-absorbing units, wherein each wave-absorbing unit comprises a substrate and TiO2The wave absorbing layer and the patterned wave absorbing layer, and the substrate of each wave absorbing unit are arranged on the patterned wave absorbing layer of the previous wave absorbing unit; wherein x is 1-19.
Preferably, the TiO of each wave absorbing element2The thickness of the layer is 50 μm to 90 μm.
Preferably, the thickness of the patterned wave-absorbing layer of each wave-absorbing element is 30-70 μm.
Preferably, x is 4 to 14.
The third aspect of the invention provides a wave-absorbing coating material prepared by the method, as shown in fig. 1, wherein the wave-absorbing coating material comprises a plurality of superposed wave-absorbing units, and each wave-absorbing unit comprises a substrate 1 and TiO sequentially formed on the substrate2The wave-absorbing layer comprises a layer 2 and a patterned wave-absorbing layer 3, wherein the patterned wave-absorbing layer 3 is formed by printing the wave-absorbing coating ink; the pattern of the patterned wave absorbing layer 3 obtained by printing is a point array, a line array or an orthogonal linear array; the number of the plurality is 2-20; the wave-absorbing frequency band of the wave-absorbing coating material is 2500-5500 MHz.
Preferably, the material of the wave-absorbing coating comprises poly (3, 4-ethylenedioxythiophene), a magnetic nano material, polyvinylpyrrolidone, polyvinyl alcohol and glycol.
Preferably, the magnetic nanomaterial comprises NiZnFe2O4/SiO2、Fe3O4、NiZnFe2O4、BaZnCoCuFe2O4And NiZnCuFe2O4One or more of (a).
Preferably, the plurality is 5-15.
Preferably, the TiO of each wave absorbing element2The thickness of the layer is 50 μm to 90 μm.
Preferably, the thickness of the patterned wave-absorbing layer of each wave-absorbing element is 30-70 μm.
The invention compounds poly (3, 4-ethylenedioxythiophene), magnetic nano material, dispersant, polyvinylpyrrolidone, polyvinyl alcohol and glycol to obtain the ink for the wave-absorbing coating, and then forms TiO through a printing method2The patterned wave-absorbing layer is constructed on the substrate of the layer, so that the prepared wave-absorbing coating material has the advantages of strong wave-absorbing capability of low frequency band (2500-. The preparation process is simple, the cost is low, and the industrial production is easy to realize.
Drawings
FIG. 1 is a schematic representation of a wave-absorbing coating material of the present invention;
FIG. 2a is a scanning electron micrograph of a patterned microwave absorbing layer of the present invention in the form of an array of dots;
FIG. 2b is a scanning electron micrograph of a patterned absorbing layer of the present invention in the form of a linear array;
FIG. 2c is a scanning electron microscope image of a patterned absorbing layer of the present invention with a pattern of orthogonal linear arrays;
fig. 3 is an absorption curve of different patterns.
Description of the reference numerals
1. Substrate 2, TiO2Layer 3, patterned wave-absorbing layer
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides ink for a wave-absorbing coating, which comprises 2-20 wt% of poly (3, 4-ethylenedioxythiophene), 10-39 wt% of magnetic nano material, 35-65 wt% of dispersing agent, 1-2 wt% of polyvinylpyrrolidone, 1.5-2 wt% of polyvinyl alcohol and 0.5-2 wt% of glycol.
In the invention, the magnetic nano material can be NiZnFe2O4/SiO2、Fe3O4、NiZnFe2O4、BaZnCoCuFe2O4And NiZnCuFe2O4One or more of (a).
In a preferred embodiment of the present invention, the magnetic nanomaterial has a particle size of 30 to 70 nm.
In the present invention, the poly (3, 4-ethylenedioxythiophene), also called PEDOT, is not particularly limited with respect to parameters such as the molecular weight of PEDOT, and is available from Aldrich, for example.
In the present invention, the dispersant is used for sufficiently dispersing poly (3, 4-ethylenedioxythiophene), magnetic nano-materials, polyvinylpyrrolidone, polyvinyl alcohol and ethylene glycol, and may be, for example, but not limited to, one or more of ethylene glycol methyl ether, ethanol and deionized water.
The invention provides a preparation method of a wave-absorbing coating material in a second aspect, which comprises the following steps:
(A) formation of TiO on a substrate 12 Layer 2, and applying the absorbing coating ink on TiO2Printing the surface of the layer 2 to form a patterned wave-absorbing layer 3 and drying to obtain the film containing the substrate 1 and TiO2The wave absorbing units of the layer 2 and the patterned wave absorbing layer 3;
(B) repeating the step (A) to form x wave-absorbing units, wherein each wave-absorbing unit comprises a substrate and TiO2The wave absorbing layer and the patterned wave absorbing layer, and the substrate of each wave absorbing unit are arranged on the patterned wave absorbing layer of the previous wave absorbing unit; wherein x is 1-19.
According to the method of the invention, TiO of each wave absorbing element2The thickness of the layer may be 50 μm to 90 μm. TiO at the thickness2The layer can obtain a better patterned wave-absorbing layer after being printed, so that the prepared wave-absorbing coating material has the advantages of strong wave-absorbing capability in a low frequency range (2500 + 5500MHz) and wide absorbed frequency band.
According to the method, the thickness of the patterned wave-absorbing layer of each wave-absorbing unit can be 30-70 μm. This thickness facilitates the absorption of the low frequency band waves.
According to a preferred embodiment of the invention, said x is from 4 to 14.
According to the method of the present invention, the method of printing may be, but is not limited to, an ink jet printing method.
According to the method of the present invention, although fig. 2a, 2b and 2c are scanning electron microscope images of the pattern of the patterned wave-absorbing layer, the printed patterned wave-absorbing layer is also shown as a dot array, a linear array or an orthogonal linear array in fig. 2a, 2b and 2 c. Wherein, the orthogonal linear array means that the horizontal lines with equidistant discontinuity are printed first, and then the vertical lines are printed vertically, preferably, the vertical lines intersect with the centers of the horizontal lines to form the graph shown in fig. 2 c.
In the present invention, the pitch of the dot array shown in FIG. 2a can be, but is not limited to, 100-300 μm, preferably 120-200 μm.
In the present invention, the pitch of the line array as shown in FIG. 2b may be, but is not limited to, 80-200 μm, preferably 100-150 μm.
In the present invention, the horizontal pitch (discontinuity distance) of the transverse lines of equidistant discontinuities of the orthogonal linear array as shown in FIG. 2c may be, but is not limited to, 10-150 μm, preferably 20-80 μm. The vertical pitch of the equally spaced horizontal lines of the orthogonal linear array as shown in FIG. 2c may be, but is not limited to, 150-. The horizontal pitch of the vertical lines of the orthogonal linear array as shown in FIG. 2c may be, but is not limited to, 80-200 μm, preferably 100-150 μm.
According to the method of the present invention, the drying temperature is for the purpose of drying the patterned wave-absorbing layer sufficiently, and may be, for example, 30 to 60 ℃, preferably 40 to 50 ℃.
The third aspect of the invention provides a wave-absorbing coating material prepared by the method, as shown in fig. 1, wherein the wave-absorbing coating material comprises a plurality of superposed wave-absorbing units, and each wave-absorbing unit comprises a substrate 1 and TiO sequentially formed on the substrate2The wave-absorbing layer comprises a layer 2 and a patterned wave-absorbing layer 3, wherein the patterned wave-absorbing layer 3 is formed by printing the wave-absorbing coating ink; the pattern of the patterned wave absorbing layer 3 obtained by printing is a point array, a line array or an orthogonal linear array; the number of the plurality is 2-20; the wave-absorbing frequency band of the wave-absorbing coating material is 2500-5500 MHz.
In the present invention, the pattern of the patterned wave-absorbing layer 3 obtained by printing may be, but is not limited to: an array of dots as shown in figure 2a, an array of lines as shown in figure 2b, and an orthogonal linear array as shown in figure 3.
In the invention, the material of the wave-absorbing coating comprises poly (3, 4-ethylenedioxythiophene), a magnetic nano material, polyvinylpyrrolidone, polyvinyl alcohol and glycol.
In the present invention, the magnetic nanomaterial comprises NiZnFe2O4/SiO2、Fe3O4、NiZnFe2O4、BaZnCoCuFe2O4And NiZnCuFe2O4One or more of (a).
In a preferred embodiment of the invention, said plurality is 5 to 15. That is, 5-15 wave-absorbing units are provided, each wave-absorbing unit comprises a substrate and TiO formed on the substrate in sequence2The wave absorbing layer comprises a layer and a patterned wave absorbing layer, and the substrate of each wave absorbing unit is arranged on the patterned wave absorbing layer of the previous wave absorbing unit.
In the invention, TiO of each wave absorbing unit2The thickness of the layer may be 50 μm to 90 μm. TiO at the thickness2The layer can obtain a better patterned wave-absorbing layer after being printed, so that the prepared wave-absorbing coating material has the advantages of strong wave-absorbing capability in a low frequency range (2500 + 5500MHz) and wide absorbed frequency band.
In the invention, the thickness of the patterned wave-absorbing layer of each wave-absorbing element can be 30-70 μm. This thickness facilitates the absorption of the low frequency band waves.
In the invention, the material of the substrate can be any material which needs to absorb waves, such as aluminum, titanium alloy and the like. Since paraffin does not affect the result of the absorption test and is often used as a test substrate in the field, paraffin is also used as the substrate in the embodiment of the present invention.
The present invention will be described in detail below by way of examples.
In the present invention, poly (3, 4-ethylenedioxythiophene), also known as PEDOT, is available from Aldrich.
Ethyl Orthosilicate (TEOS) was purchased from Chemicals, Inc., national drug group, and was analytically pure.
Ethylene Glycol (EG) was purchased from national pharmaceutical group chemical reagents, Inc. and was analytically pure.
Polyvinyl alcohol (PVA) was purchased from Aldrich.
Ethylene glycol methyl ether was purchased from Aldrich.
Ferric nitrate (Fe (NO)3)3·9H2O) was purchased from national pharmaceutical group chemical reagents, Inc., and was analytically pure.
Zinc nitrate (Zn (NO)3)2·6H2O) was purchased from national pharmaceutical group chemical reagents, Inc., and was analytically pure.
Nickel nitrate (Ni (NO)3)2·6H2O) was purchased from national pharmaceutical group chemical reagents, Inc., and was analytically pure.
Cobalt nitrate (Co (NO)3)2·6H2O) was purchased from national pharmaceutical group chemical reagents, Inc., and was analytically pure.
Copper nitrate (Cu (NO)3)2·3H2O) was purchased from national pharmaceutical group chemical reagents, Inc., and was analytically pure.
Barium nitrate (Ba (NO)3) Analytically pure) purchased from national drug group chemical agents, ltd.
The nitric acid is purchased from chemical reagents of national drug group, Inc., and is analytically pure.
Polyvinylpyrrolidone (PVP) was purchased from Aldrich.
Polyvinyl alcohol (PVA) was purchased from Aldrich.
Titanium dioxide (TiO)2) Purchased from Aldrich.
Paraffin wax was purchased from the national pharmaceutical group chemical reagents, Inc.
The ink jet printer was manufactured by Fuji photo film company under model number DMP-2831.
SEM scanning electron microscope is manufactured by Japan Electron (Jie Ou Lu) corporation, and is JSM-7500F.
The vector network analyzer is manufactured by Agilent, USA, and is HP8722 ES.
Preparation example 1
2ml of Ethylene Glycol (EG), 20ml of deionized water, and 0.5ml of nitric acid were dispersed in 80ml of ethylene glycol monomethyl ether, and stirred for ten minutes. Then 1.48g of Zn (NO) are weighed out3)2·6H2O, 1.45g of Ni (NO)3)2·6H2O, 8.08g Fe (NO)3)3·9H2And adding O into the solution, and fully stirring to obtain a tan transparent sol A. 4.72g of ethyl orthosilicate was dissolved in ethylene glycol methyl ether to obtain a solution B. The solution B is added dropwise under the stirring state, and the mixture is stirred for 5 hours at room temperature. After aging the sample for 24h, putting the sample into a water bath at 80 ℃ for 12h, and then drying the sample in a drying oven at 100 ℃ for 24h to obtain xerogel. Putting the xerogel into a muffle furnace at 900 ℃ for annealing for 4h, then grinding a sample into powder by using a mortar, washing the powder for three times by using deionized water, then drying the sample in vacuum at 80 ℃ for 10h, and then grinding the sample into powder to obtain NiZnFe2O4/SiO2The magnetic nano material has the particle size of 35-45 nm.
Preparation example 2
2ml of Ethylene Glycol (EG), 20ml of deionized water, and 0.5ml of nitric acid were dispersed in 80ml of ethylene glycol methyl ether, and stirred for ten minutes. Then 0.59g of Zn (NO) is weighed out3)2·6H2O, 0.87g of Ni (NO)3)2·6H2O, 8.08g Fe (NO)3)3·9H2O, 1.21g of Cu (NO)3)2·3H2And adding O into the solution, and fully stirring to obtain a tan transparent sol. Aging the sample for 24h, placing the sample into a water bath at 80 ℃ for 12h, and then drying the sample in a drying oven at 100 ℃ for 24h to obtain the productTo a xerogel. Putting the dried gel into a muffle furnace at 1000 ℃ for annealing for 4h, grinding a sample into powder by using a mortar, washing the powder for three times by using deionized water, then drying the powder for 10h at 80 ℃, grinding the sample into powder, and finally obtaining the NiZnCuFe2O4The magnetic nano material has the grain diameter of 30-50 nm.
Examples 1-5 are intended to illustrate the process of the invention.
Example 1
(A) 16g of NiZnFe2O4/SiO2The magnetic nano material (obtained in preparation example 1) is dispersed into 136g of ethylene glycol monomethyl ether (the mass concentration is 10 weight percent), PEDOT is added into the ethylene glycol methyl ether, and polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and Ethylene Glycol (EG) are sequentially added in the stirring process, wherein NiZnFe2O4/SiO2: PEDOT: PVP: PVA: the weight ratio of EG is 16:5:1:1:1, ultrasonic dispersion is carried out for 20min, and mixing and stirring are carried out for 2 h. Obtaining PEDOT-NiZnFe2O4/SiO2The wave-absorbing material is printed with ink.
(B) Filtering the printing ink with 1 μm filter membrane, filling into DMP2800 cartridge, inputting the pre-designed dot array printing pattern into computer, placing the cartridge into printer according to Fujifilm Damatix printer software, setting the printing dot spacing to 120 μm, and placing TiO2Paraffin printing substrate for printing (TiO formation on Paraffin 1)2Layer 2) of which TiO2The thickness of the layer was 90 μm. And forming a patterned wave-absorbing layer with the thickness of 50 microns, and obtaining the patterned wave-absorbing layer of the point array shown in figure 2a through SEM representation. Then drying in a drying oven at 50 ℃ to obtain the product containing the substrate 1 and TiO2A wave absorbing element of the layer 2 and the patterned wave absorbing layer 3.
(C) Repeating the step (A) to form 9 wave-absorbing units, wherein each wave-absorbing unit comprises a substrate and TiO2The wave absorbing layer and the patterned wave absorbing layer, and the substrate of each wave absorbing unit are arranged on the patterned wave absorbing layer of the previous wave absorbing unit. Finally, 10 wave-absorbing units are formed, as shown in figure 1.
(D) And measuring the wave absorbing capacity of the patterned sample in the frequency range of 2500-5500MHz by using a vector network analyzer. The results are shown in FIG. 3 (dot array).
Example 2
(A) 16g of NiZnFe2O4/SiO2The magnetic nano material (obtained in preparation example 1) is dispersed into 136g of ethylene glycol monomethyl ether (the mass concentration is 10 weight percent), PEDOT is added into the ethylene glycol methyl ether, and polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and Ethylene Glycol (EG) are sequentially added in the stirring process, wherein NiZnFe2O4/SiO2: PEDOT: PVP: PVA: the weight ratio of EG is 16:5:1:1:1, ultrasonic dispersion is carried out for 20min, and mixing and stirring are carried out for 2 h. Obtaining PEDOT-NiZnFe2O4/SiO2The wave-absorbing material is printed with ink.
(B) Filtering the printing ink with 1 μm filter membrane, filling into DMP2800 cartridge, inputting the pre-designed linear array printing pattern into computer, placing the cartridge into printer according to Fujifilm Damatix printer software, setting printing line interval at 100 μm, and placing TiO2Paraffin printing substrate for printing (TiO formation on Paraffin 1)2Layer 2) of which TiO2The thickness of the layer was 90 μm. And forming a patterned wave-absorbing layer with the thickness of 50 microns, and obtaining the patterned wave-absorbing layer of the line array shown in figure 2b through SEM representation. Then drying in a drying oven at 50 ℃ to obtain the product containing the substrate 1 and TiO2A wave absorbing element of the layer 2 and the patterned wave absorbing layer 3.
(C) Repeating the step (A) to form 9 wave-absorbing units, wherein each wave-absorbing unit comprises a substrate and TiO2The wave absorbing layer and the patterned wave absorbing layer, and the substrate of each wave absorbing unit are arranged on the patterned wave absorbing layer of the previous wave absorbing unit. Finally, 10 wave-absorbing units are formed, as shown in figure 1.
(D) According to the method of the embodiment 1, the wave absorbing capacity of the patterned sample is measured in the frequency band of 2500-5500MHz by using a vector network analyzer. The results are shown in FIG. 3 (line array).
Example 3
(A) 16g of NiZnFe2O4/SiO2The magnetic nano material (obtained in preparation example 1) was dispersed in 136g of ethylene glycol methyl ether (mass concentration: 10 wt%), PEDOT was added thereto, and polyvinyl pyrrole was sequentially added during stirringAlkanone (PVP), polyvinyl alcohol (PVA), Ethylene Glycol (EG), wherein NiZnFe2O4/SiO2: PEDOT: PVP: PVA: the weight ratio of EG is 16:5:1:1:1, ultrasonic dispersion is carried out for 20min, and mixing and stirring are carried out for 2 h. Obtaining PEDOT-NiZnFe2O4/SiO2The wave-absorbing material is printed with ink.
(B) Filtering the printing ink with 1 μm filter membrane, filling into DMP2800 cartridge, inputting the pre-designed orthogonal linear array printing pattern into computer, placing the cartridge into printer according to Fujifilm Damatix printer software, setting horizontal spacing of printing transverse lines to 20 μm, vertical spacing of transverse lines to 200 μm, vertical spacing of vertical lines to 120 μm, and placing TiO2Paraffin printing substrate for printing (TiO formation on Paraffin 1)2Layer 2) of which TiO2The thickness of the layer was 90 μm. And forming a patterned wave-absorbing layer with the thickness of 50 microns, and obtaining the patterned wave-absorbing layer of the orthogonal linear array shown in figure 2c through SEM representation. Then drying in a drying oven at 50 ℃ to obtain the product containing the substrate 1 and TiO2A wave absorbing element of the layer 2 and the patterned wave absorbing layer 3.
(C) Repeating the step (A) to form 9 wave-absorbing units, wherein each wave-absorbing unit comprises a substrate and TiO2The wave absorbing layer and the patterned wave absorbing layer, and the substrate of each wave absorbing unit are arranged on the patterned wave absorbing layer of the previous wave absorbing unit. Finally, 10 wave-absorbing units are formed, as shown in figure 1.
(D) According to the method of the embodiment 1, the wave absorbing capacity of the patterned sample is measured in the frequency band of 2500-5500MHz by using a vector network analyzer. The results are shown in FIG. 3 (orthogonal linear array).
Example 4
(A) 20g of NiZnCuFe2O4The magnetic nanomaterial obtained in preparation example 2 was dispersed in 170 wt% ethanol (10 wt%) to which PEDOT was added, and polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and Ethylene Glycol (EG) were sequentially added during stirring, wherein NiZnCuFe was used2O4: PEDOT: PVP: PVA: the weight ratio of EG is 20:4:2:3:1, ultrasonic dispersion is carried out for 20min, and mixing and stirring are carried out for 2 h. Obtaining PEDOT-NiZnCuFe2O4The wave-absorbing material is printed with ink.
(B) Filtering the printing ink with 1 μm filter membrane, filling into DMP2800 cartridge, inputting the pre-designed dot array printing pattern into computer, placing the cartridge into printer according to Fujifilm Damatix printer software, setting printing dot spacing, and placing TiO2Paraffin printing substrate for printing (TiO formation on Paraffin 1)2Layer 2) of which TiO2The thickness of the layer was 70 μm. And forming a patterned wave-absorbing layer with the thickness of 30 microns, and obtaining the patterned wave-absorbing layer of the point array shown in figure 2a through SEM representation. Then dried in a drying oven at 30 ℃ to obtain the product containing the substrate 1 and TiO2A wave absorbing element of the layer 2 and the patterned wave absorbing layer 3.
(C) Repeating the step (A) to form 4 wave-absorbing units, wherein each wave-absorbing unit comprises a substrate and TiO2The wave absorbing layer and the patterned wave absorbing layer, and the substrate of each wave absorbing unit are arranged on the patterned wave absorbing layer of the previous wave absorbing unit. Finally, 5 wave-absorbing units are formed, as shown in figure 1.
(D) According to the method of the embodiment 1, the wave absorbing capacity of the patterned sample is measured in the frequency band of 2500-5500MHz by using a vector network analyzer. The wave-absorbing property change trend is similar to that of example 1.
Example 5
(A) 20g of Fe3O4Dispersing the magnetic nano material into 170g of deionized water (the mass concentration is 10 weight percent), adding PEDOT into the deionized water, and sequentially adding polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and Ethylene Glycol (EG) in the stirring process, wherein Fe3O4: PEDOT: PVP: PVA: the weight ratio of EG is 19.5:10:1:1:1, ultrasonic dispersion is carried out for 20min, and mixing and stirring are carried out for 2 h. Obtaining PEDOT-Fe3O4The wave-absorbing material is printed with ink.
(B) Filtering the printing ink with 1 μm filter membrane, filling into DMP2800 cartridge, inputting the pre-designed dot array printing pattern into computer, placing the cartridge into printer according to Fujifilm Damatix printer software, setting printing dot spacing, and placing TiO2Paraffin printing substrate for printing (TiO formation on Paraffin 1)2Layer 2) of which TiO2The thickness of the layer was 70 μm. Patterning to a thickness of 70 μmAnd (3) the wave-absorbing layer is characterized by SEM to obtain the patterned wave-absorbing layer of the point array shown in figure 2 a. Then drying in a drying oven at 60 ℃ to obtain the product containing the substrate 1 and TiO2A wave absorbing element of the layer 2 and the patterned wave absorbing layer 3.
(C) Repeating the step (A) to form 14 wave-absorbing units, wherein each wave-absorbing unit comprises a substrate and TiO2The wave absorbing layer and the patterned wave absorbing layer, and the substrate of each wave absorbing unit are arranged on the patterned wave absorbing layer of the previous wave absorbing unit. Finally, 15 wave-absorbing units are formed, as shown in figure 1.
(D) According to the method of the embodiment 1, the wave absorbing capacity of the patterned sample is measured in the frequency band of 2500-5500MHz by using a vector network analyzer. The wave-absorbing property change trend is similar to that of example 1.
Comparative example 1
(A) PEDOT-NiZnFe obtained according to the procedure of example 12O4/SiO2The wave-absorbing material is printed with ink.
(B) The printing ink of example 1 was mixed with the first paraffin wax in an equal weight, and then TiO was prepared2Paraffin wax (first TiO formation on first paraffin wax 1)2Layer 2), i.e. mixing the wave-absorbing material into paraffin, TiO2The surface of the layer is not patterned.
(C) Repeating the step (A) to form 9 wave-absorbing units, wherein each wave-absorbing unit comprises a substrate and TiO2Layer (all mixing wave-absorbing material into paraffin, TiO)2The surface of the layer is not patterned), and the substrate of each wave-absorbing element is on the TiO of the previous wave-absorbing element2On top of the layer. Finally forming 10 wave-absorbing units.
(D) According to the method of the embodiment 1, the wave absorbing capacity of the patterned sample is measured in the frequency band of 2500-5500MHz by using a vector network analyzer. The results are shown in fig. 3 (no patterning).
As can be seen from the results of the embodiment and the comparative example, when the incident electromagnetic wave is tested, the wave-absorbing coating material prepared by the method has the advantages of strong wave-absorbing capability in a low frequency band (2500 + 5500MHz), wide wave-absorbing frequency band, wide application range and low cost. As can be seen from the figure 3 of the drawings,with PEDOT-NiZnFe2O4/SiO2The wave-absorbing peak of the composite material moves to a high-frequency region due to the change of the pattern of the patterned wave-absorbing layer, when the printed pattern is an orthogonal linear array, the wave-absorbing performance of the sample is optimal, the maximum absorption peak value is-41.6 dB, and compared with a sample without the pattern, the absorption peak value is improved from-17.4 dB to-41.6 dB, which shows that the wave-absorbing coating material prepared by the method has the advantages of strong wave-absorbing capability of a low-frequency band and wide application range.
The method has simple process and low cost, and is easy to realize industrial production.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A preparation method of a wave-absorbing coating material comprises the following steps:
(A) forming TiO on a substrate (1)2Layer (2) and applying an ink to the TiO for absorbing the wave2Printing the surface of the layer (2), forming a patterned wave-absorbing layer (3) and drying to obtain the composite material containing the substrate (1) and TiO2The wave absorbing units of the layer (2) and the patterned wave absorbing layer (3);
(B) repeating the step (A) to form x wave-absorbing units, wherein each wave-absorbing unit comprises a substrate and TiO2The wave absorbing layer and the patterned wave absorbing layer, and the substrate of each wave absorbing unit are arranged on the patterned wave absorbing layer of the previous wave absorbing unit; wherein x is 4-14, and x +1 wave-absorbing units are finally formed;
the ink for the wave-absorbing coating comprises 2-20 wt% of poly (3, 4-ethylenedioxythiophene), 10-39 wt% of magnetic nano material, 35-65 wt% of dispersant, 1-2 wt% of polyvinylpyrrolidone, 1.5-2 wt% of polyvinyl alcohol and 0.5-2 wt% of glycol;
the magnetic nano material is NiZnFe2O4/SiO2、Fe3O4、NiZnFe2O4、BaZnCoCuFe2O4And NiZnCuFe2O4One or more of;
the pattern of the patterned wave absorbing layer (3) obtained by printing is a point array, a line array or an orthogonal linear array;
the wave-absorbing frequency band of the wave-absorbing coating material is 2500-5500 MHz.
2. The method of claim 1, wherein the magnetic nanomaterial has a particle size of 30-70 nm.
3. The method of claim 1, wherein the dispersant is one or more of ethylene glycol methyl ether, ethanol, and deionized water.
4. A method according to claim 1, wherein the TiO of each absorbing element2The thickness of the layer is 50 μm to 90 μm.
5. A method according to claim 1, wherein the thickness of the patterned wave-absorbing layer of each wave-absorbing element is 30-70 μm.
6. A wave-absorbing coating material prepared by the method of any one of claims 1 to 5, wherein the wave-absorbing coating material comprises a plurality of superposed wave-absorbing elements, each wave-absorbing element comprising a substrate (1) and TiO formed in sequence on the substrate2A layer (2) and a patterned wave-absorbing layer (3),
the patterned wave-absorbing layer (3) is formed by printing ink for a wave-absorbing coating; the pattern of the patterned wave absorbing layer (3) obtained by printing is a point array, a line array or an orthogonal linear array;
the number of the plurality is 5-15;
the wave-absorbing frequency band of the wave-absorbing coating material is 2500-5500 MHz;
the ink for the wave-absorbing coating comprises 2-20 wt% of poly (3, 4-ethylenedioxythiophene), 10-39 wt% of magnetic nano material, 35-65 wt% of dispersing agent, 1-2 wt% of polyvinylpyrrolidone, 1.5-2 wt% of polyvinyl alcohol and 0.5-2 wt% of glycol.
7. The wave-absorbing coating material of claim 6, wherein the dispersant is one or more of ethylene glycol methyl ether, ethanol, and deionized water.
8. The wave-absorbing coating material of claim 6, wherein the magnetic nanomaterial comprises NiZnFe2O4/SiO2、Fe3O4、NiZnFe2O4、BaZnCoCuFe2O4And NiZnCuFe2O4One or more of (a).
9. The wave-absorbing coating material of claim 8, wherein the magnetic nanomaterial has a particle size of 30-70 nm.
10. The wave-absorbing coating material of claim 6, wherein the TiO of each wave-absorbing element2The thickness of the layer is 50 μm to 90 μm.
11. The wave-absorbing coating material of claim 6, wherein the thickness of the patterned wave-absorbing layer of each wave-absorbing element is 30-70 μm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711448686.0A CN109971243B (en) | 2017-12-27 | 2017-12-27 | Ink for wave-absorbing coating, wave-absorbing coating material and preparation method thereof |
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| CN201711448686.0A CN109971243B (en) | 2017-12-27 | 2017-12-27 | Ink for wave-absorbing coating, wave-absorbing coating material and preparation method thereof |
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| CN101444979A (en) * | 2008-12-30 | 2009-06-03 | 北京化工大学 | Frequency selection surface wave-absorbing material and preparation method thereof |
| CN102634169B (en) * | 2011-02-15 | 2014-08-20 | 中国科学院理化技术研究所 | Wave-absorbing material composited by magnetic material and conducting polymer as well as preparation method thereof |
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