CN109971243A - Microwave absorbing coating ink, wave-absorbing coating material and preparation method thereof - Google Patents
Microwave absorbing coating ink, wave-absorbing coating material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to absorbing material fields, disclose microwave absorbing coating ink, wave-absorbing coating material and preparation method thereof.A kind of microwave absorbing coating ink, the ink contains the ethylene glycol of poly- (3,4-rthylene dioxythiophene) of 2-20 weight %, the magnetic Nano material of 10-39 weight %, the dispersing agent of 35-65 weight %, the polyvinylpyrrolidone of 1-2 weight %, the polyvinyl alcohol of 1.5-2 weight % and 0.5-2 weight %.The wave-absorbing coating material has the advantages that low-frequency range wave-sucking performance is strong, inhales wave frequency bandwidth, is applied widely, low in cost.
Description
Technical field
The present invention relates to absorbing material fields, and in particular to microwave absorbing coating ink, wave-absorbing coating material and its preparation side
Method.
Background technique
With the development of modern science and technology, stealth technology is as the existence of raising weapon system, prominent anti-and deep strike
The effective means of ability, have become in the three-dimensional modern war of the sextuple one of collection land, sea, air, outer space, electricity, magnetic it is mostly important,
Maximally efficient air defense penetration tactics technological means, and the great attention by countries in the world.Radar is detectd as a kind of military affairs of maturation
Survey means are widely used, and therefore, stealth technology research is attached most importance to the radar signature signal control of target, while being unfolded red
Outside, the research work of the other features signal such as sound, video control, finally develops to multi-functional, high performance stealthy direction and has become
For the emphasis studied both at home and abroad.Either in the stealthy or living environment of military installations the pollution control of electromagnetic wave all with inhale wave
Material is closely related, finds a kind of material-absorbing material that can be kept out and weaken electromagenetic wave radiation, it has also become material science
Key subjects.Ideal absorbing material should have the characteristics that strong absorption, wide-band, thickness be thin, light weight.Currently, both at home and abroad
Experts and scholars have done in-depth study to absorbing material, for example, CN106479433A discloses a kind of graphene composite wave-absorbing
Material and preparation method thereof, 1.5~4.0mm of thickness, 2~18GHz of frequency of use, absorptivity reach as high as -41.83dB；
CN105255446A discloses a kind of redox graphene and the compound microwave absorbing material and preparation method of nano-cerium oxide,
It is -32~- l0dB that 1.5~4.0mm of thickness, which is absorptivity at 4.3~17GHz in frequency,；The iron of Nippon Electric Company, Ltd.'s preparation
Oxysome and Fe3O4The composite wave-suction material of material, 1.5~2.5mm of thickness, 5~10GHz of frequency of use, absorptivity reach -30dB；Beauty
The standby polycrystalline iron fiber microwave absorbing material of state's GAMMA corporation, frequency of use are 2~18GHz, the reachable -34dB of absorption maximum.
However, people are very few for the research of low-frequency range (500~5500MHz) composite wave absorption material.Therefore, absorbing material is improved to exist
Absorbing property under low frequency condition has become hot spot.
Ferrite Material be research it is more and develop comparative maturity a kind of low-frequency wave-absorbing material, with high magnetic permeability,
The advantages that high resistivity, and have dielectric property since it is not only magnetic, thus have both magnetic and two kinds of materials of dielectric loss
Feature makes electromagnetic wave easily enter simultaneously rapid decay.Therefore, ferrite is widely used in the anti-electricity of communication and navigation system
The fields such as magnetic disturbance, electromagnetic compatibility, waveguide or coaxial absorber element, electromagnetic pollution prevention and treatment and stealth technology.And in the micro- of low frequency
In wave wave band, ferritic dielectric constant adjusting range is smaller, causes dielectric loss smaller, to influence mentioning for absorbing property
High and absorption band extension.
Summary of the invention
The purpose of the invention is to overcome, low-frequency range wave-sucking performance of the existing technology is weak, inhales that wave frequency band is narrow asks
Topic, provides microwave absorbing coating ink, wave-absorbing coating material and preparation method thereof, which there is low-frequency range to inhale wave energy
Power is strong, inhales wave frequency bandwidth, advantage applied widely, low in cost.
To achieve the goals above, first aspect present invention provides a kind of microwave absorbing coating ink, wherein the ink contains
There are point of poly- (the 3,4- ethene dioxythiophene) of 2-20 weight %, the magnetic Nano material of 10-39 weight %, 35-65 weight %
Powder, the polyvinylpyrrolidone of 1-2 weight %, the polyvinyl alcohol of 1.5-2 weight % and 0.5-2 weight % ethylene glycol.
Preferably, the magnetic Nano material is NiZnFe2O4/SiO2、Fe3O4、NiZnFe2O4、BaZnCoCuFe2O4With
NiZnCuFe2O4One of or it is a variety of
Preferably, the partial size of the magnetic Nano material is 30-70nm.
Second aspect of the present invention provides a kind of preparation method of wave-absorbing coating material, method includes the following steps:
(A) TiO is formed on the base 12Layer 2, and by above-mentioned microwave absorbing coating ink in TiO2The surface of layer 2 is beaten
Print forms patterning and inhales wave layer 3 and be dried, obtains comprising substrate 1, TiO2Layer 2 and patterning inhale the suction wave list of wave layer 3
Member；
(B) repeat step (A), form x suction wave unit, and each suction wave unit includes substrate, TiO2Layer and figure
Caseization inhales wave layer and each substrate for inhaling wave unit and inhales the upper surface of wave layer in the previous patterning for inhaling wave unit；Wherein,
X is 1-19.
Preferably, each TiO for inhaling wave unit2Layer with a thickness of 50 μm -90 μm.
Preferably, it is each inhale wave unit patterning inhale wave layer with a thickness of 30-70 μm.
Preferably, the x is 4-14.
Third aspect present invention is provided by the wave-absorbing coating material of above-mentioned method preparation, as shown in Figure 1, wherein should
Wave-absorbing coating material includes the suction wave unit of multiple superpositions, and each wave unit of inhaling includes substrate 1 and sequentially forms in substrate
TiO2Layer 2 and patterning inhale wave layer 3, wherein the patterning inhales wave layer 3 and passes through printing side by above-mentioned microwave absorbing coating ink
Formula is formed；The obtained patterning that prints inhales the pattern of wave layer 3 for lattice array, linear array or orthogonal straight lines array；It is described more
A is 2-20；The suction wave frequency section of the wave-absorbing coating material is 2500-5500MHz.
Preferably, the material of the microwave absorbing coating includes poly- (3,4-rthylene dioxythiophene), magnetic Nano material, polyethylene
Pyrrolidones, polyvinyl alcohol and ethylene glycol.
Preferably, the magnetic Nano material includes NiZnFe2O4/SiO2、Fe3O4、NiZnFe2O4、BaZnCoCuFe2O4
And NiZnCuFe2O4One of or it is a variety of.
Preferably, the multiple is 5-15.
Preferably, each TiO for inhaling wave unit2Layer with a thickness of 50 μm -90 μm.
Preferably, it is each inhale wave unit patterning inhale wave layer with a thickness of 30-70 μm.
The present invention is by poly- (3,4- ethene dioxythiophene), magnetic Nano material, dispersing agent, polyvinylpyrrolidone, poly- second
Enol and ethylene glycol progress are compound, obtain microwave absorbing coating ink, then by Method of printing, are being already formed with TiO2Layer
Building patterning inhales wave layer in substrate, so that the wave-absorbing coating material of preparation has low-frequency range (2500-5500MHz) wave-sucking performance
By force, the advantages of the bandwidth of absorption.Preparation process is simple, low in cost, it is easy to accomplish industrialized production.
Detailed description of the invention
Fig. 1 is the schematic diagram of wave-absorbing coating material of the invention；
Fig. 2 a is that the pattern that patterning of the invention inhales wave layer is the scanning electron microscope (SEM) photograph of lattice array；
Fig. 2 b is that the pattern that patterning of the invention inhales wave layer is the scanning electron microscope (SEM) photograph of linear array；
Fig. 2 c is that the pattern that patterning of the invention inhales wave layer is the scanning electron microscope (SEM) photograph of orthogonal linear array；
Fig. 3 is the absorption curve of different pattern.
Description of symbols
1, substrate 2, TiO2Layer 3, patterning inhale wave layer
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
First aspect present invention provides a kind of microwave absorbing coating ink, wherein the ink contains the poly- of 2-20 weight %
(3,4- ethene dioxythiophene), the magnetic Nano material of 10-39 weight %, the dispersing agent of 35-65 weight %, 1-2 weight %
The ethylene glycol of polyvinylpyrrolidone, the polyvinyl alcohol of 1.5-2 weight % and 0.5-2 weight %.
In the present invention, the magnetic Nano material can be NiZnFe2O4/SiO2、Fe3O4、NiZnFe2O4、
BaZnCoCuFe2O4And NiZnCuFe2O4One of or it is a variety of.
In the preferred embodiment of the present invention, the partial size of the magnetic Nano material is 30-70nm.
In the present invention, poly- (3,4-rthylene dioxythiophene), also known as PEDOT, for parameters such as the molecular weight of PEDOT
It is not particularly limited, such as Aldrich can be purchased from.
In the present invention, the dispersing agent is can fully disperse poly- (3,4-rthylene dioxythiophene), magnetic Nano material
For the purpose of material, polyvinylpyrrolidone, polyvinyl alcohol and ethylene glycol, for example, can be but be not limited to ethylene glycol monomethyl ether, ethyl alcohol and
One of deionized water is a variety of.
Second aspect of the present invention provides a kind of preparation method of wave-absorbing coating material, method includes the following steps:
(A) TiO is formed on the base 12Layer 2, and by above-mentioned microwave absorbing coating ink in TiO2The surface of layer 2 is beaten
Print forms patterning and inhales wave layer 3 and be dried, obtains comprising substrate 1, TiO2Layer 2 and patterning inhale the suction wave list of wave layer 3
Member；
(B) repeat step (A), form x suction wave unit, and each suction wave unit includes substrate, TiO2Layer and figure
Caseization inhales wave layer and each substrate for inhaling wave unit and inhales the upper surface of wave layer in the previous patterning for inhaling wave unit；Wherein,
X is 1-19.
According to the method for the present invention, each TiO for inhaling wave unit2The thickness of layer can be 50 μm -90 μm.Under the thickness
TiO2Layer can obtain preferably patterning after printing inhales wave layer, so that the wave-absorbing coating material of preparation has low-frequency range
The advantages of (2500-5500MHz) wave-sucking performance is strong, the bandwidth of absorption.
According to the method for the present invention, it can be 30-70 μm that each patterning for inhaling wave unit, which inhales the thickness of wave layer,.The thickness
Be conducive to the absorption of low-frequency range wave.
According to the present invention in preferred embodiment, the x is 4-14.
According to the method for the present invention, the method for the printing can be but be not limited to ink-jet printing.
According to the method for the present invention, although Fig. 2 a, 2b and 2c are the scanning electron microscope (SEM) photograph for the pattern that patterning inhales wave layer, printing
Patterning inhale wave the layer also lattice array as shown in Fig. 2 a, 2b and 2c, linear array or orthogonal straight lines array.Wherein, orthogonal straight lines
Array, which refers to, first prints equidistant intermittent horizontal line, then vertically prints vertical line again, it is preferable that and vertical line intersects with the center of horizontal line,
Form figure as shown in Figure 2 c.
In the present invention, the spacing of lattice array as shown in Figure 2 a can be but be not limited to 100-300 μm, preferably 120-
200μm。
In the present invention, the spacing of linear array as shown in Figure 2 b can be but be not limited to 80-200 μm, preferably 100-
150μm。
In the present invention, the horizontal space (turn-off of the equidistant intermittent horizontal line of orthogonal straight lines array as shown in Figure 2 c
From) can be but be not limited to 10-150 μm, preferably 20-80 μm.Orthogonal straight lines array as shown in Figure 2 c it is equidistant intermittent
The vertical interval of horizontal line can be but be not limited to 150-500 μm, preferably 200-300 μm.Orthogonal straight lines battle array as shown in Figure 2 c
The horizontal space of the vertical line of column can be but be not limited to 80-200 μm, preferably 100-150 μm.
According to the method for the present invention, the drying temperature so that patterning inhale wave layer it is sufficiently dry for the purpose of, such as can
Think 30-60 DEG C, preferably 40-50 DEG C.
Third aspect present invention is provided by the wave-absorbing coating material of above-mentioned method preparation, as shown in Figure 1, wherein should
Wave-absorbing coating material includes the suction wave unit of multiple superpositions, and each wave unit of inhaling includes substrate 1 and sequentially forms in substrate
TiO2Layer 2 and patterning inhale wave layer 3, wherein the patterning inhales wave layer 3 and passes through printing side by above-mentioned microwave absorbing coating ink
Formula is formed；The obtained patterning that prints inhales the pattern of wave layer 3 for lattice array, linear array or orthogonal straight lines array；It is described more
A is 2-20；The suction wave frequency section of the wave-absorbing coating material is 2500-5500MHz.
In the present invention, the pattern for printing obtained patterning suction wave layer 3 can be but be not limited to: as shown in Figure 2 a
Lattice array, linear array as shown in Figure 2 b can also orthogonal straight lines array as shown in Figure 3.
In the present invention, the material of the microwave absorbing coating includes poly- (3,4-rthylene dioxythiophene), magnetic Nano material, gathers
Vinylpyrrolidone, polyvinyl alcohol and ethylene glycol.
In the present invention, the magnetic Nano material includes NiZnFe2O4/SiO2、Fe3O4、NiZnFe2O4、
BaZnCoCuFe2O4And NiZnCuFe2O4One of or it is a variety of.
In the preferred embodiment of the present invention, the multiple is 5-15.That is there is 5-15 suction wave unit,
Each suction wave unit includes substrate and the TiO sequentially formed in substrate2Layer and patterning suction wave layer, and each suction wave unit
Substrate inhales the upper surface of wave layer in the previous patterning for inhaling wave unit.
In the present invention, each TiO for inhaling wave unit2The thickness of layer can be 50 μm -90 μm.TiO under the thickness2Layer
It can obtain preferably patterning after printing and inhale wave layer, so that the wave-absorbing coating material of preparation has low-frequency range (2500-
The advantages of 5500MHz) wave-sucking performance is strong, the bandwidth of absorption.
In the present invention, it can be 30-70 μm that each patterning for inhaling wave unit, which inhales the thickness of wave layer,.The thickness is conducive to
The absorption of low-frequency range wave.
In the present invention, the material of the substrate inhale for any need the material of wave, such as aluminium, titanium alloy.
Since paraffin will not have an impact to wave test result is inhaled, frequently as the test substrate of this field, therefore, the embodiment of the present invention
In also will select paraffin as substrate.
The present invention will be described in detail by way of examples below.
In the present invention, poly- (3,4-rthylene dioxythiophene), also known as (PEDOT) are purchased from Aldrich.
Ethyl orthosilicate (TEOS) is purchased from Sinopharm Chemical Reagent Co., Ltd., analyzes pure.
Ethylene glycol (EG) is purchased from Sinopharm Chemical Reagent Co., Ltd., analyzes pure.
Polyvinyl alcohol (PVA) is purchased from Aldrich.
Ethylene glycol monomethyl ether is purchased from Aldrich.
Ferric nitrate (Fe (NO3)3·9H2O it) is purchased from Sinopharm Chemical Reagent Co., Ltd., is analyzed pure.
Zinc nitrate (Zn (NO3)2·6H2O it) is purchased from Sinopharm Chemical Reagent Co., Ltd., is analyzed pure.
Nickel nitrate (Ni (NO3)2·6H2O it) is purchased from Sinopharm Chemical Reagent Co., Ltd., is analyzed pure.
Cobalt nitrate (Co (NO3)2·6H2O it) is purchased from Sinopharm Chemical Reagent Co., Ltd., is analyzed pure.
Copper nitrate (Cu (NO3)2·3H2O it) is purchased from Sinopharm Chemical Reagent Co., Ltd., is analyzed pure.
Barium nitrate (Ba (NO3)) it is purchased from Sinopharm Chemical Reagent Co., Ltd., it analyzes pure.
Nitric acid is purchased from Sinopharm Chemical Reagent Co., Ltd., analyzes pure.
Polyvinylpyrrolidone (PVP) is purchased from Aldrich.
Polyvinyl alcohol (PVA) is purchased from Aldrich.
Titanium dioxide (TiO2) it is purchased from Aldrich.
Paraffin is purchased from Sinopharm Chemical Reagent Co., Ltd..
Ink-jet printer is Fuji Photo Film Co., Ltd.'s production, model DMP-2831.
SEM scanning electron microscope is the production of Japan Electronics (Jie Oulu) company, model JSM-7500F.
Vector network analyzer is Agilent company of the U.S. production, model HP8722ES.
Preparation example 1
Ethylene glycol (EG), 20ml deionized water, the 0.5ml nitric acid of 2ml are distributed in 80ml ethylene glycol monomethyl ether, stirring ten
Minute.Then Zn (the NO of 1.48g is weighed3)2·6H2O, the Ni (NO of 1.45g3)2·6H2O, the Fe (NO of 8.08g3)3·9H2O adds
Enter into above-mentioned solution, be sufficiently stirred, obtains sepia vitreosol A.4.72g ethyl orthosilicate is dissolved in ethylene glycol monomethyl ether,
Obtain solution B.While stirring, solution B is added dropwise in A, and 5h is stirred at room temperature.After sample ageing for 24 hours, it is put into 80 DEG C of water-baths
Middle 12h, then drying for 24 hours, obtains xerogel in 100 DEG C of drying boxes.Xerogel is put into 900 DEG C of Muffle furnaces, when annealing
Between be 4h, sample grind into powder is flushed three times using mortar using deionized water then, is then dried in vacuo at 80 DEG C
10h, then by sample grind into powder, obtain NiZnFe2O4/SiO2Magnetic Nano material, partial size 35-45nm.
Preparation example 2
2ml ethylene glycol (EG), 20ml deionized water, 0.5ml nitric acid are distributed in 80ml ethylene glycol monomethyl ether, stirring is very
Clock.Then Zn (the NO of 0.59g is weighed3)2·6H2O, the Ni (NO of 0.87g3)2·6H2O, the Fe (NO of 8.08g3)3·9H2O、
Cu (the NO of 1.21g3)2·3H2O is added in above-mentioned solution, is sufficiently stirred, and sepia vitreosol is obtained.Sample is aged for 24 hours
Afterwards, it is put into 12h in 80 DEG C of water-baths, then drying for 24 hours, obtains xerogel in 100 DEG C of drying boxes.Xerogel is put into 1000 DEG C
In Muffle furnace, then annealing time 4h is flushed three times sample grind into powder, then using mortar using deionized water
It is dried in vacuo 10h at 80 DEG C, then by sample grind into powder, finally obtains NiZnCuFe2O4Magnetic Nano material, partial size 30-
50nm。
Embodiment 1-5 is for illustrating method of the invention.
Embodiment 1
(A) by the NiZnFe of 16g2O4/SiO2Magnetic Nano material (preparation example 1 obtains) is distributed to 136g ethylene glycol monomethyl ether
In (mass concentration be 10 weight %), PEDOT is added to it, polyvinylpyrrolidone (PVP), poly- is sequentially added in whipping process
Vinyl alcohol (PVA), ethylene glycol (EG), wherein NiZnFe2O4/SiO2: the weight ratio of PEDOT:PVP:PVA:EG is 16:5:1:1:
2h is mixed in 1, ultrasonic disperse 20min.Obtain PEDOT-NiZnFe2O4/SiO2Absorbing material marking ink.
(B) marking ink pours into the print cartridge of DMP2800 through 1 μm of membrane filtration, the lattice array printed drawings that will be pre-designed
Shape inputs computer, and print cartridge is placed in printer according to Fujifilm Damatix printer software step, print point spacing is arranged
It is 120 μm, places TiO2/ paraffin print substrate, which is printed, (forms TiO on paraffin 12Layer is 2), wherein TiO2The thickness of layer
It is 90 μm.The patterning for forming 50 μ m thicks inhales wave layer, is characterized by SEM, obtains the patterning of lattice array as shown in Figure 2 a
Inhale wave layer.Then dry in 50 DEG C of drying boxes, it obtains comprising substrate 1, TiO2Layer 2 and patterning inhale the suction wave unit of wave layer 3.
(C) repeat step (A), form 9 suction wave units, and each suction wave unit includes substrate, TiO2Layer and figure
Caseization inhales wave layer and each substrate for inhaling wave unit and inhales the upper surface of wave layer in the previous patterning for inhaling wave unit.Finally
10 suction wave units are formed altogether, as shown in Figure 1.
(D) wave-sucking performance of Patterned Sample is surveyed in 2500-5500MHz frequency range using vector network analyzer
Amount.As a result as shown in Figure 3 (lattice array).
Embodiment 2
(A) by the NiZnFe of 16g2O4/SiO2Magnetic Nano material (preparation example 1 obtains) is distributed to 136g ethylene glycol monomethyl ether
In (mass concentration be 10 weight %), PEDOT is added to it, polyvinylpyrrolidone (PVP), poly- is sequentially added in whipping process
Vinyl alcohol (PVA), ethylene glycol (EG), wherein NiZnFe2O4/SiO2: the weight ratio of PEDOT:PVP:PVA:EG is 16:5:1:1:
2h is mixed in 1, ultrasonic disperse 20min.Obtain PEDOT-NiZnFe2O4/SiO2Absorbing material marking ink.
(B) marking ink pours into the print cartridge of DMP2800 through 1 μm of membrane filtration, the linear array printed drawings that will be pre-designed
Shape inputs computer, and print cartridge is placed in printer according to Fujifilm Damatix printer software step, print wire spacing is arranged
100 μm, place TiO2/ paraffin print substrate, which is printed, (forms TiO on paraffin 12Layer is 2), wherein TiO2Layer with a thickness of
90μm.The patterning for forming 50 μ m thicks inhales wave layer, is characterized by SEM, and the patterning for obtaining linear array as shown in Figure 2 b is inhaled
Wave layer.Then dry in 50 DEG C of drying boxes, it obtains comprising substrate 1, TiO2Layer 2 and patterning inhale the suction wave unit of wave layer 3.
(C) repeat step (A), form 9 suction wave units, and each suction wave unit includes substrate, TiO2Layer and figure
Caseization inhales wave layer and each substrate for inhaling wave unit and inhales the upper surface of wave layer in the previous patterning for inhaling wave unit.Finally
10 suction wave units are formed altogether, as shown in Figure 1.
(D) according to the method for embodiment 1, using vector network analyzer in 2500-5500MHz frequency range to patterning sample
The wave-sucking performance of product measures.As a result as shown in Figure 3 (linear array).
Embodiment 3
(A) by the NiZnFe of 16g2O4/SiO2Magnetic Nano material (preparation example 1 obtains) is distributed to 136g ethylene glycol monomethyl ether
In (mass concentration be 10 weight %), PEDOT is added to it, polyvinylpyrrolidone (PVP), poly- is sequentially added in whipping process
Vinyl alcohol (PVA), ethylene glycol (EG), wherein NiZnFe2O4/SiO2: the weight ratio of PEDOT:PVP:PVA:EG is 16:5:1:1:
2h is mixed in 1, ultrasonic disperse 20min.Obtain PEDOT-NiZnFe2O4/SiO2Absorbing material marking ink.
(B) marking ink pours into the print cartridge of DMP2800 through 1 μm of membrane filtration, the orthogonal straight lines array that will be pre-designed
Printing curve inputs computer, and print cartridge is placed in printer, setting printing according to Fujifilm Damatix printer software step
20 μm of horizontal line horizontal space, 200 μm of horizontal line vertical interval, 120 μm of vertical line spacing, place TiO2/ paraffin print substrate is beaten
Print (forms TiO on paraffin 12Layer is 2), wherein TiO2Layer with a thickness of 90 μm.The patterning for forming 50 μ m thicks inhales wave layer, leads to
SEM characterization is crossed, the patterning for obtaining orthogonal straight lines array as shown in Figure 2 c inhales wave layer.It is then dry in 50 DEG C of drying boxes,
It obtains comprising substrate 1, TiO2Layer 2 and patterning inhale the suction wave unit of wave layer 3.
(C) repeat step (A), form 9 suction wave units, and each suction wave unit includes substrate, TiO2Layer and figure
Caseization inhales wave layer and each substrate for inhaling wave unit and inhales the upper surface of wave layer in the previous patterning for inhaling wave unit.Finally
10 suction wave units are formed altogether, as shown in Figure 1.
(D) according to the method for embodiment 1, using vector network analyzer in 2500-5500MHz frequency range to patterning sample
The wave-sucking performance of product measures.As a result as shown in Figure 3 (orthogonal straight lines array).
Embodiment 4
(A) by the NiZnCuFe of 20g2O4(preparation example 2 obtains) magnetic Nano material is distributed to 170 ethyl alcohol, and (mass concentration is
10 weight %), PEDOT is added to it, sequentially add in whipping process polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA),
Ethylene glycol (EG), wherein NiZnCuFe2O4: the weight ratio of PEDOT:PVP:PVA:EG is 20:4:2:3:1, ultrasonic disperse
2h is mixed in 20min.Obtain PEDOT-NiZnCuFe2O4Absorbing material marking ink.
(B) marking ink pours into the print cartridge of DMP2800 through 1 μm of membrane filtration, the lattice array printed drawings that will be pre-designed
Shape inputs computer, and print cartridge is placed in printer according to Fujifilm Damatix printer software step, print point spacing is arranged,
Place TiO2/ paraffin print substrate, which is printed, (forms TiO on paraffin 12Layer is 2), wherein TiO2Layer with a thickness of 70 μm.Shape
Wave layer is inhaled at the patterning of 30 μ m thicks, is characterized by SEM, the patterning for obtaining lattice array as shown in Figure 2 a inhales wave layer.So
It is dry in 30 DEG C of drying boxes afterwards, it obtains comprising substrate 1, TiO2Layer 2 and patterning inhale the suction wave unit of wave layer 3.
(C) repeat step (A), form 4 suction wave units, and each suction wave unit includes substrate, TiO2Layer and figure
Caseization inhales wave layer and each substrate for inhaling wave unit and inhales the upper surface of wave layer in the previous patterning for inhaling wave unit.Finally
5 suction wave units are formed altogether, as shown in Figure 1.
(D) according to the method for embodiment 1, using vector network analyzer in 2500-5500MHz frequency range to patterning sample
The wave-sucking performance of product measures.Absorbing property variation tendency is similar to Example 1.
Embodiment 5
(A) by the Fe of 20g3O4Magnetic Nano material is distributed in 170g deionized water (mass concentration is 10 weight %), to
PEDOT is added in it, sequentially adds polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), ethylene glycol (EG) in whipping process,
In, Fe3O4: the weight ratio of PEDOT:PVP:PVA:EG is 19.5:10:1:1:1, ultrasonic disperse 20min, and 2h is mixed.It obtains
PEDOT-Fe3O4Absorbing material marking ink.
(B) marking ink pours into the print cartridge of DMP2800 through 1 μm of membrane filtration, the lattice array printed drawings that will be pre-designed
Shape inputs computer, and print cartridge is placed in printer according to Fujifilm Damatix printer software step, print point spacing is arranged,
Place TiO2/ paraffin print substrate, which is printed, (forms TiO on paraffin 12Layer is 2), wherein TiO2Layer with a thickness of 70 μm.Shape
Wave layer is inhaled at the patterning of 70 μ m thicks, is characterized by SEM, the patterning for obtaining lattice array as shown in Figure 2 a inhales wave layer.So
It is dry in 60 DEG C of drying boxes afterwards, it obtains comprising substrate 1, TiO2Layer 2 and patterning inhale the suction wave unit of wave layer 3.
(C) repeat step (A), form 14 suction wave units, and each suction wave unit includes substrate, TiO2Layer and figure
Caseization inhales wave layer and each substrate for inhaling wave unit and inhales the upper surface of wave layer in the previous patterning for inhaling wave unit.Finally
15 suction wave units are formed altogether, as shown in Figure 1.
(D) according to the method for embodiment 1, using vector network analyzer in 2500-5500MHz frequency range to patterning sample
The wave-sucking performance of product measures.Absorbing property variation tendency is similar to Example 1.
Comparative example 1
(A) PEDOT-NiZnFe is obtained according to the method for embodiment 12O4/SiO2Absorbing material marking ink.
(B) marking ink of the weight such as embodiment 1 is mixed with the first paraffin, then prepares TiO2/ paraffin is (
The first TiO is formed on one paraffin 122) absorbing material, is also mixed into paraffin, TiO by layer2The surface pattern-free of layer.
(C) repeat step (A), form 9 suction wave units, and each suction wave unit includes substrate and TiO2Layer is (
Absorbing material is mixed into paraffin, TiO2Layer surface pattern-free) and it is each inhale wave unit substrate previous
Inhale the TiO of wave unit2The upper surface of layer.10 suction wave units are finally formed altogether.
(D) according to the method for embodiment 1, using vector network analyzer in 2500-5500MHz frequency range to patterning sample
The wave-sucking performance of product measures.As a result as shown in Figure 3 (pattern-free).
It can be seen that by the result of embodiment and comparative example when incident electromagnetic wave is tested, using present invention side
The wave-absorbing coating material of method preparation have low-frequency range (2500-5500MHz) wave-sucking performance is strong, inhale wave frequency bandwidth, is applied widely,
Advantage low in cost.As can be seen from Figure 3, with PEDOT-NiZnFe2O4/SiO2The change of the pattern of (namely patterning inhales wave layer)
Change, the suction wave crest of composite material is mobile to high frequency region, and when the pattern of printing is orthogonal linear array, the absorbing property of sample is most
Good, maximum absorption peak is -41.6dB, and compared to pattern-free sample, absorption peak is increased to -41.6dB from -17.4dB,
Illustrate that the wave-absorbing coating material of method preparation of the invention has the advantages that low-frequency range wave-sucking performance is strong, applied widely.
And the method for the present invention simple process and low cost, it is easy to accomplish industrialized production.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited thereto.At this
, can be with various simple variants of the technical solution of the present invention are made in the range of the technology design of invention, including each technical characteristic
It is combined with any other suitable method, these simple variants and combination equally should be considered as in disclosed in this invention
Hold, all belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of microwave absorbing coating ink, which is characterized in that the ink contains poly- (3, the 4- ethylene dioxy thiophenes of 2-20 weight %
Pheno), the magnetic Nano material of 10-39 weight %, the dispersing agent of 35-65 weight %, 1-2 weight % polyvinylpyrrolidone,
The polyvinyl alcohol of 1.5-2 weight % and the ethylene glycol of 0.5-2 weight %.
2. microwave absorbing coating ink according to claim 1, wherein the magnetic Nano material is NiZnFe2O4/SiO2、
Fe3O4、NiZnFe2O4、BaZnCoCuFe2O4And NiZnCuFe2O4One of or it is a variety of；
Preferably, the partial size of the magnetic Nano material is 30-70nm.
3. microwave absorbing coating ink according to claim 1, wherein the dispersing agent is ethylene glycol monomethyl ether, ethyl alcohol and goes
One of ionized water is a variety of.
4. a kind of preparation method of wave-absorbing coating material, method includes the following steps:
(A) TiO is formed on substrate (1)2Layer (2), and by microwave absorbing coating ink described in any one of claim 1-3
In TiO2The surface of layer (2) is printed, and is formed patterning and is inhaled wave layer (3) and be dried, obtains comprising substrate (1), TiO2Layer
(2) and patterning inhale wave layer (3) suction wave unit；
(B) repeat step (A), form x suction wave unit, and each suction wave unit includes substrate, TiO2Layer and patterning are inhaled
Wave layer and each substrate for inhaling wave unit inhale the upper surface of wave layer in the previous patterning for inhaling wave unit；Wherein, x 1-
19。
5. according to the method described in claim 4, wherein, each TiO for inhaling wave unit2Layer with a thickness of 50 μm -90 μm.
6. according to the method described in claim 4, wherein, each patterning for inhaling wave unit inhale wave layer with a thickness of 30-70 μm.
7. according to the method described in claim 4, wherein, the x is 4-14.
8. the wave-absorbing coating material of the preparation of the method as described in any one of claim 4-7, wherein the wave-absorbing coating material
Suction wave unit including multiple superpositions, it is each to inhale wave unit to include TiO substrate (1) and sequentially formed in substrate2Layer (2) and
Patterning inhales wave layer (3),
Wherein, the patterning inhales wave layer (3) microwave absorbing coating as described in any one of claim 1-3 with ink by beating
India side formula is formed；The obtained patterning that prints inhales the pattern of wave layer (3) for lattice array, linear array or orthogonal straight lines array；
The multiple is 2-20；
The suction wave frequency section of the wave-absorbing coating material is 2500-5500MHz.
9. wave-absorbing coating material according to claim 8, wherein the material of the microwave absorbing coating includes poly- (3,4- ethylene
Dioxy thiophene), magnetic Nano material, polyvinylpyrrolidone, polyvinyl alcohol and ethylene glycol；
Preferably, the magnetic Nano material includes NiZnFe2O4/SiO2、Fe3O4、NiZnFe2O4、BaZnCoCuFe2O4With
NiZnCuFe2O4One of or it is a variety of；
Preferably, the multiple is 5-15.
10. wave-absorbing coating material according to claim 8, wherein each TiO for inhaling wave unit2Layer with a thickness of 50 μm-
90μm；
Preferably, it is each inhale wave unit patterning inhale wave layer with a thickness of 30-70 μm.
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