CN115820038B - Particle-free iron-based conductive ink for electromagnetic function and preparation method thereof - Google Patents
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Abstract
The application discloses particle-free iron-based conductive ink for electromagnetic functions and a preparation method thereof, and relates to the technical field of conductive ink. The ink raw material comprises the following components in percentage by mass: 5-40% of ferrous metal precursor, 10-60% of chelating agent or complexing agent, 2-10% of reducing agent, 0.001-10% of organic additive and the balance of solvent. The particle-free iron-based conductive ink prepared by the application supplements the types of the existing particle-free conductive ink, fills the blank of the iron-based particle-free conductive ink in application, and can fully adjust the viscosity and the surface tension of the iron-based conductive ink so as to be suitable for different printing modes. The material has excellent electromagnetic function and simple process, and is suitable for large-scale production.
Description
Technical Field
The application relates to the technical field of conductive ink, in particular to particle-free iron-based conductive ink for electromagnetic function and a preparation method thereof.
Background
As electronic information technology is mature, electromagnetic waves are not only used in civil information, but also widely applied in military detection, so that the problems of electromagnetic pollution, electromagnetic interference, electromagnetic compatibility and the like are brought into wide attention while the national security is ensured and the living convenience is provided, and particularly the electronic equipment is widely used nowadays, and the electromagnetic interference in the existing space is more remarkable.
Microwave absorbing materials (MAMs, also known as radar absorbing materials) play an irreplaceable role in attenuating electromagnetic interference or electromagnetic wave detection signals. In recent years, research on microwave absorbing materials having a small thickness, light weight, high efficiency and wide frequency band has become a hot spot in this field. Some MAMs have been shown to be effective in achieving electromagnetic shielding performance by means of reflection losses, etc. As a key component in practical applications, MAMs should meet specific requirements, such as thin thickness, light weight, high efficiency, wide frequency band, etc. MAMs can be classified into dielectric loss materials and magnetic loss materials according to absorption mechanisms due to coexistence of electric and magnetic field components during microwave transmission. Materials with complex dielectric constants and magnetic permeabilities can produce dielectric losses and magnetic losses, respectively. The higher the imaginary value, the stronger the loss capacity. However, the dielectric constant and magnetic permeability values should be kept within appropriate ranges to match the free space impedance and reduce the surface reflection of the incident electromagnetic wave so that more transmitted waves can be scheduled inside the material. Some conductive materials, such as graphene, carbon Nanotubes (CNTs), mxnes, carbon black, silicon carbide, and the like, have shown effective dielectric loss capabilities. Magnetic losses stem from hysteresis, eddy currents and resonance losses are common in many magnetic materials including ferrites and magnetic metals.
In MAMs, fe 3 O 4 Is a stable oxide with complex dielectric constant and permeability, and has been widely used as an effective absorber with synergistic effects of magnetic loss and dielectric loss. In inverse spinel Fe 3 O 4 In the structure, fe 2+ And Fe (Fe) 3+ The sites of the octahedral interstitials are randomly distributed and thus electrons can rapidly transfer between the two oxidation states, resulting in excellent conductivity. In particular Fe 3 O 4 The nanostructured wave absorbing film not only shows excellent intrinsic properties (chemically stable, uniform), but also shows excellent dielectric loss and enhances magnetic loss due to its stronger anisotropy. Patterning Fe, in particular on films 3 O 4 The wave absorbing characteristic of the whole film can be effectively enhanced.
At present, the method for preparing the electromagnetic functional material film, in particular to the method for preparing the electromagnetic functional material on the film by patterning, which is mostly an etching method, has the problems of serious material waste, complex preparation process, high cost, serious environmental pollution and the like. The printing electronic technology is used as a technology with the advantages of high precision, strong stability, high printing speed, wide selection of base materials, environmental protection, flexibility, large-area manufacture and the like, and gradually becomes an important innovation in the field of microelectronics. Therefore, the preparation and application of the functionalized conductive ink are widely focused as the core of the printing electronic technology. Particularly, the problems of complex preparation process flow, long time consumption, high cost, easy pollution formation, low wave absorption efficiency and the like in the current stage can be effectively solved by developing the iron-based particle-free ink for electromagnetic functions to prepare the microwave absorbing material.
Conductive inks for printing electronics are generally divided into two categories: both granular and non-granular. The particle type conductive ink generally refers to an ink prepared by dispersing conductive metal particles in a solvent and adding an auxiliary agent such as a dispersant. Particle-type inks have many inherent disadvantages in preparation and storage, such as complex preparation of conductive particles, high decomposition temperature of the ink, poor conductivity, particle settling, and the like, which tend to clog the inkjet heads in inkjet printing. Particle-free inks are typically metal precursor solutions in which the metal is present in ionic form, so that the ink has good stability, high metal content, relatively low firing temperatures, and is not prone to clogging of the jets in inkjet printing. The range of applications is broader and the choice of substrate is broader thanks to the lower sintering temperature, in particular paper, plastics, fabrics, etc. Meanwhile, the method is suitable for developing novel sintering modes such as microwave sintering, photon sintering and the like.
At present, no particle-free iron-based conductive ink truly suitable for electromagnetic function is reported in the prior art, and meanwhile, no technology for preparing an electromagnetic functional film from the particle-free iron-based ink by a printed electronic technology is reported.
Disclosure of Invention
The application aims to provide particle-free iron-based conductive ink for electromagnetic functions and a preparation method thereof, so as to solve the problems in the prior art and realize excellent performance of electromagnetic shielding materials.
In order to achieve the above object, the present application provides the following solutions:
one of the technical schemes of the application is as follows: the particle-free iron-based conductive ink for electromagnetic functions is provided, and comprises the following raw materials in percentage by mass:
5-40% of ferrous metal precursor, 10-60% of chelating agent or complexing agent, 2-10% of reducing agent, 0.001-10% of organic additive and the balance of solvent;
the chelating or complexing agent contains an amino group.
Further, the reducing agent is effective to reduce the decomposition temperature of the ink, and the component may comprise one of glycerol and glycol containing hydroxyl groups, or one or more of glucose, tartaric acid, citric acid, ascorbic acid, sodium borohydride, ammonium sulfide, formic acid, and formaldehyde.
Further, the organic additives include a surface tension modifier, a viscosity modifier, a film forming aid, or an antifoaming agent.
Further, the particle-free iron-based conductive ink for electromagnetic function has a viscosity of 1-60 mPa.s at 25 ℃ and a surface tension of 5-60 mN/m.
The second technical scheme of the application is as follows: the preparation method of the particle-free iron-based conductive ink for electromagnetic function comprises the following steps:
complexing the chelating agent or complexing agent and the ferrous metal precursor in the solvent, and adding the reducing agent and the organic additive to obtain the particle-free iron-based conductive ink for electromagnetic function.
Preferably, after the addition of the reducing agent and the organic additive, a step of filtration through a 0.22 electric microporous filter membrane is further included.
The particle-free ink can be printed (e.g., gravure, ink jet) onto a variety of substrates and cryogenically decomposed to form a magnetic-containing ferroferric oxide film. The particle-free iron-based functional material ink has the advantages of simple preparation method, low curing temperature and good stability, and can be widely applied to the electromagnetic field.
The third technical scheme of the application: the semiconductor film for the electromagnetic function is obtained by sintering the particle-free iron-based conductive ink for the electromagnetic function.
Further, the method for preparing the semiconductor film for electromagnetic function comprises the following steps:
the electromagnetic function is coated on a substrate with a particle-free iron-based conductive ink, and then the formed coating film is sintered.
The preferred coating parameters are as follows: the spin coating rotating speed is 100-500rpm, the spin coating time is 20s, the spin coating rotating speed is 1000-5000rpm, and the spin coating time is 20s.
Further, the sintering temperature is 150-800 ℃ and the sintering time is 30min; the temperature rising rate of the sintering is 10-20 ℃/min.
The fourth technical scheme of the application: the application of the particle-free iron-based conductive ink for electromagnetic function and the semiconductor film for electromagnetic function as electromagnetic wave absorbing materials is provided.
The present application provides an iron-based particle-free ink capable of forming an electromagnetic functional thin film by a simple heat treatment method, which can be stably applied to the subsequent operation of printed electronics.
The metal ferrous precursor is a first ligand, the cation of the first ligand is ferrous ion, and the anion can be oxygen ion, chloride ion, bromide ion, sulfate radical, phosphate radical, nitrate radical or carboxylate radical. The carboxylate may be one or more of an aliphatic carboxylate, an aromatic carboxylate, a hydroxycarboxylic acid, or a cycloaliphatic carboxylate. The aliphatic ferrous carboxylate, the aromatic ferrous carboxylate, the hydroxy ferrous carboxylate or the alicyclic ferrous carboxylate have 1-3 carboxyl groups, 0-2 hydroxyl groups and 1-17 carbon atoms.
One of the features of the particle-free ink of the present application is the complexation of the ferrous metal precursor with an amino-containing chelating or complexing agent. Thus, the second ligand in the present application is an amino group-containing chelating or complexing agent, wherein the chelating or complexing agent is one or a mixture of several of ammonia water, aliphatic amine, alcohol amine, amide and aromatic amine, and examples of the second ligand include ethylamine, isopropylamine, isopropanolamine, octylamine, oleylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ethylenediamine, propylene diamine, 1, 2-diaminopropane, diethyl ethylenediamine, dihydroxyethylenediamine and trihydroxyethylenediamine, etc.
In the present application, the first ligand and the second ligand are chemically coordinated in a solvent, and the solvent may be one or a mixture of a plurality of organic solvents such as an aqueous solvent, an alcohol, an aliphatic alcohol, etc. As the main solvent, a solvent having a boiling point of 300℃or lower at normal pressure (one atmosphere pressure) is preferable, and otherwise film forming property is liable to be impaired. The water solvent, alcohol and fatty alcohol all contain 1-3 hydroxyl functional groups and 1-12 carbon atoms. The organic solvent may be an aromatic solvent, a non-aromatic solvent, or a mixture of aromatic and non-aromatic solvents. Examples include methanol, ethanol, ethylene glycol, isopropanol, 1, 2-butanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and the like.
The particle-free iron-based ink contains organic additives besides a main solvent, and mainly comprises a surface tension regulator, a viscosity regulator, a film forming auxiliary agent and a defoaming agent. By including a surface tension regulator and a viscosity regulator in the ink, the viscosity of the ink is regulated within a range suitable for ink-jet printing, the film-forming auxiliary agent can effectively ensure that the composition in the ink does not deposit and improve the film-forming property of the ink on a substrate, and the foam generated by the additive can be effectively eliminated by the defoamer. As the surface tension modifier, viscosity modifier, film forming auxiliary agent and defoamer, additives compatible with the main solvent are preferable.
The surface tension adjuster is preferably an auxiliary agent capable of adjusting the surface tension to 5 to 60mN/m, and the surface tension adjuster is preferably an auxiliary agent having a boiling point of 300 ℃ or less at one atmosphere. Specifically, cationic or anionic surfactants, alcohols, glycolic acid, lactic acid, and mixtures thereof may be selected. The surface tension modifier content is preferably in the range of 0.001wt% to 5wt%.
The ink viscosity modifier is preferably an auxiliary agent capable of adjusting the viscosity of the ink to 1 to 60mpa·s at room temperature of 25 ℃, specifically, gum such as acacia, pectin, agar, gelatin, alginate, carrageenan, general gelatin, polysaccharide derivative, and the like, and chemical such as di-n-butyl ether, sodium alginate, methylcellulose, ethylcellulose, propylene glycol alginate, sodium carboxymethyl cellulose, sodium alginate, sodium polyacrylate, polyoxyethylene, polyvinylpyrrolidone (PVP), and the like may be selected. The viscosity modifier content is preferably in the range of 0.001wt% to 5wt%.
As to defoamers, adjuvants that reduce or eliminate other additives are non-limiting ranges of fluorosilicone, mineral oil, vegetable oil, polysiloxanes, ester waxes, fatty alcohols, glycerin, stearates, silicones, polypropylene-based polyethers, and mixtures thereof. The preferred range is 0.001wt% to 5wt%.
The surface tension of the ink is preferably 5 to 60mN/m, particularly preferably 10 to 50mN/m, by adding the main solvent and the auxiliary agent. The viscosity at 25℃is preferably from 1 to 60 mPas, particularly preferably from 5 to 50 mPas.
Specifically, the ink of the application can be prepared by firstly complexing a first ligand and a second ligand in a main solvent, adding a reducing agent, and adding a proper amount of organic additive according to the need to adjust the viscosity, the surface tension, the film forming property after sintering, the stability and other properties of the ink, thus obtaining the target particle-free iron-based ink.
The obtained particle-free ink is formed into a film by various film forming modes including dripping, coating, spraying, laminating and suspension coating; patterning means include screen printing, ink jet printing, roll-to-roll printing, screen printing, offset printing, flexographic printing, lithographic printing, gravure printing, pad printing, or any other method of applying a film to various substrates such as polyethylene terephthalate (PET), polyimide (e.g., kapton (tm)), polyetherimide (e.g., ultem), thermoplastic Polyurethane (TPU), silicone film, printed wiring board substrates (e.g., FR 4), indium Tin Oxide (ITO), silver, copper, silicon, and the like. The film is preferably heat treated at 150 to 900 c, more preferably 150 to 800 c, which may be performed in stages, the ink coating being first dried and the decomposition coating being then sintered. The drying may be carried out at any suitable temperature, in the range of 20-150℃for a period of 5min-24h. The sinter-decomposition of the ink is carried out at a sufficient balance between a suitable temperature and time. The sintering atmosphere is particularly preferably one in which the ink is sintered and decomposed under inert atmosphere (e.g., nitrogen and/or argon), reducing atmosphere (e.g., hydrogen), mixed atmosphere (e.g., different ratios of hydrogen to nitrogen), and vacuum conditions.
The application provides iron-based particle-free ink for electromagnetic function. The ink adopts an iron precursor component and an amino group-containing compound to form a stable complex, and the complex is dissolved in an organic solvent to form the ink. Reducing agents, organic substances and the like are added for reducing the decomposition temperature and adjusting the microstructure of the film after sintering.
The amount of the metal precursor ink blended in the particle-free iron-based ink is preferably 5 to 40wt%, and most preferably 5 to 35wt%. By increasing the compounding amount of the metal precursor to the range, the complexing efficiency of the metal precursor can be improved, the stability of the ink can be improved, the film prepared by the compounding amount is uniform, the sintered particles are uniform, and good interaction is provided, so that the wave absorbing effect is fully optimized.
The film obtained by sintering has wave-absorbing characteristics, the electromagnetic functional film reaches the maximum bandwidth at-10 dB in the frequency range of 2-18GHz, and the minimum reflection loss proves that the film has good wave-absorbing efficiency.
In addition, the application provides a semiconductor film for electromagnetic function, which is prepared by simply sintering the coating film after the particle-free iron-based ink patterning treatment, wherein the formed film reaches the maximum bandwidth at-10 dB in the frequency range of 2-18GHz, and the minimum reflection loss proves that the film has good wave absorption efficiency and reaches the national military standard (GJB 5239-2004 "method for testing wave absorption performance of radio frequency wave absorption material" and GJB 2038A-2011 "method for testing reflectivity of radar wave absorption material").
The application fills the blank of the prior art, and can obtain Fe with electromagnetic functionality through simple heat treatment or photon sintering or microwave sintering 3 O 4 Thin films, such low cost particle free iron-based inks would be of immediate commercial value.
The application discloses the following technical effects:
the existing electromagnetic functional film is prepared by adopting the modes of mechanical ball milling, chemical synthesis of complex composite materials, mixing slurry, spraying or knife coating or traditional etching of metal plates, and the modes face the problems of complex process, high cost, long period, environmental pollution and the like. Aiming at the defects of the existing preparation of the electromagnetic functional film, the application provides a novel method for preparing the electromagnetic functional film by adopting the particle-free iron-based ink through a printed electronic technology and simple thermal sintering, which has the advantages of simple process, low cost, short period and environmental friendliness.
The particle-free iron-based conductive ink prepared by the application supplements the types of the existing particle-free conductive ink, fills the blank of the iron-based particle-free conductive ink in application, and can fully adjust the viscosity and the surface tension of the iron-based conductive ink so as to be suitable for different printing modes.
The iron-based conductive ink provided by the application is particle-free, and particularly does not block a spray head in the full-printing electronic technology/digital ink-jet printing technology.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of the ferroferric oxide film prepared in example 1;
fig. 2 is a scan of the ferroferric oxide film prepared in example 1.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The ferrous carboxylate, chelating agent or complexing agent, reducing agent, organic additive and solvent adopted in the embodiment of the application are all commercial products.
Example 1
The high-stability particle-free iron-based ink comprises the following raw materials in percentage by mass:
15% ferrous acetate (first ligand), 20% ethylenediamine (second ligand), 2% formic acid (reducing agent), 0.1% sodium carboxymethylcellulose (organic additive), 0.001% polyvinylpyrrolidone (organic additive), 0.001% gelatin (organic additive), ethanol (solvent) and the balance.
The preparation method of the high-stability particle-free iron-based ink comprises the following steps:
according to the proportion, firstly mixing ethylenediamine and solvent ethanol, adding ferrous acetate after uniformly mixing, stirring for two hours at room temperature until the ferrous acetate is fully dissolved, and respectively adding formic acid and organic additives until the formic acid and the organic additives are fully dissolved and filtered to obtain the high-stability particle-free iron-based conductive ink of the embodiment; the viscosity was 4 mPas and the surface tension was 31mN/m.
The high-stability particle-free iron-based ink is prepared into a film (ferroferric oxide film) by the following steps:
and (3) taking 200 mu L of the ink, spin-coating the ink on a 3 x 3cm metal substrate, wherein spin-coating parameters are set to be uniform coating rotating speed of 100rpm, uniform coating time of 20s, and spin-coating rotating speed of 1000rpm and spin-coating time of 20s in the spin-coating process. By photon sintering, the temperature is raised to 400 ℃ at a heating rate of 20 ℃/min, and the film is obtained through heat treatment for 30min, wherein the reflection attenuation is 90% at-10 dB within the range of 2-18 GHz. The adhesive force of the test film can reach 5B.
Example 2
The high-stability particle-free iron-based ink comprises the following raw materials in percentage by mass:
12% ferrous oxalate (first ligand), 25% ethanolamine (second ligand), 3% glycerol (reducing agent), 0.1% methylcellulose (organic additive), 0.001% polyvinylpyrrolidone (organic additive), 0.001% phenolic resin (organic additive), ethanol (solvent) and the balance.
The preparation method of the high-stability particle-free iron-based ink comprises the following steps:
according to the proportion, firstly, mixing ethanolamine and a solvent, adding ferrous oxalate into the mixed solution after uniform mixing, stirring for two hours at room temperature until the ferrous oxalate is fully dissolved, respectively adding glycerol and an organic additive until the ferrous oxalate is fully dissolved, and filtering to obtain the high-stability particle-free iron-based conductive ink of the embodiment, wherein the viscosity is 2mPa & s, and the surface tension is 22mN/m;
the high-stability particle-free iron-based ink is prepared into a film (ferroferric oxide film) by the following steps:
200 mu L of the ink is taken and spin-coated on a 3 x 3cm metal substrate, spin-coating parameters are set to be spin-coating rotation speed of 500rpm, spin-coating time of 20s, spin-coating rotation speed of 5000rpm and spin-coating time of 20s in the spin-coating process. By utilizing microwave sintering, the temperature is increased to 400 ℃ at the heating rate of 20 ℃/min, and the heat treatment is carried out for 30min, so that the reflection of the obtained film is attenuated by 92% in the range of 2-18GHz and at the temperature of-10 dB. The adhesive force of the test film can reach 5B.
Example 3
The high-stability particle-free iron-based ink comprises the following raw materials in percentage by mass:
18% ferrous oxalate (first ligand), 30% isopropanolamine (second ligand), 3% formaldehyde (reducing agent), 0.1% ethylcellulose (organic additive), 0.001% polyvinylpyrrolidone (organic additive), 0.001% gelatin (organic additive), ethanol (solvent) and the balance.
The preparation method of the high-stability particle-free iron-based ink comprises the following steps:
according to the proportion, firstly mixing isopropanolamine and a solvent, adding ferrous oxalate into the mixed solution after uniformly mixing, stirring for two hours at room temperature until the ferrous oxalate is fully dissolved, and then respectively adding formaldehyde and an organic additive until the formaldehyde and the organic additive are fully dissolved and filtered to obtain the high-stability particle-free iron-based conductive ink of the embodiment, wherein the viscosity is 3 mPa.s and the surface tension is 30mN/m.
The high-stability particle-free iron-based ink is prepared into a film (ferroferric oxide film) by the following steps:
200 mu L of the ink is taken and spin-coated on a 3 x 3cm metal substrate, spin-coating parameters are set to be uniform coating rotating speed of 300rpm, uniform coating time of 20s, spin-coating rotating speed of 3000rpm and spin-coating time of 20s in the spin-coating process. Heating to 400 ℃ at a heating rate of 20 ℃/min, and carrying out heat treatment for 30min to obtain the film, wherein the reflection attenuation is 91% at-10 dB within the range of 2-18 GHz. The adhesive force of the test film can reach 5B.
Example 4
The high-stability particle-free iron-based ink comprises the following raw materials in percentage by mass:
18% ferrous acetate (first ligand), 31% triethanolamine (second ligand), 2% formic acid (reducing agent), 0.1% hydroxyethylcellulose (organic additive), 0.001% polyvinylpyrrolidone (organic additive), ethanol (solvent) balance.
The preparation method of the high-stability particle-free iron-based ink comprises the following steps:
according to the proportion, firstly, the triethanolamine and the solvent are mixed uniformly, then the ferrous acetate is added into the mixed solution, after stirring for two hours at room temperature until the ferrous acetate is fully dissolved, the formic acid and the organic additive are respectively added until the ferrous acetate is fully dissolved and filtered, and the high-stability particle-free iron-based conductive ink is obtained, wherein the viscosity of the high-stability particle-free iron-based conductive ink is 5 mPa.s, and the surface tension of the high-stability particle-free iron-based conductive ink is 303mN/m.
The high-stability particle-free iron-based ink is prepared into a film (ferroferric oxide film) by the following steps:
200 mu L of the ink is taken and spin-coated on a 3 x 3cm glass substrate, spin-coating parameters are set to be spin-coating rotation speed of 500rpm, spin-coating time of 20s, spin-coating rotation speed of 5000rpm and spin-coating time of 20s in the spin-coating process. Heating to 500 ℃ at a heating rate of 10 ℃/min, and carrying out heat treatment for 30min to obtain the film, wherein the reflection attenuation is 95% at-10 dB within the range of 2-18 GHz. The adhesion of the test film reaches 5B.
The ink is particle-free ink containing an iron-based complex, and a semiconductor film formed by using the iron-based particle-free ink, and the wave absorption frequency of the film is required to be smaller than-10 dB in the range of 2-18GHz as wide as possible from the application field, so that the film prepared by the method needs to integrate electromagnetic wave absorption characteristics, and the adhesiveness between the ink and various substrates, good wave absorption characteristics after forming the film and the like can be improved by modulating the iron-based particle-free ink into a specific composition.
The above embodiments are only illustrative of the preferred embodiments of the present application and are not intended to limit the scope of the present application, and various modifications and improvements made by those skilled in the art to the technical solutions of the present application should fall within the protection scope defined by the claims of the present application without departing from the design spirit of the present application.
Claims (6)
1. The particle-free iron-based conductive ink for electromagnetic functions is characterized by comprising the following raw materials in percentage by mass:
5-40% of ferrous metal precursor, 10-60% of chelating agent or complexing agent, 2-10% of reducing agent, 0.001-10% of organic additive and the balance of solvent;
the chelating agent or complexing agent is one or a mixture of a plurality of ammonia water, aliphatic amine, alcohol amine, amide and aromatic amine;
the viscosity of the particle-free iron-based conductive ink for electromagnetic function is 1-60 mPa.s at 25 ℃, and the surface tension is 5-60 mN/m;
the reducing agent comprises one or more of glycerol, glycol, glucose, tartaric acid, citric acid, ascorbic acid, sodium borohydride, ammonium sulfide, formic acid or formaldehyde;
the organic additives include a surface tension modifier, a viscosity modifier, a film forming aid, or an antifoaming agent.
2. The method for preparing the particle-free iron-based conductive ink for electromagnetic functions as claimed in claim 1, comprising the steps of:
complexing the chelating agent or complexing agent and the ferrous metal precursor in the solvent, and adding the reducing agent and the organic additive to obtain the particle-free iron-based conductive ink for electromagnetic function.
3. A semiconductor film for electromagnetic function, characterized in that it is obtained by sintering the particle-free iron-based conductive ink for electromagnetic function according to claim 1.
4. The method for producing a semiconductor thin film for electromagnetic functions according to claim 3, comprising the steps of:
the electromagnetic function is coated on a substrate with a particle-free iron-based conductive ink, and then the formed coating film is sintered.
5. The method according to claim 4, wherein the sintering temperature is 150-800 ℃ for 30min; the temperature rising rate of the sintering is 10-20 ℃/min.
6. Use of the particle-free iron-based conductive ink for electromagnetic functions according to claim 1, the semiconductor thin film for electromagnetic functions according to claim 3 as an electromagnetic wave absorbing material.
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| EP1109434A2 (en) * | 1999-12-17 | 2001-06-20 | Nisshinbo Industries, Inc. | Transparent electromagnetic radiation shield material and method of producing the same |
| CN101010388A (en) * | 2005-03-04 | 2007-08-01 | 韩商英泰股份有限公司 | Conductive inks and manufacturing method thereof |
| JP2009033113A (en) * | 2007-06-22 | 2009-02-12 | Mitsubishi Materials Corp | Electromagnetic wave shielding composition and method of forming electromagnetic wave shield using the composition |
| CN102634779A (en) * | 2012-02-23 | 2012-08-15 | 北京航空航天大学 | Electromagnetic shielding material with chemically plated iron modified carbon nano-tubes and method for preparing same |
| CN107406699A (en) * | 2014-12-17 | 2017-11-28 | 汉高股份有限及两合公司 | Printable ferroelectricity ink |
| CN104946022A (en) * | 2015-07-10 | 2015-09-30 | 东北大学 | High-stability particle free type silver-based conductive ink and preparation method thereof |
| CN114554819A (en) * | 2022-02-25 | 2022-05-27 | 山东大学 | Electromagnetic wave absorber based on iron-based metal organic framework material and preparation method thereof |
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