阅读说明：本技术 一种可激发连续太赫兹波的水性石墨烯发热油墨及其制备方法 (Water-based graphene heating ink capable of exciting continuous terahertz waves and preparation method thereof ) 是由 解雪松 杨法杰 杨隆保 于 2018-08-26 设计创作，主要内容包括：本发明提供一种水性石墨烯导电发热油墨,同时也是一种基于石墨烯材料与组分形成太赫兹波连续发射源,是最新理疗治疗波段与新型电热技术的相统一。本发明提供的导电油墨在温度较低或长期放置后,油墨会呈胶冻状,升温或经搅拌或震动等作用后仍具有较好的流动性,用此油墨可以用到低温、高温电热膜以及其他加热元件中,并具有高通量的太赫兹波辐射,其太赫兹波辐射功率、波段范围、转化率等物理特性以及电热温度、功率由石墨烯材料本身及其所组成的水性油墨体系所决定。本发明制备的水性油墨,固化后核心石墨烯导电层作为发热单元和太赫兹波发射部件,其表面自动成膜形成一层致密的密封保护膜,具有优异的电热性能和太赫兹波产出率,满足规模应用要求。(The invention provides a water-based graphene conductive heating ink, and also provides a terahertz wave continuous emission source formed based on graphene materials and components, which is the integration of the latest physiotherapy treatment waveband and a novel electrothermal technology. The conductive ink provided by the invention is in a jelly shape after being placed at a low temperature or for a long time, and still has good fluidity after being heated or being stirred or vibrated, and can be used in low-temperature and high-temperature electrothermal films and other heating elements, and has high-flux terahertz wave radiation, wherein the physical characteristics of terahertz wave radiation power, waveband range, conversion rate and the like, the electrothermal temperature and power are determined by a graphene material and a water-based ink system formed by the graphene material. According to the water-based ink prepared by the invention, the core graphene conducting layer is used as a heating unit and a terahertz wave emitting component after being cured, a compact sealing protective film is formed on the surface of the core graphene conducting layer automatically, the water-based ink has excellent electric heating performance and terahertz wave output rate, and the requirement of scale application is met.)

1. The water-based graphene heating ink capable of exciting continuous terahertz waves and the preparation method thereof are characterized by being formed by compounding a graphene material, water-based resin, a conductive agent, an auxiliary agent and a water solvent component to form a conductive composition (conductive seasoning), wherein the conductive composition (conductive seasoning) comprises the following components in parts by weight: 10-85 parts of graphene, 3-30 parts of water-based resin, 2-20 parts of a conductive agent, 2-50 parts of water, 0.05-10 parts of an auxiliary agent and 1-10 parts of a terahertz reinforcing material.

2. The aqueous graphene exothermic ink capable of exciting continuous terahertz waves and the preparation method thereof according to claim 1, wherein graphene is one or more of single-layer graphene, multi-layer graphene, composite graphene, graphene oxide, functionalized graphene, intercalated graphene and carbon nanotube-graphene composite material.

3. The water-based graphene heating ink capable of exciting continuous terahertz waves and the preparation method thereof according to claim 1 are characterized in that the water-based resin is formed by mixing water-based polyurethane, water-based acrylic resin and water-based silicone resin according to any proportion.

4. The water-based graphene heating ink capable of exciting continuous terahertz waves and the preparation method thereof according to claim 1, wherein the conductive agent is one or more of carbon black, carbon nanotubes and carbon fibers.

5. The water-based graphene heating ink capable of exciting continuous terahertz waves and the preparation method thereof as claimed in claim 1, wherein the auxiliary agent is formed by mixing a dispersing agent, a leveling agent, a thickening agent, a corrosion inhibitor, an anti-settling agent, a rheological auxiliary agent, a defoaming agent and a pH regulator in any proportion.

6. The aqueous graphene exothermic ink capable of exciting continuous terahertz waves and the preparation method thereof according to claim 1, wherein the terahertz enhancement particles are one or more of lithium niobate, magnesium oxide, silicon dioxide, lithium tantalate and titanium dioxide inorganic materials, and the inorganic particles have a size ranging from 100nm to 100 μm.

7. The water-based graphene heating ink capable of exciting continuous terahertz waves and the preparation method thereof according to claims 1-6, wherein the preparation method of the water-based graphene conductive ink comprises two steps:

(1) putting the components into a high-speed double-planet stirrer, controlling the temperature to be 20-45 ℃, controlling the vacuum state to be less than or equal to-0.05 MPa, and controlling the rotation speed: 1000rad/min to 3000rad/min, revolution speed: 50 rad/min-500 rad/min, the stirring time can be divided into 20 min-60 min, and then the stirring speed is reduced to the self-transmission speed: 200 rad/min-500 rad/min, revolution speed: 20 rad/min-40 rad/min to obtain water-based graphene ink coarse pulp;

(2) and transferring the obtained conductive ink coarse slurry into a three-roll grinding machine or a sand mill for grinding for 2-10 hours, and sieving to obtain the final aqueous graphene conductive ink.

Technical Field

The invention provides a method for compounding terahertz waves and an electric heating technology, and particularly relates to a device giving consideration to a terahertz wave emission source based on water-based graphene heating ink and a preparation method thereof.

Background

In recent years, as a novel heating element, an electrothermal film has gained more and more attention due to high electrothermal conversion efficiency, energy conservation, environmental protection, no light pollution, long service life, wide range, strong grafting property, simple structure and the like, and the application field of the electrothermal film is continuously expanded, and the electrothermal film relates to the traditional industries of electrothermal heating, electrothermal elements for household industry, drying and drying equipment thereof, road snow melting and deicing, electronic micro-part heating and the like, and the health medical fields of novel physical therapy, health maintenance, health care and the like. The electrothermal film is used as a novel electric heating film and can be divided into a metal-based electrothermal film and a nonmetal-based electrothermal film according to different core packaging heating materials, the metal-based electrothermal film is a first-generation electrothermal film, the processing technology is complex, the cost is high, the ageing resistance is excellent, and the temperature control is accurate; the nonmetal-based electrothermal film is prepared by taking inorganic conductive materials as conductive fillers to prepare slurry, then coating the slurry on an insulating heat-resistant material, forming a resistance heating film of a conductive network through curing, and realizing the control of temperature by adjusting the size of a resistor.

The current non-metallic electrothermal film can be roughly divided into three types of carbon-based ink, carbon fiber and polymer, wherein the carbon-based ink and the carbon fiber electrothermal film occupy the whole market. The carbon-based ink occupies most of market share by virtue of excellent electrothermal performance and stability, and along with the updating of technology and material upgrading, the electrothermal conversion efficiency, heat conduction, stability and other performances of the carbon-based ink are gradually improved. In addition, the carbon chain conductive network formed by the carbon-based ink causes polymer expansion when the main body is heated, and the carbon chain is broken to sharply improve the resistivity, namely, the PTC effect is remarkable, so that the electric heating film is prevented from being damaged due to overheating. The latest research finds that graphene serving as a novel carbon-based material is remarkably improved in the aspects of improving the electrothermal property, stability and other properties of the carbon-based heating ink based on excellent physical and chemical properties of the graphene. Graphene is a hexagonal honeycomb planar structure consisting of only single carbon atoms in sp2 hybridized orbitals, is the thinnest and hardest nano material in the world at present, is far larger than carbon nanotubes and diamond, and has the resistivity of only 10^-6Omega cm, the thermal conductivity can reach 5300W/(m.K), which is 7.6 times that of carbon fiber (700W/m.k), 13.3 times that of copper (398W/m.k) and 19.4 times that of aluminum (273W/m.k).

On the other hand, with the improvement of living standard of people, the demands of civil heating elements such as heating, heaters and the like and other heating elements are not limited to heating and heating effects, and more attention is paid to the potential effects brought by the demands. The water-based graphene heating film disclosed in patent CN 107936686A is operated to be used as a far infrared radiation electric heating film for replacing the existing water heating system, so that the heating effect is met and the health care and physical therapy advantages are achieved. Also, for example, CN102563753B provides an air conditioner based on far infrared electric heating core, and CN107906582A provides a far infrared electric heating wall-mounted stove device. As described above, the development of the medical device is mainly based on the development of far infrared, and the health care, heat preservation and sterilization effects of far infrared on human bodies (organisms) are utilized. The fact proves that the far infrared health care function is mainly that the far infrared is received by epidermal cells and is transferred and permeated from the surface to the inside, the absorbed part generates a thermal effect, the body tissue cells generate resonance and resonance, the activation of cells is promoted, and the generated thermal effect expands human body micro-blood vessels, the self-discipline is improved, the blood circulation is accelerated, the material exchange between the cells and the blood is accelerated, so the metabolism of the body is promoted, the local obstruction is broken through, and the microcirculation is promoted. Meanwhile, the far infrared ray improves the phagocytic activity of phagocytes, is beneficial to dissipation of chronic inflammation, is beneficial to dissolution and absorption of pathological cells, and is suitable for treating various types of chronic inflammation.

However, although far infrared has high heating effect and health and physiotherapy characteristics, most of the far infrared is concentrated in the infrared region in terms of the wave band emitted by the current heating equipment and heating element, far infrared flux occupies only a small amount, and the penetration capability is limited, and the penetration is shallow only through the skin, thus greatly limiting the physiotherapy effect. In recent years, with the improvement of cognitive depth and dimensionality in the field of spectrums by people, detection means and measurement equipment technology are updated day by day, and people find a novel waveband, namely terahertz wave, which relates to infrared and microwave. Viewed from the frequency, the wave band is positioned between the millimeter wave and the infrared ray, belongs to the far infrared wave band, has the dual characteristics of microwave and infrared ray, and can realize the millimeter wave and the infrared rayThe function complementation, the low frequency part of the microwave is referred to as millimeter wave, the high frequency part of the microwave is referred to as far infrared region, the wave band frequency is between 0.1THz and 10THz (the wavelength is 30 mu m to 3 mm), the technical field with leading-edge science and technology is provided, and the initial research finds that the microwave can be widely applied to industrial production, medical diagnosis, detection and the like to realize nondestructive inspection. Energetically, between electrons and photons, there is low energy, only one part per million of X-rays (1/10)⁶) Can not cause ionization damage to organisms, thus being particularly suitable for the research of life health physiotherapy. It has been demonstrated that the vibrational and rotational energy levels of many biological macromolecules are in this band and can be used in the health areas of therapy, immune enhancement, health care, physical therapy, and the like. In addition, the terahertz wave photon energy has the far infrared physiotherapy effect and also has the penetrating effect of a certain depth.

Disclosure of Invention

Based on the limitation of the heat-shock infrared band of the current heating equipment and heating elements, the invention provides a continuous terahertz wave emission source based on a novel graphene material, which is used as an electrothermal core heating material and is the unification of a novel physical therapy band and a novel electrothermal technology. The physical characteristics of terahertz wave radiation power, waveband, conversion rate and the like, as well as the electrothermal temperature and power of the graphene heating film composite terahertz radiation source prepared by the technology are determined by the graphene material and a water-based ink system formed by the graphene material.

The invention provides a preparation method of water-based graphene-based ink, which is formed by compounding a graphene material, water-based resin, a conductive agent, an auxiliary agent and a water solvent component to form a conductive composition (conductive filler), and the conductive composition comprises the following components in parts by weight: 10-85 parts of graphene, 3-30 parts of water-based resin, 2-20 parts of a conductive agent, 2-50 parts of water, 0.05-10 parts of an auxiliary agent and 1-10 parts of a terahertz reinforcing material.

Preferably, the graphene is one or more of single-layer graphene, multi-layer graphene, composite graphene, graphene oxide, functionalized graphene, intercalated graphene and a carbon nanotube-graphene composite material.

Preferably, the aqueous resin is prepared by mixing aqueous polyurethane, aqueous acrylic resin and aqueous silicone resin according to any proportion.

Preferably, the conductive agent is one or a plurality of carbon black, carbon nano tube and carbon fiber.

Preferably, the auxiliary agent is formed by mixing a dispersing agent, a flatting agent, a thickening agent, a corrosion inhibitor, an anti-settling agent, a rheological auxiliary agent, a defoaming agent and a pH regulator according to any proportion.

Preferably, the terahertz enhancement particles are one or a plurality of composite inorganic materials of lithium niobate, magnesium oxide, silicon dioxide, lithium tantalate and titanium dioxide, the inorganic particles have a size range of 100 nm-100 μm, and excitation sites are provided for terahertz wave generation. On the basis of rich infrared flux of graphene, the terahertz wave enhanced particles generate frequency waves in a terahertz section range through excitation interaction with the graphene; in addition, as a particle reinforcing material, the wear resistance and pressure resistance of the ink are improved, and the hardness of the ink after curing is improved.

The preparation method of the water-based graphene conductive ink comprises the following steps: (1) putting the components into a high-speed planetary stirrer, controlling the operating temperature to be 20-45 ℃, controlling the vacuum state to be less than or equal to-0.05 MPa, and controlling the autorotation speed: 1000rad/min to 3000rad/min, revolution speed: 50 rad/min-500 rad/min, the stirring time can be divided into 20 min-60 min, and then the stirring speed is reduced to the self-transmission speed: 200 rad/min-500 rad/min, revolution speed: 20 rad/min-40 rad/min to obtain water-based graphene ink coarse pulp; (2) and transferring the obtained conductive ink coarse slurry to a three-roll grinder or a sand mill for grinding for 2-10 hours, and sieving to obtain the final aqueous graphene conductive ink.

The outstanding technical effects of the invention compared with the prior art are explained in detail as follows:

(1) the aqueous graphene-based ink prepared by the invention has the advantages that the aqueous graphene-based ink has electric conduction heating, is also used as an emission source of a novel physical therapy wave band terahertz wave, is a composite of the graphene heating ink and a terahertz wave source, the electric heating temperature and the electric heating power of the aqueous graphene-based ink are determined by a graphene material and a formula of the graphene-based aqueous ink formed by the graphene material, the physical properties such as the terahertz wave emission power, the wave band range of the emission source, the conversion rate and the like are also determined by the graphene material and the formula of the ink, and the integration of the electric heating material and the.

(2) The invention successfully introduces the graphene as a novel electric heating material, realizes high wear resistance and high hardness, and can be expanded into a whole. In addition, the terahertz enhanced particles not only serve as terahertz wave excitation sites, but also serve as resin enhanced particles, so that the rheological property and the stability of the ink are improved, the hardness and the wear resistance of a film layer formed by the ink are further improved, and the increase of the resistance of the graphene-based ink after hot pressing is reduced. Meanwhile, the adopted graphene has expandability of a microscale, so that the ductility of the ink is improved, and the ink is not microcracked after being bent.

(3) The water-based graphene-based ink prepared by the invention replaces the traditional oily solvent, realizes complete water solubility of an ink system, has no toxicity, pollution or universality of the solvent, reduces the VOC, preparation cost and preparation process requirements of the ink, generates no dense smoke, does not contain metal materials, and further reduces the composition cost and oxidation resistance of the ink. The high efficiency, energy saving and environmental protection of the graphene-based electrothermal film are improved.

(4) The water-based graphene-based ink prepared by the invention has good conductivity, strong adhesion after baking and good printing performance, and is suitable for printing ink film forming technologies such as silk screen printing, plate printing and the like.

(5) The conductive ink provided by the invention can be in a jelly shape when being placed for a long time or at low temperature, and the fluidity of the conductive ink is recovered after being stirred at low speed or under the action of vibration.

Drawings

FIG. 1 is a schematic structural diagram of a film formed by the aqueous graphene ink shown in example 1, wherein the ink film-formed structure comprises three macro-structural elements, an ink outer protective layer is an A layer, and a thin organic layer is obtained by automatic film formation after high-temperature curing; and B is a conductive seasoning formed by the graphene conductive composition, and comprises a graphene-based heating material and a terahertz wave excitation site.

Detailed Description

The present invention will be described more fully hereinafter with reference to the accompanying drawings and specific examples, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of the present invention.

The conductive composition (conductive filler) prepared from graphene materials, water-based resin, a conductive agent, an auxiliary agent and a water solvent comprises the following components in parts by weight: 30 parts of graphene, 30 parts of water-based resin, 2 parts of conductive agent, 25 parts of water, 10 parts of auxiliary agent and 8 parts of terahertz reinforcing material.

The graphene material is a composite material of single-layer graphene and multi-layer graphene, the multi-layer graphene is a graphene material with less than 10 layers, and the aqueous resin comprises aqueous polyurethane, aqueous acrylic resin and aqueous silicone resin according to a mass ratio of 1: 1: 1, mixing the components.

The conductive agent is a composite material of carbon black and carbon nanotubes.

Preferably, the auxiliary material is 5 parts, and the components are mixed and combined according to the mass ratio: 10% of dispersing agent, 20% of flatting agent, 25% of thickening agent, 5% of corrosion inhibitor, 6% of anti-settling agent, 4% of rheological additive, 20% of defoaming agent and 10% of pH regulator.

Preferably, the terahertz enhanced particles are lithium niobate inorganic materials, the scale range of the inorganic particles is 1.5-10 μm, excitation sites are provided for terahertz wave generation, and frequency waves with terahertz frequency are generated by exciting and interacting graphene and the enhanced particles on the basis of rich infrared flux of graphene.

The preparation method of the water-based graphene conductive ink comprises the following steps: (1) putting the components into a high-speed double-planet stirrer, controlling the temperature at 25 ℃, the vacuum state at-0.05 MPa, and the rotation speed: 1500rad/min, revolution speed: 100rad/min, the stirring time can be divided into 40min, and then the stirring speed is changed from the low stirring speed to the self-transmission speed: 300rad/min, revolution speed: 30rad/min to obtain water-based graphene ink coarse pulp; (2) and transferring the obtained conductive ink coarse slurry into a three-roll grinder or a sand grinder to grind for 5 hours, and sieving to obtain the final aqueous graphene conductive ink.