CN113845794A - Magnetic/high-infrared-emissivity composite material and preparation method and application thereof - Google Patents

Magnetic/high-infrared-emissivity composite material and preparation method and application thereof Download PDF

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CN113845794A
CN113845794A CN202111160841.5A CN202111160841A CN113845794A CN 113845794 A CN113845794 A CN 113845794A CN 202111160841 A CN202111160841 A CN 202111160841A CN 113845794 A CN113845794 A CN 113845794A
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magnetic
infrared
composite
composite material
emissivity
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刘华臣
黄婷
蒋慧昀
谭建
吴聪
唐良颖
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China Tobacco Hubei Industrial LLC
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China Tobacco Hubei Industrial LLC
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/23—Magnetisable or magnetic paints or lacquers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/01—Magnetic additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The application provides a magnetic/high-infrared-emissivity composite material and a preparation method and application thereof. The composite material is prepared by bonding and/or associating the modified magnetic nano material with the infrared radiation material, so that the prepared composite material has the high magnetic conductivity of the magnetic nano material and the high infrared emissivity of the infrared radiation material; the composite material is coated on the surface of an electric heating body to form a high-efficiency infrared coating, and also can be coated on the surface of a non-heating body to generate heat under the action of a magnetic field, and then the heat is transferred in the form of infrared radiation, so that the composite material has high heating efficiency and wide application range, and can realize uniform heating.

Description

Magnetic/high-infrared-emissivity composite material and preparation method and application thereof
Technical Field
The invention relates to the field of tobacco heating, in particular to a magnetic/high-infrared-emissivity composite material and a preparation method and application thereof.
Background
The heating non-combustion tobacco product is a novel tobacco product which only heats the tobacco shred without combusting the tobacco shred by utilizing a special heat source, and mainly has three characteristics: no combustion, nicotine supply to the smoker, and low tar content. Because the heating temperature (below 500 ℃) is lower than the combustion temperature (600- & lt 900- & gt) of the traditional cigarette, the harmful components generated by high-temperature combustion thermal cracking and thermal synthesis of tobacco are reduced, and the release amount of side stream smoke and environmental smoke (second-hand smoke) is greatly reduced; on the basis, nicotine in the cigarette is released, and certain tobacco characteristic feeling is provided for consumers. There are three main ways of heating a non-combustible tobacco product: electrical heating, fuel (e.g., carbon heating), and physical chemical reaction heating (e.g., physical crystallization, chemical reaction, etc.). However, the heating mode of the cigarette sold in the market at present generally has the problem of uneven heating of the cigarette releasing material, and the experience of the consumer on the product is seriously influenced.
In order to solve the problem of uneven heating of the heated cigarette, people continuously create an electrothermal film, the electrothermal film is attached to an insulating material, or a coating prepared from a high-infrared radiation material is adopted, and the infrared radiation coating is coated on the surface of a heating body to form a high-efficiency infrared coating, so that the heated cigarette is uniformly heated. However, the electrothermal film or coating can only realize heating effect on the surface of a specific object (an insulating material or a heating body), and is easy to peel off, and the heating efficiency is not high.
For example, patent No. CN 112369712 a discloses a SiC-based infrared heating composite material and a preparation method thereof, wherein the composite material is prepared by tetraethyl orthosilicate, tetrabutyl titanate, Si powder and carbon black powder through a high-temperature reaction mode, and the composite material is coated on the surface of an electric heater to heat tobacco. Patent No. CN 112383980 a discloses a composite heat-generating material, and a preparation method and use thereof, the composite heat-generating material comprises a substrate and a coating applied on a surface of the substrate, wherein the substrate comprises a ferromagnetic material, and the coating comprises a high infrared emissivity material, and by coating the high infrared emissivity material on the surface of the magnetic material, heat generated by electromagnetic induction of the substrate is partially transferred to the outside in the form of infrared radiation heating, so that the heat can be transferred in the form of conduction and radiation, and the heating efficiency is effectively improved. However, the composite material of the above technology can achieve a heating effect only by applying it to the surface of a heating body (an electric heating body or an electromagnetic induction heating body).
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a magnetic/high-infrared-emissivity composite material and a preparation method and application thereof. The composite material can be directly coated on the outer surface of an electric heating body to form a coating, generates heat after being electrified, and can also be coated on the surface of a non-heating body to generate heat under a magnetic field, so that uniform heating can be realized, and the heating efficiency is high.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a magnetic/high ir emissivity composite formed from magnetic nanomaterials bonded and/or associated with an ir-emissive material; the magnetic nano material is a modified magnetic nano material so as to enhance the bonding and/or association force of the magnetic nano material and the infrared radiation material.
It is known that infrared radiation heating does not need a transfer medium, has high heat transfer efficiency, can penetrate the surface of a heated body to a certain extent, realizes the simultaneous heating of the inside and the outside of a substance, and is an effective means for improving the heating efficiency of the heated body, reducing the temperature gradient of the heated body and saving energy consumption. The heating body of electromagnetic induction heating is mainly metal or alloy with good magnetic conductivity, and the principle is that a material with higher magnetic conductivity generates an eddy current effect in an induction coil to generate heat.
In the prior art, in order to improve the heating uniformity and the heating efficiency of the heating element, for infrared radiation heating, the focus is generally on changing the radiation performance of an infrared radiation material, for example, mixing a plurality of infrared radiation materials with excellent performance together by a certain proportion; or changing the preparation method and the like. For electromagnetic induction heating, focus is usually on the choice of magnetic material, or distribution of induction coils.
However, the above-mentioned improvement means has limitations that the infrared radiation paint can be heated only by applying it to the heat generating body, and the magnetic material is also used directly as the base material of the heat generating body, and the application range is relatively single. Based on this, the inventors of the present application have creatively proposed to compound an infrared radiation material with a magnetic material to obtain a composite material having both magnetic and infrared radiation properties. The method specifically comprises the following steps: the nanometer material with good magnetic conductivity is chemically bonded and/or associated on the infrared radiation material, the prepared composite material can be coated on the surface of a heating body, the heating effect is realized by utilizing the infrared radiation performance of the infrared radiation material, the composite material can be coated on the surface of a non-heating body, the heat is generated under the action of a magnetic field by utilizing the good magnetic conductivity of the magnetic nanometer material, meanwhile, the heat generated by electromagnetic induction is directly transmitted to tobacco in an infrared radiation mode, the conduction process of a medium is not needed, the heat loss is avoided, not only can uniform heating be realized, but also the heating efficiency is high.
The magnetic material can generate magnetization intensity or magnetic induction intensity under the action of an external magnetic field. The magnetic nano material has the advantages that the specific surface area is increased rapidly due to the superfine particle size, so that the magnetic nano material has the surface effect, small-size effect, quantum effect, macroscopic tunnel effect and the like which are not possessed by other bulk materials, and the corrosion resistance, the wear resistance, the aging resistance, the antibacterial performance and the like of a coating can be improved when the magnetic nano material is used for a heating coating. But the magnetic nano material is extremely high in surface activity, so that the magnetic nano material is extremely easy to agglomerate, and the actual application effect of the nano particles is greatly reduced or even eliminated. Therefore, the magnetic nano material is subjected to surface modification, so that the dispersibility of the nano particles can be improved, the agglomeration is reduced, and the surface of the nano particles can generate new functions such as physical, chemical or mechanical properties and the like.
Preferably, the modified magnetic nano material accounts for 20-35 wt% of the composite material, such as 20wt%, 25wt%, 30wt% and 35 wt%. If the content of the modified magnetic nano material is lower than 20%, the addition amount of the magnetic material is too small, so that the thermal efficiency generated by magnetic induction is low, and the required heating effect cannot be achieved; if the content of the magnetic nano material is higher than 35%, the addition amount of the nano material is too high, which may cause an agglomeration phenomenon.
Preferably, the modified magnetic nanomaterial is obtained by surface modification of a magnetic metal oxide by a silane coupling agent. The magnetic metal oxide has high magnetic conductivity, the surface of the magnetic metal oxide contains a large number of active hydroxyl groups, the coupling agent is a chemical substance with two group structures, and one group can react with the hydroxyl on the surface of the magnetic metal oxide, so that the surface of the magnetic metal oxide is modified.
Preferably, the magnetic metal oxide has a particle size of 5 to 50 nm. The particle size is controlled within the range, so that the specific surface area of the magnetic metal oxide can be increased, the bonding effect of the magnetic metal oxide and a silane coupling agent is better, the surface modification effect is enhanced, the dispersity is increased, and the composition with more infrared radiation materials is ensured.
In order to ensure that the prepared composite material has high magnetic permeability, the magnetic metal oxide is preferably Fe3O4、TiO2、Co3O4、NiO、CrO2、ZrO2One or more of (a). Nano Fe3O4The magnetic conductive film has strong absorption performance on electromagnetic waves in the frequency range of 1-1000MHz and high magnetic conductivity; nano TiO 22Has higher photocatalysis performance, can effectively decompose the tobacco residue attached to the surface of the heating element so as to achieve good self-cleaning effect, therefore, the magnetic nano oxide is more preferably Fe3O4And TiO2And (4) compounding.
In the present invention, the silane coupling agent is preferably at least one of WD-30, TEOS, KH-570 and KH-560. The silane coupling agent plays a role in bridging, and the magnetic metal oxide and the infrared radiation material are chemically bonded by utilizing the two groups on the silane coupling agent, for example, a chemical bond or a hydrogen bond is formed, so that the prepared composite material is more stable, and has magnetic and infrared radiation effects.
According to kirchhoff's law, the infrared emissivity of the infrared radiation material is related to the surface area of the infrared radiation material, and the larger the surface area is, the larger the effective radiation area is, which is beneficial to infrared emission. In order to ensure high infrared emissivity, the infrared radiation material is preferably one or more of carbon black, carbon nanotubes, expanded graphite and graphene. The infrared radiation material not only has large specific surface area, but also contains abundant functional groups such as hydroxyl, carboxyl and the like and chemical reaction active sites, and is favorable for chemical bonding with the magnetic nano material.
In order to realize the bonding and/or association of the magnetic nano material to the infrared radiation material, on the other hand, the invention also provides a preparation method of the magnetic/high infrared emissivity composite material, which comprises the following steps:
s1: preparing a magnetic metal oxide;
s2: dissolving the magnetic metal oxide prepared in S1 to obtain magnetic fluid, adding a silane coupling agent (adjusting the pH to be alkaline if necessary), and heating and stirring to obtain a modified magnetic nano material;
s3: and (3) fully dissolving the infrared radiation material and the modified magnetic nano material prepared by the S2, continuously stirring for 7-12h (heating if necessary), and carrying out precipitation, filtration and drying to obtain the composite material.
Preferably, the magnetic metal oxide of step S1 is prepared by a hydrothermal method. A hydrothermal method is adopted, and firstly, the magnetic performance is improved at a high temperature of 130-250 ℃; secondly, the reaction is carried out in a closed container (such as a reaction kettle), so that relative high pressure (0.3-4 MPa) can be generated, and volatilization of components is avoided.
In a further aspect, the invention also provides the use of a magnetic/high ir emissivity composite for heating a non-combustible tobacco heating device, by applying the composite to the surface of a heating element.
According to the preparation method, a silane coupling agent is bonded with hydroxyl of a magnetic metal oxide to obtain a modified magnetic nano material, and then functional groups such as hydroxyl, halogen atoms or double bonds on the modified magnetic nano material and hydroxyl, carboxyl or double bonds on the surface of an infrared radiation material are subjected to chemical reaction to form chemical bonds or hydrogen bonds, so that the composite material with both magnetism and infrared radiation property is prepared.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the application, the modified magnetic nano material is bonded and/or associated with the infrared radiation material, so that the prepared composite material has the high magnetic conductivity of the magnetic nano material and the high infrared emissivity of the infrared radiation material; the composite material is coated on the surface of an electric heating body to form a high-efficiency infrared coating, and also can be coated on the surface of a non-heating body to generate heat under the action of a magnetic field, and then the heat is transferred in the form of infrared radiation, so that the composite material has high heating efficiency and wide application range, and can realize uniform heating.
2. The magnetic nano material has electromagnetic performance and photocatalytic performance, so that the prepared composite material has a self-cleaning effect, and the phenomenon that the pumping experience is influenced by sundries remained on a heating assembly is avoided.
3. The infrared radiation material has a large specific surface area, and can load more magnetic nano materials, so that the surface roughness is increased, and the infrared radiation performance is greatly improved.
Detailed Description
The present invention will be described in further detail with reference to preferred embodiments, which are not intended to limit the scope of the present invention.
Example 1
Magnetic/high infrared emissivity composite material (modified nano Fe)3O4Magnetic nano material and graphene infrared radiation material) through the following steps:
(1) in a beaker, 10g Fe (NO)3)3·9H2Dissolving O in 20ml absolute ethyl alcohol, adding 9.8g urea after completely dissolving, stirring thoroughly, gradually generating light blue precipitate at the bottom of the beaker after a few minutes, stirring for 1h, washing with ethanol,filtering under normal pressure, and naturally drying to obtain light green precipitate iron-urea precursor. Then 1g of iron-urea precursor is put into a high-pressure reaction kettle and heated for 2 hours at the temperature of 250 ℃ to prepare the nano Fe3O4。
(2) 4g of nano Fe3O440ml of xylene and 1.2ml of distilled water are sequentially added into a 250ml three-neck flask and ultrasonically dispersed for 30min to form the magnetic fluid. Then adding 15g of 3-chloropropyltriethoxysilane (WD-30), mechanically stirring and reacting for 11 h in an oil bath at the temperature of 80 ℃ at the speed of 500 r/min, finishing the reaction, filtering, repeatedly washing with toluene for three times, and drying the product in vacuum for 24h at the temperature of 40 ℃ to obtain the modified nano Fe3O4。
(3) According to the weight percentage, 20 weight percent of modified nano Fe3O470 wt% of graphene and 10 wt% of sodium carbonate are sequentially added into 20ml of DMF, ultrasonically dispersed and stirred for 30min, then stirred for 10min in an ice water bath, and immediately placed into an oil bath pot to react for 7h at 80 ℃ after being vacuumized by a vacuum pump. Dissolving the obtained product in tetrahydrofuran, adding methanol to separate out a precipitate, filtering, washing for 3 times, and drying in vacuum at 40 ℃ for 24 hours to obtain the magnetic high-infrared-emissivity composite material.
Example 2
Magnetic/high infrared emissivity composite material (modified nano Fe)3O4Magnetic nano material and carbon nano tube infrared radiation material) through the following steps:
(1) in a beaker, 10g Fe (NO)3)3·9H2Dissolving O in 20ml of absolute ethyl alcohol, adding 9.8g of urea after the O is completely dissolved, fully stirring, gradually generating light blue precipitate at the bottom of a beaker after a few minutes, washing with ethanol after stirring for 1 hour, filtering at normal pressure, and naturally drying to obtain a light green precipitate iron-urea precursor. Then 1g of iron-urea precursor is put into a high-pressure reaction kettle and heated for 2 hours at the temperature of 250 ℃ to prepare the nano Fe3O4。
(2) 4g of nano Fe3O440ml of xylene and 1.2ml of distilled water were sequentially added to a 250ml three-necked flask and subjected to ultrasonic fractionationDispersing and stirring for 30min to form magnetic fluid. Then adding 15g of 3-chloropropyltriethoxysilane (WD-30), mechanically stirring and reacting for 11 h in an oil bath at the temperature of 80 ℃ at the speed of 500 r/min, finishing the reaction, filtering, repeatedly washing with toluene for three times, and drying the product in vacuum for 24h at the temperature of 40 ℃ to obtain the modified nano Fe3O4。
(3) According to the weight percentage, 30wt% of modified nano Fe3O460 wt% of carbon nano tube and 10 wt% of sodium carbonate are sequentially added into 20ml of DMF, ultrasonically dispersed and stirred for 30min, then stirred for 15min in an ice water bath, and immediately placed into an oil bath pot to react for 7h at 80 ℃ after being vacuumized by a vacuum pump. Dissolving the obtained product in tetrahydrofuran, adding methanol to separate out a precipitate, filtering, washing for 3 times, and drying in vacuum at 40 ℃ for 24 hours to obtain the magnetic high-infrared-emissivity composite material.
Example 3
Magnetic/high infrared emissivity composite material (modified nano TiO)2Magnetic nano material and graphene infrared radiation material) through the following steps:
(1) taking 2mol TiCl under strong stirring in ice-water bath4Slowly dropping into 100ml of distilled water, diluting to 2mol/L of stock solution with constant volume, diluting 5 ml of stock solution to 1mol/L, slowly adding 50mol/L of sodium hydroxide solution under the condition of stirring, and reacting at 30 ℃ to generate nano TiO2And (3) precursor. Subsequently adding nano TiO2Putting the precursor into a high-pressure reaction kettle, reacting for 5 h at 130 ℃, filtering and separating the product, and drying for 24h in a drying oven at 50 ℃ to obtain the nano TiO2And (3) powder.
(2) 4g of nano TiO2The powder, 40ml of xylene and 1.2ml of distilled water were sequentially added to a 250ml three-necked flask, ultrasonically dispersed and stirred for 30min to form a magnetic fluid. Then adding 15g of 3-chloropropyltriethoxysilane (WD-30), mechanically stirring and reacting for 11 h at 500 r/min in an oil bath at the temperature of 80 ℃, finishing the reaction, filtering, repeatedly washing with toluene for three times, and drying the product in vacuum for 24h at the temperature of 40 ℃ to obtain the modified nano TiO2。
(3) According to the weight percentage, 25wt% ofModified nano TiO265 wt% of graphene and 10 wt% of sodium carbonate are sequentially added into 20ml of DMF, ultrasonically dispersed and stirred for 30min, then stirred for 10min in an ice water bath, and immediately placed into an oil bath pot to react for 10h at 80 ℃ after being vacuumized by a vacuum pump. Dissolving the obtained product in tetrahydrofuran, adding methanol to separate out a precipitate, filtering, washing for 3 times, and drying in vacuum at 40 ℃ for 24 hours to obtain the magnetic high-infrared-emissivity composite material.
Example 4
Magnetic/high infrared emissivity composite material (modified nano TiO)2Magnetic nano material and carbon nano tube infrared radiation material) through the following steps:
(1) taking 2mol TiCl under strong stirring in ice-water bath4Slowly dropping into 100ml of distilled water, diluting to 2mol/L of stock solution with constant volume, diluting 5 ml of stock solution to 1mol/L, slowly adding 50mol/L of sodium hydroxide solution under the condition of stirring, and reacting at 30 ℃ to generate nano TiO2And (3) precursor. Subsequently adding nano TiO2Putting the precursor into a high-pressure reaction kettle, reacting for 5 h at 130 ℃, filtering and separating the product, and drying for 24h in a drying oven at 50 ℃ to obtain the nano TiO2And (3) powder.
(2) 4g of nano TiO2The powder, 40ml of xylene and 1.2ml of distilled water were sequentially added to a 250ml three-necked flask, ultrasonically dispersed and stirred for 30min to form a magnetic fluid. Then adding 15g of 3-chloropropyltriethoxysilane (WD-30), mechanically stirring and reacting for 11 h at 500 r/min in an oil bath at the temperature of 80 ℃, finishing the reaction, filtering, repeatedly washing with toluene for three times, and drying the product in vacuum for 24h at the temperature of 40 ℃ to obtain the modified nano TiO2。
(3) According to the weight percentage, 35wt% of modified nano TiO255 wt% of carbon nano tube and 10 wt% of sodium carbonate are sequentially added into 20ml of DMF, ultrasonically dispersed and stirred for 30min, then stirred for 10min in an ice water bath, and immediately placed into an oil bath pot to react for 10h at 80 ℃ after being vacuumized by a vacuum pump. Dissolving the obtained product in tetrahydrofuran, adding methanol to separate out precipitate, filtering, washing for 3 times, and vacuum drying at 40 deg.C for 24 hr to obtain magnetic materialAnd high infrared emissivity composite material.
Example 5
Magnetic/high infrared emissivity composite material (modified nano Fe)3O4And modified nano TiO2The mixture as a modified magnetic nanomaterial, graphene as an infrared radiation material), prepared by the following steps:
modified nano Fe was prepared by the same method as example 13O4Preparation of modified Nano TiO in the same manner as in example 32。
Then 20wt% of modified nano Fe3O415 wt% of modified nano TiO2、Adding 55 wt% of graphene and 10 wt% of sodium carbonate into 20ml of DMF in sequence, ultrasonically dispersing and stirring for 30min, stirring for 20min in an ice water bath, vacuumizing by using a vacuum pump, immediately putting into an oil bath pot, and reacting for 6h at 80 ℃. Dissolving the obtained product in tetrahydrofuran, adding methanol to separate out a precipitate, filtering, washing for 3 times, and drying in vacuum at 40 ℃ for 24 hours to obtain the magnetic high-infrared-emissivity composite material.
Example 6
A magnetic/high infrared emissivity composite material (TEOS is used as a coupling agent) is prepared by the following steps:
(1) in a beaker, 10g Fe (NO)3)3·9H2Dissolving O in 20ml of absolute ethyl alcohol, adding 9.8g of urea after the O is completely dissolved, fully stirring, gradually generating light blue precipitate at the bottom of a beaker after a few minutes, washing with ethanol after stirring for 1 hour, filtering at normal pressure, and naturally drying to obtain a light green precipitate iron-urea precursor. Then 1g of iron-urea precursor is put into a high-pressure reaction kettle and heated for 2 hours at the temperature of 250 ℃ to prepare the nano Fe3O4。
(2) 4g of nano Fe3O480ml of absolute ethyl alcohol and 20ml of distilled water are sequentially added into a 250ml three-neck flask, and ultrasonic dispersion and stirring are carried out for 30min to form the magnetic fluid. Then 2ml of 30% by mass aqueous ammonia were added dropwise to adjust the pH of the solution to 9.0, followed by 2ml of Tetraethylorthosilicate (TEOS) and a mechanical stirring at 500 r/min at 40 ℃Stirring for reaction for 24h, finishing the reaction, removing the solvent, and vacuum-drying the obtained product at 40 ℃ for 24h to obtain the modified nano Fe3O4。
(3) According to the weight percentage, 20 weight percent of modified nano Fe3O470 wt% of graphene and 10 wt% of sodium carbonate are sequentially added into 20ml of DMF, ultrasonically dispersed and stirred for 30min, and then continuously stirred for reaction for 12 h. Dissolving the obtained product in tetrahydrofuran, adding methanol to separate out a precipitate, filtering, washing for 3 times, and drying in vacuum at 40 ℃ for 24 hours to obtain the magnetic high-infrared-emissivity composite material.
Application example 1
The composite materials prepared in the embodiments 1 to 6 are put into a crucible, and subjected to heat preservation treatment, then cooled, dried, ball-milled, sieved by a 200-mesh sieve, mixed with acrylic resin and epoxy resin according to the proportion of 1:1:2 to prepare slurry, and the slurry is sprayed on the surface of an electric heating body (a ceramic heating body) to form a coating, which is respectively marked as samples 1 to 6. That is, sample 1 corresponds to example 1, sample 2 corresponds to example 2, and so on.
Application example 2
The slurry was prepared in the same manner as in application example 1, and then the slurry was sprayed on the surface of a non-heating body (high temperature resistant engineering plastic) to form a coating, which was labeled as samples 11 to 16, respectively. That is, sample 11 corresponds to example 1, sample 12 corresponds to example 2, and so on.
Comparative example 1
Modified nano Fe is not added in the preparation process of the composite material3O4Otherwise, the same procedure as in example 1 was repeated, and then a slurry was prepared and sprayed on the surface of the electric heating body in the same manner as in application example 1 to obtain comparative example 1.
Comparative example 2
Nano Fe is used in the preparation process of the composite material3O4Substitute modified nano Fe3O4Otherwise, the same procedure as in example 1 was repeated, and then a slurry was prepared and sprayed on the surface of the electric heating body in the same manner as in application example 1 to obtain comparative example 2.
Comparative example 3
The preparation process of the composite material was the same as that of example 1 except that no infrared radiation material was added, and then the composite material was made into a slurry by the same method as in application example 1 and sprayed on the surface of an electric heater to obtain a comparative sample 3.
Evaluation of
And evaluating the magnetism, the infrared emissivity, the heating uniformity and the self-cleaning effect of the prepared composite material.
A. Magnetic property
The magnetic properties of the composite materials prepared by the samples 1 to 6 and the comparative samples 2 to 3 were measured by a Vibrating Sample Magnetometer (VSM) to obtain a specific saturation magnetization. The test results are shown in Table 1.
Figure DEST_PATH_IMAGE002
As can be seen from Table 1, the samples 1 to 6 have higher specific saturation magnetization, which indicates that the composite material prepared by the method has good sensitivity to an external magnetic field and can generate magnetic induction intensity under the action of the external magnetic field;
the specific saturation magnetization of the samples 3-4 is slightly lower than that of the samples 1-2, which shows the influence of the nano materials with different magnetic conductivities on the composite material; the specific saturation magnetization of the reference sample 2 is lower than that of the sample 1, which shows the technical contribution of the modified magnetic nano material; the comparative sample 3 has a smaller change in saturation magnetization than the sample 1, indicating that the infrared radiation material has substantially no influence on the magnetic properties of the composite material.
B. Infrared emissivity
And testing the obtained samples 1-6 and the comparative samples 1-3 by using a dual-band emissivity tester to obtain the infrared emissivity of the prepared composite material in the band range of 1-25 mu m. The test results are shown in Table 2.
Figure DEST_PATH_IMAGE004
From the results of samples 1-6 in table 2, it can be confirmed that the infrared emissivity of the coating formed by coating the composite material of the present invention on the surface of the electric heater is between 0.966-0.992 in the 1-25 μm band, and the emissivity is high in the infrared response band range of tobacco, so that the composite material can effectively meet the requirements of heaters for heating non-combustion tobacco products.
The infrared emissivity of the comparative sample 1 is slightly lower than that of the sample 1, which shows that the infrared emissivity can be improved by adding the modified magnetic nano material; compared with the comparative sample 2, the infrared radiance of the sample 1 is increased, which shows the technical contribution to the modification of the magnetic nano material; the ir emissivity of sample 1 is much greater than that of comparative sample 3, indicating the technical contribution of the ir-radiating material.
C. Uniformity of heating
Electrifying two ends of the samples 1-6 for 1min respectively, and carrying out energy induction on the samples 11-16 by using an electromagnetic energy excitation device. The temperatures of the samples 1-6 and 11-16 were measured at different locations using a thermal infrared imager, respectively, and the results are shown in Table 3 below.
Figure DEST_PATH_IMAGE006
As can be seen from Table 3, the coating formed by the composite material prepared in the examples of the present application has excellent heating uniformity; furthermore, the heat generation effects of samples 1-6 indicate that the composite material of the present application can be coated on the surface of an electric heater to generate heat after being electrified, and the heat generation effects of samples 11-16 indicate that the composite material of the present application can also be coated on the surface of a non-heating body to generate heat under a magnetic field.
In addition, as can be seen from table 3, the heating temperature of sample 1 is slightly lower than that of sample 2, and sample 3 is lower than that of sample 4, indicating the influence of different infrared radiation materials on the heating performance; the heating temperature of sample 1 is higher than that of sample 3, and the heating temperature of sample 2 is higher than that of sample 4, which is the influence of different kinds of magnetic nano-oxides; the heating temperature of the sample 5 is slightly higher than that of the sample 1, which shows that the mixed magnetic nano oxide has better effect than a single type of nano oxide; meanwhile, the heating temperature of sample 6 is almost unchanged from that of sample 1, indicating that the type of silane coupling agent has almost no influence on the heating effect.
D. Self-cleaning performance test
Referring to the national standard GB/T23764-2009 photocatalytic self-cleaning material performance test method, the same amount of oleic acid (oleic acid is used as a simulated pollutant after combustion of tobacco shreds) is respectively coated on the coatings formed by the samples 1-6 and the comparative samples 1-3, the change condition of the contact angle between the surface of each coating and stains along with photocatalytic time is observed under the conditions of drying at room temperature and ultraviolet irradiation, and then the self-cleaning performance of the prepared composite material is investigated. As shown in table 4.
Figure DEST_PATH_IMAGE008
As can be seen from Table 4, the initial contact angles were as large as 80 ° or more because the surfaces of the coatings were coated with a layer of oleic acid. With the continuous irradiation of ultraviolet light, the contact angle of the comparative sample 1 is almost unchanged, which shows that the magnetic nano material makes technical contribution to self-cleaning; the contact angles of the samples 1 to 6 and the comparative samples 2 and 3 are obviously reduced, but the final contact angle of the comparative sample 2 is more than 10 degrees, which indicates the technical contribution of the modified magnetic nano material; the final contact angle of the comparative sample 3 is basically the same as that of the sample 1, which shows that the self-cleaning effect of the composite material does not depend on the infrared radiation material; compared with the sample 1, the sample 6 has basically the same change degree of the contact angle, which shows that different types of silane coupling agents have little influence on the self-cleaning effect; the final contact angle of the sample 3-5 is 0 deg., indicating the modified nano TiO2The technical contribution made.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A magnetic/high ir emissivity composite, wherein the composite is formed by bonding and/or associating magnetic nanomaterials to ir emissive materials; the magnetic nano material is a modified magnetic nano material so as to enhance the bonding and/or association force of the magnetic nano material and the infrared radiation material.
2. The magnetic/high emissivity composite of claim 1, wherein the modified magnetic nanomaterial comprises 20-35 wt% of the composite.
3. The magnetic/high infrared emissivity composite material of claim 1, wherein the modified magnetic nanomaterial is obtained by surface modification of a magnetic metal oxide with a silane coupling agent.
4. The magnetic/high IR emissivity composite of claim 3, wherein said silane coupling agent is at least one of WD-30, TEOS, KH-570, KH-560.
5. The magnetic/high emissivity composite of claim 3, wherein the magnetic metal oxide has a particle size of 5-50 nm.
6. The magnetic/high emissivity composite of claim 3, wherein said magnetic metal oxide is Fe3O4、TiO2、Co3O4、NiO、CrO2、ZrO2One or more of (a).
7. The magnetic/high emissivity composite of claim 1, wherein the infrared emissive material is one or more of carbon nanotubes, graphene, expanded graphite, and carbon black.
8. A method of making a magnetic/high ir emissivity composite as claimed in claim 1, comprising the steps of:
s1: preparing a magnetic metal oxide;
s2: dissolving the magnetic metal oxide prepared in the step S1 to obtain magnetic fluid, adding a silane coupling agent, and heating, stirring and drying to obtain a modified magnetic nano material;
s3: and dissolving the infrared radiation material and the modified magnetic nano material prepared by S2, continuously stirring for 7-12h, and separating out, filtering and drying to obtain the composite material.
9. The method of claim 8, wherein the magnetic metal oxide of step S1 is obtained by hydrothermal method.
10. Use of a magnetic/high emissivity composite material according to any one of claims 1 to 7, wherein the composite material having both magnetic and high emissivity is coated on a heated non-combustible tobacco heating device.
CN202111160841.5A 2021-09-30 2021-09-30 Magnetic/high-infrared-emissivity composite material and preparation method and application thereof Pending CN113845794A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103044981A (en) * 2012-12-23 2013-04-17 上海迪道科技有限公司 Method for manufacturing nano-coating with microwave absorbing and radiation functions
CN112369716A (en) * 2020-06-24 2021-02-19 湖北中烟工业有限责任公司 Cigarette without burning by heating and its preparing process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103044981A (en) * 2012-12-23 2013-04-17 上海迪道科技有限公司 Method for manufacturing nano-coating with microwave absorbing and radiation functions
CN112369716A (en) * 2020-06-24 2021-02-19 湖北中烟工业有限责任公司 Cigarette without burning by heating and its preparing process

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Application publication date: 20211228