CN116574445A - Preparation method of biomass-based magnetic response photo-thermal composite material - Google Patents
Preparation method of biomass-based magnetic response photo-thermal composite material Download PDFInfo
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
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- 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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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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- 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
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Abstract
A preparation method of a biomass-based magnetically-responsive photo-thermal composite material comprises the steps of firstly soaking cellulose in ferric salt solution, then drying in an oven to obtain loaded cellulose, and then calcining the loaded cellulose in a tube furnace to obtain carbonized cellulose (Fe 3 O 4 @ CF), finally, fe 3 O 4 And (3) adding the @ CF, the thermosetting resin and the curing agent into an organic solvent, spraying or dip-coating the mixture on a substrate, and curing to obtain the biomass-based magnetic response photo-thermal composite material. The preparation process of the invention is simple, fe 3 O 4 The compatibility of the @ CF and the resin is good, the constructed heat conduction network is beneficial to the rapid temperature rise of the material, and meanwhile, the good compatibility enhances the wear resistance of the material. By Fe 3 O 4 Synergy with CFThe material temperature can be quickly increased by the photo-thermal effect. The material also has excellent chemical stability and mechanical stability, and has good application prospect in the field of functional composite materials.
Description
Technical Field
The invention belongs to the technical field of surface function composite materials, and particularly relates to a preparation method of a biomass-based magnetic response photo-thermal composite material.
Background
The photo-thermal conversion material is used as a new energy utilization means, and can convert clean and sustainable solar energy into heat energy, so that the photo-thermal conversion material has attracted a great deal of attention in recent years. However, most of the photo-thermal conversion materials are difficult to prepare, have high cost, cannot meet the actual requirements under different conditions, and also cause a great amount of resource waste, so that development of a photo-thermal composite material with simple preparation and low cost is urgently needed. In addition, in daily life, the light-heat conversion efficiency is seriously reduced in environments such as pollutants, scraping, acid-base, ice and snow weather and the like, and the service performance of the material is also influenced. Therefore, there is an urgent need to develop a multifunctional composite material with excellent durability, which has great significance in reducing resource waste and realizing efficient solar energy utilization.
Li et al prepared black TiO by evaporation-induced self-assembly, high temperature hydrogenation reduction and high temperature solvothermal synthesis 2 /MoS 2 /Cu 2 S microsphere. Black TiO 2 Is the main body, moS 2 Nanoplatelets and Cu 2 S microsphere step by step grows on black TiO 2 And forming a graded tandem heterojunction. The synthesized ternary heterojunction has high-efficiency interface coupling and shows high photocatalytic hydrogen production rate of 3376.7 mu mol/(h.g) under the irradiation of visible light. (Chemical Engineering Journal,2022, 427:131830) Zhang et al dispersed a zwitterionic polymer monomer, a cationic polymer monomer, a cross-linking agent, and photothermal nanoparticles in water to obtain a precursor solution and initiated a free radical polymerization reaction to obtain an antimicrobial, salt-resistant photothermal hydrogel. (CN 114456308A) however, preparation of these photothermal composite materialsThe process is complex, and the large-scale preparation and application of the method are severely limited. Guo et al designed and prepared a polyvinylpyrrolidone and polydimethylsiloxane composite material with interphase affinity, and then combined the polyvinylpyrrolidone and the nano carbon fiber to prepare the coating with photo-thermal conversion performance. The carbon nanofibers can be rapidly heated under the irradiation of sunlight, so that an active deicing effect is realized. (chem. Eng. J2020, 402, 126161) however, such photothermal surfaces are prone to be covered by dirt or the like, which can seriously affect the absorption and conversion of light, reducing its photothermal deicing performance.
In order to solve the problems existing in the materials, a biomass-based magnetic response photo-thermal composite material is developed. The biomass material is a green nontoxic and low-cost material, and can obtain a carbon material with excellent photo-thermal performance after being carbonized, so that the biomass material can be used for efficiently absorbing solar energy. The magnetic nano particles are loaded on the surface of the ice-removing agent to cooperatively enhance the photo-thermal performance of the ice-removing agent, so that the temperature can be quickly raised under the irradiation of sunlight, ice on the surface can be quickly removed, and an active deicing effect can be realized. In addition, the surface self-cleaning, oil-water separation and magnetic response oil removal performances can be realized through the magnetic response and super-hydrophobic performance of the material. Meanwhile, the load of the rigid particles can greatly enhance the wear resistance of the material and prolong the service time of the composite material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a biomass-based magnetic response photo-thermal composite material, which takes cellulose in nature as a raw material to prepare the biomass-based magnetic response photo-thermal composite material and apply the biomass-based magnetic response photo-thermal composite material to the field of super-hydrophobic photo-thermal composite materials, so as to solve the defects that the existing material is toxic and harmful to the raw material, is not green and environment-friendly, has single protection type, the photo-thermal performance of a deicing surface can be influenced by stains, the cost of the traditional deicing method is too high, and the like.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme.
The preparation method of the biomass-based magnetic response photo-thermal composite material is characterized by comprising the following steps of:
step 1, soaking cellulose in ferric salt solution, and then putting the soaked cellulose into an oven to be dried to obtain loaded cellulose, wherein the temperature of the oven is 40-100 ℃, and the drying time is 15-200min;
step 2, placing the loaded cellulose into a tube furnace for calcination to obtain carbonized cellulose Fe 3 O 4 The temperature of the @ CF, the temperature of the tube furnace and the temperature rising rate are respectively 400-1000 ℃, 1-15 ℃/min and 30-200min;
step 3, carbonized cellulose Fe 3 O 4 Adding @ CF, thermosetting resin and a curing agent into an organic solvent, and performing ultrasonic treatment to form uniform slurry A, wherein the ultrasonic power is 20-150W, and the ultrasonic treatment time is 5-60min;
and 4, spraying or dip-coating the slurry A on a substrate, and curing to obtain the biomass-based magnetic response photo-thermal composite material, wherein the curing temperature is 60-150 ℃ and the curing time is 1-24h.
The cellulose in the step 1 is one or a mixture of a plurality of kapok fibers, cotton fibers, bamboo fibers, wood fibers and textile fibers.
The ferric salt in the step 1 is FeCl 3 、FeCl 2 、Fe(NO 3 ) 3 、FeSO 4 One or more mixtures thereof.
The carbonized cellulose Fe in the step 3 3 O 4 The concentration of @ CF in the organic solvent is 1.0-15mg/mL.
The organic solvent in the step 3 is one or a mixture of more of acetone, ethanol, toluene and ethyl acetate.
The thermosetting resin in the step 3 is one or two of epoxy resin and silicone resin.
The mass ratio of the thermosetting resin to the curing agent in the step 3 is 10:1-1:1, and the thermosetting resin and carbonized cellulose Fe are prepared by the following steps 3 O 4 The mass ratio of @ CF is 1:1-10:1.
The curing agent in the step 3 is one or two of epoxy resin curing agent and silicon resin curing agent.
In the step 4, the base material is glass, wood, fabric, metal, sponge, plastic and the like.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a biomass-based magnetic response photo-thermal composite material and a preparation method thereof, wherein the preparation method comprises the steps of firstly soaking cellulose in ferric salt solution, then putting the cellulose into an oven for drying to obtain loaded cellulose, and then putting the loaded cellulose into a tube furnace for calcining to obtain carbonized cellulose (Fe 3 O 4 @ CF), finally, fe 3 O 4 Adding the @ CF, the thermosetting resin and the curing agent into an organic solvent, performing ultrasonic treatment to form uniform slurry A, spraying or dip-coating the uniform slurry A on a substrate, and curing to obtain the biomass-based magnetic response photo-thermal composite material. The preparation process of the invention is simple, fe 3 O 4 The compatibility of the @ CF and the resin is good, the constructed heat conduction network is beneficial to the rapid temperature rise of the material, and meanwhile, the good compatibility enhances the wear resistance of the material. Under 1 sun irradiation, by Fe 3 O 4 And the cooperative photo-thermal effect of CF, the temperature of the material can be rapidly increased to 92.5 ℃ within 60 seconds. In addition, the excellent self-cleaning properties of the material can prevent stains from affecting the surface light and heat properties. Passive anti-icing performance of superhydrophobic surface and Fe 3 O 4 The active photo-thermal deicing performance of the @ CF is combined, so that the material has deicing/anti-icing performance at the same time. The material also has excellent chemical stability and mechanical stability, and after ultraviolet irradiation, high-temperature calcination and various wear-resisting tests, the surface of the material still has excellent photo-thermal performance and superhydrophobic performance, and the multifunctional composite material with excellent durability has simple preparation, is easy to realize industrialization, and has good application prospect in the field of functional composite materials.
The invention also discloses a preparation method of the biomass-based magnetic response photo-thermal composite material, which has excellent protective performance, and compared with the traditional photo-thermal deicing material, the composite material combines the passive anti-icing performance and the active deicing performance, and through absorbing clean and green sunlight, the energy consumption is avoided, and more efficient anti-icing/deicing is realized. In addition, the raw materials used by the magnetic response photo-thermal composite material are safe and nontoxic, the preparation process is simple, the large-scale preparation can be realized, and the industrialization is easy to realize. The material has excellent chemical stability and mechanical stability, and simultaneously, the excellent self-cleaning performance can prevent the influence of stains on the surface light and heat performance, and has good application prospect in the field of functional composite materials.
The invention prepares the biomass-based magnetic response photo-thermal composite material by in-situ growing magnetic nano particles on cellulose and mixing the magnetic nano particles with thermosetting resin. Cellulose widely exists in the natural world, the acquisition mode is simple, an excellent photo-thermal composite material can be obtained after the cellulose is carbonized, magnetic nano particles grow on the excellent photo-thermal composite material in situ, the obtained photo-thermal composite material has good compatibility with resin, can be uniformly dispersed in the resin, is easy to construct a heat conducting network, and is beneficial to rapid heat transfer. Meanwhile, the synergistic photo-thermal effect of the nano particles and the carbonized cellulose enhances the absorption of light and enhances the active deicing performance of the material. The super-hydrophobic property of the material can greatly prolong the icing time of water drops on the surface, so that the material has the passive anti-icing property. Under the irradiation of 1 sun, the surface of the material is rapidly heated due to the existence of a three-dimensional photo-thermal network, and the temperature of the material can reach 92.5 ℃ within 60 seconds. After 400 cycles of sand paper abrasion test under the method of 100g, the material still maintains excellent super-hydrophobic performance and photo-thermal performance. In addition, after the 150W ultraviolet irradiation for 72 hours and the high-temperature calcination at 200 ℃ for 72 hours, the material still maintains excellent superhydrophobicity and photo-thermal performance. The preparation process is simple, the material has excellent protective performance, the defect of insufficient durability of the traditional deicing material is overcome, the used raw materials are safe and nontoxic, industrialization is easy to realize, and the preparation process has good application prospect.
Drawings
FIG. 1 is a graph of contact angle and silver mirror phenomena for a material prepared in accordance with the present invention;
wherein, (a) is a photograph of contact angle; (b) drawing is silver mirror photograph;
FIG. 2 is a diagram of Fe prepared according to the present invention 3 O 4 SEM photograph of @ CF;
FIG. 3 is a graph of the temperature rise profile and photothermographic image of a material prepared according to the present invention in 1 sun;
wherein, (a) is a temperature rise curve; (b) the photo-thermal imaging picture;
FIG. 4 is a photograph of an anti-icing and deicing process for a material prepared in accordance with the present invention;
FIG. 5 is a magnetic response and magnetically responsive degreasing process for a material prepared in accordance with the present invention;
FIG. 6 is a photograph of a material prepared according to the present invention and a curve of contact angle change in a sandpaper friction test at a weight of 100g method, and a photo-thermal curve after testing;
wherein, (a) the graph shows the contact angle change in the sand paper friction experiment; (b) graph is the photo-thermal curve after testing;
Detailed Description
The invention is described in further detail below with reference to the attached drawings and specific examples, but the invention is not limited to the following examples:
the preparation method of the biomass-based magnetically-responsive photo-thermal composite material specifically comprises the following steps:
(1) Soaking cellulose in ferric salt solution, and then drying in an oven at 40-100deg.C for 15-200min to obtain loaded cellulose. Wherein the ferric salt is FeCl 3 、FeCl 2 、Fe(NO 3 ) 3 、FeSO 4 Is a mixture of one or more of the following.
(2) Calcining the loaded cellulose in a tube furnace at 500-1000deg.C at a heating rate of 1-15deg.C/min for 30-200min to obtain carbonized cellulose (Fe) 3 O 4 @CF)。
(3) Fe is added to 3 O 4 The @ CF, thermosetting resin, and curing agent are added to an organic solvent and sonicated to form a uniform slurry a. Wherein Fe is 3 O 4 The concentration of CF in the organic solvent is 1.0-15mg/mL, the amount of the organic solvent is 10-100mL, the organic solvent is one or more mixtures of acetone, ethanol, toluene and ethyl acetate, the resin is one or more mixtures of epoxy resin and silicone resin, the mass ratio of the thermosetting resin to the curing agent is 10:1-1:1, and the thermosetting resin to Fe is the same as that of the epoxy resin 3 O 4 The mass ratio of @ CF is 1:1-10:1. The ultrasonic power is 20-150W, and the ultrasonic time is 5-60min.
(3) And spraying or dip-coating the slurry A on a substrate, and curing to obtain the biomass-based magnetic response photo-thermal composite material. Wherein, the base material can be glass, wood, fabric, metal, plastic, etc., when spraying, the spray gun forms an angle of 45-90 degrees with the surface of the base material, and the spray gun is 10-30cm away from the surface of the base material. The soaking time is 5-60min during dip-coating. And then curing for 1-24 hours at the temperature of 60-150 ℃ to obtain the biomass-based magnetic response photo-thermal composite material.
Example 1
Placing cellulose into FeCl 3 Soaking in the solution, and then drying in a drying oven at 40 ℃ for 30min to obtain the loaded cellulose. Then placing the loaded cellulose into a tube furnace for calcination, wherein the temperature of the tube furnace is 500 ℃, the heating rate is 2 ℃/min, and the calcination time is 40min, so as to obtain carbonized cellulose (Fe) 3 O 4 @CF)。
Fe is added to 3 O 4 @ CF, 0.5g silicone and 0.05g curative were added to a mixture of acetone (15 mL) and ethyl acetate (25 mL) and sonicated to form a uniform slurry A. Wherein Fe is 3 O 4 The concentration of @ CF in the organic solvent is 1.0-15mg/mL, the ultrasonic power is 20W, and the ultrasonic time is 60min.
Dip-coating the slurry A on a fabric substrate, and curing for 1h at 100 ℃ to obtain the biomass-based magnetic response photo-thermal composite material. As shown in fig. 1, the water drop takes a spherical shape on the surface of the material, and has a large contact angle. When the material is immersed in water, a remarkable silver mirror phenomenon can be observed, which indicates that the coating has excellent superhydrophobic performance.
Example 2
Placing cellulose into FeCl 3 Soaking in the solution, and then drying in a drying oven at 50 ℃ for 50min to obtain the loaded cellulose. Then placing the loaded cellulose into a tube furnace for calcination, wherein the temperature of the tube furnace is 600 ℃, the heating rate is 3 ℃/min, and the calcination time is 50min, so as to obtain carbonized cellulose (Fe) 3 O 4 @CF)。
Fe is added to 3 O 4 @ CF, 1g silicone and 0.1g curative were added to a mixture of toluene (20 mL) and acetone (20 mL) and sonicated to form a uniform slurry A. Wherein Fe is 3 O 4 The concentration of @ CF in the organic solvent was 4mg/mL, the ultrasonic power was 30W, and the ultrasonic time was 50min.
Spraying the slurry A on a wood substrate, and curing for 3 hours at 110 ℃ to obtain the biomass-based magnetic response photo-thermal composite material. As shown in FIG. 2, the surface of the carbonized cellulose is uniformly distributed with Fe 3 O 4 And (3) nanoparticles. Fe with magnetism 3 O 4 The nano particles have excellent near infrared light response performance, and cooperate with carbonized cellulose to endow the material with excellent photo-thermal performance.
Example 3
Cellulose is put into Fe (NO) 3 ) 3 Soaking in the solution, and then drying in a drying oven at 60 ℃ for 80min to obtain the loaded cellulose. Then placing the loaded cellulose into a tube furnace for calcination, wherein the temperature of the tube furnace is 700 ℃, the heating rate is 5 ℃/min, and the calcination time is 60min, so as to obtain carbonized cellulose (Fe) 3 O 4 @CF)。
Fe is added to 3 O 4 @ CF, 1.5g epoxy resin, and 0.5g curative were added to toluene (15 mL) And ethyl acetate (25 mL), and ultrasonically forming a uniform slurry a. Wherein Fe is 3 O 4 The concentration of @ CF in the organic solvent was 6mg/mL, the ultrasonic power was 40W and the ultrasonic time was 40min.
Spraying the slurry A on a plastic substrate, and curing for 6 hours at 120 ℃ to obtain the biomass-based magnetic response photo-thermal composite material. The resulting material was tested for photo-thermal properties as shown in fig. 3. It can be seen that the material temperature rapidly increased at 1 sun, rapidly to 92.5 ℃ within 60 s. Excellent photo-thermal properties provide preconditions for photo-thermal deicing.
Example 4
Placing cellulose into FeSO 4 Soaking in the solution, and then drying in a drying oven at 70 ℃ for 100min to obtain the loaded cellulose. Then placing the loaded cellulose into a tube furnace for calcination, wherein the temperature of the tube furnace is 800 ℃, the heating rate is 10 ℃/min, and the calcination time is 80min, so as to obtain carbonized cellulose (Fe) 3 O 4 @CF)。
Fe is added to 3 O 4 CF, 2g epoxy resin and 0.5g curative were added to a mixture of acetone (20 mL) and ethyl acetate (20 mL) and sonicated to form a uniform slurry A. Wherein Fe is 3 O 4 The concentration of @ CF in the organic solvent was 8mg/mL, the ultrasonic power was 50W, and the ultrasonic time was 30min.
Spraying the slurry A on an iron sheet substrate, and curing for 4 hours at 130 ℃ to obtain the biomass-based magnetic response photo-thermal composite material. As shown in fig. 4, the prepared material was subjected to anti-icing and photo-thermal deicing performance test, and water drops were dropped on a bare glass sheet and a glass sheet coated with a photo-thermal composite material at-20 ℃, the water drops on the bare glass sheet were completely frozen at 72s, and the water drops were not completely frozen until 420s on the glass sheet coated with the photo-thermal composite material. In addition, in the photo-thermal deicing test, under 1 solar irradiation, the ice layer with the thickness of 3mm is quickly melted and completely disappears within 12 minutes, deicing can be realized without external consumption of external energy, and has excellent deicing performance.
Example 5
Placing cellulose into FeCl 3 And FeSO 4 Soaking in the mixed solution, and then putting into a baking oven to be dried to obtain the loaded cellulose, wherein the temperature of the baking oven is 80 ℃, and the drying time is 120min. Then placing the loaded cellulose into a tube furnace for calcination, wherein the temperature of the tube furnace is 500 ℃, the heating rate is 5 ℃/min, and the calcination time is 100min, so as to obtain carbonized cellulose (Fe) 3 O 4 @CF)。
Fe is added to 3 O 4 To a mixture of ethanol (10 mL) and ethyl acetate (30 mL) was added @ CF, 2.5g epoxy resin, and 0.5g curative, and the mixture was sonicated to form a uniform slurry A. Wherein Fe is 3 O 4 The concentration of @ CF in the organic solvent was 9mg/mL, the ultrasonic power was 60W, and the ultrasonic time was 30min.
And dip-coating the slurry A on a sponge substrate, and curing for 6 hours at 110 ℃ to obtain the biomass-based magnetic response photo-thermal composite material. As shown in fig. 5 and 6, the magnetic response and mechanical stability of the prepared material were tested, and the material was able to easily remove oil stains floating on the water surface under the magnetic force of the magnet. In addition, the coating still maintains excellent hydrophobic and photo-thermal properties after 400 cycles of rubbing with sandpaper at a weight of 100 g. This demonstrates that the materials produced have versatility and excellent durability.
Example 6
Placing cellulose into FeCl 2 And FeSO 4 Soaking in the mixed solution, and drying in an oven at 90deg.C for a period of time to obtain loaded cellulose100min. Then placing the loaded cellulose into a tube furnace for calcination, wherein the temperature of the tube furnace is 900 ℃, the heating rate is 2 ℃/min, and the calcination time is 120min, so as to obtain carbonized cellulose (Fe) 3 O 4 @CF)。
Fe is added to 3 O 4 @ CF, 3g silicone and 1g curative were added to a mixture of acetone (30 mL) and ethyl acetate (10 mL) and sonicated to form a uniform slurry a. Wherein Fe is 3 O 4 The concentration of @ CF in the organic solvent was 10mg/mL, the ultrasonic power was 80W, and the ultrasonic time was 50min.
Spraying the slurry A on an iron sheet substrate, and curing for 10 hours at 100 ℃ to obtain the biomass-based magnetic response photo-thermal composite material.
Example 7
Cellulose is put into Fe (NO) 3 ) 3 And FeSO 4 Soaking in the mixed solution, and then putting into a drying oven to obtain the loaded cellulose, wherein the temperature of the drying oven is 100 ℃, and the drying time is 50min. Then placing the loaded cellulose into a tube furnace for calcination, wherein the temperature of the tube furnace is 1000 ℃, the heating rate is 10 ℃/min, and the calcination time is 30min, so as to obtain carbonized cellulose (Fe) 3 O 4 @CF)。
Fe is added to 3 O 4 @ CF, 2.5g silicone and 0.25g curative were added to a mixture of acetone (25 mL) and ethanol (15 mL) and sonicated to form a uniform slurry a. Wherein Fe is 3 O 4 The concentration of @ CF in the organic solvent was 15mg/mL, the ultrasonic power was 100W, and the ultrasonic time was 30min.
Spraying the slurry A on an iron sheet substrate, and curing for 16 hours at 130 ℃ to obtain the biomass-based magnetic response photo-thermal composite material.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. The preparation method of the biomass-based magnetic response photo-thermal composite material is characterized by comprising the following steps of:
step 1, soaking cellulose in ferric salt solution, and then putting the soaked cellulose into an oven to be dried to obtain loaded cellulose, wherein the temperature of the oven is 40-100 ℃, and the drying time is 15-200min;
step 2, placing the loaded cellulose into a tube furnace for calcination to obtain carbonized cellulose Fe 3 O 4 The temperature of the @ CF, the temperature of the tube furnace and the temperature rising rate are respectively 400-1000 ℃, 1-15 ℃/min and 30-200min;
step 3, carbonized cellulose Fe 3 O 4 Adding @ CF, thermosetting resin and a curing agent into an organic solvent, and performing ultrasonic treatment to form uniform slurry A, wherein the ultrasonic power is 20-150W, and the ultrasonic treatment time is 5-60min;
and 4, spraying or dip-coating the slurry A on a substrate, and curing to obtain the biomass-based magnetic response photo-thermal composite material, wherein the curing temperature is 60-150 ℃ and the curing time is 1-24h.
2. The method for preparing a biomass-based magnetically responsive photo-thermal composite material according to claim 1, wherein the cellulose in the step 1 is one or more of kapok fiber, cotton fiber, bamboo fiber, wood fiber, and fabric fiber.
3. The method for preparing a biomass-based magnetically responsive photo-thermal composite material according to claim 1, wherein the iron salt in step 1 is FeCl 3 、FeCl 2 、Fe(NO 3 ) 3 、FeSO 4 One or more mixtures thereof.
4. The method for preparing a biomass-based magnetically responsive photo-thermal composite material according to claim 1, wherein the carbonized cellulose Fe in the step 3 3 O 4 The concentration of @ CF in the organic solvent is 1.0-15mg/mL.
5. The method for preparing a biomass-based magnetically responsive photo-thermal composite material according to claim 1, wherein the organic solvent in the step 3 is one or more of acetone, ethanol, toluene and ethyl acetate.
6. The method for preparing the biomass-based magnetically responsive photo-thermal composite material according to claim 1, wherein the thermosetting resin in the step 3 is one or two of epoxy resin and silicone resin.
7. The preparation method of the biomass-based magnetic response photo-thermal composite material according to claim 1, wherein the mass ratio of the thermosetting resin to the curing agent in the step 3 is 10:1-1:1, and the thermosetting resin to the carbonized cellulose Fe 3 O 4 The mass ratio of @ CF is 1:1-10:1.
8. The method for preparing the biomass-based magnetic response photo-thermal composite material according to claim 1, wherein the curing agent in the step 3 is one or two of epoxy resin curing agent and silicone resin curing agent.
9. The method for preparing a biomass-based magnetically responsive photo-thermal composite material according to claim 1, wherein the substrate in the step 4 is glass, wood, fabric, metal, sponge, plastic or the like.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002069351A1 (en) * | 2001-02-26 | 2002-09-06 | University Of Utah Research Foundation | Magnetic activated carbon particles for adsorption of solutes from solution |
RU2013119975A (en) * | 2013-04-30 | 2014-11-10 | Федеральное Государственное Бюджетное Учреждение Науки Институт Биохимической Физики Им. Н.М. Эмануэля Российской Академии Наук (Ибхф Ран) | METHOD FOR PRODUCING A FERROMAGNETIC CARBON SORBENT |
CN109036874A (en) * | 2018-06-12 | 2018-12-18 | 中国林业科学研究院林业新技术研究所 | A kind of composite electrochemical energy storage Carbon Materials and its preparation method and application |
CN113462357A (en) * | 2021-07-02 | 2021-10-01 | 合肥工业大学 | Wave-absorbing particles and preparation method and application of composite material thereof |
CN114350259A (en) * | 2022-01-27 | 2022-04-15 | 陕西科技大学 | Photo-thermal heating biomass-based multifunctional photo-thermal protective coating and preparation method thereof |
-
2023
- 2023-05-12 CN CN202310535251.9A patent/CN116574445A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002069351A1 (en) * | 2001-02-26 | 2002-09-06 | University Of Utah Research Foundation | Magnetic activated carbon particles for adsorption of solutes from solution |
RU2013119975A (en) * | 2013-04-30 | 2014-11-10 | Федеральное Государственное Бюджетное Учреждение Науки Институт Биохимической Физики Им. Н.М. Эмануэля Российской Академии Наук (Ибхф Ран) | METHOD FOR PRODUCING A FERROMAGNETIC CARBON SORBENT |
CN109036874A (en) * | 2018-06-12 | 2018-12-18 | 中国林业科学研究院林业新技术研究所 | A kind of composite electrochemical energy storage Carbon Materials and its preparation method and application |
CN113462357A (en) * | 2021-07-02 | 2021-10-01 | 合肥工业大学 | Wave-absorbing particles and preparation method and application of composite material thereof |
CN114350259A (en) * | 2022-01-27 | 2022-04-15 | 陕西科技大学 | Photo-thermal heating biomass-based multifunctional photo-thermal protective coating and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
YANG LIU等: "In-Situ Growth and Graphitization Synthesis of Porous Fe3O4/Carbon Fiber Composites Derived from Biomass as Lightweight Microwave Absorber", SUSTAINABLE CHEMISTRY&ENGINEERING, vol. 7, 7 February 2019 (2019-02-07), pages 5318 - 5328 * |
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