CN112251153B - Carbon nanofiber membrane/silica gel composite material and preparation method thereof - Google Patents
Carbon nanofiber membrane/silica gel composite material and preparation method thereof Download PDFInfo
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- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 191
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 168
- 239000012528 membrane Substances 0.000 title claims abstract description 166
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 238000001723 curing Methods 0.000 claims description 20
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J183/04—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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
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Abstract
The application provides a carbon nanofiber membrane/silica gel composite material and a preparation method thereof, belonging to the technical field of composite materials. The composite material comprises a carbon nanofiber membrane permeated with silica gel and a silica gel layer continuously covering the surface of the carbon nanofiber membrane. Because the carbon nanofiber membrane has numerous pores and has better compatibility with silica gel, the liquid silica gel can fully infiltrate the carbon nanofiber membrane to form a composite material, and the preparation method of the composite material comprises the following steps: and compounding the carbon nanofiber membrane and the liquid silica gel layer, and then controlling the liquid silica gel layer to be cured and molded. The composite material not only has excellent electromagnetic shielding performance, but also has good flexibility; has good bonding effect on various surfaces, and can further prevent electromagnetic wave leakage.
Description
Technical Field
The application relates to the technical field of composite materials, in particular to a carbon nanofiber membrane/silica gel composite material and a preparation method thereof.
Background
The high molecular material has wide source, various varieties, simple forming and low price, can meet various processing requirements, and has become a packaging and decorating material of various electronic products, but the high molecular material generally has no electromagnetic shielding performance, and along with the rapid development and wide application of electronic, computer and telecommunication technologies, the electromagnetic environment becomes increasingly complex, wherein the problems of electromagnetic radiation and electromagnetic interference not only affect the normal operation of communication equipment, but sometimes even harm the health of people. In order to reduce or eliminate the harm caused by electromagnetic radiation, an electromagnetic shielding auxiliary agent is often added into the polymer material. The common electromagnetic shielding additive is metal powder or conductive carbon material, wherein the metal powder has high density, poor compatibility with high polymer materials and poor forming performance, and is not beneficial to the miniaturization and light weight of electronic products. Therefore, most of the existing electromagnetic shielding additives are conductive carbon powder materials.
However, the continuity of the conductive carbon powder material is poor, and the electromagnetic shielding performance is poor after the conductive carbon powder material is compounded with a high polymer material.
Disclosure of Invention
The application aims to provide a carbon nanofiber membrane/silica gel composite material and a preparation method thereof, which have excellent electromagnetic shielding performance and good flexibility; the adhesive has good adhesion effect on the surfaces of various electronic products, and can further prevent electromagnetic wave leakage.
In a first aspect, the present application provides a carbon nanofiber membrane/silica gel composite material comprising a carbon nanofiber membrane permeated with silica gel and a silica gel layer continuously covering the surface of the carbon nanofiber membrane.
Silica gel permeating into the carbon nanofiber membrane is distributed in pores of the carbon nanofiber membrane, so that air holes and cracks in the composite material are reduced, the electromagnetic shielding performance of the composite material is better, and the flexibility of the composite material is better. The silica gel layer is arranged on the surface of the carbon nanofiber membrane, so that the carbon nanofibers can be protected from being damaged in the using process, the service life is prolonged, meanwhile, the flexibility of the composite material is better, the silica gel layer is attached to the surfaces of various electronic products, a good attaching effect is achieved, and electromagnetic wave leakage can be further prevented.
In one possible embodiment, the thickness of the carbon nanofiber membrane is 20-200 μm, the conductivity is 2000-5000S/m, and the diameter of the carbon fiber is 100-200 nm.
The silica gel material is easy to permeate into the carbon nanofiber membrane meeting the conditions, so that the composite material with better electromagnetic wave leakage prevention effect is formed.
In one possible embodiment, the method comprises the following steps: silica gel layers are arranged on two surfaces of the carbon nanofiber membrane. The two surfaces of the carbon nanofiber membrane are continuously covered with the silica gel layers, so that the flexibility of the composite material is better, any surface of the composite material can be well attached to the surface of an electronic product, and the leakage effect of preventing electromagnetic waves is better.
In a second aspect, the present application provides a method for preparing a carbon nanofiber membrane/silica gel composite, comprising: compounding the carbon nanofiber membrane with liquid silica gel, and then solidifying and molding the liquid silica gel to ensure that silica gel permeates into the carbon nanofiber membrane and the surface of the carbon nanofiber membrane is covered with a continuous silica gel layer.
The carbon nanofiber membrane can enable a part of liquid silica gel to enter pores of the carbon nanofiber membrane without surface oxidation treatment, and a part of liquid silica gel is positioned on the surface of the carbon nanofiber membrane; after the liquid silicon adhesive layer is cured and formed, the electromagnetic shielding performance of the composite material is better, and the flexibility of the composite material is better. The surface of the carbon nanofiber membrane is provided with the silica gel layer, the flexibility of the composite material is better, and the silica gel layer has a good laminating effect when being laminated on the surfaces of various electronic products, so that electromagnetic wave leakage can be further prevented.
In one possible embodiment, the liquid silica gel is uniformly coated on the substrate to form a liquid silica gel layer; soaking the carbon nanofiber membrane in a liquid silica gel layer; and curing the liquid silica gel layer.
Silica gel is fully filled in the inner pores of the carbon nanofiber membrane, silica gel layers are formed on two surfaces of the carbon nanofiber membrane, the flexibility of the composite material can be better, the composite material can be conveniently attached to the surface of an electronic product, and the electromagnetic wave prevention effect is better.
In one possible embodiment, the method comprises the following steps: and arranging the carbon nanofiber membrane on an unwinding device of a calender. Unreeling the carbon nanofiber membrane, enabling the carbon nanofiber membrane to pass through a coating section of a calender, and controlling a coating device on the coating section to coat liquid silica gel on the carbon nanofiber membrane to form a liquid silica gel layer. And controlling the coated carbon nanofiber membrane to pass between two opposite rollers of a calender, adjusting the surface temperature of the rollers, and pressing, curing and molding the liquid silica gel layer through the rollers to obtain the composite material. And (4) rolling the molded composite material by using a rolling device of the calender.
In the prior art, when the carbon nanofiber membrane and the liquid polymer material are compounded, the carbon nanofiber membrane is usually placed in a vacuum flat plate hot press, and then the liquid polymer is infiltrated into the carbon nanofiber membrane in a pressurizing manner to prepare the material, so that the continuous preparation can not be generally realized, and the production effect is low. In this application, because the infiltration effect of liquid silica gel in carbon nanofiber membrane is better, need not pressurize just can realize the infiltration, and does not contain the solvent in the liquid silica gel, the shrink of silica gel solidification is reduced, can carry out the coating on liquid silica gel layer, the infiltration and the solidification of silica gel on the calender, unreel through receiving and realize combined material's production, convenient serialization preparation.
In one possible embodiment, the spacing between the roll surfaces of the two rolls is 100 and 180 μm. Composite materials with a thickness of 100-180 μm can be obtained.
In one possible embodiment, the roll surface temperature of the two rollers is 80-160 ℃, and the running speed of the carbon nanofiber membrane on the calender is 300-900 mm/min. The running speed and the roll surface temperature of the carbon nanofiber membrane can better meet the curing requirement of the liquid silica gel layer, and the performance of the carbon nanofiber membrane is improved to a certain extent.
In one possible embodiment, the viscosity of the liquid silica gel is 2000-. The liquid silica gel can well penetrate into pores of the carbon nanofiber membrane, so that the composite material has better flexibility.
In one possible embodiment, the thickness of the liquid silica gel layer is greater than the thickness of the carbon nanofiber membrane. The silica gel layers are formed on the two surfaces of the carbon nanofiber membrane more easily, so that the laminating effect of the composite material on the surface of an electronic product is better, and the performance of preventing electromagnetic wave leakage is improved.
In one possible embodiment, the thickness of the liquid silicone gel layer is 100-. The thickness of the silica gel layer on the surface of the carbon nanofiber membrane can be more proper, the waste of silica gel is avoided, and the manufacturing cost is saved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments are briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive efforts and also belong to the protection scope of the present application.
FIG. 1 is a cross-sectional view of a carbon nanofiber membrane/silica gel composite provided herein;
FIG. 2 is a scanning electron microscope photograph of the carbon nanofiber membrane provided in example 1 of the present application;
fig. 3 is a graph of electromagnetic shielding effectiveness of the filamentous nanocarbon/silica gel composite material provided in example 1 of the present application;
FIG. 4 is a photograph of a carbon nanofiber membrane/silica gel composite provided in example 1 of the present application;
fig. 5 is a graph showing the electromagnetic shielding effectiveness of the filamentous nanocarbon film provided in comparative example 1 of the present application.
Icon: 110-carbon nanofiber membrane infiltrated with silica gel; 120-silica gel layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described below with reference to the drawings in the embodiments of the present application.
The application provides a preparation method of a carbon nanofiber membrane/silica gel composite material, which comprises the following steps: compounding the carbon nanofiber membrane with liquid silica gel, and then solidifying and molding the liquid silica gel to ensure that silica gel permeates into the carbon nanofiber membrane and the surface of the carbon nanofiber membrane is covered with a continuous silica gel layer.
On one hand, the carbon nanofiber membrane can enable liquid silica gel to enter pores of the carbon nanofiber membrane without surface oxidation treatment; on the other hand, the liquid silica gel does not contain a solvent, the shrinkage of the silica gel during curing is small, the film structure of the composite material is basically not changed after the liquid silica gel layer is cured and formed, and the forming effect is better.
Fig. 1 is a cross-sectional view of a filamentous nanocarbon/silica gel composite provided by the present application. Referring to fig. 1, the composite material prepared by the above method includes a carbon nanofiber membrane 110 permeated with silica gel and a silica gel layer 120 continuously covering the surface of the carbon nanofiber membrane.
The nano carbon fiber membrane is of a porous structure (a plurality of pores are formed in the nano carbon fiber membrane), and when the liquid silica gel is compounded with the nano carbon fiber membrane, silica gel is filled in at least one part of the pores, or silica gel is filled in all the pores; after silica gel is filled in the inner pores, the silica gel is contacted with the carbon fibers of the carbon nanofiber membrane, the carbon nanofibers have the effects of reinforcing and toughening, and the silica gel layer protects the carbon nanofibers from being damaged, so that the mechanical property of the composite material is improved.
The two surfaces of the carbon nanofiber membrane are continuously covered with the silica gel layer 120, the silica gel layer 120 can enable the flexibility of the composite material to be better, and the silica gel layer 120 has a good laminating effect (the laminating effect between the surface of the electronic product and the silica gel layer 120 is good) when being laminated on the surfaces of various electronic products, so that electromagnetic wave leakage can be further prevented.
Optionally, the thickness of the carbon nanofiber membrane is 20-200 μm, the conductivity is 2000-5000S/m, and the diameter of the carbon fiber is 100-200 nm. The carbon fibers with the diameter form the carbon nanofiber membrane with the thickness, and the pores in the carbon nanofiber membrane are moderate enough to enable liquid silica gel to enter the pores; and communicated pore channels are easy to form, so that the silica gel has good wettability to the carbon nanofiber membrane, and the composite material with better flexibility is obtained.
In some possible embodiments, the carbon nanofiber membrane has a thickness of 20 μm, 50 μm, 100 μm, or 200 μm; the conductivity of the carbon nanofiber membrane is 2000S/m, 3000S/m, 4000S/m or 5000S/m; the carbon fiber diameter of the carbon nanofiber membrane is 100nm, 120nm, 140nm, 160nm, 180nm or 200 nm.
Optionally, the carbon nanofiber membrane is prepared by electrostatic spinning, pre-oxidation, carbonization and graphitization. The method comprises the following specific steps: electrostatic spinning: preparing a PAN solution, setting the voltage to be 12-15kV, the spinning distance to be 10-18cm, and the concentration of the PAN solution to be 5-15%; and (3) preparing the PAN nanofiber membrane by electrostatic spinning of the PAN solution. Pre-oxidation: pre-oxidizing the PAN nanofiber membrane at the pre-oxidation temperature of 250-300 ℃ for 1-3 h. Carbonizing: carbonizing the PAN pre-oxidation film at the temperature of 1000-1400 ℃ for 1-3 h. Graphitization: graphitizing the carbonized film at 2000-2400 ℃ for 1-3 h.
The carbon nanofiber membrane is formed directly in an electrostatic spinning mode and subjected to subsequent pre-oxidation, carbonization and graphitization without being woven, so that carbon nanofibers can be connected and are in close contact with one another to form a developed conductive network.
The inventor further researches and discovers that the nano carbon fiber film has good electromagnetic shielding performance, but the nano carbon fiber film is small in diameter and easy to break and fall off from the film when being subjected to external force, so that the electromagnetic shielding performance is influenced, and the nano carbon fiber film is easy to break due to uneven stress when being attached to the surface of a special-shaped electronic product. Therefore, it is particularly important to improve the flexibility of the carbon nanofiber film and the bonding performance of the carbon nanofiber film to electronic products.
When the silica gel enters the pores of the carbon nanofiber membrane and a continuous silica gel layer is formed on the surface of the carbon nanofiber membrane, the flexibility of the carbon nanofiber membrane composite material can be effectively improved, the bonding performance of the carbon nanofiber membrane composite material and an electronic product can be improved, and therefore electromagnetic wave leakage is prevented.
Optionally, the thickness of the silica gel layer is 100-. Under the condition that the silica gel material is used relatively less, the flexibility of the composite material is better, and the composite material has better performance of preventing electromagnetic wave leakage. For example: the thickness of the silica gel layer is 100 μm, 120 μm, 140 μm, 160 μm, 180 μm or 200 μm.
In order to form continuous silica gel layers on both surfaces of the carbon nanofiber membrane, more liquid silica gel is immersed into the pores of the carbon nanofiber membrane. The preparation method of the composite material comprises the following steps: uniformly coating the liquid silica gel on the substrate to form a liquid silica gel layer; soaking the carbon nanofiber membrane in a liquid silica gel layer; curing the liquid silica gel layer (for example, pressing and curing the layer by a pressing plate under the condition of 80-160 ℃ temperature).
In the preparation method, the amount of the liquid silica gel is relatively large (the volume of the liquid silica gel is larger than that of the carbon nanofiber membrane), after the carbon nanofiber membrane is soaked in the liquid silica gel layer, the upper surface and the lower surface of the carbon nanofiber membrane are both provided with the liquid silica gel, and the liquid silica gel can also be soaked in pores of the carbon nanofiber. After the liquid silica gel is rolled and cured, solid silica gel is filled in the pores of the carbon nanofiber membrane, and silica gel layers are formed on two surfaces of the carbon nanofiber membrane.
When the composite material is attached to the surface of an electronic product, the attachment effect of any one of the two surfaces of the composite material and the surface of the electronic product is good, the application range of the composite material is enlarged, and the composite material can have a good effect of preventing electromagnetic wave leakage.
In the embodiment of the present application, the viscosity of the liquid silica gel is 2000-. The liquid silica gel can well permeate into the pores of the carbon nanofiber membrane, so that the pores of the carbon nanofiber membrane are completely filled with the liquid silica gel, and the composite material has better flexibility.
Alternatively, the liquid silica gel may be dihydroxypolydimethylsiloxane, polytrifluoropropylmethylsiloxane, polynitrile ethylmethylsiloxane, or the like.
In order to form a silica gel layer on the surface of the carbon nanofiber membrane uniformly, and the liquid silica gel is immersed into the pores of the carbon nanofiber membrane. The preparation method of the composite material comprises the following steps: and arranging the carbon nanofiber membrane on an unwinding device of a calender. Unreeling the carbon nanofiber membrane, enabling the carbon nanofiber membrane to pass through a coating section of a calender, and controlling a coating device on the coating section to coat liquid silica gel on the carbon nanofiber membrane to form a liquid silica gel layer. And controlling the coated carbon nanofiber membrane to pass between two opposite rollers of a calender, adjusting the surface temperature of the rollers, and pressing, curing and molding the liquid silica gel layer through the rollers to obtain the composite material. And (4) rolling the molded composite material by using a rolling device of the calender.
The coating of the liquid silica gel layer, the infiltration and the solidification of the silica gel are carried out on the calender, the composite material can be prepared in a winding and unwinding mode, the whole preparation process is simpler, the preparation of the composite material can be completed on the same equipment, the solidification is carried out after the midway transfer, and the continuous preparation is convenient. In the process of curing the silica gel, the silica gel is rolled, so that more liquid silica gel can enter pores of the carbon nanofiber membrane, the generation of defects such as bubbles is reduced, the compactness of the composite material is better, and the surface is smoother. Since the shrinkage of the cured silica gel is relatively small, the overall shape of the cured silica gel is not changed basically, and continuous production can be performed on a calender (if the shrinkage after curing is relatively large, the material after curing is deformed, so that the material cannot be well filmed on a roller, and the film is easy to break).
Alternatively, the spacing between the roll surfaces of the two rolls is 100-180 μm, which can make the thickness of the composite material 100-180 μm. For example: the spacing between the roll surfaces of the two rolls was 100 μm, 120 μm, 140 μm, 160 μm or 180 μm. The distance is greater than the film thickness of the carbon nanofibers, and optionally, the difference between the distance and the thickness of the carbon nanofibers is the thickness of the surface silica gel layer.
Furthermore, the roll surface temperature of the two rollers is 80-160 ℃, so that the liquid silica gel can be solidified in the continuous production process, and the production efficiency is improved. For example: the roll surface temperature of the two rolls was 80 ℃, 100 ℃, 120 ℃, 140 ℃ or 160 ℃.
Further, the running speed of the carbon nanofiber membrane on the calender is 300-900 mm/min. The running speed of the carbon nanofiber membrane can meet the requirement of curing the liquid silica gel layer, and the performance of the carbon nanofiber membrane is improved to a certain extent. For example: the running speed of the carbon nanofiber membrane on the calender is 300mm/min, 400mm/min, 500mm/min, 600mm/min, 700mm/min, 800mm/min or 900 mm/min. The running speed is matched with the temperature of the roller surface, so that the silica gel can be completely solidified in the rolling process to obtain the composite material.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Preparing a carbon nanofiber membrane: dissolving 12g of PAN powder in 50mL of DMF to prepare a PAN solution with the concentration of 24%, loading the PAN solution into a syringe, setting the spinning distance to be 15cm, the pushing speed to be 2.5mL/h and the spinning voltage to be 15kV, and carrying out electrostatic spinning to prepare the PAN nanofiber membrane; placing the PAN nanofiber membrane in a pre-oxidation furnace, setting the pre-oxidation temperature to be 260 ℃ and the pre-oxidation time to be 120min, and performing pre-oxidation to obtain a PAN pre-oxidation membrane; placing the PAN pre-oxidation film in a carbonization furnace, setting the carbonization temperature at 1400 ℃ for 120min, and carbonizing to obtain a carbonized film; and (3) placing the carbonized film in a graphitization furnace, setting the temperature at 2400 ℃ for 120min, and performing graphitization treatment to obtain the carbon nanofiber film with the thickness of 100 microns. Fig. 2 shows a scanning electron micrograph of the carbon nanofiber membrane prepared in this example, and it can be seen from the figure that the carbon nanofiber has a diameter of 100-200nm, and the fibers are in close contact with each other to form a developed conductive network.
Placing the carbon nanofiber membrane with the thickness of 100 mu m on an unreeling device of a calender, unreeling the carbon nanofiber membrane, and enabling the carbon nanofiber membrane to pass through a coating section of the calender; adjusting the height of a coating device on the coating section to be 140 microns, and uniformly coating liquid silica gel with the viscosity of 10000cps on the carbon nanofiber membrane through the coating device to form a liquid silica gel layer with the thickness of about 140 microns; and (2) enabling the carbon nanofiber membrane and the liquid silica gel layer on the carbon nanofiber membrane to pass between two opposite rollers of a calender together, wherein the roller surface temperature of the two rollers of the calender is 120 ℃, the roller surface distance between the two rollers is 120 mu m, the running speed of the carbon nanofiber membrane is 300mm/min, and the carbon nanofiber membrane and the liquid silica gel are calendered and cured to obtain the carbon nanofiber membrane/silica gel composite material.
Fig. 3 shows the electromagnetic shielding effectiveness of the carbon nanofiber membrane/silica gel composite material prepared in this example in the range of 30MHz to 18GHz, and it can be seen from the figure that the carbon nanofiber membrane/silica gel composite material has a good shielding effect (shielding effectiveness is about 70dB) on electromagnetic waves with different wavelengths. Fig. 4 is a photograph showing a sample of the filamentous nanocarbon/silica gel composite material prepared in this example, wherein the silica gel is uniformly distributed in the pores of the filamentous nanocarbon film without pores and cracks, and a silica gel layer is formed on the filamentous nanocarbon film, and the surface of the silica gel layer is smooth.
Example 2
This example is substantially the same as example 1, except that: the thickness of the coated liquid silica gel layer was 140 μm, and the roll surface distance between the two rolls of the calender was 140 μm, under the same conditions as in example 1.
In the composite material prepared by the embodiment, the silica gel is uniformly distributed in the pores of the carbon nanofiber membrane, the surface of the carbon nanofiber membrane is covered with the silica gel, but the carbon nanofiber membrane has wrinkles, is not completely spread and has a small amount of air holes. In contrast to example 1, it was found that for smooth spreading of the nanocarbon fibre films in the composite, the calendering thickness should be less than the thickness of the coated silica gel layer.
Example 3
This example is substantially the same as example 1, except that: the thickness of the applied liquid silicone layer was 200 μm, the roll surface distance between the two rolls of the calender was 180 μm, and the other conditions were the same as in example 1.
In the composite material prepared by the embodiment, the silica gel is uniformly distributed in the pores of the carbon nanofiber membrane, but the thicknesses of the silica gel layers on the two sides of the carbon nanofiber membrane are different. In comparison with example 1, it was found that in order to obtain uniform and consistent thickness of the silica gel layer on both surfaces of the carbon nanofiber membrane during calendering and to save the amount of silica gel, the thickness of the silica gel layer of the coating liquid should be slightly larger than the thickness of the carbon nanofiber membrane.
Example 4
This example is substantially the same as example 1, except that: the roll surface temperature of the two rollers of the calender is 80 ℃, the running speed of the carbon nanofiber membrane is 300mm/min, and other conditions are the same as those of the embodiment 1.
In the composite material obtained in this example, the silica gel is not completely cured, and compared with example 1, it can be found that the curing speed of the liquid silica gel is slower when the curing temperature is 80 ℃.
Example 5
This example is substantially the same as example 1, except that: the roll surface temperature of the two rollers of the calender is 160 ℃, the running speed of the carbon nanofiber membrane is 300mm/min, and other conditions are the same as those of the embodiment 1.
In the composite material obtained in the embodiment, the silica gel is completely cured, and compared with the examples 1 and 5, it can be found that the curing speed of the liquid silica gel is higher when the curing temperature is 160 ℃, but the heating temperature is higher and the energy consumption is higher than that of the example 1.
Example 6
This example is substantially the same as example 1, except that: the roll surface temperature of the two rollers of the calender is 160 ℃, the running speed of the carbon nanofiber membrane is 900mm/min, and other conditions are the same as those of the embodiment 1.
In the composite material obtained in the embodiment, the carbon nanofiber membrane is not completely infiltrated by the silica gel, the pores appear in the material, and the silica gel is not completely cured, as compared with the composite material obtained in the embodiment 1 and the embodiment 6, it can be found that when the winding speed is 900mm/min, the coated silica gel layer has insufficient time to infiltrate the carbon nanofiber membrane due to the excessively fast winding speed, so that the pores appear, and meanwhile, the liquid silica gel does not have sufficient curing reaction due to the excessively short heating time.
Example 7
This example is substantially the same as example 1, except that: the roll surface temperature of the two rollers of the calender is 160 ℃, the running speed of the carbon nanofiber membrane is 600mm/min, and other conditions are the same as those of the embodiment 1.
In the composite material obtained in this embodiment, the silica gel can be completely cured, but the carbon nanofiber membrane is not completely soaked by the liquid silica gel, and pores appear in the material, as compared with examples 1 and 6, it can be found that, when the winding speed is 600mm/min, although the heating time is enough to enable the liquid silica gel to generate a sufficient curing reaction, the winding speed is still too fast from the effect of soaking the carbon nanofiber membrane by the liquid silica gel. Therefore, in order to obtain good liquid silica gel infiltration effect and curing effect, the rolling speed of the calender should not be too high.
Example 8
This example is substantially the same as example 1, except that: liquid silica gel with the viscosity of 1000cps was coated on the substrate to form a liquid silica gel layer with the thickness of 140 μm, and a carbon nanofiber membrane with the thickness of 100 μm was placed in the liquid silica gel layer and impregnated under the same conditions as in example 1.
The thickness of the composite material obtained in the embodiment is about 100 μm, and since the liquid silica gel has low viscosity and good fluidity, and the coated liquid silica gel layer cannot maintain the original thickness, the thickness of the silica gel layer is equivalent to the thickness of the carbon nanofiber membrane when the composite material is rolled by a calendar, and the composite material is not rolled by a roller, so that the surface flatness of the obtained composite material is poor, and the silica gel layer does not completely and uniformly cover the surface of the carbon nanofiber membrane.
Comparative example 1
The carbon nanofiber membrane with the thickness of 100 mu m is not compounded with silica gel. Fig. 5 is a graph showing the electromagnetic shielding effectiveness of the filamentous nanocarbon film provided in comparative example 1. As can be seen from comparison between fig. 3 and fig. 5, the shielding effectiveness of the carbon nanofiber membrane provided in comparative example 1 is significantly reduced (about 60 dB), and it can be seen that the carbon nanofiber membrane silica gel composite material provided in the present application has better electromagnetic shielding effectiveness.
Comparative example 2
This example is substantially the same as example 1, except that: the thickness of the coated liquid silicone layer was 140 μm, the roll surface distance between the two rolls of the calender was 100. mu.m, and the other conditions were the same as in example 1.
In the composite material prepared by the embodiment, the silica gel is uniformly distributed in the pores of the carbon nanofiber membrane, but the surface of the carbon nanofiber membrane is not completely and continuously covered by the silica gel, part of fibers are exposed outside, and the surface of the prepared carbon nanofiber/silica gel composite material is uneven. In comparison with example 1, it can be found that the silica gel layer cannot completely cover the carbon nanofiber membrane when the rolling thickness is the same as the carbon nanofiber membrane thickness, and the rolling thickness should be larger than the carbon nanofiber membrane thickness to obtain a silica gel composite material with a smooth surface.
Comparative example 3
This example is substantially the same as example 1, except that: the thickness of the applied liquid silicone layer was 90 μm, the roll surface spacing between the rolls was 120. mu.m, and the other conditions were the same as in example 1.
The carbon nanofiber membrane cannot be completely soaked by the silica gel in the composite material obtained by the embodiment, the surface of the carbon nanofiber membrane is not completely and continuously covered by the silica gel layer, part of the carbon nanofiber membrane is exposed outside the silica gel layer, due to the lack of protection of the silica gel layer, the exposed part of the carbon nanofiber membrane is easy to damage, the bonding effect with the surface of a shielded object is poor, the electromagnetic shielding performance is reduced to some extent, and the surface of the obtained composite material is not flat due to the fact that the thicknesses of the carbon nanofiber membrane and the silica gel layer are smaller than the distance between the roll surfaces of two rollers, and the rolling effect cannot be achieved when the carbon nanofiber membrane passes through the rollers.
In which the electromagnetic shielding effectiveness of the composite materials provided in examples 1 to 8 and the filamentous nanocarbon films provided in comparative examples 1 to 3 were examined. The detection method adopts standard GJB6190-2008 'electromagnetic shielding material shielding effectiveness measurement method' to test, the electromagnetic wave frequency range is 30MHz-18GHz, and the preparation method and the detection result are summarized to obtain table 1.
TABLE 1 preparation and Properties of carbon nanofiber membrane/silica gel composites
As can be seen from table 1, in comparison between examples 1 to 8 and comparative examples 1 to 3, the electromagnetic shielding performance of the filamentous nanocarbon silicone composite material can be improved by forming a silicone layer in the inner part and on at least one surface of the filamentous nanocarbon film.
Comparing example 1 with example 2, it can be seen that if the distance between the roll surfaces between the two rollers is too large (the distance between the roll surfaces is consistent with the thickness of the liquid silica gel layer), the silica gel cannot penetrate into the carbon nanofiber membrane well, which is not beneficial to improving the electromagnetic shielding performance of the carbon nanofiber membrane silica gel composite material.
Comparing example 1 with example 3, it can be seen that if the thickness of the liquid silica gel layer and the roll surface distance between the two rollers are increased, the electromagnetic shielding performance of the carbon fiber film silica gel composite material is not affected, but the use of the silica gel material is increased, and the manufacturing cost is increased.
It can be seen from the comparison between example 1, example 4 and example 7 that the selection of the curing temperature and the operation speed can be performed according to the characteristics of the silica gel material, so as to improve the electromagnetic shielding performance of the carbon nanofiber membrane silica gel composite material.
Comparing example 1 with example 8, it is known that the viscosity of the silica gel layer is relatively low, which is not beneficial to improving the electromagnetic shielding performance of the carbon nanofiber membrane silica gel composite material.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (6)
1. A preparation method of a carbon nanofiber membrane/silica gel composite material is characterized by comprising the following steps:
arranging the carbon nanofiber membrane on an unwinding device of a calender;
unreeling the carbon nanofiber membrane, enabling the carbon nanofiber membrane to pass through a coating section of the calender, and controlling a coating device on the coating section to coat liquid silica gel on the carbon nanofiber membrane to form a liquid silica gel layer; the thickness of the liquid silica gel layer is larger than that of the carbon nanofiber membrane;
controlling the coated carbon nanofiber membrane to pass between two opposite rollers of the calender, adjusting the surface temperature of the rollers, and pressing, curing and molding the liquid silica gel layer through the rollers to obtain a composite material;
rolling the molded composite material by using a rolling device of the calender;
the carbon nanofiber membrane/silica gel composite material comprises: the nano carbon fiber membrane is permeated with silica gel, and the silica gel layer completely and continuously covers the surface of the nano carbon fiber membrane.
2. The method as claimed in claim 1, wherein the carbon nanofiber membrane has a thickness of 20-200 μm, an electrical conductivity of 2000-5000S/m, and a carbon fiber diameter of 100-200 nm.
3. The method according to claim 1, wherein the distance between the roll surfaces of the two rolls is 100-180 μm.
4. The preparation method of claim 1, wherein the roll surface temperature of the two rollers is 80-160 ℃, and the running speed of the carbon nanofiber membrane on the calender is 300-900 mm/min.
5. The method as claimed in any one of claims 1 to 4, wherein the liquid silica gel has a viscosity of 2000-.
6. The method as claimed in claim 1, wherein the thickness of the liquid silica gel layer is 100-200 μm.
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