CN115538157B - Method for producing carbon nanotube modified silicon carbide fiber by continuous vapor deposition method - Google Patents
Method for producing carbon nanotube modified silicon carbide fiber by continuous vapor deposition method Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 80
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 79
- -1 carbon nanotube modified silicon carbide Chemical class 0.000 title claims abstract description 50
- 238000007740 vapor deposition Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 80
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 52
- 239000007789 gas Substances 0.000 claims description 50
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 49
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000004590 computer program Methods 0.000 claims description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 4
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
Abstract
The invention discloses a method for producing carbon nanotube modified silicon carbide fiber by a continuous vapor deposition method, which utilizes continuous vapor deposition wire-moving equipment to continuously produce the carbon nanotube modified silicon carbide fiber, the equipment creates a closed environment required by continuous wire-moving reaction through a front liquid seal box and a rear liquid seal box, and conditions such as atmosphere proportion, total amount of atmosphere, reaction temperature, wire moving speed and the like are regulated by arranging a gas input device, a tubular furnace body, a wire collecting machine and a wire discharging machine, so that the wire moving can be accurately regulated according to requirements, the controllability, accuracy and diversity of CVD preparation are ensured, technical support is provided for continuous large-scale CVD preparation of composite fiber, carbon deposition and the like, and the prepared carbon nanotube modified silicon carbide fiber has better dielectric property and mechanical property and can be widely applied to the fields of wave absorbing materials, composite material reinforcement and the like.
Description
Technical Field
The invention relates to a production method of carbon nanotube modified silicon carbide fibers, in particular to a method for producing carbon nanotube modified silicon carbide fibers by a continuous vapor deposition method, and belongs to the technical field of fiber material reinforcement.
Background
The silicon carbide fiber has excellent physicochemical properties of high strength, high modulus, corrosion resistance, acid and alkali resistance and the like, and is a ceramic fiber with light texture and small density. Compared with Carbon Nanotubes (CNTs), the nano-composite material has good high-temperature resistance and oxidation resistance. The silicon carbide fiber has great application prospect in the aspects of wave-absorbing materials, high-temperature sensors, composite material reinforcement, supported dispersion catalysts and the like, and also has wide application in the national defense fields of aerospace and the like.
The carbon nanotubes are used as novel carbon-based nano materials and have excellent performances in the aspects of mechanics, electrothermal science and the like. The tensile strength of the fiber can reach 200GPa, the elastic modulus can reach 1TPa, and the fiber has excellent elasticity, toughness and fatigue resistance, and is an ideal choice for being used as a reinforcing material of high-performance fiber. The high specific surface area of the carbon nano tube can cause multiple scattering, and electromagnetic waves in all directions are absorbed under the action of the matrix; the small size effect can cause resonance absorption; the small diameter is easy to form a large number of interfaces, and the polarization of the interfaces is favorable for electromagnetic wave absorption. The silicon carbide fiber modified by the carbon nano tube has improved dielectric property and mechanical property, and has wide application prospect in the fields of wave-absorbing materials and composite material reinforcement.
Currently, literature (ACS Applied Materials & Interfaces,2020, 12 (18): 20775-20784.) reports a very efficient short-time induction heating process for the synthesis of carbon nanotubes on silicon carbide fibers and discloses the effect of carbon nanotube content, material thickness and loading on the wave-absorbing properties. The literature shows that when the carbon nano tube is filled in the composite material with the mass fraction of 0.72%, the effective bandwidth can reach 8.8GHz; when the thickness is 4mm, the minimum reflection loss value can reach-62.5 dB, and the carbon nano tube modified silicon carbide fiber has excellent performance and wide prospect. At present, the carbon nanotube modified silicon carbide fiber is still in a laboratory small-scale synthesis stage, large-scale continuous production is not realized, and the uncontrollable morphology of the carbon nanotube in the continuous production process of the carbon nanotube modified silicon carbide fiber is a technical problem.
Disclosure of Invention
Aiming at the technical defects that the continuity cannot be realized, the morphology of the carbon nano tube is uncontrollable and the like in the production of the carbon nano tube modified silicon carbide fiber in the prior art, the invention aims to provide a method for producing the carbon nano tube modified silicon carbide fiber by using a continuous vapor deposition method wire feeding device to realize the deposition of the carbon nano tube on the surface of the silicon carbide fiber, thereby not only realizing the continuous production of the carbon nano tube modified silicon carbide fiber, but also uniformly growing the carbon nano tube on the surface of the silicon carbide fiber, improving the dielectric property and the mechanical property of the silicon carbide fiber, being widely applied to the fields of wave absorbing materials, composite material enhancement and the like and overcoming the defects in the production of the existing carbon nano tube modified silicon carbide fiber.
In order to achieve the technical aim, the invention provides a method for producing carbon nano tube modified silicon carbide fibers by a continuous vapor deposition method, which utilizes a continuous vapor deposition method wire feeding device to continuously produce the carbon nano tube modified silicon carbide fibers;
the continuous vapor deposition wire feeding equipment comprises a quartz tube, a guide wheel mechanism, a liquid seal box, a gas input device, a tail gas treatment device, a wire feeding machine and a wire collecting machine, wherein one end of the quartz tube is provided with a gas inlet and a wire feeding port, the other end of the quartz tube is provided with a tail gas outlet and a wire discharging port, the middle part of the inner cavity of the quartz tube is a reaction zone, the reaction zone of the quartz tube is arranged in a heating zone of a tube furnace body, the gas inlet of the quartz tube is communicated with the outlet of the gas input device through a pipeline, the tail gas outlet of the quartz tube is communicated with the inlet of the tail gas treatment device through a pipeline, the liquid seal box comprises a front liquid seal box and a rear liquid seal box, the wire feeding port of the quartz tube is arranged below the liquid level in the front liquid seal box, and the wire discharging port of the quartz tube is arranged below the liquid level in the rear liquid seal box; the guide wheel mechanism is used for conveying silicon carbide fibers in the inner cavity of the quartz tube;
the continuous production process of the carbon nanotube modified silicon carbide fiber by using the continuous vapor deposition wire-moving equipment comprises the following steps: the silicon carbide fiber in the filament releasing machine is continuously output and then is conveyed through a guide wheel mechanism, a preposed liquid seal box filled with catalyst solution is introduced, then the catalyst solution is introduced from a filament inlet of a quartz tube, passes through a reaction zone in the middle of an inner cavity of the quartz tube, is led out from a filament outlet of the quartz tube, and finally is continuously received in a filament collecting machine; the atmosphere and the temperature of the reaction zone are respectively regulated and controlled by a gas input device and a heating zone through a computer program.
According to the continuous vapor deposition method wire feeding equipment, on one hand, a guide wheel mechanism is used for controlling silicon carbide fibers to be led in from a wire inlet of a quartz tube, pass through a reaction zone in the middle of an inner cavity of the quartz tube and be led out from a wire outlet; on the other hand, the atmosphere proportion and the atmosphere type in the quartz tube are regulated and controlled through the gas input device, the reaction temperature of the quartz tube reaction zone is set through the tube furnace body, the sealed environment required by continuous wire feeding reaction is created through the front liquid seal box and the rear liquid seal box, the continuous production of the carbon nano tube modified fiber with the specific morphology is realized through the cooperative cooperation of the structures, and the dielectric property and the mechanical property of the silicon carbide fiber can be improved.
As a preferable scheme, two ends of the quartz tube are respectively provided with a wire inlet tube and a wire outlet tube which are vertically arranged with the quartz tube, the wire inlet tube and the wire outlet tube are communicated with the inner cavity of the quartz tube, one ends of the wire inlet tube and the wire outlet tube are respectively connected with the quartz tube in a sealing way, the other ends of the wire inlet tube and the wire outlet tube are respectively formed with a wire inlet and a wire outlet, and the wire inlet tube and the wire outlet tube at two ends of the quartz tube are respectively arranged in a front liquid seal box and a rear liquid seal box and are sealed below the liquid level
As a preferable scheme, the wire unwinding machine is arranged on one side of a wire inlet of the quartz tube, the wire winding machine is arranged on one side of a wire outlet of the quartz tube, the wire unwinding machine comprises a wire unwinding wheel driven to rotate by a first driving device, the wire winding machine comprises a wire winding wheel driven to rotate by a second driving device, the wire unwinding wheel outputs silicon carbide fibers, and the output silicon carbide fibers sequentially penetrate through the wire inlet, a quartz tube reaction zone and the wire outlet to be collected on the wire winding wheel.
As a preferable scheme, the wire collecting machine and/or the wire releasing machine are/is provided with a pre-tightening wheel, the silicon carbide fiber is connected with a guide wheel mechanism through the pre-tightening wheel, the pre-tightening wheel is provided with a pressure sensor, and the pressure sensor is connected with a first driving device and a second driving device through a control system. The tensioning force of the silicon carbide fibers is set through the control system, the speed of the wire unwinding wheel and the speed of the wire winding wheel are regulated through the first driving device and the second driving device, so that the tensioning force of the fibers is in a set range, the stress of the silicon carbide fibers in the interior can be effectively reduced, the occurrence of wire breakage is prevented, the probability of shutdown maintenance is reduced, and the production efficiency is improved.
As a preferable scheme, the guide wheel mechanism comprises a first fixed pulley, a second fixed pulley, a third fixed pulley, a fourth fixed pulley, a fifth fixed pulley and a sixth fixed pulley, wherein the first fixed pulley is arranged below a wire inlet of the front liquid seal box, the sixth fixed pulley is arranged below a wire outlet of the rear liquid seal box, the second fixed pulley is arranged at the wire inlet position in the quartz tube, the fifth fixed pulley is arranged at the wire outlet position in the quartz tube, the third fixed pulley and the fourth fixed pulley are respectively arranged at the inlet end and the outlet end of a reaction zone in the quartz tube, and carbon fibers output by the wire unwinding wheel sequentially bypass the first fixed pulley, the second fixed pulley, the fourth fixed pulley, the third fixed pulley, the fifth fixed pulley and the sixth fixed pulley to be connected with the wire winding wheel.
As a more preferable scheme, U-shaped grooves which are matched with the silicon carbide fibers in size and distributed along the circumferential direction are formed in the first fixed pulley, the second fixed pulley, the third fixed pulley, the fourth fixed pulley, the fifth fixed pulley and the sixth fixed pulley. Thereby effectively reducing the wire-stripping probability.
As a more preferable scheme, a plurality of U-shaped grooves can be correspondingly arranged on the third fixed pulley and the fourth fixed pulley along the axial direction. The silicon carbide fiber can be wound repeatedly on the third fixed pulley and the fourth fixed pulley, so that the wire running times of the silicon carbide fiber in the reaction area are increased, the growth time of the carbon nano tube in unit area is prolonged, and the efficiency is improved.
As a preferable scheme, the front liquid seal box and the rear liquid seal box are respectively internally provided with a catalyst solution liquid seal and a water seal.
As a preferable scheme, the top openings of the front liquid seal box and the rear liquid seal box are respectively provided with a cover plate for sealing, the cover plates are provided with openings at the positions matched with the wire inlet pipe and the wire outlet pipe, and the cover plates are provided with grooves at the positions matched with the silicon carbide fibers. The volatilization of the solution in the liquid seal box can be reduced as much as possible through the sealing of the cover plate, so that the production resources are saved, and the utilization rate is improved.
On the basis of using continuous vapor deposition wire moving equipment, the invention can enable the surface of the silicon carbide fiber to uniformly grow the carbon nano tube with specific morphology and uniform morphology by regulating vapor deposition conditions, and can effectively improve the dielectric property and mechanical property of the silicon carbide.
As a preferred embodiment, the catalyst solution is a ferrocene xylene solution having a concentration of 0.02-0.05 g/mL. In the preferable catalyst solution concentration range, the growth length of the carbon nano tube can be improved, the effective interval of vapor deposition can be improved, and when the catalyst solution concentration exceeds 0.05g/ml and is lower than 0.02g/ml, the overall growth index of the carbon nano tube is drastically reduced.
As a preferable scheme, the regulation and control process of the atmosphere and the temperature of the reaction zone is as follows: introducing inert gas to remove air, then introducing reducing gas when the temperature is programmed to 500-550 ℃ under the condition of introducing the inert gas, simultaneously programming to 650-800 ℃, and introducing a gas carbon source after the temperature is stable, so as to carry out vapor deposition of the silicon carbide fiber. At the preferred vapor deposition temperature, the overall growth of carbon nanotubes is good, while below 650 ℃, the growth of carbon nanotubes is slow, while above 800 ℃, the regularity of carbon nanotubes is low.
As a preferable scheme, the conveying speed of the silicon carbide fiber is 0.05-0.3 m/min. The residence time of the silicon carbide fiber in the reaction zone is 5-20 min. The time and rate of the silicon carbide fiber passing through the reaction zone have obvious influence on the growth length, quantity, regular uniformity degree and the like of the carbon nano tubes. The conveying speed of the silicon carbide fiber, namely the wire drawing speed(s), is calculated from the required reaction time (t), the length (l) of the reaction zone and the wire running frequency (n) in the reaction zone. The formula is as follows: s=nl/t. The slower the filament drawing speed is, the longer the reaction time is, the better the growth condition of the carbon nano tube is, but the lower the efficiency is, but the too low filament drawing speed can damage the growth of the carbon nano tube, and the too high speed can cause the unstable growth environment of the carbon nano tube, and the growth condition can be influenced.
As a preferable mode, the total amount of the inert gas, the reducing gas and the gaseous carbon source is 900-1000 sccm, wherein the inert gas is 700-900 sccm, the reducing gas is 80-180 sccm, and the gaseous carbon source is 5-25 sccm. Inert gases such as argon mainly play a role in filling and protecting; the ratio of the reducing gas to the gaseous carbon source, such as hydrogen and acetylene, has a great influence on the growth of the carbon nanotubes produced by the continuous vapor deposition process. Reducing gas, such as hydrogen, is controlled in the interval of 80-180 sccm, carbon nano tubes grow well, the morphology of carbon nano tubes lower than 80sccm or higher than 180sccm is poor, and the hydrogen is preferably controlled in the interval of 120-180 sccm; in the interval of 5-25 sccm, the whole growth index (such as length and morphology) of the carbon nano tube is improved along with the increase of the acetylene ratio, and the whole growth index of the carbon nano tube is reduced after the acetylene ratio is lower than 5sccm or exceeds 25sccm.
As a more preferable scheme, the inert gas is argon, the reducing gas is hydrogen, and the gaseous carbon source is acetylene.
After the continuous vapor deposition method wire feeding equipment is started, the silicon carbide fiber in the wire unwinding machine is connected with the wire winding machine through each pulley in the equipment, the front end of the quartz tube is connected with the gas input device in a sealing way through a pipeline, the rear end of the quartz tube is connected with the tail gas treatment device in a sealing way through a pipeline, and the wire inlet and the wire outlet of the quartz tube are required to be in a liquid sealing state, so that the air tightness of a reaction environment is ensured; the gas input device controls the gas conveying capacity and different atmospheres through a computer program, the heating area of the reaction area controls the temperature rising rate, the heating temperature, the heat preservation time and the like through the computer program, and the silicon carbide fiber can be continuously produced by the wire feeding machine and the wire receiving machine through the same and uniform speed.
The quartz tube of the invention is exemplified by a conventional tube furnace without furnace plug with the tube diameter of 45 mm.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the production process of the carbon nanotube modified silicon carbide fiber is realized based on a continuous vapor deposition method wire feeding device, the device creates a closed environment required by continuous wire feeding reaction through a front liquid seal box and a rear liquid seal box, and conditions such as atmosphere proportion, total atmosphere, reaction temperature, wire feeding speed and the like are adjusted through arranging a gas input device, a tubular furnace body, a wire collecting machine and a wire discharging machine, so that the wire feeding can be accurately adjusted according to requirements, the controllability, accuracy and diversity of CVD preparation are ensured, and technical support is provided for continuous large-scale CVD preparation of composite fiber, carbon deposition and the like.
The carbon nanotube modified silicon carbide fiber can effectively regulate and control the growth length, the number, the regular uniformity degree and the like of the carbon nanotubes grown in situ on the silicon carbide fiber by controlling the vapor deposition condition on the basis of using the continuous vapor deposition wire moving equipment so as to obtain the carbon nanotube modified silicon carbide fiber with optimal performances such as dielectric property, mechanical property and the like.
Drawings
FIG. 1 is a schematic diagram of a continuous vapor deposition wire feeding device;
1, a quartz tube; 11. a wire feeding pipe; 12. a wire outlet pipe; 13. a first fixed pulley; 14. a second fixed pulley; 15. a third fixed pulley; 16. a fourth fixed pulley; 17. a fifth fixed pulley; 18. a sixth fixed pulley; 2. a gas input device; 3. a tail gas treatment device; 4. a wire feeding machine; 5. a wire collecting machine; 6. leading a liquid seal box; 7. post liquid sealing; 8. a tubular furnace body; 81. and heating the region.
Fig. 2 is a microscopic morphology of the carbon nanotube-modified silicon carbide fiber prepared in example 2.
FIG. 3 is a graph of the microscopic morphology of the carbon nanotube-modified silicon carbide fiber prepared in comparative example 1.
Fig. 4 is a microscopic morphology graph of the carbon nanotube-modified silicon carbide fiber prepared in comparative example 2.
Fig. 5 is a microscopic morphology graph of the carbon nanotube-modified silicon carbide fiber prepared in comparative example 3.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the technical solutions, and when the technical solutions are contradictory or cannot be implemented, the combination of the technical solutions should be considered as not existing, and not falling within the scope of protection claimed by the present invention.
Example 1
In the embodiment of the invention, as shown in fig. 1, a continuous vapor deposition method wire feeding device comprises a quartz tube 1, a guide wheel mechanism, a liquid seal box, a wire feeding machine 4, a wire collecting machine 5, a gas input device 2 and a tail gas treatment device 3, wherein one end of the quartz tube 1 is provided with an atmosphere inlet and a wire feeding port, the other end of the quartz tube 1 is provided with a tail gas outlet and a wire feeding port, the middle part of an inner cavity of the quartz tube 1 is a reaction zone, the reaction zone of the quartz tube 1 is arranged in a heating zone 81 of a tubular furnace body 8, the atmosphere inlet of the quartz tube 1 is communicated with the outlet of the gas input device 2 through a pipeline, the tail gas outlet of the quartz tube 1 is communicated with the inlet of the tail gas treatment device 3 through a pipeline, two ends of the quartz tube 1 are respectively provided with a wire feeding tube 11 and a wire feeding tube 12 which are vertically arranged with the quartz tube 1, one ends of the wire feeding tube 11 and the wire feeding tube 12 are in sealing connection with the quartz tube 1, the other ends of the wire feeding tube 11 and the wire feeding port are formed, the liquid seal box comprises a front liquid level 6 and a rear liquid seal box 7, and the liquid seal box 7 is arranged below the front liquid seal box 1 and the front liquid seal box 7 is arranged below the front liquid seal box 7; the wire winding machine 4 sets up in quartz tube 1 wire inlet one side, the wire winding machine 5 sets up in quartz tube 1 wire outlet one side, wire winding machine 4 includes the wire winding wheel of driving rotation through first drive arrangement, wire winding machine 5 includes the wire winding wheel of driving rotation through the second drive arrangement, the winding has the carborundum fibre of waiting to process on the wire winding wheel, all be equipped with guide pulley mechanism in quartz tube 1, leading liquid seal box 6 and the post liquid seal box 7, wire winding wheel output carborundum fibre, the carborundum fibre of output passes wire inlet, quartz tube 1 reaction zone, wire outlet in proper order and collects on wire winding wheel. The guide wheel mechanism comprises a first fixed pulley 13, a second fixed pulley 14, a third fixed pulley 15, a fourth fixed pulley 16, a fifth fixed pulley 17 and a sixth fixed pulley 18, wherein the first fixed pulley 13 is arranged below a wire inlet of the front liquid seal box 6, the sixth fixed pulley 18 is arranged below a wire outlet of the rear liquid seal box 7, the second fixed pulley 14 is arranged at the position of the quartz tube 1 and the outlet of the wire inlet tube 11, the fifth fixed pulley 17 is arranged at the position of the quartz tube 1 and the inlet of the wire outlet tube 12, the third fixed pulley 15 and the fourth fixed pulley 16 are respectively arranged at the inlet end and the outlet end of a reaction zone in the quartz tube 1, and silicon carbide fibers to be treated on the wire discharge wheel sequentially bypass the first fixed pulley 13, the second fixed pulley 14, the fourth fixed pulley 16, the third fixed pulley 15, the fifth fixed pulley 17 and the sixth fixed pulley 18 and are connected with a wire collecting wheel; u-shaped grooves which are matched with the silicon carbide fibers to be treated in size and distributed along the circumferential direction are formed in the first fixed pulley 13, the second fixed pulley 14, the third fixed pulley 15, the fourth fixed pulley 16, the fifth fixed pulley 17 and the sixth fixed pulley 18, so that the wire stripping probability is effectively reduced; the third fixed pulley 15 and the fourth fixed pulley 16 can be correspondingly provided with a plurality of U-shaped grooves along the axial direction, and the silicon carbide fiber to be treated can be wound repeatedly on the third fixed pulley 15 and the fourth fixed pulley 16 for a plurality of times, so that the number of times of filament running of the fiber to be treated in the reaction area is increased, the number of times of filament running in the reaction area is set to be n, the length of a main heating area in the quartz tube is t, the length of the fiber to be treated in the reaction area is l, the moving speed of the fiber to be treated in the reaction area is s, st=nl, and thus the number of filament running can be judged according to the mechanical properties of fiber bundles or deposition templates.
In this embodiment, the quartz tube is a high temperature resistant quartz tube, and the front liquid seal box 6 and the rear liquid seal box 7 are respectively realized by liquid seal and water seal by adopting a catalyst solution. The top openings of the front liquid seal box 6 and the rear liquid seal box 7 are provided with cover plates, the positions of the cover plates matched with the wire inlet pipe 11 and the wire outlet pipe 12 are provided with openings, and the positions of the cover plates matched with the silicon carbide fibers to be treated are provided with grooves, so that volatilization of solution in the liquid seal box can be reduced as much as possible, production resources are saved, and the utilization rate is improved.
In this embodiment, the speeds of the wire collecting machine 5 and the wire releasing machine 4 are controllable, the wire collecting machine 5 and the wire releasing machine 4 are provided with pre-tightening wheels, the pre-tightening wheels are provided with pressure sensors, and the pressure sensors are connected with a first driving device and a second driving device through a control system; the tensioning force of the fibers is set through the control system, the speeds of the wire unwinding wheel and the wire winding wheel are regulated through the first driving device and the second driving device, so that the tensioning force of the fibers is in a set range, the stress of the fibers in the fibers can be effectively reduced, the occurrence of wire breakage is prevented, the probability of shutdown maintenance is reduced, and the production efficiency is improved.
In this embodiment, the gas input device 2 is provided with a gas path flow control system, and the gas path flow control system can adjust the component ratio, the entering time and other operation details of the multi-atmosphere entering the quartz tube 1, and can be adjusted according to the needs. An exhaust device is arranged in the tail gas treatment device 3, and can exhaust the reaction gas in the quartz tube 1.
After the device is adopted, all equipment systems are assembled, the fibers are connected with the wire collecting machine 5 and the wire releasing machine 4 through all rollers in the system, and the carbon nano tube modified silicon carbide fibers with specific morphology can be produced by changing the conditions of atmosphere proportion, atmosphere types, reaction temperature, catalyst types, fiber types and the like, so that the dielectric property and the mechanical property of the carbon nano tube modified silicon carbide fibers are improved, and the carbon nano tube modified silicon carbide fibers have good application prospects in the fields of wave absorbing materials, composite material reinforcement and the like. The whole equipment has simple structure and convenient operation, and can realize continuous CVD production.
Example 2
The apparatus of example 1 was used to achieve continuous production of carbon nanotube-modified silicon carbide fibers.
And assembling the system equipment according to a flow chart, and confirming that the air passage is smooth and has no air leakage blocking phenomenon. The silicon carbide fiber is connected with a wire collecting machine and a wire releasing machine through various pulleys in the system, so that the fact that the fiber is de-glued is confirmed, and the surface is not damaged obviously.
The ferrocene is weighed by an electronic scale and added into the dimethylbenzene, and the ultrasound is carried out for 30min, so as to prepare the ferrocene/dimethylbenzene catalyst with the concentration of 0.05 g/ml. Then adding the mixture into a front water tank, adding deionized water into a rear water tank, confirming the liquid seal state, and ensuring that the gas in the reaction environment finally passes through a tail gas treatment device.
Argon is introduced for 30min, air in the reaction environment is discharged as much as possible, a heating program (argon is always introduced during the period, the total flow is 800 sccm), and when the temperature is raised to 500 ℃, hydrogen is introduced, and the flow is 180sccm. When the temperature is raised to 740 ℃, the reaction temperature is kept constant after the temperature is stabilized for 5min, acetylene is introduced, the flow is 25sccm, a wire collecting machine and a wire discharging machine are started to start wire drawing, the wire drawing speed is 0.05m/min, and the time for growing the carbon nano tube in the reaction environment by silicon carbide is 7min.
The product was placed under a scanning electron microscope to observe morphology and resistivity tests were performed.
The original resistivity of the silicon carbide fiber is 40 Ω & cm, and the resistivity of the silicon carbide fiber modified by the carbon nano tube is 0.79 Ω & cm.
The scanning electron microscope images of the carbon nano tube modified silicon carbide fiber under different multiplying powers are shown in fig. 2, and the regular and uniform appearance of the carbon nano tube modified on the silicon carbide surface can be seen from the images.
Comparative example 1
Compared with example 2, the difference is that: the flow rate of the introduced hydrogen gas was 70sccm and 200sccm as a control.
The resistivity of the carbon nano tube modified silicon carbide fiber prepared when the hydrogen flow is 70sccm is 13.03 ohm cm;
the resistivity of the carbon nano tube modified silicon carbide fiber prepared by the hydrogen flow of 200sccm is 5.78Ω & cm;
the scanning electron microscope diagram of the carbon nanotube modified silicon carbide fiber is shown in fig. 3, and the left diagram is the carbon nanotube modified silicon carbide fiber prepared under the condition of low hydrogen flow rate and 70sccm flow rate; the right graph shows that the carbon nano tube modified silicon carbide fiber prepared under the condition of high hydrogen flow rate and 200sccm flow rate has poor morphology of the carbon nano tube surface modified under the condition of low hydrogen flow rate and high hydrogen flow rate. Experiments prove that when the hydrogen flow is 80-180 sccm, the carbon nano tube has good morphology characteristics, and the growth of the carbon nano tube is influenced when the hydrogen flow is higher than 180sccm or lower than 80sccm.
Comparative example 2
Compared with example 2, the difference is that: the reaction temperatures of 600℃and 900℃were used as controls.
Under the condition of lower temperature and at the reaction temperature of 600 ℃, the resistivity of the prepared carbon nanotube modified silicon carbide fiber is 23.16Ω & cm;
under the condition of higher temperature, when the reaction temperature is 900 ℃, the resistivity of the prepared carbon nano tube modified silicon carbide fiber is 17.72 Ω & cm;
the scanning electron microscope diagram of the carbon nanotube modified silicon carbide fiber is shown in fig. 4, and the left diagram is the prepared carbon nanotube modified silicon carbide fiber at 600 ℃ under the condition of lower temperature; the right graph shows that the carbon nano tube modified silicon carbide fiber prepared at 900 ℃ under the condition of higher temperature has poor appearance of the carbon nano tube modified on the surface of the silicon carbide. Experiments prove that at the preferred vapor deposition temperature, the whole growth of the carbon nano tube is good, and the growth of the carbon nano tube is slow below 650 ℃, or the whole growth of the carbon nano tube is reduced above 800 ℃.
Comparative example 3
Compared with example 2, the difference is that: the reaction time was 4min as a control.
Under the condition of short reaction time, the resistivity of the prepared carbon nanotube modified silicon carbide fiber is 21.05Ω & cm when the reaction time is 4 min;
the scanning electron microscope image of the carbon nanotube modified silicon carbide fiber is shown in fig. 5, and the appearance of the carbon nanotube modified on the surface of the silicon carbide is poor and the carbon nanotube is not grown completely.
Claims (7)
1. A method for producing carbon nanotube modified silicon carbide fibers by a continuous vapor deposition method is characterized by comprising the following steps of: continuously producing carbon nano tube modified silicon carbide fibers by utilizing continuous vapor deposition wire moving equipment;
the continuous vapor deposition wire feeding equipment comprises a quartz tube (1), a guide wheel mechanism, a liquid seal box, a gas input device (2), a tail gas treatment device (3), a wire feeding machine (4) and a wire collecting machine (5), wherein one end of the quartz tube is provided with a gas inlet and a wire feeding port, the other end of the quartz tube is provided with a tail gas outlet and a wire discharging port, the middle part of an inner cavity of the quartz tube is a reaction zone, the reaction zone of the quartz tube is arranged in a heating zone (81) of a tube furnace body (8), the gas inlet of the quartz tube is communicated with the outlet of the gas input device through a pipeline, the tail gas outlet of the quartz tube is communicated with the inlet of the tail gas treatment device through a pipeline, the liquid seal box comprises a front liquid seal box (6) and a rear liquid seal box (7), and the wire feeding port of the quartz tube is arranged below the liquid level in the front liquid seal box; the guide wheel mechanism is used for conveying silicon carbide fibers in the inner cavity of the quartz tube;
the continuous production process of the carbon nanotube modified silicon carbide fiber by using the continuous vapor deposition wire-moving equipment comprises the following steps: the silicon carbide fiber in the filament releasing machine is continuously output and then is conveyed through a guide wheel mechanism, a preposed liquid seal box filled with catalyst solution is introduced, then the catalyst solution is introduced from a filament inlet of a quartz tube, passes through a reaction zone in the middle of an inner cavity of the quartz tube, is led out from a filament outlet of the quartz tube, and finally is continuously received in a filament collecting machine; the atmosphere and the temperature of the reaction zone are respectively regulated and controlled by a gas input device and a heating zone through computer programs;
the pre-tightening wheel is arranged on the wire collecting machine and/or the wire releasing machine, the silicon carbide fiber is connected with the guide wheel mechanism through the pre-tightening wheel, the pressure sensor is arranged on the pre-tightening wheel, and the pressure sensor is connected with the first driving device and the second driving device through the control system;
the conveying speed of the silicon carbide fiber is 0.05-0.3 m/min; the residence time of the silicon carbide fiber in the reaction zone is 5-20 min;
the catalyst solution is ferrocene dimethylbenzene solution with concentration in the range of 0.02-0.05 g/mL.
2. The method for producing carbon nanotube-modified silicon carbide fibers by continuous vapor deposition according to claim 1, wherein the method comprises the steps of: the utility model discloses a quartz capsule, including quartz capsule, front liquid seal box, rear liquid seal box, wire inlet pipe, wire outlet, wire inlet pipe (11) and wire outlet pipe (12) that the both ends of quartz capsule were provided with respectively with quartz capsule perpendicularly layout, wire inlet pipe and wire outlet pipe all communicate with quartz capsule inner chamber, wire inlet pipe and wire outlet pipe's one end all with quartz capsule sealing connection, the other end forms respectively wire inlet with wire outlet, wire inlet pipe and wire outlet pipe at quartz capsule both ends set up respectively in front liquid seal box and rear liquid seal box, and seal below the liquid level.
3. The method for producing carbon nanotube-modified silicon carbide fibers by continuous vapor deposition according to claim 1, wherein the method comprises the steps of: the wire feeding machine is arranged on one side of a wire inlet of the quartz tube, the wire collecting machine is arranged on one side of a wire outlet of the quartz tube, the wire feeding machine comprises a wire collecting wheel which is driven to rotate by a first driving device, the wire collecting machine comprises a wire collecting wheel which is driven to rotate by a second driving device, the wire collecting wheel outputs silicon carbide fibers, and the output silicon carbide fibers sequentially pass through the wire inlet, a quartz tube reaction area and the wire outlet to be collected on the wire collecting wheel.
4. A method for producing carbon nanotube-modified silicon carbide fibers by continuous vapor deposition as claimed in claim 3, wherein: the guide wheel mechanism comprises a first fixed pulley (13), a second fixed pulley (14), a third fixed pulley (15), a fourth fixed pulley (16), a fifth fixed pulley (17) and a sixth fixed pulley (18), wherein the first fixed pulley is arranged below a wire inlet of the front liquid seal box, the sixth fixed pulley is arranged below a wire outlet of the rear liquid seal box, the second fixed pulley is arranged at an outlet position of a wire inlet pipe in the quartz tube, the fifth fixed pulley is arranged at an inlet position of the wire outlet pipe in the quartz tube, the third fixed pulley and the fourth fixed pulley are respectively arranged at an inlet end and an outlet end of a reaction zone in the quartz tube, and carbon fibers output by the wire discharge wheel sequentially bypass the first fixed pulley, the second fixed pulley, the fourth fixed pulley, the third fixed pulley, the fifth fixed pulley and the sixth fixed pulley to be connected with the wire collecting wheel.
5. The method for producing carbon nanotube-modified silicon carbide fibers by continuous vapor deposition according to any one of claims 1 to 4, wherein the method comprises the steps of: the regulation and control process of the atmosphere and the temperature of the reaction zone comprises the following steps: introducing inert gas to remove air, then introducing reducing gas when the temperature is programmed to 500-550 ℃ under the condition of introducing the inert gas, simultaneously programming to 650-800 ℃, and introducing a gas carbon source after the temperature is stable, so as to carry out vapor deposition of the silicon carbide fiber.
6. The method for producing carbon nanotube-modified silicon carbide fibers by continuous vapor deposition according to claim 5, wherein the method comprises the steps of: the total amount of the inert gas, the reducing gas and the gaseous carbon source is 900-1000 sccm, wherein the inert gas is 700-900 sccm, the reducing gas is 80-180 sccm, and the gaseous carbon source is 5-25 sccm.
7. The method for producing carbon nanotube-modified silicon carbide fibers by continuous vapor deposition according to claim 6, wherein the method comprises the steps of: the inert gas is argon, the reducing gas is hydrogen, and the gaseous carbon source is acetylene.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009110885A1 (en) * | 2008-03-03 | 2009-09-11 | Performance Polymer Solutions, Inc. | Continuous process for the production of carbon nanotube reinforced continuous fiber preforms and composites made therefrom |
| CN102021817A (en) * | 2010-11-11 | 2011-04-20 | 中国人民解放军国防科学技术大学 | Silicon carbide fiber solid fabric for in-situ growing carbon nano tubes, composite material and preparation method thereof |
| CN102199872A (en) * | 2011-03-29 | 2011-09-28 | 北京航空航天大学 | Method for in-situ growing carbon nanotubes on fiber surfaces |
| CN106367849A (en) * | 2016-02-22 | 2017-02-01 | 河北陆元新材料科技有限公司 | Continuous silicon carbide fiber production system |
| CN206396529U (en) * | 2016-12-12 | 2017-08-11 | 山东大学 | The device of CNT is grown in serialization carbon fiber surface |
| CN108221361A (en) * | 2016-12-12 | 2018-06-29 | 山东大学 | In the device and method of serialization carbon fiber surface growth carbon nanotube |
| CN108588902A (en) * | 2018-04-18 | 2018-09-28 | 复旦大学 | A kind of extensive continuous preparation device and method of carbon nano tube composite fibre |
| CN114808196A (en) * | 2022-04-19 | 2022-07-29 | 江西省纳米技术研究院 | Carbon nanotube preparation device, injection assembly thereof and carbon nanotube preparation method |
| CN114887552A (en) * | 2022-05-20 | 2022-08-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Injection structure for preparing carbon nanotube material and application thereof |
-
2022
- 2022-10-27 CN CN202211329154.6A patent/CN115538157B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009110885A1 (en) * | 2008-03-03 | 2009-09-11 | Performance Polymer Solutions, Inc. | Continuous process for the production of carbon nanotube reinforced continuous fiber preforms and composites made therefrom |
| CN102021817A (en) * | 2010-11-11 | 2011-04-20 | 中国人民解放军国防科学技术大学 | Silicon carbide fiber solid fabric for in-situ growing carbon nano tubes, composite material and preparation method thereof |
| CN102199872A (en) * | 2011-03-29 | 2011-09-28 | 北京航空航天大学 | Method for in-situ growing carbon nanotubes on fiber surfaces |
| CN106367849A (en) * | 2016-02-22 | 2017-02-01 | 河北陆元新材料科技有限公司 | Continuous silicon carbide fiber production system |
| CN206396529U (en) * | 2016-12-12 | 2017-08-11 | 山东大学 | The device of CNT is grown in serialization carbon fiber surface |
| CN108221361A (en) * | 2016-12-12 | 2018-06-29 | 山东大学 | In the device and method of serialization carbon fiber surface growth carbon nanotube |
| CN108588902A (en) * | 2018-04-18 | 2018-09-28 | 复旦大学 | A kind of extensive continuous preparation device and method of carbon nano tube composite fibre |
| CN114808196A (en) * | 2022-04-19 | 2022-07-29 | 江西省纳米技术研究院 | Carbon nanotube preparation device, injection assembly thereof and carbon nanotube preparation method |
| CN114887552A (en) * | 2022-05-20 | 2022-08-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Injection structure for preparing carbon nanotube material and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 原位生长碳纳米管及其在SiC_f/SiC复合材料中的应用;周新贵;余金山;孙科;赵爽;;中国有色金属学报(第10期) * |
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