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Definitions

• This application relates to the field of chemical vapor deposition (CVD) equipment for growing carbon nanomaterials (such as graphene or carbon nanotubes, etc.), in particular to a continuous input of metal foil from the atmosphere to the equipment under micro-positive or positive pressure conditions Belt, after the CVD process, the metal foil belt is continuously output, and the surface of the output foil belt has grown an open type continuous growth carbon nano material device and a preparation method of the desired product.
• CVD chemical vapor deposition
• Graphene and carbon nanotubes like diamond and graphite, are allotropes of carbon.
• Graphene can be visually understood as a two-dimensional crystal extracted from a single-crystal graphite crystal with a thickness of only one atom. Without strict conditions, nanomaterials composed of a few layers of graphene are also called graphene.
• Carbon nanotubes are divided into single-wall carbon nanotubes and multi-wall carbon nanotubes.
• the single-walled carbon nanotube can be understood as a seamless tube with a nanometer diameter scale formed by winding a single layer of graphene in a certain direction.
• Multi-walled carbon nanotubes can be understood as carbon nanotubes made of two or more single-walled carbon nanotubes of different diameters nested with each other like a Russian matryoshka, and the spacing between layers is close to that of graphite. Since carbon nanomaterials have extremely excellent chemical and physical properties, they have extremely broad application prospects in many fields such as mechanics, optics, electricity, and thermals.
• CVD is considered to be the most promising method for preparing high-quality carbon nanomaterials.
• CVD is Chemical Vapor
• the abbreviation of Deposition refers to the gas phase reaction at high temperature, for example, the thermal decomposition of metal halides, organic metals, hydrocarbons, etc., the reduction of hydrogen or the chemical reaction of its mixed gas at high temperature to precipitate
• Methods of inorganic materials such as metals, oxides, carbides, etc., are currently widely used in the purification of high-purity metals, powder synthesis, semiconductor thin films, etc., which is a characteristic technical field.
• the traditional CVD method is to place the substrate material in a closed cavity, heat the sample under vacuum, low pressure or normal pressure, and then introduce hydrogen gas and carbon-containing gas diluted or not diluted by the carrier gas.
• the desired carbon nanomaterial is grown on the bottom surface, and finally cooled and the sample is taken out. Due to the limited substrate size, long heating and cooling process, the production efficiency is extremely low, which also severely restricts the application of carbon nanomaterials.
• the roll-to-roll equipment must still be a closed system working at low pressure and normal pressure. After a roll is produced, it must be stopped and replaced. The production efficiency is still limited, and continuous open-end production of graphene under the atmosphere cannot be achieved. Not to mention integration with graphene end product production lines.
• the purpose of this application is to overcome the deficiencies described in the prior art, thereby providing an open continuous growth device and method for carbon nanomaterials, which can not only continuously grow high-quality large-area carbon nanomaterials on a large scale, Really continuous uninterrupted growth 24 hours a day, greatly improving production efficiency, and can also be integrated into the production line of application products, reduce the damage of carbon nanomaterials in the intermediate process, and improve the yield; this method will carbon nanomaterials from growth to processing Until the end product is prepared to form a continuous production line, it can be continuously produced without having to be in a sealed space, and the production efficiency is high.
• An open-type equipment for continuously growing carbon nanomaterials including a metal foil tape feeding system, a CVD system, and a collection system all in an open gas;
• the metal foil tape feeding system is used to transport the metal foil tape from the atmosphere To the CVD system;
• the CVD system is used to react to generate carbon nanomaterials, and the metal foil tape enters the collection system after attaching carbon nanomaterials in the CVD system;
• the CVD system includes a CVD furnace and a control system, the CVD furnace is in signal connection with the control system, and a slit coupler is sealed and coupled at the inlet and outlet of the CVD furnace, respectively.
• a slit coupler is sealed and coupled at the inlet and outlet of the CVD furnace, respectively.
• at least one slit connected to the CVD furnace at one end and open to the atmosphere at the other end is provided, and the slits on the two slit couplers correspond to each other in one-to-one correspondence.
• the slit enters and exits the CVD furnace;
• Each of the slit couplers is provided with at least one cooling circuit.
• the cooling circuit is composed of cooling water inlet and outlet pipes arranged around the slit, and cooling water is provided in the cooling water inlet and outlet pipes Slit coupling for cooling;
• Each of the slit couplers is also provided with a plurality of air inlet pipes, and the end of each air inlet pipe is sealed and leads to different parts of the CVD furnace, the carrier gas required by the CVD system and The reaction gas passes through the gas inlet pipe into various parts of the CVD furnace, and keeps the inside of the CVD furnace in a positive or slightly positive pressure state.
• the gas inlet pipe is configured to provide the CVD furnace with the required The only channel for carrier gas and reaction gas;
• a protective gas injection port communicating with the slit is also opened on the slit coupler, and the protective gas required by the CVD system is directly led to the slit coupler through the protective gas injection port In the slit; the exhaust gas generated inside the CVD system is discharged through the slits at both ends, and mixed with the shielding gas in the slit, and then ejected from the open end of the slit, the exhaust gas and the shielding gas The effect of erupting to the outside of the slits keeps all the slits dynamically sealed at all times to prevent air leakage or penetration into the CVD furnace through the slits.
• each of the slit couplers is provided with a plurality of slits, and each slit on the two slit couplers corresponds one-to-one.
• an online quality monitoring feedback device is also provided in the CVD system, the online quality monitoring feedback device is in signal connection with the control system, and the online quality monitoring feedback device is used for online monitoring of the passage of the metal foil tape
• the CVD system generates the status of the carbon nanomaterial, and feeds back a signal to the control system, and the control system controls the growth conditions of the carbon nanomaterial in the CVD furnace according to the signal.
• the CVD system is located in a fume hood, the exhaust pipe of the fume hood is connected to the exhaust gas treatment unit, and the exhaust volume of the fume hood is much greater than the total exhaust gas of the CVD system the amount.
• a safety monitoring control subsystem is provided in the control system, and the safety monitoring control subsystem controls the flow rates of the carrier gas, the reaction gas and the shielding gas.
• the safety monitoring control subsystem controls the flow rates of the carrier gas, the reaction gas and the shielding gas.
• the airflow sensor reports to the safety
• the monitoring and control system sends a signal, and after receiving the signal, the safety monitoring and control system forcibly cuts off the heating power of the CVD furnace and the carrier gas and the reaction gas in the intake pipe and issues an alarm;
• a gas concentration sensor is also provided in the CVD system, and the gas concentration sensor is in signal connection with the safety monitoring control subsystem for monitoring the concentration of combustible and explosive gas discharged from the slit of the CVD furnace;
• the safety monitoring control subsystem for monitoring the concentration of combustible and explosive gas discharged from the slit of the CVD furnace;
• a second gas concentration sensor may be additionally provided in the workshop where the fume hood is located, and the second gas concentration sensor is connected to the safety monitoring and control subsystem signal to monitor the combustible and explosive gas, oxygen and carbon monoxide in the workshop Concentration, when the second gas concentration sensor detects that the concentration of the combustible and explosive gas is close to the lower explosion limit, when the concentration of oxygen decreases to the warning concentration or the concentration of carbon monoxide exceeds the standard, a danger signal is sent to the safety monitoring control subsystem After receiving the danger signal, the safety monitoring control subsystem forcibly cuts off the flow of the combustible and explosive gas or even the carrier gas and the protective gas, and at the same time turns off the heating power of the CVD system and alarms.
• the metal foil tape feeding system includes a discharge roller, a drive roller and a guide roller; the discharge roller is used to support the metal foil tape; the drive roller is used to drive the The metal foil belt moves forward; the guide roller is used to adjust the movement trajectory of the metal foil belt; a collecting roller is provided in the collection system, and the collecting roller is used to attach the carbon nanomaterial The metal foil tape is collected by winding, and the unwinding roller, the driving roller, the guide roller and the receiving roller are respectively connected to the control system in signal;
• the adjacent unwinding rollers, drive rollers, guide rollers and take-up rollers are asynchronous rollers; and at least a stress sensor and / or on A torque sensor is provided on the feed roller, the drive roller, the guide roller and the take-up roller, and the stress sensor and / or the torque sensor are respectively connected to the control system signal, and the control system is based on The signals transmitted by the stress sensor and / or the torque sensor regulate the rotation speed and torque of the unwinding roller, the driving roller, the guide roller, and the receiving roller.
• the metal foil tape roll feeding system further includes a pretreatment system, which is provided on the running track of the metal foil tape and is used for cleaning, polishing and / or cleaning the metal foil tape Or coating a surface catalyst;
• the cleaning includes but not limited to surface degreasing, removing impurities and removing oxides;
• the polishing includes but not limited to one or more of mechanical polishing, chemical polishing or electrolytic polishing;
• the method of coating the surface catalyst includes, but is not limited to, one or more of physical coating, chemical coating, or electrochemical coating.
• the CVD furnace is a high temperature heating furnace with a closed inlet and outlet
• the high temperature heating furnace is an integrated furnace with independent control of multiple sections
• at least one temperature sensor is provided in each section of the CVD furnace
• the temperature sensor is signal-connected to the control system, and the control system adjusts the temperature of different sections of the CVD furnace and the heating or cooling rate during the heating or cooling process according to the signals transmitted by the temperature sensor.
• the collection system is further provided with a post-processing system, and the post-processing system is disposed between the second slit coupler and the take-up roller.
• a method for continuously growing graphene by using the equipment includes the following steps:
• Argon gas or nitrogen gas is introduced into the CVD furnace as a carrier gas and a protective gas, and hydrogen gas and at least one carbon-containing gas are introduced into the CVD system as the reaction gas of the CVD furnace, while controlling the CVD
• the growth temperature of the furnace is 500-1200 ° C; after the graphene is generated on the surface of the metal foil belt, it is sent to the collection system for output.
• a method for continuously growing carbon nanotubes using the equipment in an open manner includes the following steps:
• the catalyst-coated metal foil tape is continuously transported to the CVD system through the metal foil tape feeding system, and argon or nitrogen gas is introduced into the CVD system as the Carrier gas and protective gas of the CVD furnace, and hydrogen gas and at least one carbon-containing gas are introduced into the CVD system as the reaction gas of the CVD furnace, and the growth temperature of the CVD furnace is controlled to 400-1000 ° C; After the carbon nanotubes are generated on the surface of the metal foil belt, they are sent to the collection system for output, and
• the catalyst is a nano film or nano particles composed of one or more of iron, cobalt and nickel, or a nano film or nano particles of oxides and salts thereof; the catalyst can pass through the pretreatment system
• the metal foil tape is pre-treated, and the pretreatment includes the steps of directly coating the catalyst on the surface of the metal foil tape, or first coating the transition layer on the surface of the metal foil tape, and then coating the catalyst.
• the slit coupler of the present application can achieve reliable sealed coupling with the CVD furnace to form a whole, in which the slit coupler simultaneously plays a guiding role on the metal foil tape, a blocking effect on air and a cooling effect, CVD
• the carrier gas and reaction gas used in the furnace can only be conducted to different parts in the CVD furnace through the air inlet pipe on the slit coupler, and the protective gas is directly filled in each slit.
• the gas in the CVD furnace is full At positive pressure or slightly positive pressure, the resulting exhaust gas is mixed with the protective gas in the slit and finally passes through
• the slits of the slit coupler at both ends of the CVD furnace are erupted at high speed to the outside world.
• the CVD system is installed in the fume hood. After the exhaust gas is discharged into the fume hood, it is discharged through the exhaust device of the fume hood. It is precisely because of the role of exhaust gas and protective gas erupting outside the slit that the slit is always maintained Dynamic sealing to prevent air leakage or penetration into the CVD furnace through the slit, so the metal foil tape feeding system, CVD system and collection system can be placed in the atmosphere without being isolated from the air, so as to pass through the metal foil tape.
• the feeding system continuously feeds to the CVD system, the collection system can form the finished carbon nanomaterials out of the warehouse without interruption, and finally achieve real continuous growth 24 hours a day, greatly improving the production efficiency of the product. Reduce the damage to products caused by the intermediate process and further improve the yield;
• This application also provides an online quality monitoring feedback system and a safety monitoring subsystem that are respectively connected to the control system signal, which can maximize the protection of personal and property safety, and the quality inspection results of the online quality monitoring feedback system can be fed back to the control system , So as to automatically adjust the flow rate and ratio of various gases and the temperature in the CVD furnace to achieve the optimal control of the quality of carbon nanomaterials; on the one hand, the safety monitoring subsystem will be based on the signal sent by the gas concentration sensor installed in the CVD system.
• Combustible and explosive gases such as hydrogen and carbon-containing gases are diluted by the carrier gas and protective gas to a concentration below the explosion limit.
• the heating power of the CVD furnace is turned off and the combustible and explosive gas is cut off. Gas and even carrier gas and protective gas flow rate and alarm.
• FIG. 1 is a schematic structural diagram of an embodiment of the present application
• FIG. 2 is a partial schematic diagram of a CVD system according to an embodiment of this application.
• Example 3 is a Raman spectrum of graphene and copper foil tape prepared in Example 2 of the present application.
• Figure 5 is the graphene prepared in Example 2 transferred to 300nm Optical micrograph on SiO2 / Si;
• Figure 6 is the transfer of graphene prepared in Example 2 to 300nm Raman spectrum on SiO2 / Si;
• Example 7 is a Raman spectrum of continuous multilayer graphene grown on a nickel foil tape in Example 3.
• Example 8 is an electron micrograph of carbon nanotubes grown on both sides of an aluminum foil tape in Example 4.
• Discharging roller 2. Metal foil belt; 3. Guide roller or driving roller; 4. Fume hood; 5. Slot coupler; 6. CVD furnace; 7. Exhaust pipe of fume hood; 8. Airflow sensor; 9. Online quality monitoring feedback system; 10. Receiving roller; 11. Pretreatment system; 12. Slit; 13. Intake pipe; 14. Cooling water pipe; 15. Protective gas injection port; 16. Post-processing system.
• connection should be understood in a broad sense, for example, it can be fixed or detachable Connected, or connected integrally; either mechanically or electrically; directly connected, or indirectly connected through an intermediary, or internally connected between two components.
• installation should be understood in a broad sense, for example, it can be fixed or detachable Connected, or connected integrally; either mechanically or electrically; directly connected, or indirectly connected through an intermediary, or internally connected between two components.
• the present application provides an apparatus for continuously growing carbon nanomaterials, including a metal foil tape feeding system I, a CVD system II, and a collection system III all in an open gas; the metal foil tape feeding
• the system I is used to transfer the metal foil tape 2 from the atmosphere to the CVD system II;
• the CVD system II is used to react to generate carbon nanomaterials.
• the metal foil tape 2 is attached to the carbon nanomaterial in the CVD system II and enters the collection system III; wherein,
• the CVD system II includes a CVD furnace 6 and a control system (not shown in the figure).
• the CVD furnace 6 is in signal connection with the control system.
• a slit coupler 5 is sealed and coupled to the inlet and outlet of the CVD furnace 6
• the slit coupler 5 has at least one slit 12 connected to the CVD furnace 6 at one end and open to the atmosphere at the other end in the axial direction, and each slit 12 on the two slit couplers 5 corresponds to each other, and the metal foil tape 2 Only enter and exit the CVD furnace 6 through each pair of slits 12; each slit coupler 5 is provided with a cooling circuit, which is composed of a cooling water inlet and outlet pipe 14 provided around the slit 12 The cooling water inlet and outlet pipes 14 are provided with cooling water for the slit coupler 5 Cooling; each slit coupler 5 is also provided with a plurality of air inlet pipes 13, the end of each air inlet pipe 13 leads to different parts of the CVD furnace 6, the carrier gas required by the CVD system II and The reaction gas passes into various parts of the CVD furnace 6 through the gas inlet pipe 13 and keeps the CVD furnace 6 in a
• the gas inlet pipe 13 constitutes the carrier gas and the reaction gas required to supply the CVD furnace 6
• the only channel of the slit coupler 5 is also provided with a shield gas injection port 15 communicating with the slit 12, the shielding gas required by the CVD system II is directly led to the slit coupler 5 through the shield gas injection port 15 In the slit; the exhaust gas generated in the CVD system II is discharged through the slit 12 at both ends, and mixed with the shielding gas in the slit 12 and is ejected from the open end of the slit 12, the exhaust gas and the shielding gas are erupted outside the slit 12 The effect of this is to keep all slits 12 dynamically sealed at all times to prevent air leakage or penetration into the CVD furnace 6 through the slits 12.
• the slit coupler 5 of the present application can achieve reliable sealed coupling with the CVD furnace 6 to form a whole, in which the slit coupler 5 simultaneously guides the metal foil tape 2, blocks air, and cools,
• the carrier gas and reaction gas used in the CVD furnace 6 can only be conducted to different parts in the CVD furnace 6 through the gas inlet pipe 13 on the slit coupler 5, the protective gas is directly filled to the open end of each slit 12, when When the gas in the CVD furnace 6 is filled with positive pressure or micro-positive pressure, the generated exhaust gas is mixed with the shielding gas in the slit and finally erupts at high speed through the slit 12 of the slit coupler 5 at both ends of the CVD furnace 6
• the CVD system II can be installed in the fume hood 4, after the exhaust gas is discharged to the fume hood 4, and then through the exhaust device of the fume hood 4 to the exhaust gas treatment unit, in the exhaust gas treatment unit After being harmlessly treated and discharged into
• the metal foil tape feeding system 1 includes a discharge roller 1, a drive roller 3, and a guide roller 3; the discharge roller 1 is used to support the rolled metal foil tape 2, and the drive roller 3 Used to drive the metal foil belt 2 forward; the guide roller 3 is used to adjust the movement trajectory of the metal foil belt 2; of course, the metal foil belt feeding system I can also include a pretreatment system 11, which can be provided on the metal foil The running track of the belt 2 is used for cleaning, polishing and / or coating the surface catalyst on the metal foil belt 2.
• cleaning includes but is not limited to surface degreasing, impurity removal and oxide removal, etc .
• polishing includes but not limited to mechanical polishing, chemical polishing, electrolytic polishing and their comprehensive polishing
• catalyst coating includes but not limited to physical coating, Chemical coating, electrochemical coating and its comprehensive coating.
• the metal foil tape feeding system I integrated with the pretreatment system 11 is preferably adopted, so as to further improve the quality of the prepared carbon nanomaterial product or further reduce the cost. For example, it is reported in the literature that by cleaning and polishing, the quality of graphene prepared on the copper foil tape can be significantly improved.
• the metal foil tape 2 refers to a foil that can be wound with a thickness ranging from micrometers to millimeters, a width ranging from millimeters to meters, and a length ranging from meters to kilometers or even infinitely long Band welded together).
• Metals include but are not limited to aluminum, copper, iron, cobalt, nickel, and alloys or coatings thereof.
• the required metal foil tape can also be prepared by electroplating or chemically plating a copper film or other metal film on the low-cost metal foil tape 2, such as an iron foil tape.
• the optimal temperature for growing graphene on a copper foil tape is close to the melting point of copper, if the graphene is grown on a roll-to-roll basis, the growth temperature must be appropriately lowered, otherwise the copper foil tape may be easily pulled during the growth process. Break.
• a copper film is chemically coated or electrochemically coated on the surface of the iron foil tape, so as to achieve the growth of graphene at the optimal temperature.
• the price of iron foil tape is significantly better than that of copper foil tape, if the process control is reasonable, it may further reduce costs.
• Carbon nanomaterials include but are not limited to graphene and carbon nanotubes.
• Graphene includes but is not limited to discontinuous graphene, continuous graphene, single-layer graphene, multi-layer graphene and mixtures thereof.
• Carbon nanotubes include but are not limited to single-walled carbon nanotubes, multi-walled carbon nanotubes and mixtures thereof.
• the carbon nanotubes may be an array of carbon nanotubes perpendicular to the surface of the metal foil tape 2, or may be randomly oriented.
• the CVD system II can be either a vertical layout, a horizontal layout, or a 0-90o tilt layout.
• the system is installed in the fume hood 4 in whole or in part.
• the metal foil tape 2 can enter and exit the CVD furnace 6 either from top to bottom or from bottom to top.
• This embodiment is preferably a vertical layout.
• the guide roller 3 and the driving roller 3 can be separately provided between the CVD system II and the metal foil belt feeding system I, and also between the CVD system II and the collection system III The guide roller 3 and the driving roller 3 are separately provided. Due to the effects of thermal expansion and contraction, the metal foil tape 2 will have different sizes of deformation at different temperatures.
• all rollers include a discharge roller 1, a driving roller 3, a guide roller 3, and the one provided in the collection system III
• the receiving rollers 10 are all asynchronous rollers; at least one temperature sensor (not shown in the figure) is provided in the CVD system II, and at least one stress sensor (not shown in the figure) is provided on the metal foil strip 2 (Shown), or at least one torque sensor (not shown in the figure), temperature sensor and stress sensor on the discharge roller 1, drive roller 3, guide roller 3 and take-up roller 10 respectively And / or torque sensors are connected to the signal of the control system respectively, the control system will adjust the torque of each roller according to the real-time feedback signal of the stress sensor and or torque sensor, or control the different sections of the CVD furnace 6 according to the signal transmitted by the temperature sensor The temperature and the heating or cooling rate during the heating or cooling process prevent the metal foil strip 2 from wrinkling or sagging due to high-temperatur
• the CVD furnace 6 can be an integrated furnace with single-zone independent control or an integrated furnace with multi-zone independent control, or a combined furnace composed of multiple single-zone independent control CVD furnaces. If multiple furnaces are used, the furnace Use sealed pipeline connection with the furnace.
• the CVD furnace 6 in this embodiment is preferably a tube-type (quartz tube, corundum tube) high-temperature heating furnace, and more preferably a multi-zone independently controlled quartz tube-type high-temperature heating integrated furnace, so as to realize annealing of the metal foil strip 2 in different sections , Carbon nanomaterial growth, etc. The specific situation depends on the production requirements.
• the CVD furnace 6 may be composed of a metal foil belt preheating annealing furnace and a growth furnace or an integrated furnace that can be divided into at least two independent sections, and the atmosphere and temperature in each section Independent controllable, so as to achieve preheating annealing and growth in different sections.
• the present application adopts a scheme of providing a plurality of slits 12 on the slit coupler 5, wherein the slits 12 on the two oppositely arranged slit couplers 5
• the shielding gas is directly led into each slit 12 through the shielding gas injection port 15.
• a plurality of slits 12 can simultaneously enter and exit a plurality of metal foil tapes 2, thereby simultaneously growing carbon nanomaterials on the plurality of metal foil tapes 2 in the CVD furnace 6 and improving mass production.
• the cross-section of the slit 12 may be, but not limited to, rectangular, trapezoidal, or other more complex shapes, as long as it facilitates the guidance, cooling, and air barrier of the metal foil strip 2, for example, the cross-section is a toothed quadrilateral, and the longitudinal cross-section (with metal The movement direction of the foil belt is the same).
• the reaction gases used in the present application include but are not limited to hydrogen, carbon-containing gases such as methane, ethane, ethylene, acetylene, alcohol (vaporization), etc. and mixtures thereof.
• the type of shielding gas is similar to the carrier gas, and the same gas as the carrier gas can be selected, or different gases can be selected.
• the carrier gas and shielding gas include but are not limited to argon, helium, nitrogen, etc. and their mixed gases. From the standpoint of the preparation quality of the carbon nanomaterials alone, the carrier gas and the shielding gas are preferably argon; in consideration of cost, nitrogen gas from vaporization of liquid nitrogen is preferable.
• the carbon-containing gas depends on which carbon nanomaterial is prepared. For example, methane is preferred for preparing single-layer high-quality continuous graphene.
• the low temperature deposited multilayer graphene is preferably acetylene or ethylene.
• an online quality monitoring feedback device 9 is also provided in the CVD system II of the present application.
• the online quality monitoring feedback device 9 is in signal connection with the control system.
• the online quality monitoring feedback device 9 is used to online monitor the metal foil strip 2 in the CVD furnace 6
• the growth status of the carbon nanomaterials, and the quality inspection results are fed back to the control system.
• the control system adjusts the flow rate and ratio of various gases and the temperature of the CVD furnace 6 according to the signals to achieve optimal control of the quality of the carbon nanomaterials.
• this application installs the CVD system II in the fume hood 4, and connects the exhaust pipe of the fume hood 4 to the exhaust gas treatment unit (not shown in the figure), and is also installed in the control system Safety monitoring and control subsystem (not shown in the figure), by setting various airflow sensors, cooling water flow sensors, gas concentration sensors (not shown in the figure) in the CVD system and workshop, and setting in the fume hood 4 Airflow sensor 8, etc., and connect various sensors to the control system signal, the safety monitoring and control subsystem can form three safety protection barriers:
• the flow rate of combustible and explosive gas (hydrogen, methane, etc.), carrier gas and protective gas into the CVD furnace is controlled by a gas flow sensor (such as a mass flow meter), and the dilution effect of the carrier gas and protective gas, Reduce the concentration of combustible and explosive gas discharged from the slit of the CVD furnace below the explosion limit to form the first safety protection barrier; when the flow rate of the carrier gas is insufficient to dilute the combustible and explosive gas below the explosion limit, the CVD furnace cannot be started 6 or automatically turn off the heating power of the running CVD furnace 6, cut off the flow of combustible gas and alarm.
• a gas flow sensor such as a mass flow meter
• the combustible and explosive gas concentration sensor, cooling water sensor and fume hood 4 provided in the CVD system form a second safety guarantee.
• the combustible and explosive gas sensor provided in the CVD system is used to monitor the combustible and combustible gas discharged from the slit in the CVD furnace The concentration of the explosive gas.
• the airflow sensor 8 in the fume hood 4 is used to monitor the exhaust volume of the fume hood.
• the exhaust volume of the fume hood 4 is designed to be much larger than the total discharge of various gases in the CVD system.
• the gas is collected by the fume hood 4 and discharged to the exhaust gas treatment unit by the fume hood exhaust pipe 7.
• the concentration of combustible and explosive gas exceeds the standard, the cooling water flow rate is abnormally reduced, and the airflow sensor 8 detects that the airflow does not reach the safety threshold, the CVD furnace 6 cannot be started or the power supply of the CVD furnace 6 that is already in operation is forcibly turned off to cut off the combustible gas And alarm.
• a second gas concentration sensor (not shown in the figure) is installed in the workshop where the fume hood is located to form a third safety barrier.
• the second gas concentration sensor is used to monitor the concentration of combustible and explosive gases oxygen and carbon monoxide in the workshop.
• the safety monitoring control subsystem will also turn off the heating power of the CVD furnace 6, cut off all carriers, and protect the gas And alarm the flow rate of the reaction gas. Specifically, if there is a decrease in oxygen content or an increase in carbon monoxide, it means that the previous safety protection measures have failed for some reason, resulting in lack of oxygen.
• the fume hood 4 has not exhausted all the gas, but has been discharged to the workshop. Therefore, it is necessary to cut off all gases to prevent the oxygen concentration from further decreasing.
• the problems related to explosion generally only the flow of combustible and explosive gas is cut off, and the residual combustible and explosive gas is further diluted by continuing to discharge protective gas and carrier gas.
• the collection system III is used to directly wind the metal foil tape 2 grown with carbon nanomaterials onto the take-up roller 10 without any post-processing, or a post-processing system 16 can also be provided in the collection system III through integration
• the post-processing system 16 performs post-processing and even directly produces carbon nanomaterial end products, thereby forming a complete continuous production line including carbon nanomaterial growth, addition, and end product preparation.
• the post-processing includes separating and processing the grown carbon nanomaterial from the metal foil tape 2 into an end product, or further strengthening the adhesion of the carbon nanomaterial to the surface of the metal foil tape 2.
• the graphene is separated from the metal foil tape 2 in the post-processing process, and electronic devices based on graphene, such as touch screens and sensors, are produced.
• the carbon nanotubes it may be necessary to perform a gluing process through post-processing to fill the gaps between the carbon nanotubes and significantly strengthen the adhesion between the carbon nanotubes and the metal foil tape 2.
• the metal foil tape feeding system is shown in FIG. 1 and does not include the pretreatment system 11.
• the CVD system II is not equipped with an online quality monitoring system 9.
• the CVD furnace 6 is a vertical single-zone quartz tube type single heating furnace with a diameter of 25 mm and only one slit 12 per slit coupler.
• the collection system III does not include the post-processing system 16.
• the carrier gas and shielding gas are both argon, and the reaction gases are hydrogen and methane.
• the concentration of hydrogen and methane is diluted by argon below the explosion limit.
• methane can also be replaced by ethane, acetylene, ethylene, (vaporized) alcohol and many more.
• gases are high-purity gases, which are transported by pipeline to the equipment room through centralized gas supply.
• the flow of gas is controlled by a mass flow meter,
• the temperature of the CVD furnace 6 is monitored by thermocouples and regulated by a power supply with PID function.
• Hydrogen and methane gas are mixed with the carrier gas at a rate of 80-150 sccm and 0.5-5 sccm through a mass flowmeter, and then passed into the quartz tube from the slit coupler.
• the power supply of the copper foil belt can be stopped (including the unwinding roller 1, the receiving roller 10 and all driving rollers 3, the guide roller 3), manually replace a new roll of raw copper foil tape and weld it with the copper foil tape that is about to be used up.
• Restarting the power supply of the copper foil tape can smoothly import and export the new copper foil tape into and out of the CVD system II.
• the power supply of the copper foil tape can be stopped again, the copper foil tape is cut at the welding place, the copper foil tape roll where the graphene has been grown is taken out, and the new copper foil tape is wound onto the newly replaced receiving roller 10, and start the copper foil belt to deliver power again. This process can be automated in the future.
• Embodiment 2 uses the equipment described in Embodiment 1 to grow a multilayer continuous graphene film on a nickel foil tape.
• the difference from Embodiment 2 is that:
• Metal foil tape 2 adopts nickel foil tape (11mm wide, 25 ⁇ m thick, purity 99.9%).
• the conveying speed of nickel foil belt is 300-600mm / min.
• the set temperature range for growth is 500-900 ° C, preferably 750-900 ° C.
• the higher the temperature the faster the growth rate and the faster the conveying speed of the nickel foil tape.
• the conveying speed is the same, the slower the conveying speed of the nickel foil tape, the more layers of graphene; or the higher the temperature, the more the number of graphene layers when the conveying speed of the nickel foil tape is constant.
• Embodiment 2 uses the equipment described in Embodiment 1 plus a metal foil tape pretreatment system to grow an array of carbon nanotubes on a metal aluminum foil tape.
• the difference from Embodiment 2 is that:
• a layer of catalyst is applied to the surface of the metal aluminum foil 2 by adding a pretreatment system 11.
• the catalyst may be a nano film or nano particles composed of one or more of iron, cobalt and nickel, or a nano film or nano particles of oxides and salts thereof.
• ferrous chloride is used as
• the specific implementation is to add a ferrous chloride solution pool between the discharge roller 1 and the CVD system II. A certain concentration of ferrous chloride is pre-dispensed in the pool. Its concentration is monitored by the liquid concentration sensor. When the concentration decreases The solvent is added automatically to keep the concentration constant.
• the metal foil tape 2 passes through the discharge roller 1 and passes through the solution pool (immersed in the solution pool); after exiting from the solution pool, a ferrous chloride film is formed on the surface of the metal aluminum foil tape 2 by drying during the traveling process;
• the size of the iron concentration depends on the performance of the desired carbon nanotube growth, the speed at which the metal aluminum foil tape 2 travels, and the total length of the immersion in the solution pool. Since an aluminum oxide passivation layer is inherent on the surface of the metal aluminum foil tape 2 and functions as a transition layer, it is not necessary to apply a transition layer between the metal foil tape 2 and the catalyst in this embodiment. Of course, for other metal foil tapes, you can also apply a transition layer on the surface of the metal foil tape 2 before applying the catalyst. The transition layer helps prevent the catalyst from reacting with the metal foil tape during the carbon nanotube growth process and promotes the catalyst. Particle formation, improve the stability of the catalyst particles, thereby promoting the growth of carbon nanotubes;
• the carrier gas and the protective gas introduced into the CVD system II are both argon or nitrogen, and the reaction gas of the CVD furnace is hydrogen and at least one carbon-containing gas , such as methane, ethane, acetylene, ethylene, (vaporized) alcohol, etc., in this embodiment, acetylene is taken as an example;
• the growth temperature of the CVD furnace 6 is 580-600 °C, in which ferrous chloride is reduced by a high-temperature reducing gas And forming iron nanoparticles, and further reacting with acetylene to form carbon nanotubes on the iron nanoparticles, thereby generating the carbon nanotube array in the metal foil tape 2 in the CVD system II (as shown in FIG. 8), and then Collected or processed directly through the collection system III for output as end products.

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