An apparatus for preparing a structural coupling carbon-carbon composite

Abstract

The application discloses a preparation device for structure-coupled carbon-carbon composite material and relates to the technical field of composite material preparation devices.The preparation device comprises a first atomization spraying system, a first liquid inlet unit, a second atomization deposition system and a second liquid inlet unit.The first liquid inlet unit provides a catalyst solution to the first atomization spraying system.The first atomization spraying system atomizes the catalyst solution and can spray the catalyst solution in multiple directions on a preform in a spraying cavity, and can also dry the preform after the catalyst solution is sprayed on the preform.The second liquid inlet unit provides a carbon source precursor to the second atomization deposition system.The second atomization deposition system atomizes the carbon source precursor and sprays the atomized carbon source precursor into a deposition cavity, and can heat the deposition cavity to make the atomized carbon source precursor deposit on the preform.The preparation device for structure-coupled carbon-carbon composite material can improve the efficiency and qualified rate of the preparation of the integrated structure of the carbon-carbon composite material.

Description

Technical Field

[0001] This invention relates to the field of composite material preparation apparatus, and in particular to an apparatus for preparing structurally coupled carbon-carbon composite materials. Background Technology

[0002] Carbon-carbon composites are a new type of high-performance material composed of carbon fiber reinforcement and a carbon matrix. Their unique covalent bond structure endows them with outstanding comprehensive properties: they can withstand temperatures above 2000℃ for extended periods in an inert atmosphere, and even reach temperatures above 3000℃ for short-term use; their flexural strength at room temperature can reach 200-500 MPa, with a high high-temperature strength retention rate; they also possess excellent thermal shock resistance, ablation resistance, and low thermal conductivity. These properties make them indispensable core materials in extreme environment fields such as aerospace and nuclear energy. In particular, integrated carbon-carbon composites, by avoiding interface defects caused by traditional splicing processes, offer greater advantages in load-bearing capacity and reliability, making them the preferred material form for high-end equipment.

[0003] Chemical vapor deposition (CVD) is a core process for preparing integrated carbon-carbon composite structures. Its basic principle is as follows: carbon fiber preforms are placed in a high-temperature reaction chamber, and carbon source precursors (such as methane, propylene, acetylene, ethanol, methanol, etc.) are introduced. The precursors undergo a cracking reaction at high temperatures (usually 800-1600℃) to generate active carbon groups. These carbon groups diffuse to the carbon fiber surface and deposit to form a carbon matrix, which finally fills the pores of the preform and forms a dense composite structure.

[0004] However, traditional CVD processes face the following technical bottlenecks when fabricating integrated structures (especially complex morphological structures):

[0005] 1. Poor catalyst loading uniformity affects deposition efficiency and uniformity; catalysts (such as transition metals Fe, Ni, Co and their compounds) can significantly reduce the activation energy of carbon source cracking and promote rapid growth of carbon matrix during CVD, but their loading effect directly determines the deposition quality.

[0006] 2. Low carbon source deposition efficiency; liquid carbon source precursors are limited by diffusion rate, and for large-size or high-porosity preforms, the internal pore filling cycle can take several hours, resulting in extremely low production efficiency.

[0007] 3. The process parameters of the two stages of "catalyst loading-carbon source deposition" are incompatible, the operation is complicated and prone to errors. Traditional processes often use a single liquid inlet system and atomization unit, which is difficult to meet the above-mentioned process differences. This results in frequent equipment adjustments during process switching, which is complicated and prone to errors. Summary of the Invention

[0008] The purpose of this invention is to provide a device for preparing structurally coupled carbon-carbon composite materials, so as to solve the problems existing in the prior art and improve the efficiency and yield of preparing integrated carbon-carbon composite materials.

[0009] To achieve the above objectives, the present invention provides the following solution:

[0010] This invention provides an apparatus for preparing structurally coupled carbon-carbon composite materials, comprising a first atomizing spraying system, a first liquid inlet unit, a second atomizing deposition system, and a second liquid inlet unit. The first liquid inlet unit is connected to the first atomizing spraying system and is used to provide a catalyst solution to the first atomizing spraying system. The first atomizing spraying system has a spraying chamber for containing a preform, and is used to atomize the catalyst solution and spray the preform in multiple directions within the spraying chamber. The first atomizing spraying system can also dry the preform after spraying the catalyst solution. The second liquid inlet unit is connected to the second atomizing deposition system and is used to provide a carbon source precursor to the second atomizing deposition system. The second atomizing deposition system has a deposition chamber for containing the preform after catalyst loading, and is used to atomize and spray the carbon source precursor into the deposition chamber and can be heated within the deposition chamber to deposit the atomized carbon source precursor onto the preform.

[0011] Preferably, the first atomizing spraying system includes a drying module and at least one set of first nozzle assemblies; the first nozzle assembly is disposed on the upper side of the spraying chamber and positioned above the preform, the first nozzle assembly is connected to the first liquid inlet unit and is capable of spraying the preform in multiple directions; the drying module is disposed in the spraying chamber and is used to perform gradient drying on the preform.

[0012] Preferably, the first nozzle assembly includes a rotary drive and a plurality of first atomizing nozzles, the plurality of first atomizing nozzles being circumferentially distributed above the preform, the rotary drive being disposed on the inner wall of the spraying chamber and connected to each of the first atomizing nozzles, the rotary drive being able to drive the plurality of first atomizing nozzles to deflect, so as to spray the preform in multiple directions.

[0013] Preferably, the second atomized deposition system includes a drying chamber and a second atomizing nozzle; the drying chamber has the deposition chamber and the temperature inside the deposition chamber can be gradually adjusted; the second atomizing nozzle is disposed in the drying chamber and its outlet is located inside the deposition chamber; the second atomizing nozzle is connected to the second liquid inlet unit and is used to atomize and spray the carbon source precursor into the deposition chamber, and the distance between the second atomizing nozzle and the preform can be adjusted; an inert gas can also be introduced into the deposition chamber.

[0014] Preferably, both the first liquid inlet unit and the second liquid inlet unit include a storage tank, a filter assembly, and a delivery pump; the storage tank is used to store the corresponding catalyst solution or carbon source precursor, and the storage tank is connected to the corresponding first atomizing spray system or second atomizing deposition system through a pipeline, and the delivery pump and the filter assembly are provided on the pipeline, the delivery pump is used to provide delivery power, and the filter assembly is used to filter impurities in the catalyst solution or carbon source precursor; and each pipeline is provided with a flow monitoring device.

[0015] Preferably, the first liquid inlet unit further includes a concentration monitoring device disposed on the storage tank, the concentration monitoring device being used to monitor the catalyst concentration information of the catalyst solution; the second liquid inlet unit further includes a liquid level monitoring device disposed on the storage tank, the liquid level monitoring device being used to monitor the liquid level information.

[0016] Preferably, the system further includes a conveying assembly that extends through the spraying chamber and the deposition chamber, the conveying assembly being used to carry and convey the preform.

[0017] Preferably, both the first atomizing spraying system and the second atomizing deposition system include a temperature monitoring component, which is disposed in the corresponding spraying chamber or deposition chamber and is used to monitor the temperature information of different parts of the corresponding preform or the temperature information in the deposition chamber.

[0018] Preferably, both the first atomizing spraying system and the second atomizing deposition system include an atomizing particle size monitoring component. The atomizing particle size monitoring component is disposed in the corresponding spraying chamber or the deposition chamber and is used to monitor the atomizing particle size information in the corresponding spraying chamber or the deposition chamber.

[0019] Preferably, it also includes a central control system, which is communicatively connected to the first atomizing spraying system, the first liquid inlet unit, the second atomizing deposition system, and the second liquid inlet unit, and is capable of information transmission and action control.

[0020] The present invention achieves the following technical effects compared to the prior art:

[0021] Catalyst loading uniformity is significantly improved: The first atomizing spraying system sprays the preform with catalyst from multiple directions, improving distribution uniformity and reducing catalyst loading deviation on the complex preform surface. Simultaneously, the instant drying function effectively prevents catalyst agglomeration, improving catalyst particle dispersion and laying the foundation for subsequent uniform deposition.

[0022] The carbon source deposition efficiency is significantly improved: the second atomization deposition system can realize the simultaneous deposition of carbon source and high-temperature heating, eliminating the transmission loss of carbon source particles and greatly improving the carbon source utilization rate; combined with the instantaneous pyrolysis of carbon source particles in the high-temperature field, the deposition rate is improved and the preparation cycle is shortened.

[0023] Significantly improved process compatibility and automation level: The design of the dual liquid inlet system and independent atomization system is adapted to the differentiated parameter requirements of the two-stage "catalyst loading-carbon source deposition", greatly shortening the process changeover time, facilitating automated control, greatly improving the product qualification rate, and significantly reducing labor costs and scrap rate. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 This is a schematic diagram of the apparatus for preparing structurally coupled carbon-carbon composite materials provided in Embodiment 1 of the present invention;

[0026] Figure 2 This is a schematic diagram of the internal structure of the first atomizing spraying system provided in Embodiment 1 of the present invention;

[0027] Figure 3 This is a schematic diagram of the internal structure of the second atomized spray deposition provided in Embodiment 1 of the present invention;

[0028] Figure 4 The images shown are SEM images of the original sample and the composite material prepared in Example 2.

[0029] Figure 5 The image shows the Raman spectroscopy results of the composite material prepared in Example 3.

[0030] Figure 6 The image shows the XRD (X-ray diffraction) test pattern of the composite material prepared in Example 4.

[0031] Figure 7 This is a schematic diagram showing the change in electrical conductivity of the composite material prepared in Example 5.

[0032] In the figure: 1-First atomizing spraying system; 110-Spraying chamber; 120-Drying module; 130-First nozzle assembly; 131-Rotary drive component; 132-First atomizing nozzle; 2-First liquid inlet unit; 3-Second atomizing deposition system; 310-Deposition chamber; 320-Drying box; 330-Second atomizing nozzle; 4-Second liquid inlet unit; 5-Storage tank; 6-Filter assembly; 7-Transfer pump; 8-Concentration monitoring component; 9-Liquid level monitoring component; 10-Transfer assembly; 11-Temperature monitoring component; 12-Atomized particle size monitoring component; 13-Central control system; 14-Precast body. Detailed Implementation

[0033] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] The purpose of this invention is to provide a device for preparing structurally coupled carbon-carbon composite materials, so as to solve the problems existing in the prior art and improve the efficiency and yield of preparing integrated carbon-carbon composite materials.

[0035] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0036] Example 1

[0037] This embodiment provides an apparatus for preparing structurally coupled carbon-carbon composite materials. Please refer to [link to apparatus]. Figures 1-3 The system includes a first atomizing spraying system 1, a first liquid inlet unit 2, a second atomizing deposition system 3, and a second liquid inlet unit 4. The first liquid inlet unit 2 is connected to the first atomizing spraying system 1 and is used to provide a catalyst solution to the first atomizing spraying system 1. The first atomizing spraying system 1 has a spraying chamber 110 for accommodating a preform 14. The first atomizing spraying system 1 is used to atomize the catalyst solution and can spray the preform 14 in multiple directions within the spraying chamber 110. The first atomizing spraying system 1 can also dry the preform 14 after spraying the catalyst solution. The second liquid inlet unit 4 is connected to the second atomizing deposition system 3 and is used to provide a carbon source precursor to the second atomizing deposition system 3. The second atomizing deposition system 3 has a deposition chamber 310 for accommodating the preform 14 after catalyst loading. The second atomizing deposition system 3 is used to atomize and spray the carbon source precursor into the deposition chamber 310 and can be heated within the deposition chamber 310 to deposit the atomized carbon source precursor onto the preform 14.

[0038] The first atomizing spraying system 1 sprays the preform 14 with catalyst from multiple directions, significantly improving the uniformity of catalyst loading and reducing the loading deviation of catalyst on the complex surface of the preform 14. Simultaneously, the drying function effectively avoids catalyst agglomeration, improving catalyst particle dispersion. This achieves a synergistic effect of "multi-directional spraying + immediate drying," laying the foundation for subsequent uniform deposition. The second atomizing deposition system 3 enables simultaneous carbon source deposition and high-temperature heating, achieving integrated synergy of "atomization-high-temperature reaction," eliminating carbon source particle transport losses, significantly improving carbon source utilization, and substantially increasing carbon source deposition efficiency. Combined with the immediate pyrolysis of carbon source particles in the high-temperature field, the deposition rate is increased, and the preparation cycle is shortened. The design of the dual liquid inlet system and the independent atomizing system adapts to the differentiated parameter requirements of the two stages of "catalyst loading-carbon source deposition," greatly shortening process changeover time, facilitating automated control, significantly improving product qualification rate, and substantially reducing labor costs and scrap rate.

[0039] In the optional embodiments of this example, more preferably, the first atomizing spraying system 1 includes a drying module 120 and at least one set of first nozzle assemblies 130; the first nozzle assembly 130 is disposed on the upper side inside the spraying chamber 110 and placed above the preform 14, the first nozzle assembly 130 is connected to the first liquid inlet unit 2 and can spray the preform 14 in multiple directions; the drying module 120 is disposed inside the spraying chamber 110 and is used to perform gradient drying on the preform 14.

[0040] In this process, while the first nozzle assembly 130 sprays the catalyst in multiple directions, the drying module 120 performs gradient drying on the preform 14, which effectively reduces the loading deviation of the catalyst on the surface of the complex preform 14. At the same time, the instant gradient drying function effectively avoids catalyst agglomeration and improves the dispersion of catalyst particles, laying the foundation for subsequent uniform deposition.

[0041] In the optional embodiment, more preferably, the first nozzle assembly 130 includes a rotary drive 131 and a plurality of first atomizing nozzles 132. The plurality of first atomizing nozzles 132 are circumferentially distributed above the preform 14. The rotary drive 131 is disposed on the inner wall of the spraying chamber 110 and connected to each of the first atomizing nozzles 132. The rotary drive 131 can drive the plurality of first atomizing nozzles 132 to deflect so as to spray the preform 14 in multiple directions.

[0042] Multiple first atomizing nozzles 132 can be fixedly mounted on a connecting plate and evenly distributed circumferentially. The rotary drive component 131 can be configured as multiple swing motors. Each first atomizing nozzle 132 is connected to the connecting plate via a swing motor. The swing motor drives the corresponding first atomizing nozzle 132 to deflect vertically within its cross-section. The deflection angle can be set to a range of -60° to +60° or other ranges to adjust the spraying range as needed. Furthermore, the connecting plate can also be connected to the top of the spraying chamber 110 via a rotary motor as needed. The rotary motor drives the connecting plate and each first atomizing nozzle 132 to rotate as a whole around a vertical axis to further adjust the spraying range as needed. Specifically, the number of first atomizing nozzles 132 is determined according to actual needs, such as three or four. In addition, it should be noted that the specific drive mechanism of the first atomizing nozzle 132 can also adopt other methods, such as adjusting the position and angle using a conventional micro-robotic arm, as long as the required adjustment function can be achieved.

[0043] Specifically, the first atomizing nozzle 132 can be a conventional high-pressure pneumatic atomizing nozzle, such as a two-fluid atomizing nozzle, with a working pressure range of 0.2-0.8MPa. The atomized particle size can be continuously adjusted from 5-50μm, and the distribution uniformity is ≤15%, ensuring that the catalyst solution can penetrate into the micropores of the preform 14 without being too fine and thus avoiding scattering and loss. The spray distance of the first atomizing nozzle 132 can be adjusted by an internal fine-tuning mechanism, with an adjustment range of 50-300mm, to adapt to preforms 14 of different sizes.

[0044] More preferably, the drying module 120 can use multiple sets of surrounding infrared heating tubes, which can be fixed in different positions within the spraying chamber 110 by means of bolts, etc., so as to avoid interference with the working position of the nozzle, so as to achieve the gradient drying requirements of different parts of the preform 14; wherein, the specific setting and number of infrared heating tubes can be determined according to the actual situation, the power of the infrared heating tubes can be adjusted independently, the heating temperature range is 30-200℃, and the temperature control accuracy is ±3℃.

[0045] More preferably, a hot air flow field regulating unit can be provided inside the spraying chamber 110 to form a hot air flow inside the spraying chamber 110, thereby accelerating the solvent evaporation of the catalyst solution inside the spraying chamber 110 and preventing vapor from condensing in the cold zone; specifically, the hot air flow field regulating unit includes a micro fan fixedly installed inside the spraying chamber 110 to provide airflow.

[0046] In an optional embodiment, more preferably, the second atomizing deposition system 3 includes a drying chamber 320 and a second atomizing nozzle 330; the drying chamber 320 has a deposition chamber 310 and can be gradient-adjusted in temperature within the deposition chamber 310; the second atomizing nozzle 330 is disposed in the drying chamber 320 and its outlet is located within the deposition chamber 310; the second atomizing nozzle 330 is connected to the second liquid inlet unit 4 and is used to atomize and spray the carbon source precursor into the deposition chamber 310; the second atomizing nozzle 330 can adjust the distance between itself and the preform 14; an inert gas can also be introduced into the deposition chamber 310.

[0047] The drying chamber 320 is a conventional CVD high-temperature oven. The second atomizing nozzle 330 is directly integrated and embedded in the drying chamber 320. The atomizing outlet is connected to the deposition chamber 310, so that the atomized carbon source particles do not need to be transported over long distances and can directly enter the high-temperature deposition chamber 310, which greatly reduces particle agglomeration and loss. The CVD high-temperature oven has an adjustable temperature range of 800-1600℃ and can be adapted to the needs of different deposition stages through temperature gradient adjustment. The deposition chamber 310 is not sealed and can be vented with different inert gases for synergistic effect.

[0048] Specifically, the second atomizing nozzle 330 is set as a conventional ultrasonic atomizing nozzle, such as model MSK-SP-01A, with an operating frequency of 40kHz. The atomized particle size can be precisely controlled from 1 to 40μm through frequency adjustment, and the atomization volume can be adjusted from 10 to 100mL / h, ensuring that the carbon source particles can not only diffuse uniformly into the pores of the preform 14, but also have sufficient activity for deposition. Furthermore, an inert gas guide ring is also provided at the nozzle outlet, through which nitrogen or argon gas is introduced to form a protective sheath layer, avoiding thermal damage to the nozzle at high temperatures and extending its service life. The second atomizing nozzle 330 can be connected to the inside of the deposition chamber 310 via a telescopic motor to adjust the distance between the second atomizing nozzle 330 and the preform 14.

[0049] In the optional scheme of this embodiment, more preferably, both the first atomizing spraying system 1 and the second atomizing deposition system 3 include a temperature monitoring component 11. The temperature monitoring component 11 is disposed in the corresponding spraying chamber 110 or deposition chamber 310 and is used to monitor the temperature information of different parts of the corresponding preform 14 or the temperature information in the deposition chamber 310.

[0050] The temperature monitoring component 11 in the spraying chamber 110 includes an array of multiple temperature sensors (≥6 temperature measurement points) to monitor the surface temperature of the preform 14 in real time, ensuring uniform temperature during the drying process and preventing catalyst decomposition due to local overheating. The temperature sensors can be non-contact sensors such as infrared temperature sensors, and the specific location and number can be determined according to actual needs, while avoiding interference with the working position of the spray head. The temperature monitoring component 11 in the deposition chamber 310 can be set as a conventional temperature sensor to monitor the internal temperature information of the deposition chamber 310.

[0051] In the optional scheme of this embodiment, more preferably, both the first atomizing spraying system 1 and the second atomizing deposition system 3 include an atomizing particle size monitoring component 12. The atomizing particle size monitoring component 12 is disposed in the corresponding spraying chamber 110 or deposition chamber 310 and is used to monitor the atomizing particle size information in the corresponding spraying chamber 110 or deposition chamber 310.

[0052] The atomized particle size monitoring component 12 uses a conventional particle size monitoring sensor, which is fixedly connected to the inside of the cavity by conventional means such as bolts to monitor and obtain particle size information in real time, so as to facilitate parameter adjustment.

[0053] In the optional embodiments of this example, more preferably, both the first liquid inlet unit 2 and the second liquid inlet unit 4 include a storage tank 5, a filter assembly 6, and a delivery pump 7; the storage tank 5 is used to store the corresponding catalyst solution or carbon source precursor, and the storage tank 5 is connected to the corresponding first atomizing spray system 1 or second atomizing deposition system 3 through a pipeline, and the pipeline is equipped with a delivery pump 7 and a filter assembly 6, the delivery pump 7 is used to provide delivery power, and the filter assembly 6 is used to filter impurities in the catalyst solution or carbon source precursor; and the pipeline is equipped with a flow monitoring device.

[0054] Furthermore, the first liquid inlet unit 2 also includes a concentration monitoring device 8 installed on the storage tank 5, which is used to monitor the catalyst concentration information of the catalyst solution; the second liquid inlet unit 4 also includes a liquid level monitoring device 9 installed on the storage tank 5, which is used to monitor the liquid level information.

[0055] Specifically, regarding the first liquid inlet unit 2, the storage tank 5 has a volume of 1L and can be equipped with a stirring device (stirring speed 0-300r / min) and a constant temperature control module such as water bath heating to maintain the uniformity and stability of the catalyst solution; the filter assembly 6 sequentially includes a pre-filtration layer, a fine filtration layer and an ultrafiltration layer, and is installed on the pipeline to ensure that the particulate impurity content in the catalyst solution is ≤0.1mg / L; the transfer pump 7 is set as a high-precision peristaltic pump with a flow rate adjustment range of 0.1-5mL / min; the pipeline can also be equipped with a flow monitoring device such as a flow sensor for flow monitoring; the storage tank 5 is also equipped with a solution concentration monitoring device 8 such as an online concentration monitoring sensor to provide real-time feedback on the catalyst concentration.

[0056] Specifically, the second liquid inlet unit 4 has a liquid tank volume of 1L and can be equipped with a liquid level monitoring device 9, such as a liquid level sensor, to trigger an alarm and activate an automatic or manual liquid replenishment device when the liquid level is too low; the transfer pump 7 is set as a high-precision peristaltic pump with a flow rate adjustment range of 0.5-20mL / min; the filter assembly 6 uses a composite filter element of activated carbon and molecular sieve, which is installed on the pipeline and has a purification efficiency of ≥99.5% for carbon source precursors, ensuring atomization stability; a flow monitoring device, such as a flow sensor, can also be installed on the pipeline for flow monitoring.

[0057] In the optional scheme of this embodiment, more preferably, the preparation device for structurally coupled carbon-carbon composite material provided in this embodiment further includes a conveying component 10, which penetrates the spraying chamber 110 and the deposition chamber 310, and is used to carry the conveying preform 14.

[0058] The conveying component 10 can be configured as a conveyor belt assembly that passes through the spraying chamber 110 and the sedimentation chamber 310, which is conducive to the automated transfer of the preform 14. It should be noted that when the conveyor belt assembly passes through the spraying chamber 110 and the sedimentation chamber 310, it should avoid interfering with the internal structure of the chamber.

[0059] In the optional scheme of this embodiment, more preferably, the preparation device for structurally coupled carbon-carbon composite materials provided in this embodiment further includes a central control system 13. The central control system 13 is communicatively connected to the first atomizing spraying system 1, the first liquid inlet unit 2, the second atomizing deposition system 3, and the second liquid inlet unit 4, and is capable of information transmission and action control.

[0060] The central control system 13 can be configured as a display screen, and is communicatively connected to each sensor and actuator in the structurally coupled carbon-carbon composite material preparation device provided in this embodiment, such as the first atomizing spraying system 1, the first liquid inlet unit 2, the second atomizing deposition system 3, and the second liquid inlet unit 4, so as to enable real-time data transmission and control. It can display real-time parameter curves, historical data queries, and fault alarm information (alarm response time ≤ 0.5s). The central control system 13 can also support 4G / Ethernet communication according to the remote communication module, so as to realize remote monitoring and parameter adjustment.

[0061] Thus, the apparatus for preparing structurally coupled carbon-carbon composite materials provided in this embodiment has the following technical effects:

[0062] 1. Catalyst loading uniformity is significantly improved.

[0063] By employing a multi-directional adjustable first atomizing nozzle 132 combined with multi-stage filtration and precise flow control, the catalyst loading deviation on the surface of the complex preform 14 can be controlled within 5%. Simultaneously, the instant gradient drying function effectively prevents catalyst agglomeration, increasing catalyst particle dispersion by over 60%, laying the foundation for subsequent uniform deposition.

[0064] 2. Carbon source deposition efficiency is significantly improved.

[0065] The integrated design of the ultrasonic atomizing nozzle and the CVD high-temperature oven eliminates the transmission loss of carbon source particles and greatly improves the utilization rate of carbon source; combined with the instantaneous pyrolysis in the high-temperature field, the deposition rate is increased by 1-2 times and the preparation cycle is shortened.

[0066] 3. Significantly improved adaptability to complex structures and consistency of material properties.

[0067] The adjustable angle and position of the atomizing nozzles minimize the deposition deviation in different areas of irregularly shaped and large-sized integrated structures; zoned temperature control ensures uniform material density, meeting the stringent requirements of high-end equipment for material consistency.

[0068] 4. Significantly improved process compatibility and automation level

[0069] The dual liquid inlet system and independent atomization unit design perfectly adapt to the differentiated parameter requirements of the two-stage "catalyst loading-carbon source deposition" process, reducing the process changeover time from the traditional 20-30 hours to less than 30 minutes; the intelligent control system enables real-time monitoring and automatic adjustment of parameters throughout the process, greatly improving the product qualification rate and significantly reducing labor costs and scrap rate.

[0070] 5. The equipment has strong versatility and expandability.

[0071] By adjusting parameters (such as atomization particle size, temperature, and flow rate), different types of catalysts (metal-based and non-metal-based) and carbon source precursors (gaseous, liquid, and mixed states) can be adapted, making it suitable for various preform types such as woven bodies, wound bodies, needled bodies, and carbon felts, providing a flexible platform for the diversified preparation of carbon-carbon composite materials.

[0072] Example 1

[0073] This embodiment provides a preparation method based on the preparation apparatus for structurally coupled carbon-carbon composite materials in Embodiment 1, for preparing carbon-carbon composite materials using carbon felt as raw material:

[0074] First atomizing spraying system 1: 3 first atomizing nozzles 132 (deflection angle -45° +45°); atomized particle size 20μm; drying module 120 adopts gradient temperature 80℃ (15min) → 120℃ (30min).

[0075] First liquid inlet unit 2: The catalyst solution is 0.5wt% ferrocene ethanol solution; the storage tank 5 has a volume of 1L, and the transfer pump 7 has a flow rate of 1mL / min.

[0076] Second atomization deposition system 3: Second atomizing nozzle 330, frequency 5kHz, atomized particle size 30μm; CVD high temperature oven set at 1100℃ (heating rate 5℃ / min); inert guiding gas (argon) flow rate 200mL / min.

[0077] Second liquid inlet unit 4: The carbon source precursor is an ethanol-methanol mixture (volume ratio 9:1); the storage tank 5 has a volume of 1L; the transfer pump 7 has a flow rate of 2mL / min.

[0078] Intelligent control system: Real-time monitoring parameters include chamber temperature, liquid flow rate, and atomized particle size, with a sampling frequency of 1Hz; automatic adjustment response time ≤0.8s.

[0079] Preparation steps:

[0080] S1. Pre-treatment of precast body 14:

[0081] S11. Select carbon felt (density 1.0 g / cm³). 3 The product was ultrasonically cleaned with acetone, rinsed with deionized water, and vacuum dried (100℃, 3h).

[0082] S12. Fix the prefabricated body 14 to the platform of the conveying assembly 10, ensuring that the central axis coincides.

[0083] S2. Catalyst loading stage:

[0084] S21. Switch to the first atomization spray mode and set the nozzle angle from -45° to +45°;

[0085] S22. Start the first liquid inlet unit 2, deliver ferrocene solution (flow rate 1 mL / min), and spray for 12 min (load 0.3 wt%).

[0086] S23. The drying module 120 is heated in a gradient from 80℃ (15min) to 120℃ (30min), with multiple temperature measurements to ensure a temperature difference of ≤5℃;

[0087] S24. After spraying, keep drying for 30 minutes until completely dry.

[0088] S3. Carbon source deposition stage

[0089] S31. Switch to the second atomization deposition mode and introduce argon gas (200 mL / min).

[0090] S32. Start the CVD high-temperature oven, heat it to the set temperature of 1100℃, stabilize it for 5 minutes, and then move the second atomizing nozzle 330 to a distance of 150mm from the surface of the preform 14.

[0091] S33. Start the second liquid inlet unit 4 to deliver the carbon source precursor (flow rate 2 mL / min) and ultrasonically atomize it (5 kHz); during this period, the control system adjusts the parameters in real time to ensure that the temperature fluctuation is ≤ ±5℃ and the flow rate deviation is ≤ ±2%.

[0092] S4. Post-processing stage:

[0093] S41. After deposition is complete, shut off the second liquid inlet unit 4 and maintain the temperature and argon supply for 30 minutes;

[0094] S42. Cool to room temperature at a rate of 3℃ / min under argon protection;

[0095] S43. Remove the product, clean the surface carbon, and test its performance.

[0096] Example 2

[0097] This embodiment provides a method for preparing porous carbon-carbon composite materials based on the preparation apparatus for structurally coupled carbon-carbon composite materials in Embodiment 1, thereby preparing porous carbon-carbon composite material channels:

[0098] First atomizing spraying system 1: 3 first atomizing nozzles with an angle of -60° to +60°, atomizing particle size of 15μm; drying temperature 100℃ (20min) → 150℃ (40min).

[0099] First liquid inlet unit 2: The catalyst solution is 0.8wt% ferric chloride solution; the flow rate of the transfer pump 7 is 1.5mL / min.

[0100] Second atomization deposition system 3: Second atomizing nozzle 330, frequency 2.2kHz, atomized particle size 3μm; CVD high temperature oven temperature 1400℃ (temperature gradient 10℃ / min); preheating temperature 250℃; protective argon flow rate 200mL / min.

[0101] Second liquid inlet unit 4: The carbon source precursor is methanol; the transfer pump 7 has a flow rate of 3 mL / min.

[0102] Preparation steps:

[0103] S1. Pretreatment: Carbon fiber wound porous preform 14 (density 1.1 g / cm³) 3 After purification and drying, it is fixed on the stage and evacuated to 3 Pa for 60 min.

[0104] S2. Catalyst loading: Spray ferric chloride solution for 18 min (loading 0.5 wt%), then dry in a gradient drying process for 30 min.

[0105] S3. Carbon source deposition: Deposition at 1400℃ for 0.5h, with real-time adjustment to ensure parameter stability.

[0106] S4. Post-processing: Performance is tested after cooling.

[0107] Performance test results: such as Figure 5 As shown, the Raman spectra of the porous carbon-carbon composite channel were analyzed. The Raman spectra were compared with those of the original carbon sample to reveal the carbon structural characteristics: both exhibited the typical D peak (~1350 cm⁻¹) of carbon materials. -1 (corresponding to defect / disordered structure) and G peak (~1580cm) -1 (corresponding to a graphitized ordered structure), but the D and G peak intensities of the carbon-carbon composite fiber are much higher than those of the original sample, indicating that the carbon structure has a more prominent signal proportion (or a higher relative carbon content) in the carbon-carbon composite fiber. Simultaneously, the D and G peaks of the carbon-carbon composite fiber are sharper, while the peaks of the original sample are wider and weaker. Combining peak shape and intensity, it can be inferred that the I... D / I G The ratio is relatively lower, and its carbon structure has fewer defects and better order than the original sample.

[0108] Example 3

[0109] This embodiment provides a preparation method based on the preparation apparatus for structurally coupled carbon-carbon composite materials in Embodiment 1, for preparing carbon-carbon composite materials with carbon fiber woven fabric laminates:

[0110] First atomizing spraying system 1 - Nozzle layout: adopts 4 sets of ring array nozzles (distributed at 90° around the prefabricated body 14), each set contains 4 independently deflectable first atomizing nozzles 132, with a deflection angle of -30° to +30° (adapted to the upper and lower surfaces and edge areas of the flat plate structure).

[0111] Atomization parameters: High-pressure pneumatic atomization, distribution uniformity ≤12%.

[0112] Drying module 120: 6 sets of surrounding infrared heating tubes (3 sets each on the top and bottom of preform 14), gradient temperature 90℃ (20min) → 130℃ (25min), temperature control accuracy ±2℃, temperature measuring points are evenly distributed on the surface and central area of ​​preform 14.

[0113] First inlet unit 2 - catalyst solution: 0.6wt% acetylacetone iron-ethanol solution (with 0.1wt% dispersant PEG-400 added); delivery parameters: delivery pump 7 flow rate 0.8mL / min, storage tank 5 stirring speed 150r / min, constant temperature control 25℃, multi-stage filtration assembly 6 to ensure impurity content ≤0.08mg / L.

[0114] Second atomization deposition system 3 - atomizing nozzle: high-frequency ultrasonic atomizing nozzle with atomization particle size of 25μm, atomization volume of 60mL / h, and nozzle distance of 14mm from the surface of the preform 120mm.

[0115] CVD high-temperature oven: temperature settings are 800℃, 1000℃ and 1200℃ respectively, heating rate is 15℃ / min, heating area covers the entire preform 14 (temperature difference ≤3℃), built-in corundum support plate.

[0116] Inert gas: Argon flow rate 3L / min.

[0117] Second inlet unit 4 - Carbon source precursor: Ethanol-acetone mixture (volume ratio 8:2, with 0.5wt% xylene added as a cracking aid); Delivery parameters: Delivery pump 7 flow rate 1.8mL / min.

[0118] Intelligent control system - monitoring parameters: chamber temperature, liquid inlet flow rate (0.8±0.01mL / min / 1.8±0.02mL / min), atomized particle size (18±2μm / 25±3μm), argon flow rate (3±0.1L / min), sampling frequency 1Hz.

[0119] Preparation steps

[0120] S1. Pre-treatment of Preform 14 - Carbon Fiber Woven Fabric Lamination: After wiping with alcohol to remove oil, 5 layers of woven fabric are stacked alternately at 0° / 90° and hot-pressed (temperature 120℃, pressure 0.5MPa, holding pressure for 10min) to form preform 14 (density 1.05g / cm³). 3 Preform 14 is placed in an oven at 60°C for 120 minutes to remove interlayer air and surface adsorbed water.

[0121] S2. Catalyst loading stage - Nozzle debugging: Set the angles of the four sets of first nozzle components 130 to -20°, -10°, +10°, and +20° respectively, with a spray distance of 180mm; start the first liquid inlet unit 2 and spray continuously for 15min (catalyst loading 0.25wt%), and simultaneously turn on the drying module 120, and increase the temperature in a gradient of 90℃ (20min) → 130℃ (25min). During this period, the temperature difference between each area of ​​the preform 14 is ≤4℃ through the temperature sensor array.

[0122] S3. Carbon source deposition stage - atmosphere replacement: the preform 14 is moved into the deposition chamber 310 and argon gas is introduced.

[0123] S31. Start the CVD high-temperature oven, heat it to the target temperature and stabilize it for 10 minutes. Then start the second atomizing nozzle 330 and the liquid inlet unit to maintain atomization deposition for 0.5 hours. During this period, the control system adjusts the nozzle moving speed and liquid inlet flow rate in real time to ensure that the carbon source is evenly covered on the surface and internal pores of the preform 14.

[0124] S4. Post-processing stage - cooling: After deposition, the second liquid inlet unit 4 is turned off, the argon flow rate is kept constant, and the temperature is cooled to 200°C at a rate of 2°C / min, and then naturally cooled to room temperature to prepare samples deposited for different times.

[0125] Performance test results:

[0126] like Figure 6 As shown, XRD tests were performed on carbon-carbon composite materials with carbon fiber woven fabric laminates. This test can further reveal the crystal structure, orientation and purity of the material. The composite material has consistent orientation at different temperatures and no obvious impurity peaks, indicating that the preparation process is stable.

[0127] Example 4

[0128] This embodiment provides a method for preparing a highly conductive carbon-carbon composite material (irregular scaffold structure) based on the preparation apparatus for structurally coupled carbon-carbon composite materials in Embodiment 1, using chopped carbon fibers molded into the composite material.

[0129] First atomizing spray system 1 - Nozzle layout: The first atomizing nozzle 132 has a deflection angle of -45° to +45°, which can cover irregularly shaped supports, extend atomization time, and ensure comprehensive and uniform catalyst loading.

[0130] Atomization parameters: High-pressure pneumatic atomization, working pressure 0.3MPa, atomized particle size 12μm, distribution uniformity ≤13%.

[0131] Drying module 120: 4 sets of infrared heating tubes (2 sets on the outer periphery and 2 sets inside the support through hole), gradient temperature 85℃ (25min) → 125℃ (30min).

[0132] First inlet unit 2 - catalyst solution: 0.7wt% nickel chloride-ethanol-ethylene glycol mixture.

[0133] Delivery parameters: delivery pump 7 flow rate 0.6 mL / min, storage tank 5 stirring speed 200 r / min, constant temperature 28℃, solution concentration online monitoring sensor (detection accuracy ±0.02wt%).

[0134] Second atomization deposition system 3 - atomizing nozzle: high-frequency ultrasonic atomizing nozzle with an atomization rate of 50 mL / h;

[0135] CVD high-temperature oven: temperature setting 1150℃, heating rate 5℃ / min.

[0136] Inert gas: Nitrogen flow rate 500 mL / min.

[0137] Second inlet unit 4 - carbon source precursor: methanol, transfer pump 7 flow rate 1.5 mL / min.

[0138] Preparation steps

[0139] S1. Pre-treatment of Preform 14 - Short-cut carbon fiber molding: Short-cut carbon fibers are mixed with phenolic resin (mass ratio 7:3) and molded (temperature 150℃, pressure 1.0MPa, holding pressure for 20min) to produce irregularly shaped scaffold preform 14 (density 0.98g / cm³). 3 Preform 14 is placed in an oven and heated to 400°C at a rate of 5°C / h, held for 2 hours, and the resin matrix is ​​removed (degreasing rate ≥95%). Then it is cooled to room temperature.

[0140] S2. Catalyst loading stage - Nozzle positioning: The outer peripheral nozzle spray distance is 150mm. Start the first liquid inlet unit 2 and spray for 18min. Simultaneously turn on the drying module 120 and increase the temperature in a gradient of 85℃ (25min) → 125℃ (30min) to ensure that there is no solution residue on the inner wall of the through hole.

[0141] S3. Carbon source deposition stage - atmosphere replacement: Nitrogen gas is introduced (flow rate of 300 mL / min).

[0142] Heating and atomization: The oven temperature is raised to 1150℃ and stabilized for 15 minutes. The second atomizing nozzle 330 is started and deposition is carried out for 1 hour.

[0143] S4. Post-treatment stage - cooling: After deposition, maintain nitrogen supply and cool to 150°C at a rate of 1.5°C / min, then turn off nitrogen and allow to cool naturally to room temperature.

[0144] Performance test results:

[0145] like Figure 7 As shown, with the increase of time in the second atomization deposition system 3, the electrical conductivity of the carbon composite material gradually increases. The composite material contains a large number of unfilled pores and interfiber voids. Rapid deposition of carbon nanotubes can quickly establish continuous conductive pathways, reducing contact resistance and tunneling barriers during charge transport, thus leading to a rapid increase in electrical conductivity. The specific surface area of ​​the composite material is measured to be 75 m². 2 / g; Flexural strength: 235MPa; Electrical conductivity: 2.4×10 5 S / m.

[0146] Specific examples have been used to illustrate the principles and implementation methods of this invention. The descriptions of the above embodiments are only for the purpose of helping to understand the method and core ideas of this invention. Furthermore, those skilled in the art will recognize that, based on the ideas of this invention, there will be changes in the specific implementation methods and application scope. Therefore, the content of this specification should not be construed as a limitation of this invention.

Claims

1. An apparatus for preparing structurally coupled carbon-carbon composite materials, characterized in that: It includes a first atomizing spraying system, a first liquid inlet unit, a second atomizing deposition system, a second liquid inlet unit, and a conveying assembly; The first liquid inlet unit is connected to the first atomizing spray system and is used to provide catalyst solution to the first atomizing spray system; The first atomizing spraying system has a spraying chamber for containing the preform. The first atomizing spraying system is used to atomize the catalyst solution and can spray the preform in multiple directions within the spraying chamber. The first atomizing spraying system can also perform immediate gradient drying on the preform after spraying the catalyst solution. The second liquid inlet unit is connected to the second atomization deposition system and is used to provide a carbon source precursor to the second atomization deposition system; The second atomization deposition system has a deposition chamber for accommodating the preform after catalyst loading. The second atomization deposition system is used to atomize and spray the carbon source precursor into the deposition chamber and can be heated simultaneously in the deposition chamber so that the atomized carbon source precursor is deposited onto the preform. The conveying assembly extends through the spraying chamber and the deposition chamber, and is used to carry and convey the preform.

2. The apparatus for preparing structurally coupled carbon-carbon composite materials according to claim 1, characterized in that: The first atomizing spraying system includes a drying module and at least one set of first nozzle assemblies; the first nozzle assembly is disposed on the upper side of the spraying chamber and positioned above the preform, the first nozzle assembly is connected to the first liquid inlet unit and is capable of spraying the preform in multiple directions; the drying module is disposed in the spraying chamber and is used to perform gradient drying on the preform.

3. The apparatus for preparing structurally coupled carbon-carbon composite materials according to claim 2, characterized in that: The first nozzle assembly includes a rotary drive and a plurality of first atomizing nozzles. The plurality of first atomizing nozzles are circumferentially distributed above the preform. The rotary drive is disposed on the inner wall of the spraying chamber and connected to each of the first atomizing nozzles. The rotary drive can drive the plurality of first atomizing nozzles to deflect so as to spray the preform in multiple directions.

4. The apparatus for preparing structurally coupled carbon-carbon composite materials according to claim 1, characterized in that: The second atomized deposition system includes a drying chamber and a second atomizing nozzle; the drying chamber has the deposition chamber and can be gradient-adjusted in temperature; the second atomizing nozzle is disposed in the drying chamber and its outlet is located in the deposition chamber; the second atomizing nozzle is connected to the second liquid inlet unit and is used to atomize and spray the carbon source precursor into the deposition chamber, and the distance between the second atomizing nozzle and the preform can be adjusted; an inert gas can also be introduced into the deposition chamber.

5. The apparatus for preparing structurally coupled carbon-carbon composite materials according to claim 1, characterized in that: Both the first liquid inlet unit and the second liquid inlet unit include a storage tank, a filter assembly, and a delivery pump. The storage tank is used to store the corresponding catalyst solution or carbon source precursor. The storage tank is connected to the corresponding first atomizing spray system or second atomizing deposition system through a pipeline. The pipeline is equipped with the delivery pump and the filter assembly. The delivery pump is used to provide delivery power, and the filter assembly is used to filter impurities in the catalyst solution or carbon source precursor. Flow monitoring devices are also installed on both pipelines.

6. The apparatus for preparing structurally coupled carbon-carbon composite materials according to claim 5, characterized in that: The first liquid inlet unit further includes a concentration monitoring device disposed on the storage tank, the concentration monitoring device being used to monitor the catalyst concentration information of the catalyst solution; the second liquid inlet unit further includes a liquid level monitoring device disposed on the storage tank, the liquid level monitoring device being used to monitor the liquid level information.

7. The apparatus for preparing structurally coupled carbon-carbon composite materials according to claim 1, characterized in that: Both the first atomizing spraying system and the second atomizing deposition system include a temperature monitoring component. The temperature monitoring component is disposed in the corresponding spraying chamber or deposition chamber and is used to monitor the temperature information of different parts of the corresponding preform or the temperature information in the deposition chamber.

8. The apparatus for preparing structurally coupled carbon-carbon composite materials according to claim 1, characterized in that: Both the first atomizing spraying system and the second atomizing deposition system include an atomized particle size monitoring component. The atomized particle size monitoring component is disposed in the corresponding spraying chamber or deposition chamber and is used to monitor the atomized particle size information in the corresponding spraying chamber or deposition chamber.

9. The apparatus for preparing structurally coupled carbon-carbon composite materials according to claim 1, characterized in that: It also includes a central control system, which is communicatively connected to the first atomizing spraying system, the first liquid inlet unit, the second atomizing deposition system, and the second liquid inlet unit, and is capable of information transmission and action control.

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