Preparation method of composite CNTs with nano Ti3SiC2 generated on surface in situ
By generating nanoTi3SiC2 composite CNTs in situ on the surface, the shortcomings of traditional metal-based composite materials in nanoreinforced body dispersion and interface bonding strength are solved, and the enhanced combination of CNTs and metal matrix interfaces are achieved, thereby improving the mechanical properties of the material.
Patent Information
- Application Number
- CN202510379088.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-28
- Publication Date
- 2025-07-01
AI Technical Summary
Traditional metal-based composites have shortcomings in nanoreinforced body dispersion, interface bonding strength and versatility. In particular, the application of carbon nanotubes (CNTs) in composite materials is limited by their surface inertia and agglomeration problems.
Compound CNTs of nanoTi3SiC2 were generated by in situ on the surface, and the OP-10 deionized aqueous solution was used as the medium. The CNTs, nanoSi powder and nanoTi powder were ultrasonic dispersed and mechanically stirred, followed by vacuum drying and heat treatment to generate nanoTi3SiC2 with different structures, and the composite powder was optimized by vacuum ball milling.
The enhanced combination of CNTs and metal matrix interface is achieved, the mechanical properties of metal matrix composite materials are improved, and the overall performance of the material is improved by adjusting the interface of nano reinforcement and metal matrix.
Smart Images
Figure CN120229723A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of materials engineering, and particularly to a preparation method of composite CNTs with in-situ surface-generated nano-Ti3SiC2. Background Art
[0002] Metal matrix composites have been widely used in the fields of aerospace, automotive manufacturing, electronic devices, and energy storage due to their excellent mechanical properties, electrical conductivity, high temperature resistance, etc. However, traditional metal matrix composites still have deficiencies in terms of the dispersion of nano-reinforcements, the interfacial bonding strength, and multi-functionalization. By surface coating the nano-reinforcements and modifying them with surface nano-particles, the interfacial interaction between nano-reinforcements (such as carbon nanotubes) and the metal matrix can be optimized, thereby improving the overall performance of the composite material.
[0003] Carbon nanotubes (CNTs) have excellent electrical conductivity, mechanical strength, and thermal conductivity, and are ideal reinforcing material for metal matrix composites. However, due to surface inertness and agglomeration problems, their applications in composite materials, batteries, electrocatalysis, and other fields are limited. Approaches such as CNT surface coating, nano-particle modification, and surface modification can improve the interfacial bonding between CNTs and the metal matrix.
[0004] Currently, most studies focus on surface coating Cu, Ni, Al2O3, TiC, and SiC on the surface of CNTs, and surface nano-particle modification with Cu, Ni, and Al2O3 to improve the interfacial bonding between CNTs and the metal matrix. TiC and SiC have high strength and modulus, small difference in thermal expansion coefficient with C, and good wettability with Al. They have high melting points, avoiding the phenomenon of high-temperature dissolution and shedding similar to Cu and Ni coatings, and can also be used as nano-particles to modify the surface of CNTs or in-situ generate on the surface of CNTs to enhance the interfacial bonding between CNTs and the metal matrix.
[0005] Titanium silicon carbide (Ti3SiC2) has become a research hotspot in the field of materials in recent years due to its unique nano-layered structure and excellent properties of both metals and ceramics. This material not only exhibits high electrical conductivity (3 - 5×106 S / m) and thermal conductivity (30 - 40 W / m·K) similar to metals, but also has high flexural strength (300 - 600 MPa), excellent oxidation resistance (stable at 1200 - 1400 °C), and self-lubricating characteristics of ceramics, showing potential in the fields of high-temperature protective coatings, nuclear reactor seals, flexible electronic devices, etc. For example, the dense SiO2 / TiO2 oxide layer formed at high temperatures can effectively isolate the diffusion of oxygen, significantly enhancing the ability to withstand extreme environments. However, the synthesis of Ti3SiC2 is easily interfered by impurity phases (such as TiC and SiC), and the interlayer shear strength is relatively low, resulting in prominent macroscopic brittleness.
[0006] In summary, as reinforcement phases, CNTs and Ti3SiC2 respectively enhance the metal matrix, but there are still their respective deficiencies. Combining the advantages of CNTs and Ti3SiC2, combining CNTs and Ti3SiC2 at the nanoscale, and performing surface coating, surface particle modification or in-situ surface modification is an innovative solution in the research of nano-reinforced metal matrix composites, and it is expected to achieve breakthrough applications in the fields of aerospace, automotive manufacturing, electronic devices and energy storage. Summary of the Invention
[0007] In view of the deficiencies of the prior art, the present invention provides the following technical solutions:
[0008] A preparation method of composite CNTs with nano-Ti3SiC2 generated in-situ on the surface, comprising the following steps:
[0009] S100: Disperse surfactant OP-10 in deionized aqueous solution to obtain OP-10 deionized aqueous solution for standby;
[0010] S200: Take a certain amount of the OP-10 deionized aqueous solution prepared in S100, and add CNTs, nano-Si powder and nano-Ti powder to the OP-10 deionized aqueous solution according to a certain ratio. After fully dispersing and mixing evenly, vacuum dry to obtain a mixed powder for standby;
[0011] S300: Heat-treat the mixed powder prepared in S200, and synthesize nano-Ti3SiC2 with different structures on the surface of CNTs based on in-situ reaction to obtain the composite material;
[0012] S400: Perform vacuum ball milling on the composite material prepared in S300 to obtain Ti3SiC2 / CNTs composite material powder.
[0013] As an improvement of the above technical solution, in S200, the molar ratio of CNTs, nano-Si powder and nano-Ti is 3:1:2 to 10;
[0014] The volume ratio of CNTs, deionized water and surfactant OP-10 is 5-50 mg:50 ml:0.1-1 ml.
[0015] As an improvement of the above technical solution, in S200, the dispersion conditions are:
[0016] The dispersion process is carried out under the condition of constant temperature of 0-10 °C;
[0017] Ultrasonic probe dispersion and magnetic stirring are carried out simultaneously, the ultrasonic power is 300-800 W, the ultrasonic time is 0.5-2 h, the mechanical stirring speed is 500-1500 rpm, and the continuous stirring time is 0.5-2 h.
[0018] As an improvement of the above technical solution, in S200, the vacuum drying conditions are as follows:
[0019] The vacuum drying temperature is 50 - 100 °C, and the drying time is 0.5 - 24 h.
[0020] As an improvement of the above technical solution, in S300, the heat treatment conditions are as follows:
[0021] The heat treatment temperature is 1200 - 1600 °C, and the heat treatment time is 1 - 3 h.
[0022] As an improvement of the above technical solution, in S400, the vacuum ball milling conditions are as follows:
[0023] Ball milling is carried out for 2 - 8 h in a vacuum environment, and the ball milling speed is 200 - 400 rpm.
[0024] As an improvement of the above technical solution, the CNTs are any one or any combination of single-walled CNTs, multi-walled CNTs, graphene, nanofiber carbon, and microfiber carbon.
[0025] As an improvement of the above technical solution, the molar ratio of the nano Si powder and the nano Ti powder is 3:1, and the particle size of the nano powder is 30 - 200 nm.
[0026] Advantages of the present invention:
[0027] Under the synergistic action of ultrasonic dispersion and mechanical stirring, the CNTs, nano Si powder, and nano Ti powder are uniformly mixed, and the mixed powder is directly subjected to heat treatment. The TiC and SiC impurity phases generated during the heat treatment process have good thermal stability and wettability, and can also be used as reinforcements for metal matrix composites, enhancing the interfacial bonding between the CNTs and the metal matrix and improving the mechanical properties of the metal matrix. Description of the Drawings
[0028] Figure 1 It is a schematic diagram of the step-by-step reaction in the Ti-Si-CNTs system of the present invention. Detailed Embodiments
[0029] In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
[0030] CNTs and Ti3SiC2, as reinforcement phases, have reinforcing effects on the metal matrix respectively, but still have their own deficiencies. Combining the advantages of CNTs and Ti3SiC2, combining CNTs and Ti3SiC2 at the nanoscale, and performing surface coating, surface particle modification or in-situ surface modification is an innovative solution to the research of nano-reinforced metal matrix composites, and it is expected to achieve breakthrough applications in the fields of aerospace, automotive manufacturing, electronic devices and energy storage.
[0031] Example 1
[0032] In this example, the molar ratio of nano-Ti powder, nano-Si powder, and CNTs is 3:1:8.
[0033] See Figure 1 As shown, to solve the above technical problems, a preparation method of composite CNTs with in-situ generated nano-Ti3SiC2 on the surface is provided, including the following steps:
[0034] Measure 50 ml of deionized water and 0.1 ml of OP-10 emulsifier, stir magnetically for 30 min and then let it stand. Weigh 0.1 g of CNTs, 0.15 g of nano-Ti powder (average particle size 50 nm), and 0.029 g of nano-Si powder (average particle size 50 nm).
[0035] Then add the weighed powders into the OP-10 deionized water solution, and simultaneously perform ultrasonic dispersion and mechanical stirring. The ultrasonic power is 500 W, the mechanical stirring speed is 1000 rpm, and the continuous dispersion time is 1 h. The temperature during the dispersion process is maintained at 0 - 10 °C. After the dispersed mixed powders are filtered by suction, they are dried in a vacuum environment. The drying temperature is 80 °C and the drying time is 0.5 h to obtain uniformly dispersed CNTs-Ti-Si mixed powders.
[0036] Then put the mixed powders in an alumina crucible for vacuum heat treatment. The heat treatment temperature is 1600 °C and keep it warm for 1 h to make the nano-Ti powder, nano-Si powder and CNTs undergo in-situ reaction to generate Ti3SiC2 / CNTs composite powders with the carbon nanotube structure retained.
[0037] Finally, the heat-treated composite powders are ball-milled in a vacuum environment for 4 h at a ball-milling speed of 200 rpm. After the ball-milling is completed, relatively uniform Ti3SiC2 / CNTs composite powders are obtained.
[0038] Example 2
[0039] In this example, the molar ratio of nano-Ti powder, nano-Si powder, and CNTs is 3:1:4.
[0040] Measure 50 ml of deionized water and 0.1 ml of OP-10 emulsifier, stir magnetically for 30 min and then let it stand. Weigh 0.1 g of CNTs, 0.3 g of nano-Ti powder (average particle size 50 nm), and 0.058 g of nano-Si powder (average particle size 50 nm).
[0041] Then add the weighed powders into the OP-10 deionized water solution, and simultaneously perform ultrasonic dispersion and mechanical stirring. The ultrasonic power is 500 W, the mechanical stirring speed is 1000 rpm, and the continuous dispersion time is 1 h. During the dispersion process, the temperature is maintained at 0 - 10 °C. After the dispersion, the mixed powder is filtered by suction and dried in a vacuum environment. The drying temperature is 80 °C and the drying time is 0.5 h to obtain a uniformly dispersed CNTs-Ti-Si mixed powder.
[0042] Then place the mixed powder in an alumina crucible for vacuum heat treatment. The heat treatment temperature is 1600 °C and the heat preservation time is 1 h to cause in-situ reaction of the nano-Ti powder, nano-Si powder and CNTs to generate a Ti3SiC2 / CNTs composite material powder retaining the carbon nanotube structure.
[0043] Finally, perform ball milling on the heat-treated composite material powder in a vacuum environment for 4 h at a ball milling speed of 200 rpm. After the ball milling, a relatively uniform Ti3SiC2 / CNTs composite material powder is obtained.
[0044] Example 3
[0045] In this example, the molar ratio of nano-Ti powder, nano-Si powder, and CNTs is 3:1:2.
[0046] Measure 50 ml of deionized water and 0.1 ml of OP-10 emulsifier, stir magnetically for 30 min and then let it stand. Weigh 0.1 g of CNTs, 0.6 g of nano-Ti powder (average particle size 50 nm), and 0.117 g of nano-Si powder (average particle size 50 nm).
[0047] Then add the weighed powders into the OP-10 deionized water solution, and simultaneously perform ultrasonic dispersion and mechanical stirring. The ultrasonic power is 500 W, the mechanical stirring speed is 1000 rpm, and the continuous dispersion time is 1 h. During the dispersion process, the temperature is maintained at 0 - 10 °C. After the dispersion, the mixed powder is filtered by suction and dried in a vacuum environment. The drying temperature is 80 °C and the drying time is 0.5 h to obtain a uniformly dispersed CNTs-Ti-Si mixed powder.
[0048] Then place the mixed powder in an alumina crucible for vacuum heat treatment. The heat treatment temperature is 1600 °C and the heat preservation time is 1 h to cause in-situ reaction of the nano-Ti powder, nano-Si powder and CNTs to generate a Ti3SiC2 / CNTs composite material powder retaining the carbon nanotube structure.
[0049] Finally, the heat-treated composite powder was ball-milled in a vacuum environment for 4 h at a ball-milling speed of 200 rpm. After the ball-milling was completed, a relatively uniform Ti3SiC2 / CNTs composite powder was obtained.
[0050] Comparative Example 1
[0051] In this comparative example, the molar ratio of nano-Ti powder, nano-Si powder, and CNTs was 3:1:8.
[0052] 50 ml of deionized water and 0.1 ml of OP-10 emulsifier were measured. After magnetic stirring for 30 min, it was left to stand. 0.1 g of CNTs, 0.15 g of nano-Ti powder (average particle size 50 nm), and 0.029 g of nano-Si powder (average particle size 50 nm) were weighed.
[0053] Then, the weighed powders were added to the OP-10 deionized water solution, and ultrasonic dispersion and mechanical stirring were carried out simultaneously. The ultrasonic power was 500 W, the mechanical stirring speed was 1000 rpm, and the continuous dispersion time was 1 h. The temperature was maintained at 0-10 °C during the dispersion process. The dispersed mixed powder was filtered by suction and then dried in a vacuum environment at a drying temperature of 80 °C for 0.5 h to obtain a uniformly dispersed CNTs-Ti-Si mixed powder.
[0054] Then, the mixed powder was placed in an alumina crucible for vacuum heat treatment at a heat treatment temperature of 1300 °C for 1 h to cause an in-situ reaction of nano-Ti powder, nano-Si powder, and CNTs to generate a Ti3SiC2 / CNTs composite powder with a retained carbon nanotube structure.
[0055] Finally, the heat-treated composite powder was ball-milled in a vacuum environment for 4 h at a ball-milling speed of 200 rpm. After the ball-milling was completed, a relatively uniform Ti3SiC2 / CNTs composite powder was obtained.
[0056] Comparative Example 2
[0057] In this comparative example, the molar ratio of nano-Ti powder, nano-Si powder, and CNTs was 3:1:8.
[0058] 50 ml of deionized water and 0.1 ml of OP-10 emulsifier were measured. After magnetic stirring for 30 min, it was left to stand. 0.1 g of CNTs, 0.15 g of nano-Ti powder (average particle size 50 nm), and 0.029 g of nano-Si powder (average particle size 50 nm) were weighed.
[0059] Then, the weighed powder was added to the OP-10 deionized aqueous solution, and ultrasonic dispersion and mechanical stirring were carried out simultaneously. The ultrasonic power was 500 W, the mechanical stirring speed was 1000 rpm, and the continuous dispersion time was 1 h. During the dispersion process, the temperature was maintained at 0 - 10 °C. After filtration by suction, the dispersed mixed powder was dried in a vacuum environment. The drying temperature was 80 °C and the drying time was 0.5 h, obtaining a uniformly dispersed CNTs-Ti-Si mixed powder.
[0060] Then, the mixed powder was placed in an alumina crucible for vacuum heat treatment. The heat treatment temperature was 1400 °C and the holding time was 1 h, enabling in-situ reactions among the nano-Ti powder, nano-Si powder, and CNTs to generate a Ti3SiC2 / CNTs composite powder retaining the carbon nanotube structure.
[0061] Finally, the heat-treated composite powder was ball-milled in a vacuum environment for 4 h at a ball-milling speed of 200 rpm. After the ball milling, a relatively uniform Ti3SiC2 / CNTs composite powder was obtained.
[0062] Comparative Example 3
[0063] In this comparative example, the molar ratio of nano-Ti powder, nano-Si powder, and CNTs was 3:1:8.
[0064] 50 ml of deionized water and 0.1 ml of OP-10 emulsifier were measured. After magnetic stirring for 30 min and then standing, 0.1 g of CNTs, 0.15 g of nano-Ti powder (average particle size 50 nm), and 0.029 g of nano-Si powder (average particle size 50 nm) were weighed.
[0065] Then, the weighed powder was added to the OP-10 deionized aqueous solution, and ultrasonic dispersion and mechanical stirring were carried out simultaneously. The ultrasonic power was 500 W, the mechanical stirring speed was 1000 rpm, and the continuous dispersion time was 1 h. During the dispersion process, the temperature was maintained at 0 - 10 °C. After filtration by suction, the dispersed mixed powder was dried in a vacuum environment. The drying temperature was 80 °C and the drying time was 0.5 h, obtaining a uniformly dispersed CNTs-Ti-Si mixed powder.
[0066] Then, the mixed powder was placed in an alumina crucible for vacuum heat treatment. The heat treatment temperature was 1500 °C and the holding time was 1 h, enabling in-situ reactions among the nano-Ti powder, nano-Si powder, and CNTs to generate a Ti3SiC2 / CNTs composite powder retaining the carbon nanotube structure.
[0067] Finally, the heat-treated composite powder was ball-milled in a vacuum environment for 4 h at a ball-milling speed of 200 rpm. After the ball milling, a relatively uniform Ti3SiC2 / CNTs composite powder was obtained.
[0068] The composite powders obtained in the above three examples and three comparative examples were subjected to XRD detection and composition analysis on a fixed-target X-ray diffractometer (PANalytical X-Pert PRO MPD). The results of the composition analysis of the composite powders are shown in Table 1:
[0069]
[0070] As can be seen from Table 1, when the molar ratio of the raw materials of the Ti3SiC2 / CNTs composite material powder prepared in the present invention is nano-Ti powder:nano-Si powder:CNTs = 3:1:8, nano-Ti3SiC2 and TiC are in-situ generated on the CNTs, and a relatively complete CNTs structure is retained. The mechanical properties of the metal matrix composite material can be improved by adjusting the interfacial bonding between the nano-reinforcement and the metal matrix, and it has broad application prospects.
[0071] The above examples are only used to illustrate the technical solutions of the present invention, rather than limiting them.
Claims
1. A method for preparing composite CNTs with in-situ generation of nano-Ti3SiC2 on the surface, characterized in that: The following steps are involved: S100, dispersing the surfactant OP-10 in a deionized water solution to obtain an OP-10 deionized water solution for later use; S200, taking a certain amount of the OP-10 deionized water solution prepared in S100, adding CNTs, nano-Si powder and nano-Ti powder to the OP-10 deionized water solution according to a certain ratio, fully dispersing and then vacuum drying to obtain a mixed powder for standby use; S300, heat-treating the mixed powder obtained in S200, synthesizing nano-Ti3SiC2 with different structures on the surface of CNTs based on in-situ reaction, i.e., a composite material; S400, vacuum ball milling the composite material prepared in S300 to obtain Ti3SiC2 / CNTs composite material powder.
2. The preparation method according to claim 1, characterized in that: In S200, the molar ratio of CNTs, nano-Si powder and nano-Ti is 3:1:2-10; The volume ratio of CNTs, deionized water, and surfactant OP-10 is 5-50 mg:50 ml:0.1-1 ml.
3. The preparation method according to claim 1, characterized in that: In S200, the dispersion conditions are: The dispersion process is carried out at a constant temperature of 0 to 10°C; Ultrasonic probe dispersion and magnetic stirring are carried out simultaneously, with an ultrasonic power of 300 to 800 W, an ultrasonic time of 0.5 to 2 h, a mechanical stirring speed of 500 to 1500 rpm, and a continuous stirring time of 0.5 to 2 h.
4. The preparation method according to claim 1, characterized in that: In S200, the vacuum drying conditions are: The vacuum drying temperature is 50-100°C and the drying time is 0.5-24h.
5. The preparation method according to claim 1, characterized in that: In S300, the heat treatment conditions are: The heat treatment temperature is 1200-1600°C, and the heat treatment time is 1-3h.
6. The preparation method according to claim 1, characterized in that: In S400, vacuum ball milling conditions are: Ball milling was performed under vacuum for 2 to 8 hours at a speed of 200 to 400 rpm.
7. The preparation method according to claim 1, characterized in that: The CNTs are any one or any combination of single-walled CNTs, multi-walled CNTs, graphene, nano-carbon fibers and micron-carbon fibers.
8. The preparation method according to claim 2, characterized in that: The molar ratio of the nano-Si powder to the nano-Ti powder is 3:1, and the particle size of the nano-powder is 30-200 nm.