CN115889760A - Device and method for rapidly preparing carbon nanotube coated superfine high-entropy alloy composite powder - Google Patents
Device and method for rapidly preparing carbon nanotube coated superfine high-entropy alloy composite powder Download PDFInfo
- Publication number
- CN115889760A CN115889760A CN202211497954.9A CN202211497954A CN115889760A CN 115889760 A CN115889760 A CN 115889760A CN 202211497954 A CN202211497954 A CN 202211497954A CN 115889760 A CN115889760 A CN 115889760A
- Authority
- CN
- China
- Prior art keywords
- entropy alloy
- gas
- composite powder
- carbon nanotube
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses a device and a method for rapidly preparing carbon nanotube-coated high-entropy alloy composite powder (CNT @ HEA), which relate to the growth of carbon nanotubes and high-entropy alloy, wherein a certain amount of nitrate hydrate containing iron, cobalt, nickel and other metals which are easy to catalyze and grow the carbon nanotubes is weighed and added into an ethanol solution, argon is used for driving an independently designed gas atomization device to spray micron-sized fog beads, the ethanol and the nitrate are subjected to high-temperature cracking at the temperature of over 1100 ℃ through a vacuum tube furnace, and a carbon source and H are generated 2 And reducing to obtain fine high-entropy alloy particles, and growing the carbon nano tubes on the surfaces of the high-entropy alloy particles in situ under the catalysis of iron, cobalt and nickel. The invention utilizes the independently designed device to be fastAnd rapidly preparing the superfine high-entropy alloy, and growing the carbon nano tube on the surface of the superfine high-entropy alloy particle in situ to obtain the nano tube-coated superfine high-entropy alloy composite powder. The invention has simple process and low cost, and is suitable for the fields of energy catalysis, composite materials and the like.
Description
Technical Field
The invention belongs to the technical field of high-entropy alloy preparation, and particularly relates to a device and a method for quickly preparing carbon nano tube coated superfine high-entropy alloy composite powder.
Background
The high-entropy alloy (HEA) has unique performance and abundant atom scale adjustment possibility. For bulk HEA, its specific mechanical properties (yield strength, ductility and hardness) have been predicted and demonstrated, and the concepts of hydrogen storage capacity, thermoelectric properties, superconductivity and pseudoelements have also been explored.
In recent years, high entropy nanoparticles (HEA-NPs) have received much attention due to their multi-element composition (typically five or more elements) and uniformly mixed solid solution state, not only providing a large number of combinations for material discovery, but also having a unique microstructure for performance optimization. Recent advances in ultra-fast synthesis processes, such as those based on non-equilibrium thermal shock, have made many types of high-entropy nanoparticles free of the problem of phase separation, even in immiscible combinations of elements. The high-entropy alloy nanoparticles have excellent physicochemical properties including wide element selection, high corrosion resistance, high thermal and chemical stability, enhanced mechanical strength, and improved catalytic activity due to synergistic catalytic reaction of elements, and have received wide attention in energy and catalytic applications in recent years.
The carbon nano tube is easy to be catalyzed and grown by using metal elements such as Fe, co, ni, cu and the like. The carbon nanotubes have good electrical conductivity. Meanwhile, the Carbon Nano Tube (CNT) is a one-dimensional quantum material with a special structure (the radial dimension is in the nanometer level, the axial dimension is in the micrometer level, and two ends of the tube are basically sealed). The nano particles grow on the surface of the high-entropy alloy nano particles, so that the nano particles have larger surface area and excellent conductivity, and can be widely applied to energy and catalysis.
Disclosure of Invention
The invention provides a device and a method for rapidly preparing carbon nano tube coated superfine high-entropy alloy composite powder, aiming at the technical problems of difficulty in preparing high-entropy alloy superfine particles, complex process and low yield. The device is simple, and simultaneously can produce a large amount of CNT @ HEA ultrafine particles.
In order to realize the purpose, the invention adopts the following technical scheme:
a device for rapidly preparing carbon nano tube coated superfine high-entropy alloy composite powder comprises: flow control device, gas atomization generating device, high temperature device, collection device and tail gas processing apparatus.
Further, the flow control device, the gas atomization generating device, the high-temperature device, the collecting device and the tail gas processing device are sequentially connected in the airflow direction; the sealing performance is ensured by utilizing a sealing ring, a vacuum hoop and the like.
Further, the flow control device is a glass rotor flow meter with the range of 600mL to 6L, preferably more than 4L/min, the gas flow can be adjusted, and an Ar gas source and the gas atomization generating device are connected through a hose.
Furthermore, the gas atomization generating device is an atom absorption atomizer, a pipeline connected with the precursor solution is arranged on the left side of the atom absorption atomizer, a pipeline through Ar gas is arranged below the atom absorption atomizer, and a gas atomization nozzle is arranged on the right side of the atom absorption atomizer and connected with an inlet of the high-temperature device.
Further, the high-temperature device is a vacuum tube furnace, and the right side of the high-temperature device is connected with an inlet of the collecting device; the collecting device is composed of a container containing filter paper at the outlet of the collecting device for interceptingThe product in the airflow reaches the collection effect. The outlet of the collecting device is connected with the inlet of a tail gas treatment device, the tail gas treatment device is composed of a container containing NaOH solution, and NO generated by the tail gas treatment device are treated by the NaOH solution 2 And the like.
The invention also provides a method for rapidly preparing the carbon nano tube coated superfine high-entropy alloy composite powder by adopting the device, which comprises the following steps:
1) Preparing a precursor solution: weighing nitrate hydrate of five metals (three elements of Fe, co and Ni which mainly play a catalytic role, and other elements such as Al, ti, V, mn, cr, cu and the like) of Fe, co, ni, cr and Al, adding the nitrate hydrate into an ethanol solution, and carrying out ultrasonic treatment and stirring to uniformly mix the nitrate hydrate and the ethanol solution to obtain a precursor mixed solution;
2) Preparation of carbon nanotube coated superfine high-entropy alloy composite powder (CNT @ HEA): and (2) driving the precursor mixed solution prepared in the step (1) to an air atomization nozzle in an air atomization generating device through Ar gas for atomization, adding the precursor mixed solution and the Ar gas into a vacuum tube furnace with the temperature of more than 1000 ℃, rapidly heating the tube furnace, performing high-temperature pyrolysis on ethanol to generate a carbon source and hydrogen, rapidly reducing nitrate to obtain FeCoNiCrAl high-entropy alloy, generating CNTs on the surface of the high-entropy alloy under the catalysis of Fe, co and Ni elements to obtain the carbon nanotube-coated high-entropy alloy, rapidly cooling the product in a pipeline after the product is discharged from the vacuum tube furnace, and intercepting and collecting the product by filter paper when the product reaches a collecting device. The generated tail gas reaches the NaOH solution of the tail gas treatment device through the collection device and is absorbed.
In a preferred embodiment of the present invention, the concentration range of each metal nitrate in the ethanol solution is 0.01 to 0.2M.
As a preferable scheme of the invention, the ultrasonic time of the step 1) is 1 to 3 hours, and the stirring time is 4 to 6 hours.
In a preferred embodiment of the present invention, the flow rate of Ar gas in the step 2) is 2 to 6L/min.
Compared with the prior art, the invention has the following advantages:
1. the preparation process and the preparation cost are greatly simplified through the self-assembly device. Compared with the original carbon thermal impact method, the high-entropy alloy nanoparticles prepared by the method do not contain a carrier, and can be directly applied.
2. The invention does not need to add H 2 Reducing gas to a certain extent to reduce H 2 The danger of (2) and the cost of use.
3. The invention can control the size of high-entropy alloy particles. The control of the particle size of the finished product can be realized by adjusting the concentration of each metal nitrate in the ethanol.
4. The invention can change the variety of the high-entropy alloy by changing the components of the metal nitrate.
Drawings
FIG. 1 is a schematic diagram of a simple apparatus for preparing a carbon nanotube-coated ultra-fine high-entropy alloy; in the figure, 1 is a precursor solution container; 2 is a gas atomization generating device, and 3 is a high-temperature device; 4 is a collecting device; 5 is a tail gas treatment device; 6 is a flow control device;
FIG. 2 is a schematic diagram of an atomic absorption atomizer in a simple apparatus for preparing a carbon nanotube-coated ultra-fine high-entropy alloy; in the figure, 201 is an air atomization nozzle;
FIG. 3 is a schematic view of the structure of a collecting device in a simple device for preparing a carbon nanotube-coated ultra-fine high-entropy alloy; in the figure, a is a sealing ring to ensure the sealing performance of the device, and b is filter paper used for collecting generated CNT @ HEA powder in an intercepting manner;
FIG. 4 is an XRD diagram of CNT @ HEA prepared by a simple device of carbon nanotube coated ultra-fine high-entropy alloy;
FIG. 5 is an SEM image of CNT @ HEA prepared by a simple device of carbon nanotube coated ultra-fine high-entropy alloy; (a) The morphology of the CNT @ HEA particles in different times is shown in the (c) and (d), and the size distribution diagram of the CNT @ HEA particles is shown in the (b);
FIG. 6 is a Raman spectrum of CNT @ HEA prepared by a simple apparatus for coating ultra-fine high-entropy alloy with carbon nanotubes.
Detailed Description
The following further describes the embodiments of the present invention with reference to the attached drawings. The embodiments of the present invention are not limited to the above embodiments, and all the technical ideas defined in the claims of the present invention and other simple changes based on the technical ideas are within the scope of the present invention.
As shown in fig. 1, the simple apparatus for rapidly preparing the carbon nanotube-coated ultra-fine high-entropy alloy composite powder of the embodiment includes: the device comprises a flow control device 6, a gas atomization generating device 2, a high-temperature device 3, a collecting device 4 and a tail gas treatment device 5.
The gas atomization generating device 2 in this embodiment is an atom absorption atomizer, a pipeline connected with a precursor solution is arranged on the left side of the atom absorption atomizer, a pipeline through which Ar gas passes is arranged below the atom absorption atomizer, a gas atomization nozzle 201 is arranged on the right side of the atom absorption atomizer, and the gas atomization nozzle 201 is connected with an inlet of the high-temperature device 3; the right side of the high temperature device 3 is connected with the inlet of a collecting device 4, the collecting device 4 is composed of a container containing filter paper b, and the filter paper b is positioned at the outlet of the collecting device 5 and used for intercepting products in the airflow to achieve the collecting effect. The outlet of the collecting device 4 is connected with the inlet of the tail gas treatment device 5, the tail gas treatment device 5 consists of a container containing NaOH solution, and NO generated by the NaOH solution are treated 2 And the like.
The flow control device 6 used in this embodiment is a glass rotameter with a range of 600mL to 6L, and is connected with an Ar gas source and a gas atomization generating device through a hose.
In this embodiment, the gas atomization generating device 2 is driven by Ar gas flow to absorb and atomize the solution by the bernoulli principle, and is connected to a high temperature device (quartz tube) by using a design fitting. The atomizer is connected with the accessory by screws, and the middle sealing ring ensures the sealing property of the atomizer. And then connected to the quartz tube by a vacuum sealing clamp.
The high temperature apparatus 3 used in this example is a vacuum tube furnace with a temperature of 1200 deg.c, and the inner diameter of the quartz tube used is 20mm.
The collection device 4 used in this example was located 500mm from the hot zone of the tube furnace, at a sufficient distance to allow the product to cool.
Example 1: 0.005mol each of Fe (NO) was weighed in an equimolar amount 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O、Cr(NO 3 ) 3 ·9H 2 And O, adding the precursor solution into 100mL of ethanol solution, performing ultrasonic treatment for 2h, and performing magnetic stirring for 6h to obtain a precursor solution.
Assembling the device, introducing argon gas to ensure that inert gas is in the device, inserting the precursor solution into a liquid suction pipe of the atomic absorption atomizer 2, introducing Ar gas at 4L/min when the temperature of the vacuum tube furnace 3 is raised to 1100 ℃, driving the precursor solution to the tip of an atomizer nozzle 201 by the Ar gas to atomize the precursor solution into the vacuum tube furnace 3, and preferentially cracking ethanol to generate C and H at 1100 DEG C 2 Under the synchronous action of high temperature, the metal nitrate is rapidly cracked and reduced into high-entropy alloy, nitric oxide and nitrogen dioxide, and meanwhile, under the catalysis of Fe, co and Ni elements generated by reduction, the C grows CNT on the surface of the high-entropy alloy to finally obtain CNT @ HEA powder, namely the carbon nano tube coated superfine high-entropy alloy composite powder. After the product is discharged from the vacuum tube furnace 3, the product is rapidly cooled in the pipeline, reaches the collecting device 4 and is intercepted and collected by filter paper. The generated tail gas reaches the NaOH solution of the tail gas treatment device 5 through the collection device 4 to be absorbed.
XRD pattern of CNT @ HEA of example 1 As shown in FIG. 4, peaks of AlCrFeCoNi-based high-entropy alloy having a relatively pure FCC structure were detected, indicating that the high-entropy alloy was produced.
As shown in FIG. 5, the SEM of the product CNT @ HEA of example 1 shows that the size of the ultrafine CNT @ HEA particles is between 100nm and 8 μm, the average size is about 2 μm, and a large number of carbon nanotubes with the diameter of about 25nm grow on the surface of the particles under the scanning electron microscope.
The Raman spectrum of the product CNT @ HEA of example 1 is shown in FIG. 6, and shows I of CNTs D /I G The ratio is 0.56, and a low ID/IG ratio indicates that the primary CNTs have a structurally intact structure and few surface structural defects.
Therefore, the invention can rapidly prepare the high-entropy alloy composite powder (CNT @ HEA) with good crystallinity of the CNTs with complete surface coating structure, simplifies the preparation process and reduces the preparation cost.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A device for rapidly preparing carbon nanotube coated superfine high-entropy alloy composite powder is characterized in that: the method comprises the following steps: the device comprises a flow control device, a gas atomization generating device, a high-temperature device, a collecting device and a tail gas treatment device; the flow control device, the gas atomization generating device, the high-temperature device, the collecting device and the tail gas treatment device are sequentially connected according to the airflow direction.
2. The apparatus for rapidly preparing carbon nanotube-coated ultra-fine high-entropy alloy composite powder according to claim 1, characterized in that: the flow control device, the gas atomization generating device, the high-temperature device, the collecting device and the tail gas treatment device ensure the sealing performance through the sealing ring and the vacuum hoop.
3. The apparatus for rapidly preparing carbon nanotube-coated ultra-fine high-entropy alloy composite powder according to claim 1, characterized in that: the flow control device is a glass rotameter with a range of 600mL to 6L, and is connected with an Ar gas source and a gas atomization generating device through a hose.
4. The apparatus for rapidly preparing carbon nanotube-coated ultra-fine high-entropy alloy composite powder according to claim 1, characterized in that: the gas atomization generating device is an atom absorption atomizer, a gas atomization nozzle is arranged on the right side of the atom absorption atomizer, and the gas atomization nozzle is connected with an inlet of the high-temperature device.
5. The apparatus for rapidly preparing carbon nanotube-coated ultra-fine high-entropy alloy composite powder according to claim 1, characterized in that: the high-temperature device is a vacuum tube furnace.
6. A method for rapidly preparing carbon nanotube coated superfine high-entropy alloy composite powder by using the device of any one of claims 1 to 5 is characterized by comprising the following steps:
1) Preparing a precursor solution: weighing five or more than five metal element single nitrate hydrates, adding the nitrate hydrates into an ethanol solution, performing ultrasonic treatment, and stirring to uniformly mix the nitrate hydrates and the ethanol solution to obtain a precursor mixed solution;
2) Preparation of CNT @ HEA composite powder: the precursor mixed solution prepared in the step (1) is driven to a gas atomization nozzle through Ar gas for atomization, the precursor mixed solution and the Ar gas are introduced into a vacuum tube furnace with the temperature of more than 1000 ℃, carbon source and hydrogen are generated through the rapid heating of the vacuum tube furnace and the high-temperature cracking of ethanol, nitrate is rapidly reduced to obtain FeCoNi high-entropy alloy, CNTs are generated on the surface of the high-entropy alloy under the catalysis of Fe or Co or Ni elements to obtain carbon nano tube coated high-entropy alloy, the carbon nano tube coated high-entropy alloy enters a collecting device along with the Ar gas to be collected, and tail gas enters a tail gas treatment device through the collecting device and is filtered by NaOH solution.
7. The method of claim 6, wherein: the concentration of each metal in the precursor mixed solution in the step 1) is 0.01 to 0.2M.
8. The method of claim 6, wherein: the time of ultrasonic treatment in the step 1) is 1 to 3h, and the stirring time is 4 to 6h.
9. The method of claim 6, wherein: the five or more metal elements in the step 1) comprise three elements of Fe, co and Ni, and also comprise more than two elements of Al, ti, V, mn, cr and C.
10. The method of claim 6, wherein: the flow rate of Ar gas in the step 2) is 2 to 6L/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211497954.9A CN115889760A (en) | 2022-11-28 | 2022-11-28 | Device and method for rapidly preparing carbon nanotube coated superfine high-entropy alloy composite powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211497954.9A CN115889760A (en) | 2022-11-28 | 2022-11-28 | Device and method for rapidly preparing carbon nanotube coated superfine high-entropy alloy composite powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115889760A true CN115889760A (en) | 2023-04-04 |
Family
ID=86477509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211497954.9A Pending CN115889760A (en) | 2022-11-28 | 2022-11-28 | Device and method for rapidly preparing carbon nanotube coated superfine high-entropy alloy composite powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115889760A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117139638A (en) * | 2023-09-04 | 2023-12-01 | 苏州科技大学 | Continuous preparation method of high-entropy alloy micro-nanospheres |
-
2022
- 2022-11-28 CN CN202211497954.9A patent/CN115889760A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117139638A (en) * | 2023-09-04 | 2023-12-01 | 苏州科技大学 | Continuous preparation method of high-entropy alloy micro-nanospheres |
| CN117139638B (en) * | 2023-09-04 | 2024-03-19 | 苏州科技大学 | Continuous preparation method of high-entropy alloy micro-nanospheres |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sunny et al. | Synthesis and properties of highly stable nickel/carbon core/shell nanostructures | |
| JP5594961B2 (en) | Synthesis of narrow-diameter carbon single-walled nanotubes | |
| Mhlanga et al. | The effect of synthesis parameters on the catalytic synthesis of multiwalled carbon nanotubes using Fe-Co/CaCO3 catalysts | |
| US8187562B2 (en) | Method for producing cerium dioxide nanopowder by flame spray pyrolysis and cerium dioxide nanopowder produced by the method | |
| CN103695864B (en) | The preparation method of carbon coating cobalt metal nanoparticle | |
| He et al. | Carbon nanotubes and onions from methane decomposition using Ni/Al catalysts | |
| JP2009500281A (en) | Carbon nanoparticles, production method thereof, and use thereof | |
| CN111495381A (en) | Preparation method of flaky catalyst, flaky catalyst and application of flaky catalyst in preparation of superfine carbon nano tube | |
| CN110494390A (en) | Use the preparation method of the multi-walled carbon nanotube of continous way process | |
| CN113135562B (en) | Method and device for preparing carbon nano tube and hydrogen | |
| CN107032326A (en) | A kind of method that solid catalysis prepares spiral carbon nano pipe | |
| CN109665512A (en) | A kind of preparation method of multi-walled carbon nanotube | |
| CN115889760A (en) | Device and method for rapidly preparing carbon nanotube coated superfine high-entropy alloy composite powder | |
| CN114308049A (en) | Growth catalyst for preparing carbon nano tube with high specific surface area | |
| WO2007108455A1 (en) | Catalyst particle for production of carbon nanocoil, process for producing the same, and process for producing carbon nanocoil | |
| Hou et al. | Flame synthesis of carbon nanostructures using mixed fuel in oxygen-enriched environment | |
| CN101323446B (en) | Preparation of carbon nanosphere | |
| KR101174136B1 (en) | Method for Synthesis and Morphological Control of Carbon Nanotubes | |
| CN102745665A (en) | Method for preparing helical structure carbon nanotubes | |
| Bamoharram et al. | Synthesis of carbon nanotubes via catalytic chemical vapor deposition method and their modification with Preyssler anion,[NaP5W30O110] 14 | |
| CN105329882B (en) | Preparation method of carbon nano-tube | |
| CN112371131A (en) | Carbon nano tube growth catalyst, preparation method thereof and preparation method of carbon nano tube | |
| Wang et al. | Large-scale preparation of carbon nanotubes via catalytic pyrolysis of phenolic resin at low temperature | |
| CN113101981B (en) | Preparation method of catalyst for preparing carbon nanotube | |
| Khiriya et al. | Development of Fe/Ru Bimetallic Nanoparticles for Promising Application in the Selective Synthesis of SWNTs |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |