阅读说明：本技术 一种CNTs@TC4复合粉末的快速原位制备方法 (Rapid in-situ preparation method of CNTs @ TC4 composite powder ) 是由 陈俊锋 卢锐涵 孙君伟 梁庆津 池海涛 于 2021-07-28 设计创作，主要内容包括：本发明公开了一种CNTs@TC4复合粉末的快速原位制备方法,通过电泳沉积技术在TC4粉末表面附着纳米铁颗粒,结合等离子增强化学气相沉积技术在TC4粉末表面原位生长碳纳米管；首先对TC4粉末进行去油去脂预处理,接着以去离子水为溶剂配制硝酸铁溶液,将去油脂后的TC4粉末平铺在作为阴极的铝片上放入盛有电解质溶液的容器中进行电沉积从而制备得到用于在TC4粉末表面生长碳纳米管的催化剂前驱体,最后用等离子增强化学气相沉积法进行碳纳米管的原位生长。本发明制备所得的碳纳米管分布均匀以及具有较高的长径比,利于后续制备所得的碳纳米管增强钛基复合材料的各项性能的提升。(The invention discloses a rapid in-situ preparation method of CNTs @ TC4 composite powder, which comprises the steps of attaching nano iron particles on the surface of TC4 powder by an electrophoretic deposition technology, and growing carbon nanotubes on the surface of TC4 powder in situ by combining with a plasma enhanced chemical vapor deposition technology; firstly, performing degreasing pretreatment on TC4 powder, then preparing ferric nitrate solution by taking deionized water as a solvent, flatly paving the degreased TC4 powder on an aluminum sheet serving as a cathode, putting the aluminum sheet into a container containing electrolyte solution for electrodeposition so as to prepare a catalyst precursor for growing the carbon nano tube on the surface of the TC4 powder, and finally performing in-situ growth of the carbon nano tube by using a plasma enhanced chemical vapor deposition method. The carbon nano tube prepared by the method is uniform in distribution and high in length-diameter ratio, and is beneficial to improvement of various performances of the carbon nano tube reinforced titanium-based composite material prepared subsequently.)

1. A rapid in-situ preparation method of CNTs @ TC4 composite powder is characterized by comprising the following steps: the method comprises the following steps:

surface treatment of TC4 powder: putting TC4 powder into deionized water for ultrasonic treatment, pouring out the deionized water, putting the deionized water into absolute ethyl alcohol for ultrasonic treatment, and repeating the ultrasonic treatment for three times to finally obtain TC4 powder without grease on the surface;

preparation of TC4 powder surface nano catalyst particles: configured Fe (NO)₃)₃·9H₂O solution, step (ii)Spreading the obtained TC4 powder in an aluminum box placed in an electrophoresis tank to serve as a cathode, pouring an electrolyte solution into the aluminum box to submerge a stainless steel anode, connecting a lead, performing electrodeposition, and using an electrophoresis apparatus to carry out Fe³⁺Reducing Fe on the cathode to form a simple substance, and depositing the simple substance on the surface of TC4 powder serving as the cathode to obtain a catalyst precursor;

preparation of CNTs @ TC4 composite powder: placing the catalyst precursor obtained in the step (2) in a PECVD furnace for growing the carbon nano tube: firstly, calcining the catalyst precursor obtained in the step (2) for 1H at 400 ℃ in Ar atmosphere, then closing Ar gas, and introducing high-purity H₂Carrying out reduction reaction for 1 h; finally in Ar and CH₄Growing for 10-60 min in the mixed atmosphere to obtain the CNTs @ TC4 composite powder.

2. The rapid in situ preparation method according to claim 1, wherein: fe (NO) in step (2)₃)₃·9H₂The concentration of the O solution is 0.0025-0.01 mol/L.

3. The rapid in situ preparation method according to claim 1, wherein: and (3) starting the plasma in the whole growth process in the step (3), wherein the power is 30-200W, and the growth temperature is 450-700 ℃.

4. The method of claim 1, wherein: ar and CH in step (3)₄The mixed atmosphere of (A) and (B) is Ar: CH₄= 4: 1 gas flow ratio.

5. A CNTs @ TC4 composite powder prepared by the rapid in-situ preparation method as claimed in any one of claims 1-4.

Technical Field

The invention belongs to the technical field of composite materials, and particularly relates to a rapid in-situ preparation method of CNTs @ TC4 composite powder.

Background

The Ti-6A1-4V (TC4) titanium alloy has wide application prospects in various fields such as aerospace, metallurgy, ships, automobiles, biomedicine and the like due to excellent comprehensive performance, and has been used as a wide matrix material, and the carbon nano tube is considered as an ideal reinforcement in a composite material due to excellent mechanical property. The composite powder (CNTs @ TC4 composite powder) formed by Carbon Nanotubes (CNTs) and titanium alloy particles is an important raw material for preparing carbon nano reinforced titanium-based composite materials by the current methods of powder metallurgy, 3D printing and the like. Compared with the traditional titanium alloy, the novel carbon nano reinforced titanium-based composite material has higher specific strength and specific elastic modulus, excellent high-temperature resistance and corrosion resistance, and overcomes the defects of poor wear resistance and flame resistance of the titanium alloy, so the novel carbon nano reinforced titanium-based composite material is considered as a novel material capable of improving the performance of the titanium material and expanding the application of the titanium alloy. However, because the titanium alloy is active at high temperature, due to the problem of wettability between the carbon nanotube and the TC4 powder, it is difficult to make the carbon nanotube have good bonding force with the metal powder by using a mechanical alloying method such as ball milling, and the carbon nanotube is easily agglomerated and damaged, so that the bridging effect between the carbon nanotube and the TC4 powder cannot be fully exerted, and the excellent performance of the carbon nanotube in the subsequently prepared carbon nano reinforced titanium-based composite material cannot be fully exhibited. On the other hand, the Plasma Enhanced Chemical Vapor Deposition (PECVD) method is beneficial to growing the carbon nanotubes with complete structures on the TC4 powder surface rapidly and efficiently in situ and has strong bonding force with the surface of the matrix metal powder, but in the current research, the preparation of the CNTs @ TC4 composite powder by the chemical deposition method has the problems of poor uniformity of catalyst precursor preparation and poor interface wettability of catalyst particles and the powder surface, and the uniform distribution and moderate size of the catalyst particles significantly influence the uniform distribution and proper length-diameter ratio of the grown carbon nanotubes. There is therefore a need for an improved solution to this problem.

Catalyst attachment techniques such as precipitation deposition, impregnation, chemical plating, magnetron sputtering and the like can effectively attach catalyst nanoparticles on the surface of metal powder, but these methods have the disadvantages of uneven size of the carried catalyst particles, long time period, inconvenient operation, expensive equipment and high cost, and are not suitable for large-area popularization. The electrodeposition method is a novel and environment-friendly attachment method, utilizes current to accelerate ionization of electrolyte solution and redox reaction at two ends of a cathode and an anode, can uniformly distribute nano catalyst particles on the surface of TC4 powder, improves interface combination of the catalyst particles and TC4 powder, and simultaneously realizes good dispersibility.

Disclosure of Invention

Aiming at the problems, the invention discloses a rapid in-situ preparation method of CNTs @ TC4 composite powder, which can obviously improve the interface bonding force and distribution uniformity of a catalyst and the powder surface by depositing catalyst nano-iron particles on the surface of TC4 powder by an electrodeposition method. The process is simple to prepare and high in efficiency, the finally prepared carbon nano tube has good structural integrity and dispersibility, and the CNTs @ TC4 composite powder lays a foundation for the subsequent preparation of a high-performance carbon nano tube reinforced TC4 composite material.

In order to achieve the purpose, the invention adopts the following technical scheme:

a rapid in-situ preparation method of CNTs @ TC4 composite powder comprises the following steps:

(1) surface treatment of the powder: putting 10gTC4 powder into deionized water, performing ultrasonic treatment for 5-10min, pouring out the deionized water, putting the deionized water into absolute ethyl alcohol, performing ultrasonic treatment for 5-10min, repeating the steps for three times, and finally obtaining TC4 powder without grease on the surface;

(2) preparation of TC4 powder surface nano catalyst particles:the Fe (NO) is added in an amount of 0.0025 to 0.01mol/L₃)₃·9H₂O solution, spreading the TC4 powder obtained in the step (1) into an aluminum box placed in an electrophoresis tank to be used as a cathode, then pouring electrolyte solution into a stainless steel anode, connecting a lead, performing electrodeposition, and using an electrophoresis apparatus to carry out Fe³⁺Reducing Fe on the cathode into a simple substance, and depositing the simple substance on the surface of TC4 powder serving as the cathode to obtain catalyst precursor powder;

(3) preparation of CNTs @ TC4 composite powder: and (2) placing the catalyst precursor powder obtained in the step (1) in a PECVD furnace for growing the carbon nano tube. Firstly, calcining at 400 ℃ for 1h in an Ar atmosphere of 200sccm to obtain a small amount of Fe in the step (2)³⁺Fe (OH) bound to OH-₃Conversion to Fe₂O₃(ii) a Then Ar gas is turned off, and high-purity H of 200sccm is introduced₂Of Fe₂O₃Reducing the Fe particles into nano Fe particles for 1 h; finally, in a certain Ar: CH (CH)₄The CNTs @ TC4 composite powder is obtained by growing for 10-60 min under the atmosphere of the gas flow ratio, wherein plasma is started in the whole growing process, the power is 30-200W, and the growing temperature is 450-700 ℃.

Compared with the prior art, the invention has the following advantages:

(1) the invention uses electrochemical deposition method with Fe (NO)₃)₃·9H₂The method is characterized in that O is used as an electrolyte solution, nano catalyst Fe particles are deposited on the surface of TC4 powder, the Fe particles are used as catalyst active sites for growing CNT, and the structure of the catalyst plays a role of a template for the growth of the carbon nano tube, so that the Fe nanoparticles and the surface of the TC4 powder have good wettability and dispersibility, and a foundation is laid for the stable and uniform growth of subsequent CNTs.

(2) According to the invention, the carbon nanotubes are grown on the surface of the TC4 powder by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, plasma glow discharge promotes the cracking of CH4 gas, the activity of a C source can be better excited, the growth difficulty of CNTs is reduced, and simultaneously amorphous carbon impurities can be etched by the action of the plasma on the etched surface of the TC4 powder, so that the structural integrity and the wettability of the CNTs grown on the surface of the TC4 powder are increased, and the rapid growth of the high-quality carbon nanotubes on the surface of the TC4 powder is facilitated.

(3) The process provided by the invention is rapid and efficient, simple in flow, low in operation difficulty, low in equipment requirement, low in cost and good in popularization.

Drawings

FIG. 1 is a schematic view of an electrophoretic deposition apparatus according to the present invention;

FIG. 2 is a process flow diagram of the rapid in situ preparation method of CNTs @ TC4 composite powder according to the present invention;

FIG. 3 is a diagram of the morphology of a catalyst precursor under different methods;

FIG. 4 is a surface topography of CNTs @ TC4 composite powder under different methods;

FIG. 5 is a Raman spectrum of a composite powder of CNTs @ TC4 under a different method;

FIG. 6 is a graph of tensile strength of pure TC4 alloy with CNTs @ TC4 composites prepared by different methods.

Detailed Description

In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.

Example 1

A rapid in-situ preparation method of CNTs @ TC4 composite powder comprises the following steps:

(1) surface treatment of TC4 powder: putting 10gTC4 powder into deionized water, performing ultrasonic treatment for 5-10min, pouring out the deionized water, putting the deionized water into absolute ethyl alcohol, performing ultrasonic treatment for 5-10min, repeating the steps for three times, and finally obtaining TC4 powder without grease on the surface;

(2) preparation of TC4 powder surface nano catalyst particles: fe (NO) with 0.0025mol/L configuration₃)₃·9H₂O solution, step (ii)The obtained TC4 powder was spread into an aluminum box placed in an electrophoresis tank as a cathode, and then an electrolyte solution was poured over a stainless steel anode, and electrodeposition was performed after connecting a wire. Then Fe is added by an electrophoresis apparatus³⁺Reducing the solution to Fe simple substance on a cathodeDepositing on the surface of TC4 powder as cathode at 6V for 30min, and performing ultrasonic dispersion every 5 min; finally vacuum drying is carried out for 24 h.

(3) Preparation of CNTs @ TC4 composite powder: will be described in detailThe obtained catalyst precursor powder is placed in a PECVD furnace to carry out TC4 powder surface in-situ growth of carbon nanotubes. Firstly, calcining at 400 ℃ for 1h in an Ar atmosphere of 200sccmMiddle and small amount of Fe³⁺Fe (OH) bound to OH-₃Conversion to Fe₂O₃(ii) a Then Ar gas is turned off, and high-purity H of 200sccm is introduced₂Of Fe₂O₃Reducing the Fe particles into nano Fe particles for 1 h; finally in Ar: CH₄= 4: growing for 30min in the atmosphere with the gas flow ratio of 1 to obtain CNTs @ TC4 composite powder, wherein plasma is started in the whole growing process, the power is 175W, and the growing temperature is 600 ℃.

Example 2

A rapid in-situ preparation method of CNTs @ TC4 composite powder comprises the following steps:

(1) surface treatment of TC4 powder: putting 10gTC4 powder into deionized water, performing ultrasonic treatment for 5-10min, pouring out the deionized water, putting the deionized water into absolute ethyl alcohol, performing ultrasonic treatment for 5-10min, repeating the steps for three times, and finally obtaining TC4 powder without grease on the surface;

(2) preparation of TC4 powder surface nano catalyst particles: fe (NO) with 0.0025mol/L configuration₃)₃·9H₂O solution, step (ii)The obtained TC4 powder was spread into an aluminum box placed in an electrophoresis tank as a cathode, and then an electrolyte solution was poured over a stainless steel anode, and electrodeposition was performed after connecting a wire. Then Fe is added by an electrophoresis apparatus³⁺Reducing Fe on the cathode to deposit on the surface of TC4 powder as the cathode,the voltage is 8V, the deposition time is 20min, and ultrasonic dispersion is carried out every 5 min; finally vacuum drying is carried out for 24 h.

(3) Preparation of CNTs @ TC4 composite powder: will be described in detailThe obtained catalyst precursor powder is placed in a PECVD furnace to carry out TC4 powder surface in-situ growth of carbon nanotubes. Firstly, calcining at 400 ℃ for 1h in an Ar atmosphere of 200sccmMiddle and small amount of Fe³⁺Fe (OH) bound to OH-₃Conversion to Fe₂O₃(ii) a Then Ar gas is turned off, and high-purity H of 200sccm is introduced₂Of Fe₂O₃Reducing the Fe particles into nano Fe particles for 1 h; finally in Ar: CH₄= 4: growing for 30min in the atmosphere with the gas flow ratio of 1 to obtain CNTs @ TC4 composite powder, wherein plasma is started in the whole growing process, the power is 175W, and the growing temperature is 600 ℃.

Comparative example: the preparation method of the CNTs @ TC4 composite powder by a precipitation deposition method comprises the following steps:

(1) preparing a catalyst precursor by a precipitation deposition method: 10gTC4 powder and 2.3gFe (NO3)₃·9H₂Mixing O in deionized water (the final catalyst is Fe with the content of 3%), performing ultrasonic treatment for 5-10min, performing magnetic stirring, and simultaneously dropwise adding excessive NaOH solution to ensure that nitrate and NaOH solution fully react to generate Fe (OH)₃Stirring for 2-3h, standing for 5-6h, vacuum filtering, and adding deionized water to obtain Fe (OH)₃The @ TC4 is neutral, the water is drained, the mixture is put into a vacuum drying oven to be dried for 24 hours, and the mixture needs to be taken out, ground and sieved in the midway to ensure that the granules are fully dried;

(2) preparation of CNTs @ TC4 composite powder: will be described in detailThe obtained catalyst precursor powder is placed in a PECVD furnace for the growth of the carbon nano tube.Firstly calcining for 4h under Ar atmosphere of 200sccm, wherein the calcining is performed for 2h at 300 ℃ and 2h at 400 ℃, and the steps are as followsFe (OH) of (1)₃Conversion to Fe₂O₃Then, Ar gas is turned off, and high-purity H of 200sccm is introduced₂Of Fe₂O₃Reducing the Fe particles into nano Fe particles for 2 hours; finally in Ar: CH₄= 4: growing for 30min in the atmosphere with the gas flow ratio of 1 to obtain CNTs @ TC4 composite powder, wherein plasma is started in the whole growing process, the power is 175W, and the growing temperature is 600 ℃.

The CNTs @ TC4 composite powder prepared in the two examples is combined, and the morphology and the structural integrity of the CNTs @ TC4 composite powder prepared in the comparative example are compared.

FIG. 3 is a diagram of the morphology of a catalyst precursor under different methods; (a) example 1: electrodeposition method 6V-30min, (b) example 2: electrodeposition method 8V-20min, (c) comparative example: precipitation deposition; as can be seen from fig. 3 (a), (b) and (c), the catalyst precursor TC4 powders obtained in examples 1 and 2 have uniform adhesion distribution on the surface, small particle size and regular shape; in FIG. 3 (c), the catalyst precursor obtained by the precipitation deposition method is non-uniformly distributed, agglomerated and large in size; growth factors of the carbon nano tube are directly related to the size and distribution of catalyst particles, and the TC4 powder attached to the catalyst precursor obtained by adopting the electrodeposition method is obviously beneficial to the uniform high-quality growth of the subsequent CNTs;

FIG. 4 is a surface topography of CNTs @ TC4 composite powder under different methods; (a) example 1: electrodeposition method 6V-30min, (b) example 2: electrodeposition method 8V-20min, (c) comparative example: precipitation deposition; from fig. 4 (a), (b), it can be seen that the carbon nanotubes grown by the electrodeposition combined with the pecvd method in examples 1 and 2 have more uniform distribution, less carbon impurities and higher aspect ratio; whereas in the comparative example of FIG. 4 (c), the carbon nanotubes grown by the precipitation deposition method in combination with the plasma chemical vapor deposition method were not uniformly distributed, a large amount of carbon impurities such as carbon onion, amorphous carbon, etc. were present, and the thickness was not uniform; therefore, the CNTs @ TC4 composite powder obtained by the electrodeposition method has more excellent morphological characteristics;

FIG. 5 is a Raman spectrum of CNTs @ TC4 composite powder in different ways; the carbon nano tubes obtained by combining the electrodeposition method with the plasma enhanced chemical vapor deposition method in the embodiments 1 and 2 have higher graphitization degree, good structural integrity and less carbon impurities; in the comparative example, the carbon nanotubes grown by the precipitation deposition method combined with the plasma chemical vapor deposition method have low graphitization degree and poor structural integrity, which means that a large amount of carbon impurities such as carbon onion, amorphous carbon and the like exist; the CNTs @ TC4 composite powder obtained by adopting an electrodeposition method and a plasma enhanced chemical vapor deposition method has more excellent structural integrity and uniformity of the carbon nano tube.

FIG. 6 is a graph of tensile elongation of pure TC4 alloy with CNTs @ TC4 composites prepared by different methods; from FIG. 6, it can be seen that the CNTs @ TC4 composite prepared in example 1 has certain advantages in tensile strength compared with pure TC4 alloy and CNTs @ TC4 composite prepared by precipitation deposition. The CNTs @ TC4 composite material prepared by the method disclosed by the invention can improve the mechanical property of the material while improving the preparation efficiency.

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.