CN111333078B

CN111333078B - Preparation method of titanium diboride strip-shaped nanosheets

Info

Publication number: CN111333078B
Application number: CN202010148639.XA
Authority: CN
Inventors: 任淑彬; 贾楠; 明飞; 赵洋; 曲选辉
Original assignee: University of Science and Technology Beijing USTB
Current assignee: University of Science and Technology Beijing USTB
Priority date: 2020-03-05
Filing date: 2020-03-05
Publication date: 2021-11-26
Anticipated expiration: 2040-03-05
Also published as: CN111333078A

Abstract

The invention discloses a preparation method of titanium diboride strip-shaped nanosheets, which comprises the following steps: placing metal titanium, nickel and boron powder in a water-cooled copper crucible according to a certain proportion requirement, and melting the metal titanium, nickel and boron powder into alloy liquid in a vacuum induction melting furnace under the protection of inert gas; cooling and solidifying the alloy liquid into Ti-Ni-B alloy; carrying out electrochemical extraction treatment on the prepared alloy to remove a NiTi phase in the alloy; filtering the electrolyzed electrolyte, sequentially washing the electrolyte with distilled water and alcohol, and then drying to obtain the titanium diboride strip-shaped nano-sheets. The method adopts a mode of combining traditional casting and electrochemistry, and has the advantages of simple process, convenient operation and low cost; and the size of the titanium diboride nanosheets can be controlled according to parameters such as alloy components, smelting conditions and the like.

Description

Preparation method of titanium diboride strip-shaped nanosheets

Technical Field

The invention relates to a preparation method of titanium diboride strip-shaped nanosheets, and belongs to the technical field of preparation methods of nano materials.

Background

Titanium diboride (TiB)₂) Is the most stable compound formed between two elements of B and Ti and has a hexagonal structure. The B atomic plane and the Ti atomic plane alternately appear to form a two-dimensional network crystal structure, and the structure has covalent bonds and ionic bonds. Thus TiB₂Has high melting point, high hardness and high elastic modulus. In addition, TiB₂The ceramic nanosheet has high elastic strain and high strength, is ceramic with special physical and chemical properties, has good chemical stability, strong corrosion resistance, good wettability with a matrix, high wear resistance and excellent heat and electricity conductivity, and is often used as a reinforcing phase to be compounded with other matrixes (such as CN109207764A, CN110257655 and CN107586988B)₂The combination of the ceramic and the metal matrix is expected to obtain a new characteristic of integrating high strength and high elasticity.

Currently, there are many methods for synthesizing titanium diboride. Matsuura K et al, by a self-propagating high-temperature synthesis process, directly burn boron powder and titanium powder at 900K to synthesize TiB₂(Matsuura K,Obara Y,Kudoh M.Fabrication of TiB2 particle dispersed FeAl-based composites by self-propagating high-temperature synthesis[J]ISIJ International,2006,46(6): 871-; lu L et Al synthesized TiB2(Lu L, et Al Synthesis of titanium dioxide TiB2 and Ti-Al-B metallic compounds [ J ] by mechanical alloying]Journal of Materials Science, 2000.); gu Y synthesizes TiB by benzene thermal reaction in an autoclave under 673K by utilizing metal sodium, amorphous boron powder and titanium tetrachloride₂(Gu Y,Qian Y,Chen L,et al.A Mild Solvothermal Route to Nanocrystalline Titanium Diboride[J]Journal of Alloys and Compounds,2003,352(1-2): 325-; guo WM et al boron-on-nano TiO in vacuum₂Carries out boron thermal reduction to synthesize TiB₂Powder (Guo WM, Zhang GJ, You Y, et al. TiB2 powder Synthesis by Borothermal Reduction in TiO2 Under Vacuum [ J]Journal of the American Ceramic Society,2014,97(5): 1359-; karvankova P et al with TiCl₄、BCl₃、N₂And H₂TiB was prepared for the reactants by plasma chemical vapour deposition at a total pressure of a few mbar and a deposition temperature of 793K₂(P.Karvánková,M.G.J.

-Heijman,Zawrah M F,et al.Thermal stability of nc-TiN/a-BN/a-TiB2 nanocomposite coatings deposited by plasma chemical vapor deposition[J]Thin Solid Films,2004,467(1-2): 133-139). However, the above method only gives TiB in the form of particles₂。

Preparing TiB with special shape such as nano sheet₂The research and the report of (1) are few. Ke-Han Wu et al utilize TiO₂B and MgCl₂Starting from MgCl in flowing argon₂By carrying out TiO₂By boron thermal reduction to synthesize TiB₂Nanosheets. (Wu K H, Wang Y, Yu-Jiang, et al, Low temperature synthesis of titanium dioxide resins by molar salt of an associated borothermals reduction of TiO2[ J]Journal of Nanoparticle Research,2019,21 (5.) however, the above preparation method, it is not easy to control the size (including length and thickness) of the nanoplatelets, and TiB prepared₂The nanosheets are small and their crystallographic orientation cannot be controlled。

Disclosure of Invention

The invention aims to solve the problem of TiB in the prior art₂The preparation method of the nano-sheet is complex, the preparation method is single, and the TiB with simple process, adjustable and controllable thickness and length of the nano-sheet is provided₂A novel process for preparing nanosheets.

A preparation method of titanium diboride strip-shaped nanosheets is characterized by comprising the following steps: pure titanium (C)>99 wt%), pure nickel (C), (D) and>99 wt%) and pure boron powder (b: (b)>99 wt%) as raw material, according to mass fraction Ni: 50-59.5%, Ti: 40-50%, B: 0.1-0.5 wt% and vacuum induction smelting to obtain Ti-Ni-B ternary alloy, wherein TiB₂Precipitating from a substrate NiTi alloy in a nano sheet form, and then dissolving the substrate NiTi alloy by adopting an electrochemical extraction method to finally obtain TiB₂Strip-shaped nanosheets.

The preparation method of the titanium diboride strip-shaped nanosheet comprises the following steps:

(1) placing Ti, Ni and B powder in a vacuum induction melting furnace provided with a water-cooled copper crucible according to the proportion, heating to 1400-1500 ℃ under the protection of inert gas to melt the metal into alloy liquid, and electromagnetically stirring in the melting process to ensure that the components are uniformly melted;

(2) under the protection of inert gas, the alloy liquid is cooled and solidified into Ti-Ni-B ternary alloy which is composed of NiTi and TiB₂Two phases are formed;

(3) carrying out electrochemical extraction treatment on the prepared Ti-Ni-B alloy to remove a NiTi matrix phase in the alloy; the electrochemistry adopts a two-electrode electrochemical device, takes Ti-Ni-B as a working electrode, a graphite flake as a cathode and a mixed solution of perchloric acid and acetic acid as an electrolyte, and is electrolyzed for 4-8h at room temperature and 10V working voltage; wherein perchloric acid accounts for 21 vol% of the volume of the electrolytic solution, and the balance is acetic acid;

(4) filtering the electrolyte solution after electrochemical extraction, sequentially cleaning the electrolyte solution with distilled water and alcohol, and drying the electrolyte solution to obtain titanium diboride nanosheets and prepared TiB₂The thickness of the nano-sheet is 50-200nm, the length is 5-80 μm, and the length and the width areThe ratio is (5-10): 1.

method of the invention and existing TiB₂Compared with the preparation process of the nanosheet, the preparation method has the following advantages:

(1) the method combines the traditional casting method and the electrochemical extraction, and has simple process and low cost.

(2) The method can regulate and control the size (thickness and length) of the titanium boride nanosheet according to the components of the Ti-Ni-B alloy, smelting conditions and other parameters, and the length of the titanium boride nanosheet can reach 5-80 microns.

Detailed Description

The method takes metal titanium, nickel and boron powder as raw materials, obtains Ti-Ni-B ternary alloy castings by a smelting method, and removes a matrix phase NiTi by an electrochemical extraction method to obtain TiB₂Nanosheets. In the process of the invention, the inert gas shield is used throughout the smelting process to prevent oxidation of the metal, especially titanium, since oxygen has a significant influence on the experimental results.

The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited thereto.

Example 1

(1) Placing metal titanium, nickel and boron powder into a water-cooled copper crucible according to a ratio, melting in a vacuum induction melting furnace under the protection of argon, and electromagnetically stirring to make the alloy liquid more uniform, wherein the melting temperature is 1400 ℃, the mass fraction of Ni is 55.76%, the mass fraction of Ti is 44.14%, and the mass fraction of B is 0.1%.

(2) Casting the molten and uniformly stirred alloy liquid into a mould to obtain cylindrical Ti-Ni-B alloy with the diameter of 50mm and the length of 100mm, wherein the obtained alloy comprises NiTi and TiB₂Two phases are formed;

(3) under the conditions of room temperature and electromagnetic stirring, taking the Ti-Ni-B alloy in the step (2) as a working electrode, a graphite sheet as a cathode, a mixed solution of acetic acid and perchloric acid as an electrolyte solution, and carrying out electrolytic treatment at a working voltage of 10V to remove a NiTi phase in the alloy, wherein the treatment time is 6 hours, the perchloric acid accounts for 21% by volume, and the acetic acid accounts for 79%;

(4) filtering the electrolyte, andwashing the filtered sample with distilled water and alcohol, and drying to obtain TiB₂Nanosheets. Prepared TiB₂The thickness of the nano-sheet is 100-200nm, the length is 5-15 μm, and the ratio of the length to the width is (5-10): 1.

example 2

(1) Placing metal titanium, nickel and boron powder in a water-cooled copper crucible according to a ratio, melting in a vacuum induction melting furnace under the protection of argon, and electromagnetically stirring to make an alloy liquid more uniform, wherein the melting temperature is 1400 ℃, the mass fraction of Ni is 55.46%, the mass fraction of Ti is 44.34%, and B accounts for 0.2 wt% of the total mass;

(2) casting the melted and uniformly stirred alloy liquid to obtain cylindrical Ti-Ni-B alloy with the diameter of 50mm and the length of 100mm, wherein the obtained alloy comprises NiTi and TiB₂Two phases are formed;

(3) under the conditions of room temperature and electromagnetic stirring, taking Ti-Ni-B alloy as a working electrode, a graphite sheet as a cathode, a mixed solution of acetic acid and perchloric acid as an electrolyte solution, and working voltage of 10V, carrying out electrolytic treatment to remove a NiTi phase in the alloy, wherein the treatment time is 6 hours, the perchloric acid is 21% in volume percentage, and the acetic acid is 79%;

(4) filtering the electrolyte, washing the filtered sample with distilled water and alcohol, and drying to obtain TiB₂Nanosheets. Prepared TiB₂The thickness of the nano-sheet is 60-150nm, the length is 20-80 μm, and the ratio of the length to the width is (5-10): 1.

example 3

(1) Placing metal titanium, nickel and boron powder in a water-cooled copper crucible according to a ratio, melting in a vacuum induction melting furnace under the protection of argon, and electromagnetically stirring to make the alloy liquid more uniform, wherein the melting temperature is 1400 ℃, Ni accounts for 61% of the total mass, Ti accounts for 38.5% of the total mass, and B accounts for 0.5 wt% of the total mass.

(3) under the conditions of room temperature and electromagnetic stirring, taking Ti-Ni-B alloy as a working electrode, a graphite sheet as a cathode, a mixed solution of acetic acid and perchloric acid as an electrolyte solution, and working voltage of 10V, carrying out electrolytic treatment to remove a NiTi phase in the alloy, wherein the treatment time is 8 hours, the perchloric acid is 21% in volume percentage, and the acetic acid is 79%;

(4) filtering the electrolyte, washing the filtered sample with distilled water and alcohol, and drying to obtain TiB₂Nanosheets. Prepared TiB₂The length of the nanosheet is 5-20 μm, the thickness of the nanosheet is 0.2-25 μm, and the ratio of the length to the width is (5-10): 1.

Claims

1. a preparation method of titanium diboride strip-shaped nanosheets is characterized by comprising the following steps: pure titanium (C)>99 wt%), pure nickel (C), (D) and>99 wt%) and pure boron powder (b: (b)>99 wt%) as raw material, according to mass fraction Ni: 50-59.5%, Ti: 40-50%, B: 0.1-0.5 wt% and vacuum induction smelting to obtain Ti-Ni-B ternary alloy, wherein TiB₂Precipitating from a substrate NiTi alloy in a nano sheet form, and then dissolving the substrate NiTi alloy by adopting an electrochemical extraction method to finally obtain TiB₂Strip-shaped nanosheets;

the preparation method of the titanium diboride strip-shaped nano sheet comprises the following steps:

(4) Filtering the electrolyte solution after electrochemical extraction, sequentially cleaning the electrolyte solution with distilled water and alcohol, and drying the electrolyte solution to obtain titanium diboride nanosheets and prepared TiB₂The thickness of the nano-sheet is 50-200nm, the length is 5-80 μm, and the ratio of the length to the width is (5-10): 1.