阅读说明：本技术 一种3d打印耐磨耐蚀钛合金及其制备方法与应用 (3D printing wear-resistant corrosion-resistant titanium alloy and preparation method and application thereof ) 是由 陈伟民 于 2021-09-13 设计创作，主要内容包括：本发明公开了一种3D打印耐磨耐蚀钛合金及其制备方法与应用。该耐磨耐蚀钛合金,包括如下原子百分数计的元素成分：Nb的成分范围为16～25％,Zr的成分范围为15～30％,Cr的成分范围为0～4％,Sc的成分范围为0～0.5％,余量为Ti。该合金制备方法包括：将金属粉末按照成分配比混粉球磨,3D打印制备合金试样(激光工艺参数设定为：输出功率150～450W,光斑直径80～100μm,和扫描速率500～1500mm/s),真空环境下退火处理,冰水冷却,最终得到耐磨耐蚀钛合金。该耐磨耐蚀钛合金具有良好的耐电化学腐蚀性和耐磨性等优点,可作为高性能医用金属材料在临床修复中具有非常广阔的应用前景。(The invention discloses a 3D printing wear-resistant corrosion-resistant titanium alloy and a preparation method and application thereof. The wear-resistant corrosion-resistant titanium alloy comprises the following element components in atomic percentage: nb is 16-25%, Zr is 15-30%, Cr is 0-4%, Sc is 0-0.5%, and Ti is the rest. The preparation method of the alloy comprises the following steps: mixing and ball-milling metal powder according to the component proportion, preparing an alloy sample by 3D printing (the laser process parameters are set to be 150-450W of output power, 80-100 mu m of spot diameter and 500-1500 mm/s of scanning speed), annealing in a vacuum environment, and cooling with ice water to finally obtain the wear-resistant corrosion-resistant titanium alloy. The wear-resistant corrosion-resistant titanium alloy has the advantages of good electrochemical corrosion resistance and wear resistance and the like, and can be used as a high-performance medical metal material to have a very wide application prospect in clinical repair.)

1. The preparation method of the wear-resistant corrosion-resistant titanium alloy for 3D printing is characterized by comprising the following steps of:

(1) the pure metal powder is prepared according to the following components in atomic percentage: 16-25% of Nb, 15-30% of Zr, 0-4% of Cr, 0-0.5% of Sc and the balance of Ti; after uniformly mixing all metal powder, carrying out ball milling treatment to obtain titanium alloy powder, and preparing an alloy sample from the ball-milled titanium alloy powder in a 3D printing mode:

(2) and (2) carrying out vacuum annealing treatment on the alloy sample obtained in the step (1) to obtain the wear-resistant corrosion-resistant titanium alloy.

2. The method for preparing the 3D printing wear-resistant corrosion-resistant titanium alloy according to claim 1, wherein the pure metal powder in the step (1) is prepared according to the following components in atomic percentage: 16% of Nb, 15% of Zr and the balance of Ti.

3. The method for preparing the 3D printing wear-resistant corrosion-resistant titanium alloy according to claim 1, wherein the pure metal powder in the step (1) is prepared according to the following components in atomic percentage: 25% of Nb, 25% of Zr, 3% of Cr and the balance of Ti.

4. The method for preparing the 3D printing wear-resistant corrosion-resistant titanium alloy according to claim 1, wherein the pure metal powder in the step (1) is prepared according to the following components in atomic percentage: 23 percent of Nb, 30 percent of Zr, 3.5 percent of Cr, 0.5 percent of Sc and the balance of Ti.

5. The preparation method of the 3D printing wear-resistant corrosion-resistant titanium alloy according to claim 1, wherein the particle size of the titanium alloy powder obtained after ball milling in the step (1) is normally distributed within a range of 10-60 μm.

6. The method for preparing the wear-resistant and corrosion-resistant titanium alloy for 3D printing according to claim 1, wherein the number of powder particles with the particle size of less than or equal to 1 μm in the titanium alloy powder in the step (1) is less than 3%;

the number of powder particles with the particle size of less than or equal to 10 mu m in the titanium alloy powder is less than 10 percent;

the number of powder particles with the particle size of less than or equal to 20 mu m in the titanium alloy powder is less than 40 percent;

the number of powder particles with the particle size of less than or equal to 30 mu m in the titanium alloy powder is less than 70 percent;

the number of powder particles with the particle size of less than or equal to 40 mu m in the titanium alloy powder is less than 85 percent;

the number of powder particles with the particle size of less than or equal to 50 mu m in the titanium alloy powder is less than 90 percent;

the number of powder particles with the particle size of less than or equal to 60 mu m in the titanium alloy powder is less than 95 percent.

7. The method for preparing the 3D printing wear-resistant corrosion-resistant titanium alloy according to claim 1, wherein the laser process parameters of the 3D printing forming in the step (1) comprise a spot diameter, a laser power and a laser scanning rate; the diameter of the light spot is 80-100 mu m; the laser power is 150-450W; the laser scanning speed is 500-1500 mm/s.

8. The preparation method of the 3D printing wear-resistant corrosion-resistant titanium alloy according to claim 1, wherein the vacuum degree in the vacuum annealing process in the step (2) is less than 10Pa, the annealing temperature is 900-1200 ℃, the annealing time is 0.5-5 hours, and the cooling mode is that the alloy is placed in an ice-water mixture for quenching.

9. A wear and corrosion resistant titanium alloy prepared according to the preparation method of any one of claims 1 to 8.

10. Use of the wear and corrosion resistant titanium alloy of claim 9 in the field of medical implants.

Technical Field

The invention belongs to the technical field of metal materials, and particularly relates to a 3D printing wear-resistant corrosion-resistant titanium alloy and a preparation method and application thereof.

Background

Due to good mechanical strength, stainless steel, cobalt-chromium alloy and titanium alloy are often used as hard tissue implant materials in clinical restoration of bones, oral cavities and the like. The medical metal materials which are most widely applied at present are stainless steel, cobalt-chromium alloy and Ti-Al-V alloy, and have considerable economic benefit in the field of medical metal materials. However, the three traditional medical metal materials have high biological toxicity such as cell tissues and the like, so that the three traditional medical metal materials bring high health risks to patients and even possibly have life risks.

The titanium alloy without aluminum, vanadium and other elements has good biocompatibility and has the potential of replacing traditional clinical medical metal materials greatly. The development of novel wear-resistant and corrosion-resistant titanium alloy to replace traditional stainless steel and cobalt-chromium alloy is a hot spot and a key point in the field of current medical metal materials, and has huge potential economic value and social benefit. The currently researched medical titanium alloy is mainly prepared by smelting and hot processing, and the preparation technology is suitable for initial experimental research. However, there are significant challenges to the complex shape of the external implant during clinical use, and additive manufacturing techniques have become the current best way to make complex parts. The additive manufacturing technology can efficiently prepare samples in any shapes, and can save the cost of die manufacturing, subsequent machining and the like. In addition, the wear resistance and the corrosion resistance in clinical practical application play a very important role in the practical use process of the material. Therefore, it is very necessary to develop a wear-resistant and corrosion-resistant titanium alloy for additive manufacturing.

Disclosure of Invention

In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of a 3D printing wear-resistant corrosion-resistant titanium alloy.

The second purpose of the invention is to provide the wear-resistant corrosion-resistant titanium alloy prepared by the preparation method, and the wear-resistant corrosion-resistant titanium alloy has excellent performances such as good corrosion resistance and higher wear resistance.

The third purpose of the invention is to provide the application of the wear-resistant corrosion-resistant titanium alloy.

The primary purpose of the invention is realized by the following technical scheme:

a preparation method of 3D printing wear-resistant corrosion-resistant titanium alloy comprises the following steps:

(1) the pure metal powder is prepared according to the following components in atomic percentage: 16-25% of Nb, 15-30% of Zr, 0-4% of Cr, 0-0.5% of Sc and the balance of Ti; after uniformly mixing all metal powder, carrying out ball milling treatment to obtain titanium alloy powder, and preparing an alloy sample from the ball-milled titanium alloy powder in a 3D printing mode:

(2) and (2) carrying out vacuum annealing treatment on the alloy sample obtained in the step (1) to obtain the wear-resistant corrosion-resistant titanium alloy.

Preferably, the pure metal powder in step (1) is prepared according to the following components in atomic percentage: nb 16%, Zr 15%, and the balance Ti.

Preferably, the pure metal powder in step (1) is prepared according to the following components in atomic percentage: nb 25%, Zr 25%, Cr 3%, and the balance Ti.

Preferably, the pure metal powder in step (1) is prepared according to the following components in atomic percentage: nb 23%, Zr 30%, Cr 3.5%, Sc 0.5%, and the balance Ti.

Preferably, the particle size of the titanium alloy powder obtained after ball milling in step (1) is normally distributed within the range of 10-60 μm.

Preferably, the number of powder particles with the particle size less than or equal to 1 μm in the titanium alloy powder in the step (1) is less than or equal to 3 percent;

the number of powder particles with the particle size of less than or equal to 10 mu m in the titanium alloy powder is less than 10 percent;

the number of powder particles with the particle size of less than or equal to 20 mu m in the titanium alloy powder is less than 40 percent;

the number of powder particles with the particle size of less than or equal to 30 mu m in the titanium alloy powder is less than 70 percent;

the number of powder particles with the particle size of less than or equal to 40 mu m in the titanium alloy powder is less than 85 percent;

the number of powder particles with the particle size of less than or equal to 50 mu m in the titanium alloy powder is less than 90 percent;

the number of powder particles with the particle size of less than or equal to 60 mu m in the titanium alloy powder is less than 95 percent.

Preferably, the laser process parameters of the 3D printing and forming in step (1) include a spot diameter, a laser power and a laser scanning rate; the diameter of the light spot is 80-100 mu m; the laser power is 150-450W; the laser scanning speed is 500-1500 mm/s.

Preferably, the vacuum degree of the vacuum annealing process in the step (2) is less than 10Pa, the annealing temperature is 900-1200 ℃, the time is 0.5-5 hours, and the cooling mode is that the annealing process is carried out by placing the annealing process in an ice-water mixture for quenching.

The second purpose of the invention is realized by the following technical scheme:

the wear-resistant corrosion-resistant titanium alloy prepared by the preparation method.

The third purpose of the invention is realized by the following technical scheme:

an application of wear-resistant corrosion-resistant titanium alloy in the field of medical implants.

Compared with the prior art, the invention has the following advantages and beneficial effects:

compared with the titanium alloy prepared by the existing electric arc melting, the titanium alloy prepared by the invention has corrosion resistance and good wear resistance. The wear-resistant corrosion-resistant titanium alloy can be prepared into any shape by a 3D printing technology, and is beneficial to preparing medical implants and applied to clinical medical treatment.

Drawings

FIG. 1 is a microstructure of the wear-resistant and corrosion-resistant titanium alloy obtained in example 1 after frictional wear;

FIG. 2 is a microstructure of the wear-resistant and corrosion-resistant titanium alloy obtained in example 2 after frictional wear;

FIG. 3 shows the microstructure of the wear-resistant and corrosion-resistant titanium alloy obtained in example 3 after frictional wear.

Detailed Description

The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.

EXAMPLE 1 wear and Corrosion resistant Ti-Nb-Zr alloy

The embodiment provides a 3D printing wear-resistant corrosion-resistant Ti-Nb-Zr alloy which comprises the following components in atomic percent: the content of Nb is 16%, the content of Zr is 15%, and the balance is Ti. The method comprises the steps of taking high-purity Ti powder, high-purity Nb powder and high-purity Zr powder as raw materials, mixing the pure metal powder according to the mass ratio of 53.6:24.2:22.2, carrying out wet grinding for 2 hours at the ball milling speed of 200 r/min, drying, sieving and granulating to obtain the spherical alloy powder which is uniformly mixed and has the average grain size of about 20 mu m. Preparation of Block samples (size 10X 3 mm) by means of Selective laser melting apparatus³) The laser power (150W), spot diameter (80 μm) and scan rate (1500mm/s) were given. After printing, the printed metal ingot is obtained by wire cutting, and rough grinding treatment is carried out on the metal ingot. (2) And (3) carrying out vacuum annealing treatment on the printing sample obtained in the step (1). Putting the alloy into a vacuum sealed quartz tube filled with titanium sponge, annealing at high temperature in an annealing furnace at 900 ℃ and keeping the temperature for 5 hours, taking the quartz tube out of the annealing furnace, putting the quartz tube into ice water, and quickly breaking the quartz tube to reduce the temperature of the obtained alloy within 1 minute. (3) Performing coarse grinding, fine grinding, polishing, deionized water ultrasonic cleaning and drying treatment on the alloy sample with the components of Ti-16 at.% Nb-15 at.% Zr obtained in the step (2), performing experimental determination on the wear rate, the electrochemical corrosion performance and the like by using a multifunctional friction wear testing machine and an electrochemical workstation, and performing microstructure analysis by using a scanning electron microscope as shown in fig. 1. As can be seen from Table 1, the corrosion current of the alloy was 1.7. + -. 0.3X 10^{- 7}Acm^-2The corrosion potential is-0.4 +/-0.1V, and the abrasion volume is 1.2 +/-0.1 multiplied by 10^-11m³. The Ti-Nb-Zr alloy manufactured by the additive has good wear resistance and electrochemical corrosion performance, and has very wide application prospect in clinical repair as a high-performance medical metal material.

EXAMPLE 2 wear and Corrosion resistant Ti-Nb-Zr-Cr alloy

The embodiment provides a 3D printing wear-resistant corrosion-resistant Ti-Nb-Zr-Cr alloy which comprises the following components in atomic percent: the composition range of Nb is 25%, the composition range of Zr is 25%, the composition range of Cr is 3%, and the balance is Ti.

(1) The method comprises the steps of taking high-purity Ti powder, high-purity Cr powder, high-purity Nb powder and high-purity Zr powder as raw materials, mixing the pure metal powder according to the mass ratio of 32.1:33.2:32.5:2.2, carrying out wet grinding for 2 hours at the ball milling speed of 200 r/min, drying, sieving and granulating to obtain the spherical alloy powder which is uniformly mixed and has the average grain size of about 20 mu m. Preparation of Block samples (size 10X 3 mm) by means of Selective laser melting apparatus³) The laser power (300W), spot diameter (90 μm) and scan rate (1000mm/s) are given. After printing, the printed metal ingot is obtained by wire cutting, and rough grinding treatment is carried out on the metal ingot. (2) And (3) carrying out vacuum annealing treatment on the printing sample obtained in the step (1). Putting the alloy into a vacuum seal quartz tube filled with titanium sponge, annealing at high temperature of 1100 ℃ in an annealing furnace, keeping the temperature for 1 hour, taking out the quartz tube from the annealing furnace, putting the quartz tube into ice water, and quickly breaking the quartz tube to reduce the temperature of the obtained alloy within 1 minute. (3) Performing coarse grinding, fine grinding, polishing, deionized water ultrasonic cleaning and drying treatment on the alloy sample with the component content of Ti-25 at.% Nb-25 at.% Zr-3 at.% Cr obtained in the step (2), performing experimental determination on the wear rate, the electrochemical corrosion performance and the like by using a multifunctional friction wear tester and an electrochemical workstation, and performing microstructure analysis by using a scanning electron microscope as shown in fig. 2. As can be seen from Table 1, the corrosion current of the alloy was 1.0. + -. 0.3X 10-7Acm^-2The corrosion potential is-0.5 +/-0.1V, and the abrasion volume is 1.5 +/-0.1 multiplied by 10-11m³. The Ti-Nb-Zr-Cr alloy manufactured by the additive has good wear resistance and electrochemical corrosion performance, and has very wide application prospect in clinical repair as a high-performance medical metal material.

EXAMPLE 3 wear and Corrosion resistant Ti-Nb-Zr-Cr-Sc alloy

The embodiment provides a wear-resistant and corrosion-resistant Ti-Nb-Zr-Cr-Sc alloy for 3D printing

Comprises the following components in atomic percentage: the composition range of Nb is 23%, the composition range of Zr is 30%, the composition range of Cr is 3.5%, the composition range of Sc is 0.5%, and the balance is Ti.

(1) The method comprises the steps of taking high-purity Ti powder, high-purity Cr powder, high-purity Nb powder, high-purity Sc powder and high-purity Zr powder as raw materials, mixing the pure metal powder according to the mass ratio of 28.8:30.0:38.3:2.5:0.4, carrying out wet grinding for 2 hours at the ball milling speed of 200 revolutions per minute, drying, sieving and granulating to obtain the spherical alloy powder which is uniformly mixed and has the average grain size of about 20 mu m. Preparation of Block samples (size 10X 3 mm) by means of Selective laser melting apparatus³) The laser power (450W), spot diameter (100 μm) and scan rate (500mm/s) are given. After printing, the printed metal ingot is obtained by wire cutting, and rough grinding treatment is carried out on the metal ingot.

(2) And (3) carrying out vacuum annealing treatment on the printing sample obtained in the step (1). Putting the alloy into a vacuum sealed quartz tube filled with titanium sponge, annealing at high temperature in an annealing furnace at 1200 ℃, keeping the temperature for 0.5 hour, taking the quartz tube out of the annealing furnace, putting the quartz tube into ice water, and quickly breaking the quartz tube to reduce the temperature of the obtained alloy within 1 minute.

(3) Performing coarse grinding, fine grinding, polishing, deionized water ultrasonic cleaning and drying treatment on the Sc alloy sample with the component content of Ti-23 at.% Nb-30 at.% Zr-3.5 at.% Cr-0.5 at.% obtained in the step (2), performing experimental determination on the abrasion rate, the electrochemical corrosion performance and the like by using a multifunctional friction abrasion tester and an electrochemical workstation, and performing microstructure analysis by using a scanning electron microscope as shown in FIG. 3. As can be seen from Table 1, the corrosion current of the alloy was 0.9. + -. 0.3X 10^-7Acm^-2The corrosion potential is-0.5 +/-0.1V, and the abrasion volume is 0.9 +/-0.1 multiplied by 10^-11m³. The Ti-Nb-Zr-Cr-Sc alloy manufactured by the additive has good wear resistance and electrochemical corrosion performance, and has very wide application prospect in clinical repair as a high-performance medical metal material.

TABLE 1 tables of electrochemical corrosion resistance and frictional wear properties of the wear-resistant and corrosion-resistant titanium alloy prepared in examples 1 to 3 and the titanium alloy prepared in the arc melting furnace

Examples	Corrosion current/10-7Acm-2	Corrosion potential/V	Wear volume/m3
				Example 1	1.7±0.3	-0.4±0.1	1.2±0.1×10-11
Example 2	1.0±0.3	-0.5±0.1	1.5±0.1×10-11
				Example 3	0.9±0.3	-0.5±0.1	0.9±0.1×10-11
Arc melted Ti-Nb-Zr-Cr alloy	2.1±0.3	-0.7±0.1	2.8±0.2×10-11

。

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.