CN110499438B

CN110499438B - Material composition, titanium alloy product and preparation method thereof

Info

Publication number: CN110499438B
Application number: CN201910945630.9A
Authority: CN
Inventors: 要东明; 樊荣荣; 唐勇; 吕键; 黎波; 李明明; 张飞豹
Original assignee: Guangdong Institute Of Aeronautics And Astronautics Equipment & Technology
Current assignee: Aviation Equipment Research Institute Of Guangdong Academy Of Sciences; Guangdong Academy Of Sciences Zhuhai Industrial Technology Research Institute Co ltd
Priority date: 2019-09-30
Filing date: 2019-09-30
Publication date: 2021-06-04
Anticipated expiration: 2039-09-30
Also published as: CN110499438A

Abstract

The invention relates to a material composition, a titanium alloy product and a preparation method thereof. The material composition comprises the following components in percentage by mass: 10 to 40 percent of Nb, 54.8 to 84.95 percent of Ti, 1 to 5 percent of Mo, 0.01 to 0.1 percent of rare earth elements and a first component, wherein in the material composition, the first component comprises at least one of 1 to 5 percent of Ta, 1 to 3 percent of V, 1 to 4 percent of W, 0.01 to 0.1 percent of Fe, 0.01 to 0.3 percent of Cr, 0.01 to 0.5 percent of Cu, 1 to 3 percent of Mn and 0.01 to 0.1 percent of Si in percentage by mass. The titanium alloy product with higher tensile strength and compactness can be prepared by adopting the material composition.

Description

Material composition, titanium alloy product and preparation method thereof

Technical Field

The invention relates to the field of biological materials, in particular to a material composition, a titanium alloy product and a preparation method thereof.

Background

The titanium alloy material has the characteristics of corrosion resistance, good processability, biocompatibility and the like, and is gradually replacing traditional biomedical metal materials such as stainless steel and the like, so that the titanium alloy material becomes a novel medical carrier material for clinically diagnosing, treating and repairing or replacing human tissues and organs or enhancing the functions of the human tissues and organs. Titanium alloy products are widely used in surgical implantation, for example, as artificial knee joints, femoral joints, dental implants, gum and denture braces. However, the alloy product prepared by the traditional titanium alloy material has lower tensile strength and compactness, and can not meet the actual requirement.

Disclosure of Invention

Based on the above, there is a need for a material composition capable of producing a titanium alloy product with high tensile strength and compactness.

In addition, a titanium alloy product and a preparation method thereof are also provided.

The material composition comprises the following components in percentage by mass: 10% -40% of Nb, 54.8% -84.95% of Ti, 1% -5% of Mo, 0.01% -0.1% of rare earth elements and a first component, wherein in the material composition, the first component comprises at least one of 1% -5% of Ta, 1% -3% of V, 1% -4% of W, 0.01% -0.1% of Fe, 0.01% -0.3% of Cr, 0.01% -0.5% of Cu, 1% -3% of Mn and 0.01% -0.1% of Si in percentage by mass.

In the material composition, by limiting the mass percentage of Nb and Mo, Nb and Mo can be matched with Ti to form a solid solution, then limiting the mass percentage of the first component, Ta, V and W in the first component can be matched with Ti to form a solid solution, Fe, Cr, Cu, Mn and Si in the first component can be matched with Ti to form a precipitated phase, and then adding a rare earth element with a specific proportion to facilitate the grain structure refinement in the process of preparing a titanium alloy product by using the material composition, promote the formation of isometric crystals, improve the strength and hardness of the titanium alloy product prepared by using the material composition, and obtain the titanium alloy product with higher tensile strength and compactness. Tests prove that the titanium alloy product prepared from the material composition has the tensile strength of 840 MPa-966 MPa and the compactness of 99.4-99.84%.

In one embodiment, the chemical composition of the titanium alloy product comprises the following components in percentage by mass: 10% -40% of Nb, 54.8% -84.95% of Ti, 1% -5% of Mo, 0.01% -0.1% of rare earth elements and a first composition, wherein in the titanium alloy product, the first composition comprises at least one of 1% -5% of Ta, 1% -3% of V, 1% -4% of W, 0.01% -0.1% of Fe, 0.01% -0.3% of Cr, 0.01% -0.5% of Cu, 1% -3% of Mn and 0.01% -0.1% of Si in percentage by mass.

In one embodiment, the chemical composition of the titanium alloy product comprises the following components in percentage by mass: 10% -20% of Nb, 77.9% -84.95% of Ti, 1% -2% of Mo, 0.01% -0.05% of rare earth elements and a first composition, wherein in the titanium alloy product, the first composition comprises at least one of 1% -2% of Ta, 1% -2% of V, 1% -2% of W, 0.01% -0.05% of Fe, 0.01% -0.1% of Cr, 0.01% -0.1% of Cu, 1% -2% of Mn and 0.01% -0.1% of Si in percentage by mass.

In one embodiment, the rare earth element comprises at least one of La, Ce and Pr.

In one embodiment, the titanium alloy article is a medical titanium alloy article.

A method for preparing a titanium alloy product comprises the following steps:

3D printing is carried out on the material composition to obtain the titanium alloy product, and the chemical composition of the titanium alloy product comprises the following components in percentage by mass: 10% -40% of Nb, 54.8% -84.95% of Ti, 1% -5% of Mo, 0.01% -0.1% of rare earth elements and a first composition, wherein in the titanium alloy product, the first composition comprises at least one of 1% -5% of Ta, 1% -3% of V, 1% -4% of W, 0.01% -0.1% of Fe, 0.01% -0.3% of Cr, 0.01% -0.5% of Cu, 1% -3% of Mn and 0.01% -0.1% of Si in percentage by mass.

In one embodiment, before the step of 3D printing the material composition, the method further comprises the step of preparing the material composition: the material composition is obtained by mixing raw materials, and then sequentially grinding and sieving the raw materials to obtain the material composition, wherein the raw materials comprise 10-40% of Nb, 54.8-84.95% of Ti, 1-5% of Mo, 0.01-0.1% of rare earth elements and a first component in percentage by mass, and the first component comprises at least one of 1-5% of Ta, 1-3% of V, 1-4% of W, 0.01-0.1% of Fe, 0.01-0.3% of Cr, 0.01-0.5% of Cu, 1-3% of Mn and 0.01-0.1% of Si.

In one embodiment, the raw materials are mixed and then sequentially milled and sieved, wherein the milling mode is ball milling.

In one embodiment, the material composition has a particle size of 20 μm to 55 μm.

In one embodiment, the 3D printing is laser 3D printing, and the laser power is 250W-350W.

Drawings

FIG. 1 is a bar graph comparing the tensile strengths of the titanium alloy products of examples 1-13 and comparative examples 1-4;

FIG. 2 is a histogram comparing the densities of titanium alloy products of examples 1-13 and comparative examples 1-4.

Detailed Description

To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

The material composition of one embodiment can be used for preparing a titanium alloy product with high tensile strength and compactness. Specifically, the material composition comprises the following components in percentage by mass: 10 to 40 percent of Nb, 54.8 to 84.95 percent of Ti, 1 to 5 percent of Mo, 0.01 to 0.1 percent of rare earth elements and a first component, wherein in the material composition, the first component comprises at least one of 1 to 5 percent of Ta, 1 to 3 percent of V, 1 to 4 percent of W, 0.01 to 0.1 percent of Fe, 0.01 to 0.3 percent of Cr, 0.01 to 0.5 percent of Cu, 1 to 3 percent of Mn and 0.01 to 0.1 percent of Si in percentage by mass.

Ti is the main constituent of the material composition. The Ti has the advantages of no toxicity, light weight, high mechanical strength and excellent biocompatibility, and can be combined with other metals to form titanium alloy. Further, the mass percentage of Ti is 54.8% -84.95%. This arrangement helps to ensure that the Ti and other metallic elements are sufficiently mixed to form a titanium alloy article of good quality. Furthermore, the mass percentage of Ti is 77.9-84.95%. By optimizing the mass percentage content of Ti in the material composition, the titanium alloy product prepared by the material composition has better tensile strength, compactness and corrosion resistance. In one specific example, the Ti content is 78.07% by mass.

Nb is capable of forming a solid solution with Ti. Nb plays a role in solid solution strengthening in the process of preparing the titanium alloy product by using the material composition. Further, the mass percentage of Nb is 10-40%. The arrangement is beneficial to obtaining the titanium alloy product with higher tensile strength. Furthermore, the mass percentage of Nb is 10-20%. The tensile strength of the titanium alloy product prepared by the material composition is better by optimizing the mass percentage content of Nb in the material composition. In one specific example, the mass percentage of Nb is 15%.

Mo can form a solid solution with Ti, and the Mo plays a role in solid solution strengthening in the process of preparing the titanium alloy product by using the material composition. Further, the mass percentage of Mo is 1-5%. The arrangement is beneficial to obtaining the titanium alloy product with higher tensile strength. Furthermore, the mass percentage of Mo is 1-2%. By optimizing the mass percentage content of Mo in the material composition, the tensile strength of the titanium alloy product prepared by the material composition is better. In a specific example, the mass percentage of Mo is 1.7%.

The rare earth element is beneficial to refining the grain structure of the material and promoting the transformation of columnar crystal orientation equiaxed crystal in the process of preparing the titanium alloy product by using the material composition so as to improve the compactness of the finished product. Furthermore, the mass percentage of the rare earth elements is 0.01-0.1%. The arrangement is beneficial to obtaining the titanium alloy product with higher density. Furthermore, the mass percentage of the rare earth elements is 0.01-0.05%. The titanium alloy product prepared by the material composition has better compactness by optimizing the mass percentage content of the rare earth element in the material composition. Specifically, the rare earth element includes at least one of La, Ce, and Pr. In one specific example, the rare earth element is La. The mass percentage of the La is 0.03%. The rare earth element is not limited to the rare earth elements listed above, and may be other rare earth elements, and may be selected as needed.

The first component comprises at least one of 1-5% of Ta, 1-3% of V, 1-4% of W, 0.01-0.1% of Fe, 0.01-0.3% of Cr, 0.01-0.5% of Cu, 1-3% of Mn and 0.01-0.1% of Si in percentage by mass. The arrangement is favorable for obtaining the titanium alloy product with higher tensile strength and compactness. Wherein Ta, V and W can form a solid solution with Ti, and play a role in solid solution strengthening in the process of preparing the titanium alloy product by using the material composition. Fe. Cr, Cu, Mn and Si can form a precipitation phase with Ti, and play a role in precipitation strengthening in the process of preparing a titanium alloy product by using the material composition.

Further, the first component comprises at least one of 1-2% of Ta, 1-2% of V, 1-2% of W, 0.01-0.05% of Fe, 0.01-0.1% of Cr, 0.01-0.1% of Cu, 1-2% of Mn and 0.01-0.1% of Si in percentage by mass. The tensile strength of the titanium alloy product prepared by the material composition is better by optimizing the mass percentage of the first component in the material composition. In a specific example, the first component includes, in mass percent, 1.3% Ta, 1.2% V, 1.2% W, 0.03% Fe, 0.07% Cr, 0.05% Cu, 1.3% Mn, and 0.05% Si.

In one embodiment, the material composition comprises the following components in percentage by mass: 10 to 20 percent of Nb, 77.9 to 84.95 percent of Ti, 1 to 5 percent of Mo, 0.01 to 0.05 percent of rare earth elements and a first component, wherein in the material composition, the first component comprises at least one of 1 to 2 percent of Ta, 1 to 2 percent of V, 1 to 2 percent of W, 0.01 to 0.05 percent of Fe, 0.01 to 0.1 percent of Cr, 0.01 to 0.1 percent of Cu, 1 to 2 percent of Mn and 0.01 to 0.1 percent of Si in percentage by mass. The material composition obtained by combining the components in the mass percentage content range can be used for preparing titanium alloy products with higher tensile strength and compactness.

In one embodiment, the material composition comprises the following components in percentage by mass: 15% Nb, 78.07% Ti, 1.7% Mo, 0.03% La, 1.3% Ta, 1.2% V, 1.2% W, 0.03% Fe, 0.07% Cr, 0.05% Cu, 1.3% Mn and 0.05% Si. The titanium alloy product with higher tensile strength and compactness can be prepared by adopting the material composition.

In the material composition, by selecting a proper material range, Nb, Mo, V, W and Ta can be matched with Ti to form a solid solution, Fe, Cr, Cu, Mn and Si can be matched with Ti to form a precipitated phase, rare earth elements in a specific proportion are added to promote the grain structure refinement in the process of preparing a titanium alloy product by using the material composition, and the mass percentage of the materials is limited to obtain a better material proportion, so that the titanium alloy product prepared by using the material composition has higher tensile strength and compactness.

The titanium alloy article of an embodiment has higher tensile strength and compactness. Specifically, the chemical composition of the titanium alloy product comprises the following components in percentage by mass: 10 to 40 percent of Nb, 54.8 to 84.95 percent of Ti, 1 to 5 percent of Mo, 0.01 to 0.1 percent of rare earth element and a first composition, wherein in the titanium alloy product, the first composition comprises at least one of 1 to 5 percent of Ta, 1 to 3 percent of V, 1 to 4 percent of W, 0.01 to 0.1 percent of Fe, 0.01 to 0.3 percent of Cr, 0.01 to 0.5 percent of Cu, 1 to 3 percent of Mn and 0.01 to 0.1 percent of Si in percentage by mass.

In the chemical composition of the titanium alloy product, the mass percentage content of Nb, Ti, Mo, rare earth elements and the first composition is limited, wherein Nb, Mo, V, W and Ta can be matched with Ti to form a solid solution, Fe, Cr, Cu, Mn and Si can be matched with Ti to form a precipitated phase, and the rare earth elements in a specific proportion are added to facilitate the grain structure refinement in the process of preparing the titanium alloy product by adopting the material composition, promote the formation of isometric crystals and improve the strength and hardness of the titanium alloy product prepared by adopting the material composition so as to obtain the titanium alloy product with higher tensile strength and compactness.

Ti is the main constituent of the material composition. The Ti has the advantages of no toxicity, light weight, high mechanical strength and excellent biocompatibility, and can be combined with other metals to form titanium alloy. Further, the mass percentage of Ti is 54.8% -84.95%. This arrangement helps to ensure that the Ti and other metallic elements are sufficiently mixed to form a titanium alloy article of good quality. Furthermore, the mass percentage of Ti is 77.9-84.95%. The titanium alloy product has better tensile strength, compactness and corrosion resistance by optimizing the mass percentage of Ti in the titanium alloy product. In one specific example, the Ti content is 78.07% by mass.

Nb is capable of forming a solid solution with Ti. Nb plays a role in solid solution strengthening in the preparation process of the titanium alloy product. Further, the mass percentage of Nb is 10-40%. The arrangement is beneficial to obtaining the titanium alloy product with higher tensile strength. Furthermore, the mass percentage of Nb is 10-20%. The tensile strength of the titanium alloy product is better by optimizing the mass percentage content of Nb in the titanium alloy product. In one specific example, the mass percentage of Nb is 15%.

Mo can form a solid solution with Ti, and the Mo plays a role in solid solution strengthening in the preparation process of the titanium alloy product. Further, the mass percentage of Mo is 1-5%. The arrangement is beneficial to obtaining the titanium alloy product with higher tensile strength. Furthermore, the mass percentage of Mo is 1-2%. The tensile strength of the titanium alloy product is better by optimizing the mass percentage of Mo in the titanium alloy product. In a specific example, the mass percentage of Mo is 1.7%.

The rare earth elements play a role in refining the grain structure of the material and promoting the transformation of columnar crystal orientation equiaxed crystals in the preparation process of the titanium alloy product, and can improve the compactness of the titanium alloy product. Furthermore, the mass percentage of the rare earth elements is 0.01-0.1%. The arrangement is beneficial to obtaining the titanium alloy product with higher density. Furthermore, the mass percentage of the rare earth elements is 0.01-0.05%. The compactness of the titanium alloy product is better by optimizing the mass percentage content of the rare earth element in the titanium alloy product. Specifically, the rare earth element includes at least one of La, Ce, and Pr. In one specific example, the rare earth element is La. The mass percentage of the La is 0.03%. The rare earth element is not limited to the rare earth elements listed above, and may be other rare earth elements, and may be selected as needed.

The first composition comprises at least one of 1-5% of Ta, 1-3% of V, 1-4% of W, 0.01-0.1% of Fe, 0.01-0.3% of Cr, 0.01-0.5% of Cu, 1-3% of Mn and 0.01-0.1% of Si in percentage by mass. The arrangement is favorable for obtaining the titanium alloy product with higher tensile strength and compactness. Wherein Ta, V and W can form a solid solution with Ti, and play a role in solid solution strengthening in the preparation process of the titanium alloy product. Fe. Cr, Cu, Mn and Si can form a precipitation phase with Ti, and play a role in precipitation strengthening in the preparation process of the titanium alloy product.

Further, the first composition comprises at least one of 1-2% of Ta, 1-2% of V, 1-2% of W, 0.01-0.05% of Fe, 0.01-0.1% of Cr, 0.01-0.1% of Cu, 1-2% of Mn and 0.01-0.1% of Si in percentage by mass. The tensile strength of the titanium alloy product is better by optimizing the mass percentage of the first composition in the titanium alloy product. In a specific example, the first composition includes, in mass percent, 1.3% Ta, 1.2% V, 1.2% W, 0.03% Fe, 0.07% Cr, 0.05% Cu, 1.3% Mn, and 0.05% Si.

In one embodiment, the chemical composition of the titanium alloy product comprises the following components in percentage by mass: 10 to 20 percent of Nb, 77.9 to 84.95 percent of Ti, 1 to 5 percent of Mo, 0.01 to 0.05 percent of rare earth element and a first composition, wherein the first composition comprises at least one of 1 to 2 percent of Ta, 1 to 2 percent of V, 1 to 2 percent of W, 0.01 to 0.05 percent of Fe, 0.01 to 0.1 percent of Cr, 0.01 to 0.1 percent of Cu, 1 to 2 percent of Mn and 0.01 to 0.1 percent of Si in percentage by mass. The titanium alloy product has higher tensile strength and compactness.

In one embodiment, the chemical composition of the titanium alloy product comprises the following components in percentage by mass: 15% Nb, 78.07% Ti, 1.7% Mo, 0.03% La, 1.3% Ta, 1.2% V, 1.2% W, 0.03% Fe, 0.07% Cr, 0.05% Cu, 1.3% Mn and 0.05% Si. The titanium alloy product has higher tensile strength and compactness.

In one embodiment, the titanium alloy article is a medical titanium alloy article. Further, the titanium alloy article is a denture. The titanium alloy product is not limited to a medical titanium alloy product, and may be a titanium alloy product applied to other fields, for example, a titanium alloy product applied to the aerospace field.

In the chemical composition of the titanium alloy product, the mass percentage content of Nb, Ti, Mo, rare earth elements and the first composition is limited, wherein Nb, Mo, V, W and Ta can be matched with Ti to form a solid solution, Fe, Cr, Cu, Mn and Si can be matched with Ti to form a precipitated phase, and the rare earth elements with a specific proportion are added, so that the grain structure of the titanium alloy product is refined in the forming process, the formation of isometric crystals is increased, the strength, hardness and density of the titanium alloy product are improved, and the titanium alloy product with higher tensile strength and density is obtained.

According to the preparation method of the titanium alloy product, the titanium alloy product with high tensile strength and compactness can be prepared. Specifically, the preparation method comprises the following steps: 3D printing is carried out on the material composition to obtain a titanium alloy product, wherein the titanium alloy product comprises the following chemical components in percentage by mass: 10 to 40 percent of Nb, 54.8 to 84.95 percent of Ti, 1 to 5 percent of Mo, 0.01 to 0.1 percent of rare earth element and a first composition, wherein in the titanium alloy product, the first composition comprises at least one of 1 to 5 percent of Ta, 1 to 3 percent of V, 1 to 4 percent of W, 0.01 to 0.1 percent of Fe, 0.01 to 0.3 percent of Cr, 0.01 to 0.5 percent of Cu, 1 to 3 percent of Mn and 0.01 to 0.1 percent of Si in percentage by mass.

In one of the embodiments, the 3D printing is laser 3D printing. The material composition is melted layer by controlling the high-energy laser beam, so that the titanium alloy product undergoes rapid melting and solidification processes in the forming process, and the formed part has fine crystal grains, high density and excellent comprehensive mechanical properties. In addition, in the laser 3D printing process, the high-energy laser beam can convert columnar crystals in the molten material composition into isometric crystals, so that a titanium alloy product with an ultra-fine grain structure can be obtained, and the mechanical property of the titanium alloy product is improved.

Further, the laser power is 250W-350W. The material composition is melted by adopting the high-power laser beam, so that the melting and solidification processes of the material composition can be accelerated, and the prepared titanium alloy product has higher tensile strength and compactness. Further, the laser power was 350W. Specifically, the laser 3D printing step requires printing under vacuum or a protective atmosphere of inert gas to obtain a finished product. The arrangement can ensure the purity of the titanium alloy product and avoid the oxidation and deterioration of the material. More specifically, the laser 3D printing step requires printing under vacuum or a protective atmosphere of argon gas to obtain the finished product. The 3D printing is not limited to laser 3D printing, and may be other 3D printing technologies, and may be selected according to actual situations.

In one embodiment, the step of 3D printing the material composition further comprises the step of preparing the material composition: the raw materials are mixed, and then are sequentially ground and sieved to obtain a material composition, wherein the raw materials comprise, by mass, 10-40% of Nb, 54.8-84.95% of Ti, 1-5% of Mo, 0.01-0.1% of rare earth elements and a first component, and the first component comprises at least one of 1-5% of Ta, 1-3% of V, 1-4% of W, 0.01-0.1% of Fe, 0.01-0.3% of Cr, 0.01-0.5% of Cu, 1-3% of Mn and 0.01-0.1% of Si.

In one embodiment, the starting material is a metal powder. The metal powder is used as the raw material, so that the subsequent grinding time can be reduced, the material composition with smaller granularity can be more easily obtained, and the preparation of the titanium alloy product with higher density is facilitated.

Further, the grinding mode is ball milling. This arrangement helps to achieve sufficient grinding. Furthermore, stainless steel balls with the granularity of 3 mm-7 mm are adopted for ball milling. This arrangement helps to obtain a material composition with a smaller particle size. Specifically, stainless steel balls with a particle size of 5mm are used for ball milling. In one specific example, a planetary ball mill is used for milling. Furthermore, the rotating speed of the planetary ball mill is 100 r/min-200 r/min. This arrangement facilitates thorough mixing and grinding of the raw materials in the ball mill. Furthermore, the rotation speed of the planetary ball mill is 200 r/min. Specifically, the grinding time is 1-4 h. This arrangement facilitates thorough mixing and grinding of the raw materials in the ball mill. More specifically, the time for milling was 2 h.

In one embodiment, the particle size of the material composition is 20 μm to 55 μm. The arrangement is to obtain the material composition with small granularity and good uniformity, so that the titanium alloy product prepared by the material composition has high compactness and excellent comprehensive mechanical property. In one specific example, the particle size of the material composition is 45 μm.

The preparation method of the titanium alloy product has the following advantages:

(1) in the material composition of the titanium alloy product, by limiting the mass percentage of Nb and Mo, and Nb and Mo can be matched with Ti to form a solid solution, and then limiting the mass percentage of the first component, Ta, V and W in the first component can be matched with Ti to form a solid solution, and Fe, Cr, Cu, Mn and Si in the first component can be matched with Ti to form a precipitated phase, and then adding a rare earth element with a specific proportion to facilitate the grain structure refinement in the process of preparing the titanium alloy product by adopting the material composition, promote the formation of isometric crystals, improve the strength and hardness of the titanium alloy product prepared by adopting the material composition, and obtain the titanium alloy product with higher tensile strength and compactness. Tests prove that the tensile strength of the titanium alloy product is 840MPa to 966MPa, and the compactness is 99.4 percent to 99.84 percent.

(2) Pure titanium and Ti-6Al-4V have the advantages of high specific strength, excellent biocompatibility, good corrosion resistance and the like, and are widely applied to the field of medical implants. However, the elastic modulus of the two materials is not matched with that of human bones, and stress shielding effect can be caused during the use process, so that bone absorption is influenced, and bone loosening is caused. The Ti-Nb alloy has lower elastic modulus and is an ideal metal material for manufacturing medical implants.

(3) Due to the particularity of the 3D printing requirements on the materials and the high requirements of the medical false teeth on the materials, the traditional metal materials cannot meet the requirements of practical application. In the chemical composition of the titanium alloy product of the present application, Nb, Mo, V, W, and Ta can be used as β -phase stabilizers in the titanium alloy. The beta-phase stabilizer is helpful for reducing the phase transition temperature of the alloy and improving the supercooling degree, thereby playing a role in refining grains. In the process of laser 3D printing, the effect of stabilizing the metastable state beta phase in the structure can be provided, so that a certain amount of beta phase structure is still reserved in the structure of the material after the material is cooled to room temperature, and the beta phase structure can play a role in improving the mechanical property of the alloy material. Further, 5 elements such as Fe, Cr, Cu, Mn, and Si may form a precipitate phase with Ti, and this precipitate phase may inhibit dislocation movement in the structure and grain boundary slippage when the alloy material is deformed by an external force, and may serve the purpose of precipitation strengthening of the alloy material. Therefore, the titanium alloy product with high tensile strength and high density is prepared, and not only can the particularity of the 3D printing technology on the material be met, but also the high requirement of the medical denture on the material can be met.

(4) Through reasonable composition design, the raw materials are mixed by using a planetary ball mill, and the material composition obtained by grinding and sieving has small granularity and good uniformity, so that a titanium alloy product prepared by using the material composition has high tensile strength and compactness. By limiting the specific preparation method parameters and the mass percentage of each component in the titanium alloy product, the compactness of the prepared titanium alloy product reaches more than 99 percent, and the titanium alloy product is more suitable for preparing medical products.

The following are specific examples:

unless otherwise specified, in the following examples: elemental metal powders of Ti, Nb, Mo, V, W, Ta, Fe, Cr, Cu, Mn and Si are all available from West Anou Material science and technology Limited; the planetary ball mill was purchased from Nanjing university instruments and Equipment Co., Ltd; laser 3D printer was purchased from Hengshang technology, Inc.

Examples 1 to 11 and comparative examples 1 to 4

Titanium alloy products of examples 1 to 11 and comparative examples 1 to 4 were prepared according to the parameters in tables 1 and 2. The specific components and mass percentages of the material compositions of the titanium alloy products of examples 1 to 11 and comparative examples 1 to 4 are shown in table 1, and the unit is. The laser power and scanning speed used in the preparation of the titanium alloy articles of examples 1-11 and comparative examples 1-4 are detailed in table 2.

Specifically, the preparation process of the titanium alloy product is as follows:

(1) the raw materials are mixed and then sequentially ground and sieved to obtain the material composition. Wherein, the raw materials are evenly mixed in a planetary ball mill, the planetary ball mill adopts stainless steel balls with the granularity of 5mm to ball mill for 2 hours at the rotating speed of 200r/min, and finally, the material composition with the granularity of 45 mu m is screened out.

(2) And carrying out laser 3D printing on the material composition under the protective atmosphere of vacuum or argon to obtain the titanium alloy product. The laser power and scanning speed used are detailed in table 2.

TABLE 1

In table 1 "-" indicates that the components corresponding to the column are not added to the material composition of the titanium alloy article of this example. For example, the material composition of the titanium alloy article of comparative example 1 includes, in mass%, 15% of Nb, 79.6% of Ti, 1.7% of Mo, 1.3% of Ta, 1.2% of V, and 1.2% of W.

TABLE 2

Example 12

The titanium alloy article of this example was prepared using the same procedure as example 5, except that: in the step of "mixing the raw materials, then grinding and sieving sequentially to obtain the material composition", in this example, stainless steel balls with a particle size of 5mm were used for ball milling for 4 hours, and finally the material composition with a particle size of 20 μm was screened out.

Example 13

The titanium alloy article of this example was prepared using the same procedure as example 5, except that: in the "mixing of raw materials followed by grinding and sieving in order to obtain a material composition", this example used a stainless steel ball with a particle size of 5mm to ball mill for 1 hour, and finally a material composition with a particle size of 55 μm was screened out.

And (3) testing:

the tensile strength and the compactness of the titanium alloy products of examples 1 to 13 and comparative examples 1 to 4 are detected. The results are shown in Table 3, FIG. 1 and FIG. 2. In table 3, the results of measuring the tensile strength and the compactness of the titanium alloy products of examples 1 to 13 and comparative examples 1 to 4 are shown. FIG. 1 is a bar graph comparing the tensile strengths of the titanium alloy products of examples 1-13 and comparative examples 1-4. FIG. 2 is a histogram comparing the densities of titanium alloy products of examples 1-13 and comparative examples 1-4.

The specific test process is as follows:

at room temperature, a universal tensile testing machine is adopted to detect the tensile strength of the titanium alloy products of examples 1-13 and comparative examples 1-4, and an Archimedes drainage method is adopted to measure the compactness of the titanium alloy products of examples 1-13 and comparative examples 1-4. The results are shown in Table 3, FIG. 1 and FIG. 2.

TABLE 3

As can be seen from table 3, fig. 1 and fig. 2, the titanium alloy product of example 5 has the best tensile strength and compactness, wherein the tensile strength of the titanium alloy product is 966MPa, and the compactness is 99.84%. The titanium alloy product of comparative example 1 has a lower tensile strength and a lower compactness than those of the titanium alloy product of example 4, which shows that the presence of elements (Fe, Cr, Cu, Mn and Si) capable of forming a precipitated phase with Ti in the material composition contributes to the improvement of the tensile strength and the compactness of the titanium alloy product prepared from the material composition. The titanium alloy product of comparative example 2 has a lower tensile strength and a lower compactness than those of the titanium alloy product of example 5, which shows that the presence of rare earth elements in the material composition is helpful for improving the tensile strength and the compactness of the titanium alloy product prepared from the material composition. The tensile strength and the compactness of the titanium alloy product in the comparative example 3 are lower than those of the titanium alloy product in the example 6, which shows that the combination of the rare earth element in the material composition and the laser beam with proper power is helpful to improve the tensile strength and the compactness of the titanium alloy product prepared by the material composition. The tensile strength and the compactness of the titanium alloy product in the comparative example 4 are lower than those of the titanium alloy product in the example 5, which shows that the melting and solidification process of the material composition can be accelerated by melting the material composition by using the laser beam with proper power, and the titanium alloy product with higher tensile strength and compactness can be prepared.

In conclusion, the titanium alloy product prepared by the material composition has higher tensile strength and compactness. Tests prove that the tensile strength of the titanium alloy product is 840MPa to 966MPa, and the compactness is 99.4 percent to 99.84 percent.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. A method for preparing a titanium alloy product is characterized by comprising the following steps:

carrying out laser 3D printing on the material composition to obtain the titanium alloy product, wherein the laser power is 250-350W;

the titanium alloy product comprises the following chemical compositions in percentage by mass: 10-40% of Nb, 54.8-84.95% of Ti, 1-5% of Mo, 0.01-0.1% of rare earth elements and a first component, wherein in the titanium alloy product, the first component comprises 1-5% of Ta, 1-3% of V, 1-4% of W, 0.01-0.1% of Fe, 0.01-0.3% of Cr, 0.01-0.5% of Cu, 1-3% of Mn and 0.01-0.1% of Si in percentage by mass;

before the step of 3D printing the material composition, the method further comprises a step of preparing the material composition, wherein the step of preparing the material composition comprises the following steps: mixing the raw materials, and then grinding and sieving the raw materials in sequence to obtain the material composition, wherein the raw materials comprise the following components in percentage by mass: 10 to 40 percent of Nb, 54.8 to 84.95 percent of Ti, 1 to 5 percent of Mo, 0.01 to 0.1 percent of rare earth elements and a first component, wherein the first component comprises 1 to 5 percent of Ta, 1 to 3 percent of V, 1 to 4 percent of W, 0.01 to 0.1 percent of Fe, 0.01 to 0.3 percent of Cr, 0.01 to 0.5 percent of Cu, 1 to 3 percent of Mn and 0.01 to 0.1 percent of Si.

2. The method of claim 1, wherein the titanium alloy article has a chemical composition comprising, in mass percent: 15% of Nb, 78.07% of Ti, 1.7% of Mo, 0.03% of rare earth elements and a first component, wherein the first component comprises 1.3% of Ta, 1.2% of V, 1.2% of W, 0.03% of Fe, 0.07% of Cr, 0.05% of Cu, 1.3% of Mn and 0.05% of Si in percentage by mass.

3. The method of any one of claims 1-2, wherein the rare earth element comprises at least one of La, Ce, and Pr.

4. The method of manufacturing a titanium alloy product according to any one of claims 1 to 2, wherein the titanium alloy product is a medical titanium alloy product.

5. The method of claim 1, wherein the steps of mixing the raw materials, and then sequentially grinding and sieving are performed by ball milling.

6. The method of making a titanium alloy article according to claim 1, wherein said material composition has a particle size of 20 μ ι η to 55 μ ι η.

7. The method of making a titanium alloy article according to claim 6, wherein said material composition has a particle size of 45 μm.