A Mo-Mn biodegradable molybdenum alloy, its preparation method and application

Abstract

This invention discloses a Mo-Mn biodegradable molybdenum alloy, its preparation method, and its applications. The alloying elements include Mo and Mn, with Mn accounting for >0-30% by mass, and the remainder being Mo. Manganese-doped molybdenum powder is prepared by wet chemical methods or mechanical alloying. The manganese-doped molybdenum powder is then subjected to hot pressing sintering or multi-step spark plasma sintering to obtain the Mo-Mn alloy. The Mo-Mn biodegradable molybdenum alloy of this invention possesses excellent mechanical properties, providing long-term effective mechanical support in vivo, and exhibits good cell compatibility, blood compatibility, and tissue / organ compatibility, making it suitable for use as a biomedical implant.

Description

Technical Field

[0001] This invention belongs to the field of medical metal materials, specifically relating to a Mo-Mn biodegradable molybdenum alloy, its preparation method, and its application. Background Technology

[0002] Currently, the hot topics in medical biodegradable metal materials mainly include magnesium-based, zinc-based, and iron-based biodegradable metals, but they all have certain shortcomings in terms of degradation behavior and mechanical properties. For example, magnesium-based biodegradable metals degrade too quickly, leading to mechanical failure before tissue healing, and the generation of hydrogen gas during degradation is detrimental to tissue healing at the wound site; zinc-based biodegradable metals exhibit softening during processing, which is not conducive to strengthening mechanical properties; iron-based biodegradable metals have too slow corrosion rates, and their ferromagnetism can affect some imaging tests. Researchers have begun to search for a new biodegradable metal and its alloys. Molybdenum (Mo) is an essential element in most organisms and one of the essential trace elements for the human body. In vitro studies have shown that pure Mo exhibits uniform corrosion in simulated body fluids, with a corrosion rate of <0.02 mm / year, and the molybdenum ions dissolved during degradation do not cause apoptosis or necrosis of human endothelial cells or smooth muscle cells; in vivo animal experiments have shown that pure Mo filaments exhibit uniform degradation behavior in the arteries of mice and rats. Patent CN 114032430 A discloses a method for preparing biodegradable metallic molybdenum and its alloy for biliary stents. The alloy composition is 0.3wt%-17% Zn, 0.5wt%-15wt% Fe, and 0.5wt%-13wt% Mg, prepared by arc melting. However, due to the low melting points of the selected alloying elements, vaporization inevitably occurs during the arc melting process and the subsequent heat treatment, resulting in a lower-than-expected amount of added elements and a decrease in alloy density, which is detrimental to mechanical properties. Patent CN113930633B discloses a method for preparing a biodegradable Mo-Cu-X biomedical material, where X is one of Mg, Ag, Mn, Sr, Ca, and RE. However, this alloy exhibits poor mechanical properties, with a tensile strength of only 607.2 MPa, a yield strength of only 173.6 MPa, and an elongation of only 13.4%, indicating that the addition of alloying elements did not strengthen the material and may even have led to a degradation of mechanical properties. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the existing technology and provide a Mo-Mn biodegradable alloy, its preparation method and application, which has excellent mechanical properties, can provide long-term effective mechanical support in vivo, and has good cell compatibility, blood compatibility and tissue and organ compatibility, and can be used as a biomedical implant.

[0004] The objective of this invention is achieved through the following technical solution:

[0005] A Mo-Mn biodegradable molybdenum alloy, comprising Mo and Mn, wherein the mass percentage of Mn is >0-30%, and the remainder is Mo.

[0006] Preferably, in the Mo-Mn biodegradable molybdenum alloy, the mass percentage of Mn is >0 to 2%; more preferably, the mass percentage of Mn is 0.1% to 2%; and even more preferably, the mass percentage of Mn is 0.1% to 1%.

[0007] Specifically, the Mo-Mn biodegradable molybdenum alloy can be any of the following (1)-(10), in mass percentage:

[0008] (1) It is composed of 99.9% Mo and 0.1% Mn;

[0009] (2) It consists of 99.6% Mo and 0.4% Mn;

[0010] (3) It is composed of 99.2% Mo and 0.8% Mn;

[0011] (4) It is composed of 99.0% Mo and 1.0% Mn;

[0012] (5) It consists of 98.5% Mo and 1.5% Mn;

[0013] (6) It consists of 98.0% Mo and 2.0% Mn;

[0014] (7) It is composed of 95.0% Mo and 5.0% Mn;

[0015] (8) It is composed of 90.0% Mo and 10.0% Mn;

[0016] (9) It is composed of 75.0% Mo and 25.0% Mn;

[0017] (10) It consists of 70.0% Mo and 30.0% Mn.

[0018] The preparation method of the above-mentioned Mo-Mn biodegradable molybdenum alloy includes the following steps:

[0019] (1) Powder preparation: Manganese-doped molybdenum powder was prepared by wet chemical method or mechanical alloying.

[0020] (2) Forming and sintering: Manganese-doped molybdenum powder is hot-pressed or multi-step discharge plasma sintering to obtain Mo-Mn alloy.

[0021] In step (1), the wet chemical method uses soluble molybdenum salt and manganese-containing soluble metal salt as raw materials, and carries out precursor reduction in a hydrogen atmosphere and a temperature range of 500-1100℃ to prepare manganese-doped molybdenum powder.

[0022] Preferably, the wet chemical method includes the sol-gel method, spray drying method, or hydrothermal co-reduction method; the temperature is preferably 600-800℃.

[0023] In step (1), the mechanical alloying method uses molybdenum powder and manganese powder as raw materials. Under a high-purity protective atmosphere, a planetary ball mill is used to mechanically alloy the molybdenum powder and manganese powder to prepare manganese-doped metallic molybdenum powder.

[0024] In step (1), the average particle size of the manganese-doped molybdenum powder is preferably less than 1 μm.

[0025] The preferred process conditions for hot pressing sintering are: sintering at a pressure of 20–190 MPa and a temperature of 1150–1500 °C, holding for 1–3 hours, and sintering in a high vacuum atmosphere.

[0026] The discharge plasma sintering is a multi-step sintering process with the following conditions: first, the temperature is raised to 500–600°C and held for 3–5 minutes; then, the temperature is raised to 800–1000°C and held for 3–5 minutes; then, the temperature is raised to 1100–1400°C and held for 0.5–5 minutes for the third sintering step; the heating rate is 100°C / min; the pressure applied during sintering is 40–60 MPa; and the sintering atmosphere is high vacuum.

[0027] The Mo-Mn biodegradable molybdenum alloy prepared by the above method can also be machined to produce alloy bars with a diameter of 8–12 mm. The machining processes include rolling, forging, rapid solidification, or hot extrusion.

[0028] Before machining, the Mo-Mn biodegradable molybdenum alloy is preheated; the preheating temperature is 400℃~500℃, preferably 450℃~500℃, and the processing time is 2~4h.

[0029] The hot extrusion temperature is 1100-1300℃, preferably 1150-1250℃; the extrusion ratio is 10-36, preferably 12-20; and the extrusion speed is 0.1-10mm / s, preferably 0.5mm / s.

[0030] The surface of the Mo-Mn biodegradable molybdenum alloy is further coated with a coating. The thickness of the coating is 0.01–5 mm. The coating is at least one of a biodegradable polymer coating, a ceramic coating, and a pharmaceutical coating.

[0031] The biodegradable polymer coating is prepared by at least one of the following (1) and (2): (1) at least one of polycaprolactone, polylactic acid, polyhydroxyacetic acid, L-polylactic acid, polycyanoacrylate, polyanhydride, polydioxane, polyphosphononitrile, polyhydroxybutyrate or polyhydroxyvalerate; (2) a copolymer of at least two of polylactic acid, polyhydroxyacetic acid, L-polylactic acid, polycaprolactone and polydioxane; the molecular weight of the biodegradable polymer coating is 5,000 to 100,000.

[0032] The ceramic coating is prepared from at least one of the following materials: hydroxyapatite, anhydrous dicalcium phosphate, tricalcium phosphate, tetracalcium oxyphosphate, dicalcium phosphate, fluorapatite, octacalcium phosphate, magnesium hydroxide, or strontium phosphide.

[0033] The drug coating is at least one of the following: anticoagulant, rapamycin and its derivative coating, paclitaxel coating, everolimus coating, sirolimus coating, phosphocholine coating, radiocine D, endothelial growth factor, heparin coating, mitomycin coating, or antibacterial coating.

[0034] The application of the Mo-Mn biodegradable molybdenum alloy is for the preparation of biodegradable biomedical implants, including any one of the following (1) to (4):

[0035] (1) The application of the Mo-Mn molybdenum alloy as a biodegradable stent for biomedical use, wherein the stent includes at least one of tracheal stent, esophageal stent, intestinal stent, vascular stent, biliary stent, and urethral stent;

[0036] (2) The application of the Mo-Mn molybdenum alloy as a dental restorative instrument, wherein the dental restorative instrument includes at least one of dental implant materials and root canal files;

[0037] (3) The application of the Mo-Mn molybdenum alloy as a biodegradable suturing instrument, wherein the biodegradable suturing instrument includes at least one of absorbable skin suture staples and absorbable sutures;

[0038] (4) The application of the Mo-Mn molybdenum alloy as a biodegradable orthopedic implant, wherein the orthopedic implant includes at least one of bone plates, intramedullary nails, screws, bone pins, spinal fixation devices, patellar consolidation devices, bone repair materials, and bone tissue repair scaffolds.

[0039] The principle of this invention is as follows: First, manganese (Mn) is added as the main alloying element to provide biological functions, such as inhibiting the growth of osteosarcoma and specifically killing osteosarcoma cells. Second, the strengthening effect of manganese relative to the molybdenum matrix enhances toughness; the mechanical properties and corrosion behavior of the alloy are controlled by adjusting the manganese content. Third, the addition of manganese regulates the degradation behavior of the alloy. Since the standard electrode potential of manganese is -1.185V, much lower than that of molybdenum (-0.15V), the manganese-containing second phase in the alloy matrix will form a corrosion galvanic cell with the molybdenum matrix. By controlling the content of the alloying element, the content of the second phase in the alloy can be controlled, and theoretically, the degradation rate of the alloy can be controlled through the corrosion galvanic cell reaction.

[0040] Compared with the prior art, the present invention has the following advantages and effects:

[0041] (1) The powder making process is simple and efficient, and can be used for large-scale powder making, which greatly reduces the time required for powder making. It can meet the requirements for the preparation of manganese-doped molybdenum powder, and the powder has fine particle size, high uniformity of particle size distribution, and high sphericity, resulting in good quality.

[0042] (2) The sintering technology used simultaneously heats and pressurizes the powder, which puts the powder in a thermoplastic state with low deformation resistance. This is beneficial to the flow mass transfer process and the uniform diffusion of the powder. In addition, for the sintering process, this technology can reduce the sintering temperature and sintering time, resulting in a Mo-Mn alloy with good comprehensive performance.

[0043] (3) The data from the potentiodynamic polarization curve test show that the degradation rate of the alloy of the present invention is in the range of 0.32 to 3.05 mm / year, which proves that these alloys can meet the specific mechanical performance requirements of various parts of the body while being absorbed by the body during service.

[0044] (4) The Mo-Mn molybdenum alloy of the present invention exhibits good biocompatibility in experiments at the cellular level and is an ideal biodegradable biomaterial. Detailed Implementation

[0045] To facilitate understanding of the present invention, specific embodiments will be described in detail below. These embodiments will help those skilled in the art to further understand the present invention; however, they are not intended to limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements to the present invention without departing from its conceptual framework, and these modifications and improvements all fall within the scope of protection of the present invention.

[0046] Example 1: Preparation of sintered Mo-0.1Mn alloy (mechanical alloying powder preparation + hot pressing sintering)

[0047] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 0.1% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. The Mo-0.1Mn alloy was then prepared by hot-pressing and sintering at 1400℃ under a pressure of 60 MPa and a high vacuum atmosphere for 2 h. The relative density was 99.2%.

[0048] Example 2: Preparation of sintered Mo-0.4Mn alloy (mechanical alloying powder preparation + hot pressing sintering)

[0049] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 0.4% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. The Mo-0.4Mn alloy was then prepared by hot-pressing and sintering at 1400℃ under a pressure of 60 MPa and a high vacuum atmosphere for 2 h. The relative density was 99.8%.

[0050] Example 3: Preparation of sintered Mo-1.0Mn alloy (mechanical alloying powder preparation + hot pressing sintering)

[0051] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 1.0% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. The Mo-1.0Mn alloy was then prepared by hot-pressing and sintering at 1400℃ under a pressure of 60 MPa and a high vacuum atmosphere for 2 h. The relative density was 99.4%.

[0052] Example 4: Preparation of sintered Mo-2.0Mn alloy (mechanical alloying powder preparation + hot pressing sintering)

[0053] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 2.0% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. The Mo-2.0Mn alloy was then prepared by hot-pressing and sintering at 1300℃ under a pressure of 85 MPa and a high vacuum atmosphere for 2 h. The relative density was 98.7%.

[0054] Example 5: Preparation of sintered Mo-5.0Mn alloy (mechanical alloying powder preparation + hot pressing sintering)

[0055] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 5.0% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. The Mo-5.0Mn alloy was then prepared by hot-pressing and sintering at 1300℃ under a pressure of 85 MPa and a high vacuum atmosphere for 2 h. The relative density was 98.6%.

[0056] Example 6: Preparation of sintered Mo-10.0Mn alloy (mechanical alloying powder preparation + hot pressing sintering)

[0057] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 10.0% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. The Mo-10.0Mn alloy was then prepared by hot-pressing and sintering at 1200℃ under a pressure of 100 MPa and a high vacuum atmosphere for 2.5 h. The relative density was 98.4%.

[0058] Example 7: Preparation of sintered Mo-25.0Mn alloy (mechanical alloying powder preparation + hot pressing sintering)

[0059] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 25.0% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. The Mo-25.0Mn alloy was then prepared by hot-pressing and sintering at 1200℃ under a pressure of 100 MPa and a high vacuum atmosphere for 2.5 h. The relative density was 98.5%.

[0060] Example 8: Preparation of sintered Mo-0.1Mn alloy (mechanical alloying powder preparation + multi-step spark plasma sintering)

[0061] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 0.1% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 500℃ and held for 3 min; then, the temperature was raised to 900℃ and held for 3 min; finally, the temperature was raised to 1250℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 40 MPa, and the sintering atmosphere was high vacuum. This method successfully prepared a Mo-0.1Mn alloy with a relative density of 99.1%.

[0062] Example 9: Preparation of sintered Mo-0.4Mn alloy (mechanical alloying powder preparation + multi-step spark plasma sintering)

[0063] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 0.4% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 500℃ and held for 3 min; then, the temperature was raised to 900℃ and held for 3 min; finally, the temperature was raised to 1250℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 40 MPa, and the sintering atmosphere was high vacuum. This method successfully prepared a Mo-0.4Mn alloy with a relative density of 99.7%.

[0064] Example 10: Preparation of sintered Mo-1.0Mn alloy (mechanical alloying powder preparation + multi-step spark plasma sintering)

[0065] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 1.0% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 500℃ and held for 3 min; then, the temperature was raised to 900℃ and held for 3 min; finally, the temperature was raised to 1250℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 40 MPa, and the sintering atmosphere was high vacuum. This method successfully prepared a Mo-1.0Mn alloy with a relative density of 99.5%.

[0066] Example 11: Preparation of sintered Mo-2.0Mn alloy (mechanical alloying powder preparation + multi-step spark plasma sintering)

[0067] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 2.0% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 600℃ and held for 4 min; then, the temperature was raised to 1000℃ and held for 5 min; and finally, the temperature was raised to 1300℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 60 MPa, and the sintering atmosphere was high vacuum. This method successfully prepared Mo-2.0Mn alloy with a relative density of 98.8%.

[0068] Example 12: Preparation of sintered Mo-5.0Mn alloy (mechanical alloying powder preparation + multi-step spark plasma sintering)

[0069] Using pure molybdenum powder and pure manganese powder as raw materials, the ratio of pure molybdenum to pure manganese was calculated based on a manganese mass fraction of 5.0% in metallic molybdenum; the ball-to-powder ratio was 5:1, the ball milling medium was anhydrous ethanol, the ball milling speed was 250 rpm, and the ball milling time was 24 h, resulting in manganese-doped metallic molybdenum powder. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 600℃ and held for 4 min; then, the temperature was raised to 1000℃ and held for 5 min; finally, the temperature was raised to 1300℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 60 MPa, and the sintering atmosphere was high vacuum, thus preparing Mo-5.0Mn alloy with a relative density of 98.5%.

[0070] Example 13: Preparation of sintered Mo-10.0Mn alloy (mechanical alloying powder preparation + multi-step spark plasma sintering)

[0071] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 10.0% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 600℃ and held for 4 min; then, the temperature was raised to 1000℃ and held for 5 min; and finally, the temperature was raised to 1300℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 60 MPa, and the sintering atmosphere was high vacuum. This method successfully prepared Mo-10.0Mn alloy with a relative density of 98.7%.

[0072] Example 14: Preparation of sintered Mo-25.0Mn alloy (mechanical alloying powder preparation + multi-step spark plasma sintering)

[0073] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 25.0% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 600℃ and held for 4 min; then, the temperature was raised to 1000℃ and held for 5 min; and finally, the temperature was raised to 1300℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 60 MPa, and the sintering atmosphere was high vacuum. This method successfully prepared Mo-25.0Mn alloy with a relative density of 98.4%.

[0074] Example 15: Preparation of sintered Mo-0.1Mn alloy (wet chemical powder preparation + hot pressing sintering)

[0075] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 0.1% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Hot-pressing sintering was then performed at 1400℃ under a pressure of 60 MPa and a high vacuum atmosphere for 2 hours to prepare a Mo-0.1Mn alloy with a relative density of 99.2%.

[0076] Example 16: Preparation of sintered Mo-0.4Mn alloy (wet chemical powder preparation + hot pressing sintering)

[0077] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 0.4% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Hot-pressing sintering was then performed at 1400℃ under a pressure of 60 MPa and a high vacuum atmosphere for 2 hours to prepare a Mo-0.4Mn alloy with a relative density of 99.9%.

[0078] Example 17: Preparation of sintered Mo-1.0Mn alloy (wet chemical powder preparation + hot pressing sintering)

[0079] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 1.0% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Hot-pressing sintering was then performed at 1400℃ under a pressure of 60 MPa and a high vacuum atmosphere for 2 hours to prepare a Mo-1.0Mn alloy with a relative density of 99.6%.

[0080] Example 18: Preparation of sintered Mo-2.0Mn alloy (wet chemical powder preparation + hot pressing sintering)

[0081] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 2.0% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Hot-pressing sintering was then performed at 1300℃ under a pressure of 85 MPa and a high vacuum atmosphere for 2 hours to prepare a Mo-2.0Mn alloy with a relative density of 99.1%.

[0082] Example 19: Preparation of sintered Mo-5.0Mn alloy (wet chemical powder preparation + hot pressing sintering)

[0083] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 5.0% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. Hot pressing sintering was then performed at 1300℃ under a pressure of 85 MPa in a high vacuum atmosphere for 2 h to prepare Mo-5.0Mn alloy. The relative density was 98.9%.

[0084] Example 20: Preparation of sintered Mo-10.0Mn alloy (wet chemical powder preparation + hot pressing sintering)

[0085] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 10.0% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Hot-pressing sintering was then performed at 1200℃ under a pressure of 100 MPa and a high vacuum atmosphere for 2.5 h to prepare a Mo-10.0Mn alloy with a relative density of 99.0%.

[0086] Example 21: Preparation of sintered Mo-25.0Mn alloy (wet chemical powder preparation + hot pressing sintering)

[0087] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 25.0% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Hot-pressing sintering was then performed at 1200℃ under a pressure of 100 MPa and a high vacuum atmosphere for 2.5 h to prepare the Mo-25.0Mn alloy. The relative density was 99.1%.

[0088] Example 22: Preparation of sintered Mo-0.1Mn alloy (wet chemical powder preparation + multi-step spark plasma sintering)

[0089] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 0.1% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 500℃ and held for 3 min; then, it was raised to 900℃ and held for 3 min; finally, it was raised to 1250℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 40 MPa, and the sintering atmosphere was high vacuum. This process successfully prepared a Mo-0.1Mn alloy with a relative density of 99.2%.

[0090] Example 23: Preparation of sintered Mo-0.4Mn alloy (wet chemical powder preparation + multi-step spark plasma sintering)

[0091] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 0.4% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 500℃ and held for 3 min; then, it was raised to 900℃ and held for 3 min; finally, it was raised to 1250℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 40 MPa, and the sintering atmosphere was high vacuum. This process successfully prepared a Mo-0.4Mn alloy with a relative density of 99.8%.

[0092] Example 24: Preparation of sintered Mo-1.0Mn alloy (wet chemical powder preparation + multi-step spark plasma sintering)

[0093] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 1.0% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 500℃ and held for 3 min; then, it was raised to 900℃ and held for 3 min; finally, it was raised to 1250℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 40 MPa, and the sintering atmosphere was high vacuum. This process successfully prepared a Mo-1.0Mn alloy with a relative density of 99.6%.

[0094] Example 25: Preparation of sintered Mo-2.0Mn alloy (wet chemical powder preparation + multi-step spark plasma sintering)

[0095] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 2.0% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 600℃ and held for 4 min; then, it was raised to 1000℃ and held for 5 min; finally, it was raised to 1300℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 60 MPa, and the sintering atmosphere was high vacuum. This process successfully prepared a Mo-2.0Mn alloy with a relative density of 99.0%.

[0096] Example 26: Preparation of sintered Mo-5.0Mn alloy (wet chemical powder preparation + multi-step spark plasma sintering)

[0097] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 5.0% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 600℃ and held for 4 min; then, the temperature was raised to 1000℃ and held for 5 min; and finally, the temperature was raised to 1300℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 60 MPa, and the sintering atmosphere was high vacuum. This method successfully prepared Mo-5.0Mn alloy with a relative density of 98.8%.

[0098] Example 27: Preparation of sintered Mo-10.0Mn alloy (wet chemical powder preparation + multi-step spark plasma sintering)

[0099] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 10.0% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 600℃ and held for 4 min; then, it was raised to 1000℃ and held for 5 min; finally, it was raised to 1300℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 60 MPa, and the sintering atmosphere was high vacuum. This process successfully prepared a Mo-10.0Mn alloy with a relative density of 98.7%.

[0100] Example 28: Preparation of sintered Mo-25.0Mn alloy (wet chemical powder preparation + multi-step spark plasma sintering)

[0101] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 25.0% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. Multi-step spark plasma sintering was then performed: first, the temperature was raised to 600℃ and held for 4 min; then, it was raised to 1000℃ and held for 5 min; finally, it was raised to 1300℃ and held for 5 min for a third sintering step. The heating rate was 100℃ / min, the pressure applied during sintering was 60 MPa, and the sintering atmosphere was high vacuum. This process successfully prepared a Mo-25.0Mn alloy with a relative density of 98.9%.

[0102] Example 29: Preparation of sintered Mo-0.1Mn alloy (mechanical alloying powder preparation + conventional hot sintering)

[0103] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 0.1% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. The powder was cold-pressed under a pressure of 200 MPa, and then hot-sintered at 1400℃ for 2 h under a protective atmosphere to prepare a Mo-0.1Mn alloy with a relative density of 98.7%.

[0104] Example 30: Preparation of sintered Mo-0.4Mn alloy (mechanical alloying powder preparation + conventional hot sintering)

[0105] Using pure molybdenum powder and pure manganese powder as raw materials, with the ratio of pure molybdenum to pure manganese calculated based on a manganese mass fraction of 0.4% in metallic molybdenum; a ball-to-powder ratio of 5:1; anhydrous ethanol as the ball milling medium; a ball milling speed of 250 rpm; and a ball milling time of 24 h, manganese-doped metallic molybdenum powder was obtained. The powder was cold-pressed under a pressure of 200 MPa, and then hot-sintered at 1400℃ for 2 h under a protective atmosphere to prepare Mo-0.4Mn alloy. The relative density was 98.9%.

[0106] Example 31: Preparation of sintered Mo-0.1Mn alloy (wet chemical powder preparation + conventional hot sintering)

[0107] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 0.1% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. The powder was cold-pressed under 200 MPa pressure, and then hot-sintered at 1400℃ for 2 hours under a protective atmosphere to prepare a Mo-0.1Mn alloy with a relative density of 98.9%.

[0108] Example 32: Preparation of sintered Mo-0.4Mn alloy (wet chemical powder preparation + conventional hot sintering)

[0109] Using ammonium molybdate, manganese nitrate, ammonium nitrate, and glycine as raw materials, the ratio of ammonium molybdate to manganese nitrate was calculated based on a manganese mass fraction of 0.4% in metallic molybdenum; the ratio of ammonium nitrate to glycine was calculated based on a molar ratio of 1:2.5. All raw materials were dissolved in water to prepare a solution. The solution was heated at 200℃, and after volatilization, concentration, and combustion reactions, a precursor powder was obtained. The precursor powder was reduced in hydrogen at 800℃ to obtain manganese-doped metallic molybdenum powder. The powder was cold-pressed under 200 MPa pressure, and then hot-sintered at 1400℃ for 2 hours under a protective atmosphere to prepare a Mo-0.4Mn alloy with a relative density of 99.2%.

[0110] Table 1. Composition and Processing Technology of Mo-Mn Alloys

[0111]

[0112]

[0113]

[0114] Example 33: Preparation of hot-extruded Mo-Mn alloys

[0115] First, sintered Mo-Mn alloys were prepared according to the steps in Examples 1 to 32 of this invention. Mo-Mn alloy rods were then prepared by radial hot extrusion. The ingot was preheated for 3 hours, and the material was first held at 470°C, followed by hot extrusion at 1200°C, with an extrusion ratio of 12 and an extrusion speed of 0.5 mm / s, yielding Mo-Mn alloy rods with a diameter of 10 mm.

[0116] Example 34: Mechanical property testing of hot-extruded Mo-Mn alloys

[0117] The Mo-Mn alloy rods prepared in Example 33 were cut to specifications using an EDM wire cutter according to ASTM-E8m-09 standard, with five parallel control samples per group. The outer surface of the samples was sanded to 2000#, ultrasonically cleaned in anhydrous ethanol, and air-dried. Tensile tests were conducted at room temperature using a universal testing machine at a tensile rate of 0.05 mm / min. The tensile test results are shown in Table 2. With increasing Mn content, the tensile strength and yield strength of the alloy initially increased and then decreased, with the highest mechanical strength observed when 0.4 wt% Mn was added. Regarding alloy plasticity, with increasing Mn content, the tensile elongation at break initially increased and then decreased, with the best plasticity observed when 1.0 wt% Mn was added. For alloy materials prepared by different powder preparation processes, the samples prepared by the wet chemical method showed superior strength and plasticity compared to those prepared by the mechanical alloying method. For alloy materials prepared by different sintering processes, the mechanical properties of samples prepared by hot pressing sintering and multi-step discharge plasma sintering have been improved to varying degrees compared with those prepared by traditional hot sintering.

[0118] Table 2. Mechanical properties of Mo-Mn alloys

[0119]

[0120]

[0121]

[0122] Example 35: Corrosion Behavior Test of Mo-Mn Alloys

[0123] The Mo-Mn alloy rod prepared in Example 33 was wire-cut into sample pieces with a diameter of 10 mm and a height of 10 mm. The outer surface of the sample was polished to 2000# with sandpaper, ultrasonically cleaned in anhydrous ethanol, and air-dried. Then, a conventional three-electrode system was used, with a saturated calomel electrode as the reference electrode and a platinum electrode as the counter electrode, to perform potentiodynamic polarization curve testing. The open circuit potential (OCP) was recorded over 3600 seconds. Subsequently, linear sweep voltammetry (LSV) was performed at a scan rate of 1 mV / s, relative to the open circuit potential from -500 mV to +500 mV. The obtained voltage data are all relative to the saturated calomel electrode. The results of the Mo-Mn alloy potentiodynamic polarization curves obtained by Tafel extrapolation are shown in Table 3, and the composition of the test medium solution SBF is shown in Table 4. With increasing Mn content, the open circuit potential and corrosion potential of the Mo-Mn alloy decreased, while the corrosion current density increased, and the corrosion rate increased. By adjusting the content of the alloying element Mn, the corrosion rate of the alloy in SBF simulated body fluid can be controlled between 64 μm / y and 533 μm / y. This meets the corrosion rate requirements for biodegradable metal scaffolds (approximately 20 μm / y) and biodegradable metal orthopedic implants (approximately 500 μm / y).

[0124] Table 3. Material degradation and corrosion rates of Mo-Mn alloys calculated by Tafel extrapolation method

[0125]

[0126]

[0127]

[0128]

[0129] Table 4. Concentrations of major components in SBF simulated body fluids

[0130]

[0131] Example 36: Biocompatibility Experiment of Mo-Mn Alloys

[0132] The Mo-Mn alloy rods prepared in Example 4 were wire-cut into sample pieces with a diameter of 10 mm and a height of 2 mm. The outer surface of the sample was sanded to 2000# with sandpaper, ultrasonically cleaned in anhydrous ethanol, and air-dried. The sample was sterilized by ultraviolet light and placed in a sterile plate. DMEM cell culture medium containing 10% serum and 1% penicillin and streptomycin mixture was added to the plate at a ratio of 1.25 cm² / mL based on the surface area of ​​the sample material for extraction. The plate was incubated at 37°C, 95% relative humidity, and 5% CO₂ for 24 h to obtain the Mo-Mn alloy extract stock solution.

[0133] Extraction solution, cell seeding culture, and result observation: L929 fibroblasts were resuscitated and passaged, then suspended in DMEM cell culture medium and seeded at a density of 50,000 cells / mL in 96-well culture plates. After 24 hours of culture, the original culture medium was aspirated. Normal cell culture medium was added to the negative control group, and cell culture medium containing 10% dimethyl sulfoxide (DMSO) was added to the positive control group. The experimental groups were treated with a 25% diluted alloy extraction solution. The plates were incubated at 37°C with 5% CO2 for 24 hours. Cell viability was then tested using the Cell Counting Kit-8 (CCK-8) assay.

[0134] After 24 hours of culture in the extract, the cell viability of the three Mo-Mn alloys exceeded 75%, meeting the non-toxic requirements of GB / T16886.5. This indicates that the Mo-Mn alloys of this invention exhibit good biocompatibility. The cell viability test results using the CCK8 kit are summarized in Table 5. With increasing Mn content, the cell viability of the Mo-Mn alloy extract decreased slightly. Overall, the cell viability of all Mo-Mn alloy samples exceeded 90%, meeting the non-toxic requirements of GB / T16886.5. This indicates that the Mo-Mn alloys of this invention exhibit good biocompatibility.

[0135] Table 5. Biocompatibility test of Mo-Mn alloys (L929 fibroblasts)

[0136]

[0137]

[0138] Example 37: Preparation of Mo-0.4Mn alloy hydroxyapatite coating

[0139] The Mo-0.4Mn alloy rod prepared in Example 33 was used to prepare a sample piece with a size of φ10×2mm by wire cutting. The surface of the sample was polished smooth with 800#, 1000# and 2000# sandpaper in sequence, ultrasonically cleaned in anhydrous ethanol and acetone for 5 minutes, and dried with cold air.

[0140] Degreasing step: Soak the material in a weak alkaline solution containing 1 mol / L NaOH and 0.3 mol / L Na2CO3 to remove any small amount of oil stains that may exist on the substrate surface. The soaking temperature is 80℃ and the soaking time is 10 minutes.

[0141] Pickling step: Immerse the substrate in a weakly acidic solution containing 0.3 mol / L NH4H2PO4 and 0.01 mol / L KF to remove the small amount of residual oxide layer on the substrate surface, and immerse for 30 seconds at room temperature.

[0142] Electrodeposition steps: A constant current is used for cathodic electrodeposition, with the reaction current controlled at 1.5 mA / cm. 2 The reaction temperature was 70℃, and deionized water was used to prepare Ca(NO3). 2.4 An electrolyte solution with H2O and NH4H2PO4 concentrations of 0.2 mol / L and 0.12 mol / L, respectively, was prepared. The pH of the solution was adjusted to around 6 with ammonia and nitric acid, and the reaction time was 30 min to obtain a Mo-0.4Mn alloy with a hydroxyapatite coating.

[0143] Example 38: Preparation of Mo-0.4Mn alloy hydroxyapatite / polylactic acid composite coating

[0144] Polylactic acid (PLA) was dissolved in anhydrous ethanol to prepare a PLA solution with a concentration of 100 g / L. The Mo-0.4Mn alloy with a hydroxyapatite coating prepared in Example 37 was placed in the prepared PLA solution and immersed at room temperature for 40 s; then dried at 60 °C for 60 min to fix the PLA coating; and finally dried at 100 °C for 10 min to obtain the hydroxyapatite / PLA composite coating of the Mo-0.4Mn alloy.

[0145] Example 39: Preparation of Mo-0.4Mn alloy functional chitosan coating

[0146] The Mo-0.4Mn alloy rod prepared in Example 33 was used to prepare a sample piece with a size of φ10×2mm by wire cutting. The surface of the sample was polished smooth with 800#, 1000# and 2000# sandpaper in sequence, ultrasonically cleaned in anhydrous ethanol and acetone for 5 minutes, and dried with cold air.

[0147] The treated molybdenum alloy sheet was placed in a 25°C dopamine aqueous solution (1.5 mg / ml) and allowed to stand for 12 hours. Then, it was rinsed with deionized water to remove any unadhered dopamine and dried with nitrogen. The dopamine-treated surface was then placed in a 25°C 3% glutaraldehyde aqueous solution and stirred for 12 hours. Glutaraldehyde provides reactive aldehyde groups that covalently bond with dopamine and chitosan. The substrate was washed with deionized water to remove unbonded glutaraldehyde. The substrate was then immersed in a chitosan solution (1.5 mg / ml, dispersed in 0.1 mol / L acetic acid solution) to promote the bonding between the aldehyde groups on the alloy surface and the amino groups of the chitosan molecules, resulting in a chitosan coating.

[0148] The above description is merely an embodiment of the present invention, but the implementation of the present invention is not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention are equivalent substitutions and are included within the protection scope of the present invention.

Claims

1. A Mo-Mn-based degradable molybdenum alloy, characterized by: The alloy elements include Mo and Mn, and the mass percentage of Mn is 0.1-2%, and the rest is Mo; the Mo-Mn degradable molybdenum alloy is prepared by the following method: (1) powder preparation: the powder is prepared by wet chemical method or mechanical alloying to obtain manganese-doped metal molybdenum powder; (2) forming and sintering: the manganese-doped metal molybdenum powder is sintered by hot-pressing or multi-step spark plasma sintering to obtain Mo-Mn alloy; The process conditions of the hot-pressing sintering are: sintering at a temperature of 1150-1500 ℃ under a pressure of 20-190 MPa, and heat preservation for 1-3 h, and the sintering atmosphere is high vacuum; The spark plasma sintering is a multi-step sintering, and the process conditions are: firstly, heating to 500-600 ℃, and heat preservation for 3-5 min; then, heating to 800-1000 ℃, and heat preservation for 3-5 min; and then, heating to 1100-1400 ℃, and heat preservation for 0.5-5 min for the third step sintering; the heating rate is 100 ℃ / min; and the pressure applied during the sintering process is 40-60 MPa, and the sintering atmosphere is high vacuum.

2. The Mo-Mn-based degradable molybdenum alloy according to claim 1, characterized in that: The surface of the Mo-Mn degradable molybdenum alloy is coated with a coating, the thickness of the coating is 0.01-5 mm, and the coating is at least one of degradable polymer coating, ceramic coating and drug coating.

3. A method of producing the Mo-Mn-based degradable molybdenum alloy according to claim 1, characterized by The method comprises the following steps: (1) powder preparation: the powder is prepared by wet chemical method or mechanical alloying to obtain manganese-doped metal molybdenum powder; (2) forming and sintering: the manganese-doped metal molybdenum powder is sintered by hot-pressing or multi-step spark plasma sintering to obtain Mo-Mn alloy; The process conditions of the hot-pressing sintering are: sintering at a temperature of 1150-1500 ℃ under a pressure of 20-190 MPa, and heat preservation for 1-3 h, and the sintering atmosphere is high vacuum; The spark plasma sintering is a multi-step sintering, and the process conditions are: firstly, heating to 500-600 ℃, and heat preservation for 3-5 min; then, heating to 800-1000 ℃, and heat preservation for 3-5 min; and then, heating to 1100-1400 ℃, and heat preservation for 0.5-5 min for the third step sintering; the heating rate is 100 ℃ / min; and the pressure applied during the sintering process is 40-60 MPa, and the sintering atmosphere is high vacuum.

4. The method of claim 3, wherein the Mo-Mn-based degradable molybdenum alloy is prepared by the steps of: preparing a Mo-Mn-based alloy by mixing Mo and Mn; and performing heat treatment on the Mo-Mn-based alloy. In step (1), the wet chemical method is to use soluble molybdenum salt and soluble metal salt containing manganese as raw materials, to carry out precursor reduction in a hydrogen atmosphere and at a temperature of 500-1100 ℃, to prepare manganese-doped metal molybdenum powder.

5. The method for preparing Mo-Mn biodegradable molybdenum alloy according to claim 3, characterized in that: In step (1), the mechanical alloying method is to use molybdenum powder and manganese powder as raw materials, to carry out mechanical alloying of the molybdenum powder and the manganese powder in a high-purity protective atmosphere by using a planetary ball mill, to prepare manganese-doped metal molybdenum powder.

6. The method for preparing Mo-Mn biodegradable molybdenum alloy according to claim 3, characterized in that: The Mo-Mn degradable molybdenum alloy is mechanically processed to prepare alloy rods, and the mechanical processing is rolling, forging, rapid solidification or hot extrusion.

7. Use of the Mo-Mn-based degradable molybdenum alloy according to claim 1, characterized in that: The method is used for preparing a biomedically degradable implant, and comprises any one of the following (1)-(4): (1) The Mo-Mn system molybdenum alloy is applied as a biomedically degradable support, and the support includes at least one of a tracheal support, an esophageal support, an intestinal support, a blood vessel support, a biliary tract support, and a urethral support; (2) The Mo-Mn system molybdenum alloy is applied as a dental repair instrument, and the dental repair instrument includes at least one of a dental implant material and a root canal file; (3) The Mo-Mn system molybdenum alloy is applied as a degradable suture instrument, and the degradable suture instrument includes at least one of an absorbable skin suture nail and an absorbable suture thread; (4) The Mo-Mn system molybdenum alloy is applied as a degradable orthopedic implant, and the orthopedic implant includes at least one of a bone plate, an intramedullary nail, a screw, a bone needle, spinal internal fixation equipment, a patellar concentrator, a bone repair material, and a bone tissue repair support.

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